Polymer Handbook

Polymer_Handbook/Polymer Handbook/66286_01.pdfS E C T I O N I

N O M E N C L A T U R E R U L E S U N I T S

N o m e n c l a t u r e

W . V . M e t a n o m s k iChemical Abstracts Service, Columbus, Ohio, USA

A. Introduction 1-1B. IUPAC Recommendations 1-11. Source-Based Nomenclature I-2

1.1. Homopolymers I-21.2. Copolymers I-21.3. Nonlinear Macromolecules &

Macromolecular Assemblies I-32. Structure-Based Nomenclature

2.1. Regular Single-Strand Organic Polymers I-32.2. Regular Double-Strand Organic Polymers I-62.3. Regular Single-Strand Inorganic and

Coordination Polymers I-62.4. Regular Quasi-Single-Strand Coordination

Polymers I-72.5. Irregular Single-Strand Organic Polymers I-7

C. Use of Common and Semisystematic Names I-8D. Chemical Abstracts (CA) Index Names I-8E. Polymer Class Names 1-11F. References 1-12

A. INTRODUCTIONMacromolecular (polymer) nomenclature has an almost50-year history. As early as 1949 there existed aSubcommission on Nomenclature within the InternationalUnion of Pure and Applied Chemistry (IUPAC) under thechairmanship of Maurice L. Huggins. The Subcommissionwas part of the IUPAC Commission on Macromolecules,chaired then by Herman F. Mark. Other notable pioneers inpolymer science, Jan Joseph Hermans, Otto Kratky, HarryW. Melville, and George J. Smets, were members of theCommission.

The Subcommission produced its first official report in1952. It recognized then, what is just as true today, that thepractice in the field of small molecules of providingrigorous definitions is impractical for polymers. The latterconsist of molecules not necessarily exactly of the samesize, chemical composition, or structure. The differencesresult from the presence of end groups, branches, variationin orientation of monomeric units, and irregularity in thesequence of different types of units.

The American Chemical Society (ACS) Division ofPolymer Chemistry established its Nomenclature Commit-

tee in 1963 to try to unify earlier attempts to name polymersin some coherent way. Their first major project resulted in astructure-based nomenclature for regular linear polymers,first published in ACS Polymer Preprints in 1967, adoptedby Chemical Abstracts in 1968, and incorporated in IUPACrecommendations in 1975 [I].

When the IUPAC Commission on Macromolecules waselevated to become the IUPAC Division of MacromolecularChemistry, the latter in turn established its Commission onMacromolecular Nomenclature in 1968.

The Commission in the course of its nearly 30 years ofexistence produced a series of major documents that haveshaped modern nomenclature and terminology of polymerscience. The recommendations are being published in theIUPAC official journal, Pure and Applied Chemistry, andoccasionally are republished in the form of a "Compen-dium" which groups all the currently valid documents in asingle volume. The Commission published its "Compen-dium of Macromolecular Nomenclature" in 1991 [2]. Thebook, which IUPAC has designated the "Purple Book", inanalogy to other IUPAC books ("Blue" - organic, "Red"- inorganic, "Orange" - analytical, "Green"- physical,and "Gold" - overall chemistry), has the two most basicmacromolecular nomenclature recommendations: "nomen-clature of regular single-strand organic polymers" and"source-based nomenclature for copolymers". In morerecent years, the Commission extended that basic nomen-clature to double-strand (ladder and spiro) organic poly-mers, irregular and crosslinked polymers, and polymerblends and interpenetrating networks.

In this article, the basic structure-based and source-basednomenclature of polymers is explained and illustrated insome detail. The continuing use of common andsemisystematic nomenclature with reference to specifictables in this Handbook is highlighted. The currentChemical Abstracts (CA) index names [3] are comparedand contrasted with the IUPAC practice and typical namesemployed in the polymer journals and textbooks.

B. IUPAC RECOMMENDATIONSSince polymers, unlike low-molecular-weight compounds,have no uniform structure and are mixtures of macro-molecules of different length and different structural

arrangement, their graphical representation and their namesrequire a special approach.

Often enough, the structure of the polymer has not beensufficiently characterized and the researcher cannot draw itschemical structure. Consequently, no name of the polymerreflecting its structure is possible.

A polymerization reaction for a polymer formed froma monomer such as vinyl chloride can schematically berepresented by

That shows an idealized product. In fact, however, thepolymer consists of long-chains of various lengths. Therepeating units, - C H 2 - C H C l - , are not necessarily alluniquely oriented and joined in a regular fashion as shownin the idealized structure above. In addition to "head-to-tail" links

other links such as "head-to-head"

and "tail-to-tail"

can occur, and the exact sequence of all these repeatingunits usually is not known.

This becomes even more complicated when a copolymeris derived from more than one monomer, such as styreneand methyl acrylate, which contribute two constitutional ormonomeric units:

They can combine into a polymeric chain, resulting inmany types such as unspecified, statistical, random,alternating, periodic, block, or graft copolymers.

