Cyclopentene Safety Procedures For Haier Upcoming Project

Cyclopentene

Researched By

Waqas Akram Muhammad

Lead Safety Trainer

Prepared by Waqas Akram Muhammad

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Cyclopentene Project

Project Name Cyclopentene

Prepared By Waqas Akram Muhammad

Request By Major M Saleem

Prepared For Haier Pakistan

Submitting Date 15 August 2013


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Table of Content

Chapter 1 Cyclopentene Overview

Definitionhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip06

11 Origin and Historyhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip06

121 Mechanism helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip08

122 Methodology Developmenthelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip11

123 Use in total synthesishelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip14

1231 Trosts synthesis of aphidicolinhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip15

1232 Piers synthesis of zizaene (1979)helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip15

1233 Hudlickys synthesis of hirstuene (1980) and isocomene (1984)helliphelliphelliphelliphelliphelliphelliphelliphelliphellip16

1234 Paquettes synthesis of alpha-Vetispirene (1982)helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip16

1235 Coreys synthesis of Antheridiogen-An (1985)helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip17

1236 Njardarsons synthesis of biotin (2007)helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip17

1237 Majetichss synthesis of salviasperanol (2008)helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip18

13 Cyclopentene propertieshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip18

14 Method of producing cyclopentene and description helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip18

141 Exampleshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip24

142 Comparatives Exampleshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip26

143 Brief Description of Drawinghelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip26

144 Background of the Inventionhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip26

145 Summary of the Inventionhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip27

146 Claimshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip28


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Chapter 2 Cyclopentene uses

2 1 Cyclopenetene used in monomer synthesis of Plastichelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip31

22 Monomer helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip31

211 Polymers helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip31

212 Examples of Polymers helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip31

213 How Polymers Form helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip31

214 Monomer word Derived helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip31

215 Natural Monomers helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip32

216 Molecular Weight helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip32

217 Industrial Use helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip32

2 2 Plastics helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip33

2 21 What is Plastics helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip33

222 How to make Plastic helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip34

223 Polymers are everywhere helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip34

224 Thermoplastics and Thermosetshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip35

225 Better catalysts improve plasticshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip37

Chapter 3 Safety Procedures of Cyclopentene

31 Product Identification helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip40

32 Physical and Chemical Propertieshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip40

33 First Aid Measureshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip40

34 Handling and Storagehelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip41

35 Hazards Identificationhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip41

36 Exposure ControlsPersonal Protectionhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip41


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37 Fire Fighting Measureshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip42

38 Accidental Release Measureshelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip43

39 Stability and Reactivityhelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip43


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Cyclopentene Definitions

1 Cyclopentene is a chemical compound with the formula C5H8 It is a colorless liquid with a petrol-

like odor It is one of the cycloalkenes Cyclopentene is produced industrially in large amounts It is

used as a monomer for synthesis of plastics and in a number of chemical syntheses It can be

obtained from vinylcyclopropane in the vinylcyclopropane-cyclopentene (Source Wikipedia)

2 The term cyclopenetene is used in reference to a chemical compound that is colourless with

petrol like smell It is produced industrially in large amounts and it is mainly used as a monomer for

synthesizing plastics (Wikipedia on Askcom)

Origins and History

The vinylcyclopropane rearrangement or cyclopentene rearrangement is a ring expansion

reaction converting a vinyl-substituted cyclopropane ring into a cyclopentene ring

Intense experimental as well as computational investigations have revealed that mechanistically

the vinylcyclopropane rearrangement can be thought of as either a diradical-mediated two-step

andor orbital-symmetry-controlled pericyclic process The amount by which each of the two

mechanisms is operative is highly dependent on the substrate Due to its ability to form

cyclopentene rings the vinylcyclopropane rearrangement has served several times as a key

reaction in complex natural product synthesis

Origins and History

In 1959 a young research chemist with Humble Oil and Refining (Esso now Exxon) named

Norman P Neureiter was instructed to find new uses for the excess butadiene produced from one


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of the refinery processes Discussions about carbine chemistry with one of the companys most

respectable consultants at the time William von Eggers Doering then a professor at Yale led the

young PhD graduate from Northwestern University to follow a recent procedure combining both

carbenes and butadiene In particular the procedure described the reaction of 13-butadiene with

carbenes generated from the action of base on chloroform or bromoform which had been studied

previously by Doering Neureiter then took the resulting 11-dichloro-22-dimethylcyclopropane and

under pyrolysis conditions (above 400 degC) discovered a rearrangement to 44-

dichlorocyclopentene which today is considered to be the first thermal vinylcyclopropane-

cyclopentene rearrangement in history

The corresponding all-carbon version of the reaction was independently reported by Emanuel

Vogel and Overberger amp Borchert just one year after the Neureiter publication appeared

Interestingly Doering although actively interacting with Humble Oil and Refining - and therefore

also with Neureiter - as a consultant in a 1963 publication stated the following CREDIT for

discovery that vinylcyclopropane rearranges to cyclopentene is due to Overberger and Borchert

and Vogel et al who appear to have developed several examples of the rearrangement

independently The development of further vinylcyclopropane rearrangement variants didnt take

long as demonstrated by Atkinson amp Rees in 1967 Lwowski in 1968 and Paladini amp Chuche in

1971


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It is remarkable that the classical vinylcyclopropane rearrangement was discovered after two of its

heteroatom variants had already been reported for almost 30 years and 12 years respectively

Although it is believed that the vinylcylcopropane rearrangement must have occurred during

Nikolay Demyanovs preparation of vinylcyclopropane by Hofmann elimination at elevated

temperatures in 1922 the cyclopropylimine-pyrroline rearrangement by Cloke in 1929 and Wilsons

cyclopropylcarbaldehyde-23-dihydrofuran rearrangement in 1947 are really the only examples of

vinylcyclopropane-like rearrangements

Mechanism

The mechanistic discussion on whether the vinylcyclopropane rearrangement proceeds through a

diradical-mediated two-step or a fully concerted orbital-symmetry-controlled mechanism has been

going on for more than half a century Kinetic data together with the secondary kinetic isotope

effects observed at the vinyl terminus of the vinylcyclopropane suggest a concerted mechanism

whereas product distribution indicates a stepwise-diradidal mechanism In the 1960s shortly after

the rearrangement was discovered it was established that the activation energy for the

vinylcyclopropane rearrangement is around 50kcalmol The kinetic data obtained for this

rearrangement were consistent with a concerted mechanism where cleavage of the cyclopropyl

carbon-carbon bond was rate-limiting Albeit a concerted mechanism seemed likely it was shortly

recognized that the activation energy to break the carbon-carbon bond in unsubstituted

cyclopropane was with 63kcalmol exactly 13kcalmol higher in energy than the parent activation

energy a difference remarkably similar to the resonance energy of the allyl radical