Because the exact structure of the polymer is not alwaysknown, two systems of naming polymers exist:

source-based nomenclature,structure-based nomenclature.

1. Source-Based Nomenclature1.1. Homopolymers Homopolymers are derived fromonly one species of monomer, which may be the actualstarting reactant (or source), or be a hypothetical monomerif the homopolymer is formed by a modification of anotherhomopolymer.

The name of the polymer is formed by attaching theprefix "poly" to the name of the actual or assumedmonomer, or the starting reactant (source), from which thepolymer is derived.Examples: poly (acrylic acid)

polyacrylonitrile

polybutadienepolyethylenepoly(methyl methacrylate)poly(methyl vinyl ether)polystyrenepoly(tetrafluoroethylene)poly(vinyl alcohol)poly(vinyl acetate)poly(vinyl chloride)poly(vinylidene dichloride)

Parentheses are used when the name of the monomerconsists of two or more words, and when the monomer hassubstituents.

These are all olefinic type reactants, from which twocarbon atoms originally linked by a double bond form abivalent group:

where R and R[ represent a hydrogen atom or a substituentgroup. Many of these are joined, in turn, to each other buttheir exact orientation or sequence is seldom known.

On the other hand, different polymers derived from asingle monomer and having identical constitutional unitscan still be differentiated by additional information, such asaverage molecular weight and other chemical and physicalcharacteristics.

1.2. Copolymers For copolymers, the names of mono-mers are cited after the prefix "poly". In addition, anitalicized connective (infix) is placed between the names ofmonomers to denote the kind of sequential arrangement bywhich the constitutional (monomeric) units, derived fromeach monomer, are related in the structure [4].

Seven types of sequence arrangements are listed withtheir corresponding connectives:

Type Connective

unknown or unspecified -co-statistical (obeying known statistical laws) -stat-random (obeying Bernoullian distribution) -raft-alternating (for two monomeric units) -alt-periodic (ordered sequence of more than two) -per-block (linear arrangement of blocks) -block-graft (side blocks chains connected to -graft-

main chain)

Examples: poly[styrene-C(?-(methyl methacrylate)!poly^tyrene-statf-acrylonitrile-statf-butadiene)poly[ethylene-ran-(vinyl acetate)]poly[(ethylene glycol)-tf/r-(terephthalic acid)]poly[formaldehyde-/?er-(ethylene oxide)-per-

(ethylene oxide)]polystyrene-&/oc&-polybutadienepolybutadiene-gra/f-polystyrene

The names of the monomers are those common orsemisystematic names that are encountered most often inthe literature of polymer science. The order of citation ofmonomers in copolymer names is arbitrary.

An equally acceptable alternative scheme for namingcopolymers utilizes the prefix "copoly", followed bycitation of the names of the monomers, separated by anoblique stroke (a solidus). Parentheses are not needed toenclose monomer names consisting of two or more words.

Examples: copoly(styrene/methyl methacrylate)j"tatf-copoly(styrene/acrylonitrile/butadiene)ran-copoly(ethylene/vinyl acetate)a/f-copoly(ethylene glycol/terephthalic acid)per-copoly(formaldehyde/ethyleneoxide/ethy-

lene oxide)Wtfc/:-copoly(styrene-butadiene)gra/-copoly(butadiene-styrene)

1.3. Nonlinear Macromolecules and MacromolecularAssemblies Most recently, the source-based nomenclaturehas been extended for non-linear macromolecules andmacromolecular assemblies [5], The non-linear macromo-lecules comprise branched, graft, comb, star, cyclic, andnetwork macromolecules. The macromolecular assembliescomprise polymer blends, interpenetrating polymer net-works, and polymer-polymer complexes.

The following italicized qualifiers can be used as bothprefixes (e.g., blend-, net-) and infixes (connectives) (e.g.,-blend-, -net-) to designate the skeletal structure of non-linear macromolecules or macromolecular assemblies:

Type Connective

cyclic cyclobranched, unspecified branchshort-chain-branched sh-branchlong-chain-branched l-branchbranched with branch point

of functionality / f-branchcomb combstar starstar with / arms f-starnetwork netcrosslink t (Greek iota)polymer blend blendinterpenetrating polymer network ipnsemi-interpenetrating polymer network sipnpolymer-polymer complex compl

In naming non-linear homopolymer molecules, theitalicized prefix for the skeletal structure of the macro-molecule is placed before the source-based name of theconstituent linear chain.

Assemblies of macromolecules held together by non-covalent bonds are named by a combination of the names of

the constituent macromolecules with an italicized con-nective between them.