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Immediately people started to appreciate the possibility for a diradical intermediate arising from

homolytic cleavage of the weak C1-C2-cyclopropane bond under thermal conditions

The discussion on whether the vinylcyclopropane rearrangement proceeds via a fully concerted or

a two-step non-concerted mechanism was given further careful consideration when Woodward

and Hoffmann used the vinylcyclopropane rearrangement to exemplify [13]- sigmatropic concerted

alkyl shifts in 1969 They hypothesized that if a concerted mechanism was operative the

consequences of orbital-symmetry controlled factors would only allow the formation of certain

products According to their analysis of a vinylcyclopropane substituted with three R groups the

antarafacial [13]-shift of bond 12 to C-5 with retention at C-2 leading to the ar-cyclopentene and

the suprafacial [13]-shift of bond 12 to C-5 with inversion at C-2 leading to cyclopentene are

symmetry allowed whereas the suprafacial [13]-shift of bond 12 to C-5 with retention at C-2

leading to cyclopentene sr and the antarafacial [13]-shift of bond 12 to C-5 with inversion at C-2

leading to the ai cyclopentene are symmetry-forbidden It is important to note that Woodward and

Hoffmann based their analysis solely on the principles of the conservation of orbital symmetry

theory without however making any mechanistic or stereo chemical prediction

The attention directed towards the vinylcyclopropane rearrangement by Woodward and Hoffmann

as a representative example for [13]-carbon shifts clearly enhanced the interest in this reaction

Furthermore their analysis revealed potential experiments that would allow distinguishing between

a concerted or stepwise mechanism The stereo chemical consequences of a concerted reaction

pathway on the reaction outcome suggested an experiment where one would correlate the

obtained reaction stereochemistry with the predicted reaction stereochemistry for a model

substrate Observing the formation of ai- and sr-cyclopentene products would support the notion

that a stepwise non-concerted mechanism is operative whereas their absence would point towards


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a fully concerted mechanism As it turned out finding an appropriate substituted model substrate to

study the stereo chemical outcome of the vinylcyclopropane rearrangement was much more

challenging than initially thought since side reaction such as the homodienyl [15]-hydrogen shifts

and more so thermal stereo mutations tend to scramble stereochemical distinctions much faster

than rearrangements lead to the cyclopentene products

Even though deconvolution of the complex kinetic scenarios underlying these rearrangements was

difficult there have been several studies reported where exact and explicit deconvolutions of kinetic

and stereochemical raw data to account for the stereochemical contributions arising from

competitive stereomutations was possible


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Thereby rate constants for all four stereochemically distinct pathways of the vinylcyclopropane

rearrangement could be determined

The data clearly indicated that the mechanistic preferences of the rearrangements are system

dependent Whereas trans-vinylcyclopropanes tend to form more of the symmetry-allowed ar- and

si-cyclopentenes supportive of a concerted mechanism the cis-vinylcyclopropanes preferentially

yield the symmetry-forbidden ai- and sr- products suggesting a more stepwise diradical

mechanism The influence of substituent effects on the reaction stereochemistry also becomes

apparent from the data Substituents with increased radical stabilizing ability not only lower the

rearrangements activation energy but also reclosure of the initially formed diradical species

becomes slower relative to the rate of cyclopentene formation resulting in an overall more

concerted mechanism with less stereomutation (eg entry 6 amp 7) In all cases though all the four

products were formed indicating that both orbital-symmetry controlled pericyclic as well as

diradical-mediated two-step mechanisms are operative either way The data is consistent with the

formation of biradical species on a relatively flat potential energy surface allowing for restricted

conformational flexibility before the products are formed The amount of conformational flexibility

and therefore conformational evolution accessible to the diradical species before forming product

depends on the constitution of the potential energy surface This notion is also supported by

computational work One transition state with a high diradicaloid character was found Following

the potential energy surface of the lowest energy path of the reaction it was found that a very

shallow regime allows the diradical species to undergo conformational changes and

stereoisomerization reactions with minor energetic consequences Furthermore it was shown that

substituents can favor stereoselective pathways by destabilizing species that allow stereochemical

scrambling

Methodology development

Arguably the biggest drawback of the vinylcyclopropane rearrangement as a synthetic method is its

intrinsically high activation barrier resulting in very high reaction temperatures (500-600degC) Not

only do these high temperatures allow side reactions with similar activation energies such as

homodienyl-[15]-hydrogen shifts to occur but also do they significantly limit the functional groups

tolerated in the substrates It was well recognized by the chemical community that in order for this


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reaction to become a useful synthetic method hopefully applicable in complex natural product

settings at some point some reaction development had to be done Some of the earliest attempts

to improve the vinylcyclopropane rearrangement as a synthetic method came from the Corey group

in 1972 They found that the reaction temperature could be lowered drastically when the

cyclopropane ring contained a dithiane group Even though the dithiane-substituted

vinylcyclopropane substrates required two synthetic steps starting from the corresponding 13-

dienes the method proved itself successful for the synthesis of a variety of substituted

cyclopentenes The immediate rearrangement products could be easily converted to the

corresponding cyclopentenones

Only a year later Simpson and co-workers demonstrated that also simple methoxy-substituted

vinylcyclopropanes show significantly faster reaction rates allowing the rearrangement to take

place at 220degC

A big improvement came in the mid-1970s from Barry M Trosts group It was found that siloxyvinyl

cyclopropanes as well as the analogous sulfinylvinyl cyclopropanes could be used as substrates to

build interesting annulated cyclopentene structures Albeit these reactions still required reaction

temperatures above 300degC they were able to make really useful products arising from the

annulation of cyclopentene to a present ring system


13

Paquette demonstrated that vinylcyclopropane rearrangements can also be mediated

photochemically In a particularly intriguing example he was able to show that vinylcyclopropanes

embedded within a cyclooctane core can be converted to the corresponding [5-5]-fused ring

systems

Further reaction improvement came when Hudlicky and Brown proved that vinylcyclopropane

rearrangements are amenable to transition metal catalysts Using a Rh (I) acetate catalyst they

were able to promote rearrangements from room temperature to 80degC

Analogous to the rate acceleration observed in the anionic-oxy-Cope rearrangement Danheiser

reported a very similar effect for vinylcyclopropane substrates bearing [alkoxy] substituents

Another intriguing result was reported by Larsen in 1988 He was able to promote

vinylcyclopropane rearrangements with substrates such as the one shown in the reaction below at


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temperatures as low as -78degC The substrates were generated in situ upon ring contracting

thiocarbonyl Diels-Alder adducts under basic conditions This methodology allowed the formation

of numerous highly functionalized cyclopentenes in a stereoselective manner

Another low temperature vinylcyclopropane rearrangement was obtained by the Hudlicky group

The scope of this particular methodology is impressively broad and allows the formation of various

[5-5]- as well as [5-6]-carbon scaffolds

Use in total synthesis

Five-membered carbon rings are ubiquitous structural motifs in natural products In contrast to the

larger fully consonant cyclohexane scaffold cyclopentanes and their derivatives are dissonant

according to the Lapworth-Evans model of alternating polarities The dissonance in polarity clearly

limits the ways by which cyclopentanes can be disconnected which become evident in the

decreased number of general methods available for making five-membered rings versus the

corresponding six-membered rings Especially the fact that there is no Diels-Alder-equivalent for

the synthesis of five-membered rings has been bothering synthetic chemists for many decades


15

Consequentially after the vinylcyclopropane rearrangement was discovered around 1960 it didnt

take long for the synthetic community to realize the potential inherent to form cyclopentenes by

means of the vinylcyclopropane rearrangement As the vinylcyclopropane rearrangement

progressed as a methodology and the reaction conditions improved during the 1970s first total

syntheses making use of the vinylcycopropane rearrangement started to appear around 1980 Key

figures to apply this reaction in total synthesis were Barry M Trost Elias J Corey Thomas

Hudlicky Leo A Paquette

Trosts synthesis of aphidicolin (1979)

In 1979 Trost reported the synthesis of Aphidicolin using methodology around the

vinylcyclopropane rearrangement developed in their laboratory In one of their key steps they were

able to convert a late stage siloxyvinyllcyclopropane into a cyclopentene that contained the [6-6-

5]-fused carbon skeleton found within the natural product They were able to convert the

rearranged product into the natural product by further manipulations

Piers synthesis of zizaene (1979)

Piers synthesis of zizaene is another early example for the application of a vinylcyclopropane

rearrangement as a key disconnection


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Hudlickys synthesis of hirstuene (1980) and isocomene (1984)

Hudlicky has been one of the key figures in pushing the vinylcyclopropane rearrangements

forwards as a method and has used in multiple times in complex natural product synthesis A

particularly elegant piece of work is the chemistry developed to access both linear as well as

angular triquinanes starting from similar precursors He has been able to apply this strategy to

hirsuteneHirsutene and isocomene

Paquettes synthesis of alpha-Vetispirene (1982)

Paquette used a vinylcyclopropane rearrangement to build the spirocyclic natural product alpha-

Vetispirene in 1982


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Coreys synthesis of Antheridiogen-An (1985)

Elias J Corey has contributed heavily to the development of the vinylcyclopropane rearrangement

as a synthetic method In 1985 Corey and his student Andrew G Myers published an impressive

synthesis of Antheridiogen-an using a Lewis-acid mediated late-stage vinylcyclopropane

rearrangement

Njardarsons synthesis of biotin (2007)

More recently a copper-catalyzed heteroatom-vinylcyclopropane rearrangement was used to form

the tetrahydrothiophene core of biotin and the thiophene unit of Plavix respectively


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Majetichss synthesis of salviasperanol (2008)

In 2008 an acid-mediated vinylcyclopropane rearrangement was used to synthesize the natural

product salviasperanol

Cyclopentene properties

Nature a colorless liquid and have 07720 gcm3 density (20 degC) Melting point -135 Boiling

Point 442 degC 14225 refractive index A flash point of -34 deg C Dissolved in alcohol ether benzene

acetone and chloroform Do not dissolve in water Exist in the pyrolysis oil C5 fraction (about 2)

From cracking C5 extraction fraction obtained or by Cyclopentene dehydrated to produce

Industrial mainly by C5 fraction isolated from the selective hydrogenation Cyclopentadiene

obtained Failed to polymerization can also stimulated the two olefin copolymer conjugate Used in

various organic synthesis

Method of producing cyclopentene

A method of producing cyclopentene comprising the steps of depolymerizing dicyclopentadiene to

produce raw cyclopentadiene feeding the raw cyclopentadiene to a distillation tower having an

upper part cooled to a temperature near the boiling point of the cyclopentadiene and an outlet

maintained at 35 of 40 cyclopentadiene at the top outlet and impure components having high

boiling point at the lower outlet which are removed continuously mixing the highly pure

cyclopentadiene obtained thereby with hydrogen and reacting in a first hydrogenation reactor using

a palladium containing catalyst then mixing the resulting product with hydrogen and reacting in a

second hydrogenation reactor with a palladium containing catalyst cooling the resulting product

and separating the liquid phase from the gas phase and recirculating the gas phase for use in the

hydrogenation reactions


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14 Detailed Description


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After extensive study the inventors have discovered a method of removing substantially all

impurities of high boiling point from the raw cyclopentadiene obtained from decomposing

dicyclopentadiene and then supplying same for hydrogenation using a palladium containing

catalyst In other words the present invention encompasses a method of producing cyclopentene

combining two subprocesses one involving purifying cyclopentadiene obtained from thermal

decomposition or depolymerization of dicyclopentadiene and another involving the hydrogenation

reaction of the purified cyclopentadiene by mixing with hydrogen and reacting in the presence of a

palladium containing catalyst

The invention can be better understood with reference to the drawing in which raw material

containing a substantial portion of raw dicyclopentadiene may be supplied through pipe or inlet 1

into a depolymerization or thermal decomposition reactor 2 thereby to decompose or depolymerize

the dicyclopentadiene into raw cyclopentadiene containing various impurities such as unreacted

dicyclopentadiene co-dimer of cyclopenten etc which have a high boiling point The reactor is

maintained at 170 250 slightly higher pressure The raw dicyclopentadiene is in gaseous state The

raw cyclopentadiene produced by the depolymerization or decomposition is gaseous and contains

the above mentioned impurities and is fed through pipe 3 which cools the gas somewhat into the

midpoint 4-1 of distillation tower 4 The tower 4 comprises an upper heat exchanger 4-2 and a

lower heat exchanger 4-3 and an inlet at the midpoint between the upper and lower portions 4-1

and also the tower has an upper outlet (not labeled) connected to pipe 6 and a lower outlet (not

labeled) connected to pipe 5 The upper part 4-2 may be filled with packing material and is rapidly

cooled to a temperature of 30 outlet is maintained at 35 material and is maintained at 40 distillation

tower acts upon the raw cyclopentadiene to separate the high boiling point impurities from the

cyclopentadiene The high boiling point impurities or components are fractionated in the distillation

tower 4 and is removed continuously from the lower outlet 5 The gaseous cyclopentadiene is

removed continuously from the upper outlet 6 and is passed through pipe 6 and is then mixed with

a controlled stream of hydrogen gas passing through pipe 7 The ratio of hydrogen to purified

cyclopentadiene at this stage is 1 to 2 preferably 1 to 15 mol hydrogen per mol of

cyclopentadiene The mixture is then supplied to reactor 8 to be selectively hydrogenated in the

presence of a palladium containing catalyst The hydrogenation reactor 8 is at 50 preferably 70

slightly higher A conversion rate of 90 to 98 cyclopentene from the highly purified

cyclopentadiene was obtained


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The reaction product from reactor 8 is then again mixed at junction 10 with a controlled stream of

hydrogen gas passing through pipe 9 in the ratio of 1 to 20 preferably 1 to 7 mol of hydrogen to

one mol of unreacted cyclopentadiene and the unreacted cyclopentadiene contained in the

reaction product coming from reactor 8 is then selectively hydrogenated in the second

hydrogenation reactor 11 using a palladium containing catalyst The reactor 11 is at 50 70 slightly

higher pressure

Although shown herein to be mixed prior to hydrogenation reaction in reactors 8 and 11 the mixing

can be done within the reactors Also in place of the second hydrogenation reactor 11 the reaction

product of reactor 8 may be once liquified by cooling and then separated into gaseous and liquid

parts by a knock out pot The liquid portion may then be sent to an evaporator using a dosing pump

and the evaporated gas may be mixed with a controlled stream of hydrogen gas through pipes 9

and then introduced to the second hydrogenation reactor 11

The catalyst used in the hydrogenation reactions is a palladium containing catalyst carried for

example on alumina silica or magnesium oxide and used together with iron chromium etc The

same or different catalysts may be used in the different hydrogenation reactors 8 and 11