Examples: poly styrene-com>-poly aery lonitrilecom&-poly(styrene~statf-acrylonitrile)poly styrene-comZ?- [poly acrylonitrile;

poly(methyl methacrylate)]4-sfar-polystyrenestar-(po\yA-block-polyB-block-polyC)star-(polyA; polyB; polyC)star-(polyacrylonitrile; polystyrene)

(M1 100000:20000)fte-polystyrene--divinylbenzenen^-poly[styrene-(2.00 x 10 ~4) 130

difluoromethane)Vapor (trichloro 150 2.35 x 10"3 1 130

ethylene)Vapor (methylene 150 1.017 x 10 ~3 1 130

chloride)Vapor (3-pentanone) 145 1.5 x 10~4 165.3 125

T (K) 6.8 x 1016 exp[- 1653/RT] 125Vapor (silicon 160 1.05 xlO"3 113.0 a,i(2.6) 117

tetrafluoride) 160 1.25 x l 0 ~ 3 a,i(33) 117160 1.27 xlO"3 a,i(100) 117

Vapor (toluene) 148 9.OxIO-5 88158 2.5 xlO"4 88

Vapor 103.2 5.6xlO"7 227111.9 2.03 XlO"6 227

Notes page 11-69; References page II - 70

TABLE 3. cont'd

Number ofC atoms Initiator Solvent T(0C) A^(S"1) Ea (kj/mol) Notes Refs.

S (cont'd) tert-Butyl peroxide Vapor 120.2 6.39 x 10 "6 227129.5 1.98 XlO-5 227138.5 6.0OxIO-5 227145.4 1.24 xlO~ 4 227125 1.1 x K r 5 64135 3.6 XlO-5 64145 1.15 x l O - 4 64129.6 1.64 x l 0 ~ 5 86141.0 6.28 XlO"5 86152.5 2.25 x l O - 4 86166.8 8.92 x l O - 4 86130 1.82 x l O - 5 159.0 a 96140 5.75 x l O " 5 a 96150 1.75 x l O - 4 a 96160 4.88 x l O " 4 a 96170 1.35 x l O - 3 a 96129 1.97 x l O - 5 88138 4.3 x l O - 5 88149 1.30 x lO~ 4 88152 1.62 XlO"4 88139.7 6.OxIO-5 163.6 63147.2 1.43 x l O - 4 63154.6 3.22 x l O - 4 63159.8 5.53 x l O - 4 63

T (K) 3.2 x 1016 exp[- 163.6/RT] 63145 1.3 x l O - 4 161.5 125

T(K) 1.9xlO16 exp[-161.5//?7] 175,125149.5 1.79 XlO"4 156.5 i(37-132) 83160 4.0OxIO-4 154.8 a,i(2.6) 117160 4.53 XlO"4 a,i(33) 117160 4.83 x l O - 4 a,i(100) 117130 1.91 x 10"5 156.7 U3 277140 5.95 x l 0 ~ 5 U3 277150 1.78 x l O " 4 U3 277160 4.96 x l 0 ~ 4 U3 277

Vapor (He) 280 7.7 154.8 i(10) 111290 1.5IxIO1 i(10) 111300 2.77X101 i(10) 111310 4.87XlO1 i(10) 111320 8.34XlO1 i(10) 111330 1.38 x lO 2 KlO) 111340 2.13 x l O 2 i(lO) 111350 3.22 x l O 2 i(lO) 111

KBr pellets 109 3.8 x 10"7 159.0 h 241127 2.96 x l O - 5 241149 4.4 x l O " 4 241

terf-Butyl 2-chloro-l,l-dimethylethyl- Cumene 120 8.82 x 10~6 363peroxide 130 2.8OxIO-5 363

140 9.26 x l 0 ~ 5 363150 2.78 x l O - 4 363

sec-Butyl peroxide Toluene 100 2.7 x 10 ~6 197Vapor 100 1.5 x 10"6 197

Butyl peroxide Decane 80 1.43 x 10 "8 t6 270Dodecane 80 1.17 x l O " 8 t6 270Heptane 80 2.04 x 10~8 t6 270Hexadecane 80 8.8 x 10 ~9 t6 270Octane 80 1.58 x l O " 8 t6 270Styrene 60 3.3 x 10 ~9 142.3 92Tetradecane 80 9 .6x lO- 9 t6 270

Bromo-terf-butyl peroxide Chlorobenzene 150 3.63 x 10 "4 346Chloro-terf-butyl peroxide Chlorobenzene 150 4.15 x 10 ~A 346Bis(chloro-tert-butyl) peroxide Chlorobenzene 150 3.11 x 10 ~4 3462-terf-Butyl peroxy-2-methyl- Chlorobenzene 150 1.16 x 10 "3 346

1-propanol

TABLE 3. cont'd

Number ofC atoms Initiator Solvent J ( 0 C ) A:d (s"1) Ea (kj/mol) Notes Refs.