The reaction product from reactor 11 contains only a minute amount of cyclopentadiene monomer

about less than several hundred parts per million (ppm) It is cooled down by passing through a

cooling pipe 12 and then separated into two phases gas and liquid by a knock out pot 13 The

separated gases are sent via pipes 14 and are recycled through pipes 7 and 9 for use in the first

and second hydrogenation reactions The liquid portion containing the purified cyclopentene

passes through an outlet 15 and may be stored or sent to a further distillation process for further

use or treatment

As the distillation tower for fractionating of the raw material although it is possible to use any type

of distillation tower it is preferable to use one comprising an upper heat exchanger filled with

packing material and maintained at 30 at the upper side of an inlet used to feed in the raw

cyclopentadiene having impurities therein and a lower heat Heat exchanger located below the

inlet and filled with packing material and maintained at 40 150 gaseous state The upper outlet is

maintained at 35 C and more preferably 35 cyclopentadiene having various other impurities is

reacted to separate the impurities from the cyclopentadiene The impurities have high boiling point

and are direct to the lower outlet where such impurities are continuously removed The purified


22

gaseous cyclopentadiene is taken out continuously from the top outlet In this manner a

cyclopentadiene monomer of high purity in the range over 99 is obtained in gaseous state

Comparing the 99 purity to that degree of purity obtained by prior art methods will distinctly show

that by use of the invention an unexpected result was obtained In US Plant No 2913504 a

distillation column of 30 plates was used The inlet temperature of raw cyclopentadiene was 150 38

of reboiler being 143 produced of a purity of 952 to 978 As will be discussed hereinafter

impurities of for example 48 to 22 as present in the prior art cyclopentadienes will adversely

affect the catalytic activity and lifetime of the catalyst when used in the production of cyclopentene

by hydrogenation of the impurities containing cyclopentadiene On the other hand the present

invention produces impurities of less than 1 which extra degree of purity makes possible

industrial use of the process which would not have been previously possible

This unexpected purity of cyclopentadiene which is produced by the rectifying tower of the present

invention results it is thought from first retaining the cyclopentadiene in the tower for a relatively

short time by rapid elimination of excess heat of raw material by maintaining the temperature of

the upper portion heat exchanger at 30 80 cyclopentadiene at a desired temperature and second

the retaining of the high boiling point components for a relatively short time by removing it

continuously from the bottom of the tower by providing a heat exchanger at the lower side of the

inlet and maintaining its temperature at a temperature higher than the boiling point of

cyclopentadiene monomer but lower than the boiling point of the impurities such as

dicyclopentadiene such as within the range of 40

When cyclopentadiene is partially hydrogenated to produce cyclopentene it inevitably contains

several percent of cyclopentadiene remaining unreacted therein However in case cyclopentene is

used as a monomer to produce for example trans-polypentenamer which is a polymer becoming

more important industrially the content of cyclopentadiene in cyclopentene should be less than

several hundred ppm since the existence of diolefine especially such as cyclopentadiene disturbs

smooth polymerization reaction of cyclopentene

There are known various processes for purification of raw cyclopentene such as distillation

dimerization and treatment with maleic acid anhydride adsorption method ion exchange method

and hydrogenation method The method involving dimerization of cyclopentadiene to

dicyclopentadiene is deficient in that it is impossible to remove cyclopentadiene completely since


23

there exists a chemical equilibrium between the monomer and the dimer The method involving

treatment with maleic acid anhydride is also deficient in that the acid remains in the purified

cyclopentene in a small amount The adsorption method or the ion exchange method such as

disclosed in US Plant No 3506732 wherein an adsorbent of zinc oxide-silica-alumina system is

used or Japanese Plant No 49631972 wherein an ion exchanger of basic property is used is

deficient in that it is necessary to use a large amount of absorbent or ion exchanger compared

with the amount of cyclopentadiene to be removed and moreover there is the problem of

reactivating these materials

Also in the art US Plant No 3565963 for example discloses a method of hydrogenating

cyclopentadiene in two stages in the presence of a nickel catalyst to obtain cyclopentene The

method is deficient in that the nickel catalyst is poisoned by sulfur and thus requires further

treatment Moreover the methods hydrogenation reaction is carried out at a high temperature

under pressure

The inventors solved such difficulties as mentioned above by the two stage hydrogenation of

cyclopentadiene in the presence of palladium containing catalyst as set forth hereinabove

As the raw material used for conversion to cyclopentadiene a dicyclopentadiene whose purity is

about 95 may be used in the present invention and even if the purity of dicyclopentadiene to be

used is lower than this such as 80 to 95 it is sufficient for the method of the present invention to

add the inventive distillation apparatus to obtain a cyclopentene of sufficiently high purity for

polymerization use

In producing cyclopentene from dicyclopentadiene various problems arise due to the thermal

instability of cyclopentadiene monomer The inventive method carries out the entire process in the

gaseous system thus eliminating these problems since cyclopentadiene monomer is relatively

stable in the gaseous form Moreover the inventors have simplified the industrial plant needed to

work the process The inventive method has produced an unexpectedly low content of unreacted

cyclopentadiene in cyclopentene to an amount of less than several hundred ppm

Thus the present invention has overcome difficulties and deficiencies which previously prevented

large-scale industrial production of cyclopentene from dicyclopentadiene and moreover the

invention has provided a simiplified process To summarize some of the difficulties and deficiencies

of the prior art which have been overcome by the invention (1) it was necessary to purify


24

cyclopentadiene rapidly due to its thermal instability (2) It was necessary to prevent the

dimerization or further polymerization of cyclopentadiene by protecting it from heating or

compressing after thermal decomposition of dicyclopentadiene and use of a short retention time

(4) The selective activity of catalyst for hydrogenation must be increased to prevent the formation

of saturated compound that is cyclopentene and the removal of cyclopentadiene contained in

cyclopentene as an impurity when the cyclopentene was used as a monomer for production of

polymers (5) It was necessary to remove impurities of high boiling point such as

dicyclopentadiene co-dimers of cyclopentadiene etc which shorten the life and retard the

catalytic activity of catalysts for hydrogenation By resolving the foregoing problems the present

invention has made an important contribution to the art

The invention will be further illustrated by an actual example which is for illustrative purposes and

is not to be construed to be limiting

141 Examples

As the thermal depolymerization apparatus 2 a tubular type reactor comprising four tubes

connected to each other was used Each tube had a heating jacket with a heating medium and an

inner diameter of 216 mm φ and a length of 1 m When it was desired to have packing material

such was packed only in the last one meter The obtained results are shown in Table 1

TABLE 1______________________________________Feed Rate of Raw Material Jacket

Degree of (purity 95) Temperature Decomposition (kghr) () Packing

Material__________________________________________________20310916none20310967

filled______________________________________

As the distillation tower 4 there was used one comprising an upper heat exchanger 4-2 situated at

the upper side of inlet 4-1 into which the raw material comprising cyclopentadiene was fed and

having pipes whose dimension were 2 cm of diameter and 30 cm of length filled with packing

material and maintained at 50 lower heat exchanger 4-3 situated at the lower side of inlet 4-1

having 7 pipes whose dimensions were 2 cm diameter and 30 cm length filled with packing

material and maintained at 100 The high boiler component fractionated in the tower was

continuously removed from the bottom 5 of the tower The raw material cyclopentadiene obtained


25

from the depolymerization reactor 2 was introduced continuously in a gaseous state The obtained

results are shown in Table 2

TABLE2____________________________________________________High boiling Cyclopenta

High Boiling Cyclopenta-Feed Amount point compon-diene at point compon-diene at top Amount

removed at inlet end at inlet inlet end at top outlet from bottom(kghr) ()() outlet ()()

(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________

As the hydrogenation reaction vessels 8 11 a heat exchanger type reactor comprising 20 tubes

whose dimensions were 18 cm diameter was used The outside temperature was 120 ml at the

first step of hydrogenation and 17 ml at the second step of hydrogenation such amount being for

each reaction tube The reaction times of gas were 10 sec and 13 sec respectively The results

are shown in Table 3

TABLE 3________________________First step of hydrogenation High Boiling PtFeed Cyclo-

Cyclo-Cyclopen-Components and at inletHsub2 cyclo-pentane pentenetadiene other Csub5

Csub6 im-(kghr) pentadiene () () () purities

()________________________________________________________1811690044

10_____________________________________________Second step of hydrogenation

High Boiling Pt Cyclo-Cyclo-Cyclopen-Components and Hsub2 cyclo-pentane pentene

tadiene other Csub5 Csub6 im-pentadiene () () () purities () 24

5493613010306093070

10_____________________________________________________________________

The catalysts used in the Example were prepared by the following method After immersing a

magnesium oxide whose surface area was 1 msup2 g into a 35 aqueous solution of

hydrochloric acid containing palladium chloride and ferrous chloride reduction of metallic ions

contained in the magnesium oxide was carried out for 2 hours using an aqueous solution

containing 10 hydrazine and 10 caustic soda and the product was washed with water until the

chloride ion did not exist in the filtrate and dried at 150 carried on magnesium oxide contained

048 palladium and 032 iron

142 Comparative Example


26

In the first step of hydrogenation a cyclopentadiene whose purity was 952 and which had 40

of high boiling point components was used as raw material The experimental results are shown

below in Table 4 using the above conditions The life time of the catalyst was also decreased to 12

hours

TABLE 4_______________________________________________High Boiling PtFeed at Cyclo-

Cyclo-Cyclopent-component andinletHsub2 cyclo-pentane pentene adiene other

Csub5 Csub6 im-(kghr) pentadiene () () () purities

()______________________________________________________1811 90771 91

48_____________________________________________________________________

The foregoing description is for purposes of illustrating the principles of the invention Numerous

other variations and modifications thereof would be apparent to the worker skilled in the art All

such variations and modifications are to be considered to be within the spirit and scope of the

invention

143 Brief Description of Drawing

The single FIGURE depicts an illustrative apparatus in which the method of the invention may be

practiced

144 Background of the Invention

The present invention relates to a method of producing cyclopentene

Cyclopentene is useful for example as a raw material for producing cyclic aldehydes alcohols and

chlorinated compounds and also as fuel Recently cyclopentene has been used as a monomer

which is polymerized to a high molecular weight polymer However the amount of cyclopentene

available on the commercial market is so small and the cost thereof is so expensive that use

thereof in industrial quantities is unrealistic There are other reasons for its lack of widespread

industrial use For example there have been many difficulties encountered in the production of

cyclopentene such as during thermal depolymerization of dicyclopentadiene during selective

hydrogenation of cyclopentadiene monomer and during purification of hydrogenated cyclopentene

There is yet no known method which combines these processes into a smooth and economical

procedure to produce substantially pure cyclopentene from dicyclopentadiene


27

To combine thermal decomposition of dicyclopentadiene and hydrogenation of cyclopentadiene

many problems arise due to the thermal instability of cyclopentadiene monomer Accordingly after

thermal decomposition of dicyclopentadiene it is necessary to send the diene monomer to a

hydrogenation zone as soon as possible after a quick purification of the monomer Moreover to

prevent dimerization of the monomer it is necessary to prevent exposure thereof to pressure or to

heat before the hydrogenation

One of the important problems to be solved in the hydrogenation of cyclopentadiene is the

decrease of catalytic activity and concurrent decrease of catalytic life time by the adsorption of

impurities of high boiling point contained in cyclopentadiene such as dicyclopentadiene co-dimers

of cyclopentadiene and isoprene or pentadiene etc

145 Summary of the Invention

An object of the invention is to eliminate the deficiencies and disadvantages of the prior art

methods Another object of the invention is to provide a process which combines the

depolymerization of dicyclopentadiene and purification of the cyclopentadiene produced thereby

and the hydrogenation in at least one step thereby to produce a highly pure cyclopentene A further

object of the invention is to reduce the unwanted reduction of catalytic activity and life time

resulting from the presence of unwanted impurities in the cyclopentadiene

The foregoing and other objects of the invention are attained in a method of producing

cyclopentene comprising the steps of feeding raw dicyclopentadiene to a thermal reactor for

depolymerization at 170 to 400 substantially ordinary atmospheric pressure into cyclopentadiene

then feeding the raw cyclopentadiene to the middle part of a distillation tower having an upper part

at 30 the top thereof at 35 45 produce highly pure over 99 cyclopentadiene in gaseous form

through the upper outlet and at the lower part outlet higher boiling point components which are

continuously drained off and then feeding the highly pure cyclopentadiene to a first hydrogenation

chamber wherein hydrogen gas is reacted therewith in the ratio of 1 to 2 mol preferably 1 to 15

mol hydrogen per 1 mol of cyclopentadiene in the presence of a palladium containing catalyst

thereby to produce a conversion rate of 90 to 98 and thereafter feeding the unreacted

cyclopentadiene to a second hydrogenation chamber wherein 1 to 20 preferably 1 to 7 mol of

hydrogen is employed per mol of unreacted cyclopentadiene in the presence of a palladium

containing catalyst and thereafter cooling the resulting product separating the liquid and gas