8 (cont'd) 2-tert-Buty\ peroxy-2-methyl- Chlorobenzene 150 1.23 x 10"3 3461-propanol-di

l-Hydroxybutyl--butyi peroxide a-Methylstyrene 79.4 1.7 x 10~5 102.9 3299.4 1.06 x l O - 4 32

109.9 2.9 x l O - 4 321-Hydroxyisobutyl-isobutyl peroxide a-Methylstyrene 79.4 3.7 x 10"5 83.7 c 32

99.4 2.OxIO"4 c 32109.9 4.8 x l O - 4 c 32

1-Hydroxyisobutyl-l-di-isobutyl- a-Methylstyrene 99.5 6.9xlO~5 89.5 25l,l-d2 peroxide 109.8 1.8 x 10~4 25

122.0 4.2 x l O - 4 25Dimethylaminomethyl- Styrene 110 4 .9x lO" 5 130.7 tn 303

terf-amyl peroxide 120 1.19 x 10"4 t n 303130 3.76 x l O " 4 t n 303

Diethylaminomethyl- Styrene 110 4 . I x I O - 5 132.4 tn 303terf-butyl peroxide 120 1.35 x 10~4 tn 303

130 3.25 x l O - 4 t n 303N-Piperidinomethyl- Styrene 110 5.5 x 10"5 130.7 tn 303

tert-buty\ peroxide 120 2.66 x 10 ~4 t n 303130 4.16 x l O - 4 t n 303

9 tert-Butyl tert-amyl peroxide Cumene 110 3.86 x 10"6 363120 1.287 x lO- 5 363130 4.3OxIO-5 363140 1.406 x lO- 4 363

10 tert-Amyl peroxide Bulk 125 5.7xlO-5 202132.2 1.15 XlO"4 202

Chlorobenzene 108 1.93 x 10 ~5 344128 1.93 x lO" 4 344150 1.93 x 10-3 344

T (K) 4.02 xlO1 5 exp[- US35/RT] 344Decalin 125 2 .8x l0 - 5 202Octane 125 3 .0x l0" 5 202Triethylamine 125 3.5 x 10 ~5 202Vapor 132.2 7.2 x 10~5 154.8-171.5 i(200-225) 63

136.7 1.15 XlO"4 i(200-225) 63142.2 2.16 xlO~4 i(200-225) 63149.2 4.8 x lO" 4 i(100-200) 63136.7 1.34 x l O - 4 i(440-610) 63142.2 2.4IxIO-4 i(440-610) 63149.7 5.61 x 10"4 i(440-610) 63

tert-Butyl 1,1-dimethylbutyl Cumene 110 4.38 x lO" 6 363peroxide 120 1.537 x lO" 5 363

130 4.99 x l0~ 5 363140 1.544 x lO- 4 363

ter/-Butyl 1,1,2-trimethylpropyl Cumene 110 7.07 x 10 "6 363peroxide 120 2.374 x 10 ~5 363

130 7.62 x l 0 ~ 5 363140 2.308 xlO~4 363

2-Methyl-2-tert-butyl-peroxyacetate Chlorobenzene 150 4.12 x 10 "4 346Ethyl 2-terf-butylperoxymethyl- Triisopropylbenzene 127.5 1.63 x 10~4 C2 353

propenoate 130 1.95 x lO" 4 C2 353132.5 2.16 x lO" 4 C2 353135 2.56 x l O - 4 C2 353137.5 3.47 XlO"4 C2 353140 3.92 x l O - 4 C2 353142.5 4.68 x l O - 4 C2 353145 5.37 x l O - 4 C2 353147.5 6.3OxIO-4 C2 353150 7.76 xlO~ 4 C2 353

11 Apocamphane-1-formyl peroxide Benzene 80 2.3 x 10 ~4 24412 2,2-Bis(tert-butylperoxybutane) Benzene 85 3.OxIO-6 151 a 337

100 1.9 x l 0 ~ 5 a 337115 9.36 x l 0 ~ 5 a 337


TABLE 3. cont'd

Number ofC atoms Initiator Solvent T(0C) kd (s"1) Ea (kj/mol) Notes Refs.

12 (cont'd) tert-Butyl 1,1,3,3-tetramethylbutyl Cumene 110 1.085 x 10~5 363peroxide 120 3.73 x 10 ~5 363

130 1.141 x 10~4 363140 3.40xl0~4 363

1-Hydroxy-l-hydroperoxy- Benzene 85 9.6xlO~6 a,c2 337dicyclohexyl peroxide 100 5.1 x 10 ~5 a,c2 337

115 1.9 xlO~4 a,c2 337130 5.2 x l O - 4 a,c2 337

Di-(I -hydroxycyclohexyl)- Chlorobenzene 105 ~ 1 . 9 x l 0 ~ 5 344peroxide 120 ~1 .9xlO~ 4 344

Diisopropylaminomethyl- Styrene 110 3 .9x l0" 5 132.4 tn 303tert-amyl peroxide 120 1.21 x 10~4 tn 303

130 3.OxIO"4 tn 3031-Phenylethyl terf-butyl peroxide Chlorobenzene 129.2 3.09 x 10~5 282

13 terf-Butyla-cumyl peroxide terf-Butylbenzene 138 1.48 xlO~4 a 80158 9.62 XlO"4 a 80

Chlorobenzene 115 1.93 x 10 ~5 344136 1.93 xlO~4 344159 1.93 x l 0 ~ 3 344

T(K) 1.17 xlO1 5 exp[-146.98//?7] 344Cumene 138 1.44 xlO~4 a 80

158 8.88 xlO~4 a 80125 3.04 x l 0 ~ 5 352

Dodecane 128 4.44 x 10 ~5 146.4 a 80138 1.39 xlO~4 a 80148 3.21 x 10 ~4 a 80158 8.88 xlO~4 a 80

terf-Butyl />-chlorocumyl peroxide Cumene 125 2.42 x 10 ~5 352tert-Butyl p-nitrocumyl peroxide Cumene 125 2.20 x 10 ~5 352

14 tert-Butyl l,l-dimethyl-2-phenyl- Cumene 110 4.35 x 10 ~6 363ethyl peroxide 120 1.458 x 10~5 363

130 4.70xl0~5 363140 1.463 xlO~4 363

U-Di-(terf-butylperoxy)- Benzene 93 1.9xlO~5 a 338cyclohexane

Ethyl-3,3-di-tert-butylperoxy)-butyrate Benzene 111 1.9xl0"5 a 338l-[4-(Dimethylamino)phenyl]- Chlorobenzene 100.4 1.82 xlO~6 151.7 282

ethyl tert-butyl peroxide 110.8 6.97 x 10 ~6 282120.9 2.18 x l 0 ~ 5 282129.2 6.18 x l 0 ~ 5 282129.2 5.22 x l 0 ~ 5 m2 282

tert-Butyl /?-methoxycumyl peroxide Cumene 125 3.72 x 10 ~5 352tert-Butyl p-methylcumyl peroxide Cumene 125 3.22 x 10 ~5 352terf-Butyl m-methoxycumyl peroxide Cumene 125 2.84 x 10 ~5 352Bis(l, 1,2,2-tetramethylpropyl) peroxide Cumene 125 4.84 xlO~4 352

15 2-[4-(Dimethylamino)phenyl]- Chlorobenzene 129.2 1.51 x 10~4 m2 282propyl tert-buty\ peroxide

16 l,l-Di-(terf-amylperoxy)-cyclohexane Benzene 90 1.9xl0~5 a 338

tert-Butyl 3-isopropenyl- Chlorobenzene 104 1.93 x 10 ~5 344cumyl peroxide 126 1.93 x 10 ~4 344

152 1.93x10-3 344T(K) 1.161xl013 exp[-128.33/#7] 344

2,5-Dimethyl-2,5-di(tert-butyl- Benzene 115 1.15 x l 0 ~ 5 166.9 a 126,337peroxy)-hexane 130 6.86 x 10 ~5 a 126,337

145 4.75 xlO~4 a 126,337Chlorobenzene 115 1.93 x l 0 ~ 5 344

134 1.93 xlO~4 344156 1.93 x l 0 ~ 3 344

T (K) 1.68 x 1016 exp[- 155.49/RT] 3442,5-Dimethyl-2,5-di(terr-butyl- Benzene 115 3.91 x 10 ~6 156.9 a 126,337

peroxy)-3-hexyne 130 2.35 x 10 ~5 a 126,337145 1.14 xlO~4 a 126,337160 6.17 xlO~4 a 126,337

TABLE 3. cont'd

Number ofC atoms Initiator Solvent T(0C) ^d(S"1) Ea (kj/mol) Notes Refs.

16 (cont'd) 2,5-Dimethyl-2,5-di(terf-butyl- Chlorobenzene 120 1.93 x 10~5 344peroxy)-3-hexyne

141 1.93 xlO~4 344164 1.93 x l O - 3 344

T (K) 1.90 x 1015 exp[- 150.61/RT] 34417 rc-Butyl-4,4-bis(terf-butylperoxy)- Dodecane 100 5.83 x 10"6 a 8

valerate 115 3.53 x 10 ~5 a 8130 2 .9IxIO- 4 a 8

1,1 -Bis-(terr-butylperoxy)-3,3,5-trimethylcyclohexane Benzene 85 6.9xlO~6 138 a 337