28

portions and recirculating the gas portion for use in the hydrogenation steps The hydrogenation

reaction temperature is 50 in substantially ordinary atmospheric pressure

A feature of the invention is the use of a distillation tower having an upper part at 30 35 lower part

at 40 by supplying same to the midpoint between the upper and lower parts and having high boiling

point impurities removed continuously from the lower part and removing gaseous high purity

cyclopentadiene from the upper outlet after fractionating in the tower

A further feature of the invention is the use of the purified cyclopentadiene as raw material for use

in hydrogenation with hydrogen in a mol ratio of 1 to 2 mol preferably 1 to 15 mol hydrogen to 1

mol cyclopentadiene in a first hydrogenation reactor at 50 200 substantially ordinary atmospheric

pressure in the presence of a palladium containing catalyst

Another feature of the invention is the use of a second hydrogenation reactor immediately after the

first hydrogenation reactor wherein unreacted cyclopentadiene is reacted with hydrogen mixed in

the ratio of 1 to 20 preferably 1 to 7 mol of hydrogen and 1 mole of unreacted cyclopentadiene in

the presence of a palladium containing catalyst and the subsequent cooling of the resulting

product and the separation of the liquid and gas parts with the gaseous part being recirculated for

use in the first and second hydrogenation reactors Another feature is the use of a palladium

containing catalyst carried on alumina silica or magnesium oxide together with use of iron or

chromium

146 Claims

What is claimed is

1 A method of producing cyclopentene comprising the steps of A thermal decomposition or

depolymerization of dicyclopentadiene in a gaseous state at 170 to 400 atmospheric pressure to

produce cyclopentadiene and other high boiling point impurities

B Feeding the raw cyclopentadiene and impurities produced in step (A) into a two part distillation

tower the upper part being maintained at 30 150 maintained at 35 purity of 99 or more is

continuously removed from said top outlet and said high boiling point impurities are removed

continuously from a lower part outlet of said tower


29

C Reacting the purified cyclopentadiene of step (B) with hydrogen gas in the ratio of 1 to 15 mol

hydrogen to 1 mol cyclopentadiene in the presence of a palladium catalyst on a carrier and at a

temperature of 50 pressure thereby to produce a conversion ratio of 90 to 98 cyclopentene

remainder unreacted cyclopentadiene

D Reacting the unreacted cyclopentadiene of step (C) with hydrogen gas in the mol ratio of 1 to 7

mol hydrogen to 1 mole of unreacted cyclopentadiene in the presence of a palladium containing

catalyst at a temperature of 50 atmospheric pressure thereby to produce cyclopentene and

E Cooling the resulting product of step (D) and separating the liquid part from the gaseous part

and recirculating the gaseous part to steps (C) and (D) above

2 The method of claim 1 wherein said depolymerization or decomposition temperature is 250

outlet is 35 reaction of steps (C) and (D) is 70

3 The method of claim 1 wherein said palladium containing catalyst comprises palladium and iron

or chromium carried on a carrier of alumina silica or magnesium oxide

4 Process of purifying cyclopentadiene comprising the steps of feeding raw gaseous material

containing cyclopentadiene and impurities of high boiling point to the middle part of a distilling

tower having an upper heat exchanger an upper outlet a middle part a lower heat exchanger and

a lower outlet said upper heat exchanger maintained at 30 80 and said lower heat exchanger

maintained at 40 to 150 substantially pure cyclopentadiene of over 99 purity is removed

continuously from said upper outlet in gaseous form and said higher boiling point impurities is

removed continuously from said lower outlet

5 The process of claim 4 wherein said upper outlet is maintained at 35


30



31

21 Cyclopentene Uses Itrsquos used as a monomer for synthesis of plastics Further details

as follow

2 10 Monomer

Monomers are the building blocks of more complex molecules called polymers Polymers consist

of repeating molecular units which usually are joined by covalent bonds Here is a closer look at

the chemistry of monomers and polymers Monomers are small molecules which may be joined

together in a repeating fashion to form more complex molecules called polymers

211 Polymers

A polymer may be a natural or synthetic macromolecule comprised of repeating units of a smaller

molecule (monomers) While many people use the term polymer and plastic interchangeably

polymers are a much larger class of molecules which includes plastics plus many other materials

such as cellulose amber and natural rubber

212 Examples of Polymers

Examples of polymers include plastics such as polyethylene silicones such as silly putty

biopolymers such as cellulose and DNA natural polymers such as rubber and shellac and many

other important macromolecules

213 How Polymers Form

Polymerization is the process of covalently bonding the smaller monomers into the polymer During

polymerization chemical groups are lost from the monomers so that they may join together In the

case of biopolymers this is a dehydration reaction in which water is formed

214 Monomer word Derived A monomer pronouced mŏnə-mər or MON-uh-mer (from

Greek mono one and meros part) is a molecule that may bind chemically to other molecules to

form a polymer[1][2] The term monomeric protein may also be used to describe one of the proteins

making up a multi protein complex The most common natural monomer is glucose which is linked

by glycosidic bonds into polymers such as cellulose and starch and is over 77 of the mass of all


32

plant matter Most often the term monomer refers to the organic molecules which form synthetic

polymers such as for example vinyl chloride which is used to produce the polymer polyvinyl

chloride (PVC)

215 Natural Monomers

Amino acids are natural monomers that polymerize at ribosomes to form proteins Nucleotides

monomers found in the cell nucleus polymerize to form nucleic acids ndash DNA and RNA Glucose

monomers can polymerize to form starches glycogen or cellulose xylose monomers can

polymerise to form xylan In all these cases a hydrogen atom and a hydroxyl (-OH) group are lost

to form H2O and an oxygen atom links each monomer unit Due to the formation of water as one of

the products these reactions are known as dehydration Isoprene is a natural monomer and

polymerizes to form natural rubber most often cis-14-polyisoprene but also trans-14-

polyisoprene

216 Molecular Weight

The lower molecular weight compounds built from monomers are also referred to as dimers

trimers tetramers pentamers octamers 20-mers etc if they have 2 3 4 5 8 or 20 monomer

units respectively Any number of these monomer units may be indicated by the appropriate Greek

prefix eg a decamer is formed from 10 monomers Larger numbers are often stated in English or

numbers instead of Greek Molecules made of a small number of monomer units up to a few

dozen are called oligomers

217 Industrial Use

Considering the current tight monomers market particularly in propylene and the benefits of

membrane-based recovery processes major polyolefin producers around the world already employ

them in new state-of-the-art plants In order to enhance the competitiveness of older plants the

use of a recovery solution is becoming mandatory

2 2 Plastics

Look around you and chances are high that a variety of the things you can see are made of

plastics There are hard plastics and soft plastics clear ones and colorful ones and plastics that


33

look like leather wood or metal Developed during the twentieth century plastics have changed

the world

All plastics were soft and moldable during their production - thats why theyre called plastics The