100 5.05 x l O - 5 a 337115 2 .7IxIO- 4 a 337

18 Cumyl peroxide Benzene 115 2.05 x 10 ~5 159 a 337130 1.05 x l O - 4 a 126,337145 6.86 x l O - 4 a 126,337

terr-Butylbenzene 158 1.72 x 10 ~3 a 80Chlorobenzene 112 1.93 x IO"5 344

132 1.93 xlO~4 344154 1.93 x l O - 3 344

T (K) 9.24 x 1015 exp[- 152.61/RT] 344Cumene T (K) 4.31 x 1014 exp[- 1443/RT] 67

138 2.57 x l O - 4 a 80158 1.52 x l O - 3 a 80

Dodecane 128 8.75XlO"5 a 80138 2.31 x 10-4 a 80148 5.37 xlO~4 a 80158 1.83 x l O - 3 a 80

Diisopropylcarbinol 138 3.16 x 10~4 a 80Neat 150 3.98 x 10~3 a 371

155 4.81 x 10-3 a 371160 9.63 x l O - 3 a 371165 1.16 x l O - 2 a 371

Bicyclo[2.2.2]octane- Carbon tetrachloride 30 1.71 x 10 "4 2441-formyl peroxide 1.73 x 10 "3 n 244

1.68 x l O - 4 vi 244Chlorobenzene 30 6.2OxIO"4 244Cyclohexane 30 6 . Ix IO- 5 244Isooctane 30 5.OxIO-5 244Toluene 30 3.66 x 10 "4 244

20 a,a'-Bis(tert-butyrperoxy)- Benzene 115 1.9 x lO" 5 147 a 337diisopropyl benzene 125 4.91 x 10 ~5 a 337

130 9.61 x 10-5 a 337Chlorobenzene 114 1.93 x 10~5 344

134 1.93 x l O - 4 344156 1.93 x l O - 3 344

T(K) 7.65 xlO1 5 exp[- 152.69 kJ/RT] 344Neat 155 3.61 x 10~3 a 371

160 4.44 x lO" 3 a 371165 4.62 x l O - 3 a 371

24 2,5-Dimethyl-2,5-di-(2-ethyl- Benzene 68 1.9xlO-5 a 338hexanoylperoxy) hexane

TABLE 4. ACYL PEROXIDES

Number ofC atoms Initiator Solvent T(0C) kd (s"1) a (kj/mol) Notes Refs.

4 Acetyl peroxide Acetic acid 55.2 2.8 x 10~6 126.4 d,e 106,17664.9 9.9xlO~6 d,e 106,17675.2 3.75 x l O - 5 d,e 106,17685.2 1.3OxIO-4 d,e 106,17673.2 2.62 x l O - 5 a 100


Table 4. cont'd

Number ofC atoms Initiator Solvent J(0C) A^(S"1) Ea (kj/mol) Notes Refs.

4 (cont'd) Acetyl peroxide Benzene 35 9.5 x 10 ~7 6855 3.14 XlO"6 6865 1.27 x lO- 5 6850 1.1 x lO" 6 134 a 33770 2.39X10"5 a 126,33785 1.73 x lO" 4 a 126,33770 2.38 XlO"5 a 1660.3 5.OxIO"6 480 8.7xl0-5 2055.2 2.6 XlO"6 135.1 c,e 106,17664.9 1.07x10-5 c,e 106,17675.2 4.65x10-5 c,e 106,17685.2 1.62 XlO"4 c,e 106,176

H-Butanol 60.3 3.4xlO"5 4seoButanol 60.3 3x l0~ 5 4tert-Butanol 60.3 3 .1x l0" 6 133.9 4

80.3 4.9x10-5 4Carbon tetrachloride 26 1.08 x 10 "7 68

46 4.84 XlO"7 6865 2.11 x lO" 6 6880 5.5x10-5 20

Chloroform 80.3 ~ 5 4Cyclohexane 55.2 2.1 x 10"6 131.4 c,e 106,176

64.9 8.3 XlO"6 c,e 106,17675.2 3.6OxIO-5 c,e 106,17685.2 1.27 XlO"4 c,e 106,176

Cyclohexene 60 4.5xlO~6 133.5 2070 1.77x10-5 2080 7.0x10-5 2090 2.28 xlO"4 20

100 7.61X10"4 20Cyclopentene 70 1.6OxIO-5 137.2 20

80 7.0x10-5 2090 2.55 XlO"4 20

100 7.25 xlO"4 20Cumene 80 7 .6xl0- 5 20Decane 80 6.85 x l0~ 5 168n-Dodecane 60 2.3xlO"6 70

80 6.15x10-5 168Ethanol 60.3 1.01 x 10 "4 129.7 4

80.3 1.4OxIO-3 4Heptane 80 7.72 x 10 "5 168Hexadecane 80 5.39 x lO" 5 168-Hexane 60 3.4xlO~6 701-Hexene 70 2.35 x 10"5 132.6 20

80 8.7x10-5 2090 3.05 XlO"4 20

100 9.83 x lO" 4 202-Methyl-l-pentene 80 9.OxIO"5 126.8 20

90 3.12 XlO"4 20100 9.81 x 10 "4 20

rc-Octadecane 60 1.9xlO"6 70n-Octane 60 2.9xlO"6 70

80 7.34x10-5 168Isooctane 60 2.9xlO~6 70

55.2 2.35 x lO" 6 134.7 c,e 106,17664.9 9.4 XlO"6 c,e 106,17675.2 4.03x10-5 c,e 106,17685.2 1.49 XlO"4 c,e 106,176

1-Pentene 70 2.45 x 10 "5 2080 9.4 x 10"5 2090 3.22 XlO"4 20

Propionic acid 64.9 1.4 x lO" 5 106,17685.2 1.66 XlO"4 d,e 106,176

Table 4. cont'd

Number ofC atoms Initiator Solvent J(0C) ^d(S 1 ) Ea (kj/mol) Notes Refs.

4 (cont'd) Acetyl peroxide n-Tetradecane 60 2.OxIO"6 7080 5.9OxIO"5 168

Toluene 60.3 5 x l O " 6 129.7 455.2 2.7 xlO~6 133.9 c,e 106,17664.9 1.14 x lO" 5 c,e 106,17675.2 4.70xl0~5 c,e 106,17685.2 1.59 xlO~4 c,e 106,17673.2 3.06 XlO"5 138.1 a 10085.5 1.72 XlO"4 a 10090 7.33 x lO" 5 129.7 a 113

Vapor (toluene) 88.0 3.12 x lO" 4 123.4 105134.7 3.1 x 10"2 105150.7 1.18XlO"1 105161.7 2.77XlO"1 105170.7 6.10X10"1 105184.2 1.76 105

6 Propionyl peroxide Acetic acid 65.0 3.8xlO~5 123.0 c,e 5185.0 4.3 XlO"4 c,e 51

Acetic anhydride 65.0 3.5 x lO" 5 128.9 d,e 5185.0 4.5 x lO" 4 c,e 51

Benzene 65.0 1.88 x KT5 129.3 c,e 5185.0 2.4OxIO"4 c,e 5150 2.72 x lO" 6 127.6 a 126,33770 4.3OxIO"5 a 126,33785 2.89 XlO"4 a 126,337

Benzonitrile 65.0 3 .9x l0" 5 130.5 d,e 5185.0 5.IxIO" 4 d,e 51

Dioxane 65.0 4.5 x 10~5 116.7 c,e 5185.0 4.5 x lO" 4 c,e 51

n-Hexane 65.0 1.50x 10"5 123.8 5185.0 1.72 x lO" 4 51

Isooctane 65.0 9.8 x lO" 6 130.5 c,e 5186.5 1.44 x lO" 4 c,e 51

Nitrobenzene 65.0 3 .7xl0" 5 120.9 c,e 5185.0 4.1 x 10 "4 51

Toluene 65.0 1.87 x lO" 5 130.1 5185.0 2.54 x lO" 4 51

Vapor 65.0 1.0 x lO" 5 125.5 5185.0 1.6 xlO~4 5199.4 8 x lO" 4 125.5 85

134.4 2.6 XlO"2 85152.2 1.22XlO-1 85176.4 8.OxIO"1 85190.9 2.33 85

T (K) 2.5 x 10 "4 exp[- 125.5/RT] 852-Iodopropionyl peroxide Acetone 56 2.19 x 10 ~4 s 77

Benzene 62.5 (2.40-2.81) x 10 ~4 s 7762.5 7.12 XlO"4 n,s 7762.5 (2.36 0.07) x 10 ~4 108.8 p 77

H-Butyl vinyl ether 62.5 2.47 x 10"4 s 77Cyclohexene 62.5 2.7xlO"4 s 7795%Ethanol 62.5 4.OxIO"4 s 77

Perfluoropropionyl peroxide Freon 113 20 2.19 x 10 "5 100.1 h 28330 8.5OxIO-5 28340 3.26 XlO"4 283

T (K) 1.8 x 109 exp[- 83.8//?7] 304Isooctane T(K) 1.5xlO17 exp[- 121.5/RT} 304

2,2,3,3-Tetrafluoropropionyl Freon 113 25 2.26 x 10 "4 86.3 h 283peroxide 35 7.17 x 10 "4 283

8 tert-Butyl permaleic acid Acetone 87 1.9xlO~5 a 338Butyryl peroxide Acetic acid 65.0 4.7 x 10"5 125.1 c,e 51

85.0 5.6 x lO" 4 c,e 51Acetic anhydride 65.0 4.3 x 10 "5 51

85.0 5.5 x lO" 4 c,e 51

Notes page II - 69; References page II - 70

Table 4. cont'd

Number ofC atoms Initiator Solvent T(0C) ^ a ( S 1 ) Ea (kj/mol) Notes Refs.