Greek word plasticoacutes means to mold You can form nearly any object out of plastics from bristles

on toothbrushes to bulletproof vests to fibers for making textiles for clothes Soon tiny plastic

projectiles may be used as carriers of vaccine making it possible to swallow the vaccine instead of

getting an injection

2 21 What is Plastics

Plastics are a synthetic material which means that they are artificial or manufactured Synthesis

means that something is put together and synthetic materials are made of building blocks that

are put together in factories

The building blocks for making plastics are small organic molecules - molecules that contain

carbon along with other substances They generally come from oil (petroleum) or natural gas but

they can also come from other organic materials such as wood fibers corn or banana peels Each

of these small molecules is known as a monomer (one part) because its capable of joining with

other monomers to form very long molecule chains called polymers (many parts) during a

chemical reaction called polymerization To visualize this think of a single paper clip as a

monomer and all the paper clips in a box chained together as a polymer

1 Crude oil the unprocessed oil that comes out of the ground contains hundreds of different

hydrocarbons as well as small amounts of other materials The job of an oil refinery is to

separate these materials and also to break down (or crack) large hydrocarbons into

smaller ones

2 A petrochemical plant receives refined oil containing the small monomers they need and

creates polymers through chemical reactions

3 A plastics factory buys the end products of a petrochemical plant - polymers in the form

of resins - introduces additives to modify or obtain desirable properties then molds or

otherwise forms the final plastic products


34

222 How to make Plastic First find a suitable molecule One such molecule is the

ethylene monomer the starting point for a variety of plastics Ethylene is a small hydrocarbon

consisting of four hydrogen atoms and two carbon atoms

Polymerization is often started by combining the monomers through the use of a catalyst - a

substance that aids a chemical reaction without undergoing any permanent chemical change itself

During the chemical reaction hundreds or thousands of monomers combine to form a polymer

chain and millions of polymer chains are formed at the same time The mass of polymers that

results is known as a resin Resins are sold to plastics factories usually in the form of powder tiny

granules or pellets The plastics manufacturer adds coloring agents and other additives that

modify the properties of the material for the intended product Finally the resin is formed into the

body of a cell phone fibers for a sweater or one of a myriad of other plastic products

When you polymerize ethylene you get a polyethylene resin There are a number of polyethylene

resins families that differ by such properties as density and molecular weight and they can be

made into a huge variety of plastic products One of the most common is the plastic grocery bag

Polyethylene is made from just ethylene monomers - but its also possible to create polymers from

two or more different monomers You can make hundreds of different polymers depending on

which monomers and catalysts you use

223 Polymers are everywhere

Plastics are polymers but polymers dont have to be plastics The way plastics are made is actually

a way of imitating nature which has created a huge number of polymers Cellulose the basic

component of plant cell walls is a polymer and so are all the proteins produced in your body and

the proteins you eat Another famous example of a polymer is DNA - the long molecule in the

nuclei of your cells that carries all the genetic information about you

People have been using natural polymers including silk wool cotton wood and leather for

centuries These products inspired chemists to try to create synthetic counterparts which they

have done with amazing success

224 Thermoplastics and Thermosets


35

Plastics are classified into two categories according to what happens to them when theyre heated

to high temperatures Thermoplastics keep their plastic properties They melt when heated and

then harden again when cooled Thermosets on the other hand are permanently set once

theyre initially formed and cant be melted If theyre exposed to enough heat theyll crack or

become charred

80 of the plastics produced are thermoplastics and of these Polyethylene Polypropylene

Polystyrene and Polyvinylchoride (PVC) are the most commonly used (70)

Thermoplastics

Plastics that can be reshaped

Thermosets

Plastics that cant be reshaped

Analogies

When ice is heated it melts When a

thermoplastic object is heated it melts

as well

The melted ice can be formed into a

new shape and it will keep that shape

Just as a raw egg has the potential to

become a boiled egg a fried egg and

so on thermosetting polymers have

the potential to become all sorts of

different objects


36

when its cooled Similarly a melted

thermoplastic object can be formed

into a different shape and it will keep

that new shape when its cooled

Once an egg has been boiled

however you cant make it into a fried

egg In the same way once a

thermosetting plastic object has been

formed it cant be remade into a

different object

Reasons

for the

reactions

when

heated

Thermoplastics have long linear

polymer chains that are only weakly

chemically bonded or connected to

each other When a thermoplastic

object is heated these bonds are

easily broken which makes the

polymers able to glide past each other

like strands of freshly cooked

spaghetti Thats why thermoplastics

can readily be remolded

The weak bonds between the

polymers reform when the plastic

object is cooled which enable it to

keep its new shape

The linear chains are cross linked -

strongly chemically bonded This

prevents a thermoplastic object from

being melted and reformed

How

plastic

The most common method for making

plastics is molding To make a

Thermosets are produced in two steps


37

objects

are

formed

thermoplastic object plastic granules

known as resin are forced into a mold

under high heat and pressure When

the material has cooled down the

mold is opened and the plastic object

is complete When making plastic

fibers the molten resin is sprayed

through a strainer with tiny holes

1 Linear polymers are formed

2 The linear polymers are forced into

a mold where curing takes place

This may involve heating pressure

and the addition of catalysts During

this process a cross-linked or

networked structure forms creating a

permanently hard object that is no

longer meltable or moldable

Uses There is a huge range of uses

including plastic wrap food containers

lighting panels garden hoses and the

constantly encountered plastic bag

Thermosets are good to use for things

that will be warmed up such as

spatulas and other kitchen tools

Theyre also used in glues varnishes

and in electronic components such as

circuit boards

Recycling Thermoplastics are easy to recycle

since they can be melted and

reshaped into other products For

example a plastic bottle that contained

a soft drink could be reformed into the

fibres of a fleece jacket

Thermosets are hard to recycle but

today there are methods of crushing

the objects into a fine powder form for

use as fillers in reinforced thermosets

225 Better catalysts improve plastics

For most applications the ideal polymer is a long straight chain with a highly regular molecular

structure Early synthetic polymers however often exhibited odd little branches and other

irregularities In the 1950s German chemist Karl Ziegler (1898ndash1973) discovered that an entirely

different type of catalyst - a combination of aluminum compounds with other metallic compounds -

could solve some of these annoying problems and increase the length of a polymer chain

producing superior plastics Ziegler became a wealthy man as a result of patents for plastics such


38

as high density polyethylene (HDPE) which is used to manufacture a variety of products such as

bottles or pipe

Polymers often have short side chains which can occur on either side of the main chain If side

branches occur randomly to the left or right the polymer has an irregular structure Italian chemist

Giulio Natta (1903ndash1979) discovered that some Ziegler catalysts led to a uniform structure in which

all the side branches are on the same side This structure results in stiffer and tougher plastics that

are also lightweight which proved to be of significant economic importance especially for

polypropylene Almost immediately new and better plastic products were produced For their

innovative work in the polymerization of plastics Karl Ziegler and Giulio Natta shared the Nobel

Prize in Chemistry in 1963 Today Ziegler-Natta catalysts are used throughout the world to

produce a variety of polymers


39



40

31 Product Identification

Product Name Cyclopentene

Formula c5h8

Formula Wt 6812

Case no 00142-29-0

NioshRtecs no Gy5950000

Product Codes G101

32 Physical and Chemical Properties

Physical State Clear liquid

Appearance clear colorless

Odor None reported

PH Not available

Vapor Pressure 12 mbar 50 C

Vapor Density 23

Evaporation Rate Not available

Viscosity Not available

Boiling Point 44 deg C 76000mm Hg

FreezingMelting Point-94 deg C

Decomposition Temperature Not available

Solubility Insoluble

Specific GravityDensity7740gcm3

Molecular Formula C5H8

Molecular Weight 6811

33 First Aid Measures

Eyes Flush eyes with plenty of water for at least 15 minutes occasionally lifting the upper and

lower eyelids Get medical aid

Skin Get medical aid Flush skin with plenty of water for at least 15 minutes while removing


41

contaminated clothing and shoes Wash clothing before reuse

Ingestion Never give anything by mouth to an unconscious person Get medical aid Do NOT

induce vomiting If conscious and alert rinse mouth and drink 2-4 cupfuls of milk or water

Inhalation Get medical aid immediately Remove from exposure and move to fresh air

immediately If not breathing give artificial respiration If breathing is difficult give oxygen

Notes to Physician Treat symptomatically and supportively

34 Handling and Storage

Handling Wash thoroughly after handling Use only in a well-ventilated area

Ground and bond containers when transferring material Avoid contact with eyes

skin and clothing Empty containers retain product residue (liquid andor vapor)

and can be dangerous Keep container tightly closed Keep away from heat sparks

and flame Avoid ingestion and inhalation Do not pressurize cut weld braze

solder drill grind or expose empty containers to heat sparks or open flames

Storage Keep away from heat sparks and flame Keep away from sources of

ignition Store in a tightly closed container Store in a cool dry well-ventilated area

away from incompatible substances Flammables-area Refrigeratorflammables

35 Hazards Identification

According to Regulation (EC) No12722008

Flammable liquids (Category 2)

Acute toxicity Dermal (Category 4)

Acute toxicity Oral (Category 4)

Skin irritation (Category 2)

Eye irritation (Category 2)

Specific target organ toxicity - single exposure (Category 3)

Aspiration hazard (Category 1)

Highly flammable It is Harmful in contact with skin and if swallowed Cyclopentene Irritating to

eyes respiratory and skin system Harmful may cause lung damage if swallowed

36 Exposure ControlsPersonal Protection


42

Engineering Controls Use adequate ventilation to keep airborne concentrations low Use

process enclosure local exhaust ventilation or other engineering controls to control airborne

levels

Exposure Limits

Chemical Name ACGIH NIOSH OSHA - Final PELs

Cyclopentene none listed none listed none listed

OSHA Vacated PELs Cyclopentene No OSHA Vacated PELs are listed for this chemical

Personal Protective Equipment

Eyes Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHAs

eye and face protection regulations in 29 CFR 1910133 or European Standard EN166

Skin Wear appropriate protective gloves to prevent skin exposure

Clothing Wear a chemical apron Wear appropriate protective clothing to prevent skin exposure

Respirators Wear a NIOSHMSHA or European Standard EN 149 approved full-face piece airline

respirator in the positive pressure mode with emergency escape provisions Follow the OSHA

respirator regulations found in 29 CFR 1910134 or European Standard EN 149 Use a

NIOSHMSHA or European Standard EN 149 approved respirator if exposure limits are exceeded

or if irritation or other symptoms are experienced

37 Fire Fighting Measures

General Information As in any fire wear a self-contained breathing apparatus in pressure-

demand MSHANIOSH (approved or equivalent) and full protective gear Vapors may form an

explosive mixture with air Vapors can travel to a source of ignition and flash back Use water spray

to keep fire-exposed containers cool Containers may explode in the heat of a fire Liquid will float

and may reignite on the surface of water Flammable liquid and vapor Vapors may be heavier than

air They can spread along the ground and collect in low or confined areas Will be easily ignited by

heat

Extinguishing Media For small fires use dry chemical carbon dioxide water spray or alcohol-

resistant foam For large fires use water spray fog or alcohol-resistant foam Use water spray to

cool fire-exposed containers Water may be ineffective Do NOT use straight streams of water

Flash Point -29 deg C ( -2020 deg F) Auto ignition Temperature 395 deg C ( 74300 deg F)


43

Explosion Limits Lower150 vol Upper 00 vol NFPA Rating 1 - health 3 - flammability

1 ndash instability

38 Accidental Release Measures

SpillsLeaks Absorb spill with inert material (eg vermiculite sand or earth) then place in suitable

container Clean up spills immediately observing precautions in the Protective Equipment section

Remove all sources of ignition Use a spark-proof tool Provide ventilation A vapor suppressing

foam may be used to reduce vapors

39 Stability and Reactivity

Chemical Stability Stable under normal temperatures and pressures

Conditions to Avoid Incompatible materials ignition sources excess heat strong oxidants

Hazardous Decomposition Products Carbon monoxide carbon monoxide carbon dioxide

Hazardous Polymerization Has not been reported


1

Cyclopentene Project

Project Name Cyclopentene

Prepared By Waqas Akram Muhammad

Request By Major M Saleem

Prepared For Haier Pakistan

Submitting Date 15 August 2013


2

Table of Content























3

























4





5



6









Origins and History









Origins and History




7


















1971


8








Mechanism














9

























10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












2

Table of Content























3

























4





5



6









Origins and History









Origins and History




7


















1971


8








Mechanism














9

























10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












3

























4





5



6









Origins and History









Origins and History




7


















1971


8








Mechanism














9

























10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












4





5



6









Origins and History









Origins and History




7


















1971


8








Mechanism














9

























10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












5



6









Origins and History









Origins and History




7


















1971


8








Mechanism














9

























10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












6









Origins and History









Origins and History




7


















1971


8








Mechanism














9

























10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












7


















1971


8








Mechanism














9

























10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












8








Mechanism














9

























10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












9

























10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












10











11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












11























scrambling








12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












12












place at 220degC







13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












13




systems









14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












14
















15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












15


















16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












16









Vetispirene in 1982


17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












17





rearrangement





18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












18
























19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












19



20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












20

































21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












21






higher pressure
















use or treatment










22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












22
































23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












23













under pressure







polymerization use












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












24













141 Examples







Material__________________________________________________20310916none20310967

filled______________________________________









25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












25






(kghr)________________________________________________________208490902990

0320339590199102___________________________________________________________









()________________________________________________________1811690044




5493613010306093070

10_____________________________________________________________________










26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












26




hours




()______________________________________________________1811 90771 91

48_____________________________________________________________________




invention



practiced














27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












27
































28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












28


















chromium

146 Claims

What is claimed is









29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












29























30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












30



31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












31


as follow

2 10 Monomer





211 Polymers



















32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












32



chloride (PVC)









polyisoprene








217 Industrial Use





2 2 Plastics




33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












33


the world




















smaller ones







34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












34





























35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












35





become charred



Thermoplastics


Thermosets


Analogies



as well







different objects


36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












36










different object

Reasons

for the

reactions

when

heated














keep its new shape





How

plastic





37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












37

objects

are

formed



























circuit boards



















38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












38


bottles or pipe











39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












39



40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












40



Formula c5h8

Formula Wt 6812

Case no 00142-29-0


Product Codes G101




Odor None reported

PH Not available


Vapor Density 23















41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












41






























42



levels

Exposure Limits





















heat






43


1 ndash instability












42



levels

Exposure Limits





















heat






43


1 ndash instability












43


1 ndash instability











Technology

Cyclopentene Safety Procedures For Haier Upcoming Project