8 (cont'd) Butyryl peroxide Benzene 65.0 2.24 x 10~5 131.4 d,e 5185.0 3.02 x l O - 4 c,e 51

Benzonitrile 65.0 4.3 x 10~5 131.4 d,e 5185.0 5.8 x l O - 4 51

Dioxane 65.0 4.6xlO~5 116.3 c,e 5185.0 4.6 x lO- 4 c,e 51

Hexane 65.0 1.14 x 10~5 131.4 c,e 5185.0 1.53 x lO- 4 c,e 51

Isooctane 65.0 1.11 x 10~5 133.5 c,e 5185.0 1.56 x lO" 4 c,e 51

Toluene 65.0 2.14 x lO" 5 130.5 d,e 5185.0 2.87 x lO- 4 c,e 51

Vapor 65.0 1.6 x lO" 5 123.8 5185.0 2.OxIO-4 5196.7 8.6 x lO" 4 123.8 85

127.4 1.5 XlO"2 85158.9 3.OxIO"1 85178.9 1.27 85

T(K) 1.9 xlO~4 exp[-123.8//?7] 85Isobutyryl peroxide Acetonitrile 40 6.81 x 10 "4 1113 167

Benzene 20 1.6 x lO" 5 109 a 33730 6.75 x lO- 5 a 33740 2.59 x lO- 4 a 33740 2.38 XlO"4 In3 16740 2.4OxIO-4 148,244

Benzonitrile 40 4.2xlO~4 148tert-Butanol 40 2.5IxIO"4 148Carbon tetrachloride 40 7 .8x l0" 5 148

45 1.58 XlO"4 14850 3.05 x lO- 4 14855 5.61 x 10~4 14860 7.67 xlO~4 148

Chlorobenzene 40 1.73 x 10 "4 14823 1.93 x l O - 5 34439 1.93 x lO- 4 34457 1.93 XlO"3 344

T (K) 3.37 xlO1 4 exp[- 109.06//?7] 344Chloroform 40 7.5 x 10 ~5 148Cyclohexane 40 4.5 x 10 ~5 148

40 4.7OxIO-5 167Fluorobenzene 40 1.23 x 10 "4 148Isooctane 25 3.35 x 10 ~6 114.2 84

35 1.54 XlO"5 8445 6.14 x lO- 5 8455 2.26 x lO- 4 84

T (K) 2.8 x 1014 exp[- 1H2/RT] 8440 3.2 x lO" 5 148

Isopropanol 40 3.05 x 10~4 148Nitrobenzene 40 5.8OxIO-4 148Nujol 40 4.63 XlO"5 167Tetralin 40 1.75 x 10 ~4 148Toluene 40 1.43 x 10 ~4 148Vapor 40 -1 x 10 ~5 167p-Xylene 40 1.4OxIO-4 148

Cyclopropane formyl peroxide Carbon tetrachloride 64.5 4.4xlO"6 3470.4 9.3 x 10 ~6 3477.8 2.31 x 10-5 34

Diacetyl succinoyl diperoxide Styrene 60 5.2xlO~~6 125.5 21573.5 2.3 x lO- 5 21585 9.3 x 10-5 215

Succinoyl peroxide Acetone 70 2.8OxIO-5 99.6 a 126,33785 1.21 x 10-4 a 126,337

100 4.36 x lO- 4 a 126,337

Table 4. cont'd


9 Acetyl benzoyl peroxide Chlorobenzene 70 2 x l 0 ~ 5 15596 5.12 x lO" 4 z(25),vi3 28496 4.08 XlO"4 z(19),vi3 284

10 5-Bromo-2-thenoyl peroxide Carbon tetrachloride 75 1.53 x 10 "5 a,mi 2324-Bromo-2-thenoyl peroxide Carbon tetrachloride 75 1.14 x 10 ~5 a,mi 2325-Chloro-2-thenoyl peroxide Carbon tetrachloride 75 1.58 x 10 ~5 a,mi 232a-Chloropropionyl m-chlorobenzoyl- Acetonitrile 41 3.05 x 10 ~5 ni3 167

peroxide Cyclohexane 41 1.51xl0~5 ni3 167Cyclobutane formyl peroxide Carbon tetrachloride 65 5.15 x 10 "5 34

70 8.95,6.63 x lO" 5 3475 1.41 x 10"4 34

Cyclopropane acetyl peroxide Carbon tetrachloride 14 9.45 x 10 ~5 3425 9.75,10.57 x 10"4 3444.5 5.01 x 10 "5 101.7 2456.5 2.64 XlO"4 2444.5 6.5-8.OxIO"4 n 24

Diacetyladipoyl diperoxide Styrene 60 6.6xlO"6 21573.5 4.73 XlO"5 21585 1.84 x lO" 4 215

Difuroyl peroxide styrene 50 7 .0x l0" 7 125.7 h 28760 2.9 xlO~6 28770 1.03 XlO"5 287

2,2,3,3,4,4,5,5-Octafluoropentanoylperoxide Freon 113 20 3.29 x 10 "5 100.6 h 283

30 1.27 XlO"4 28340 5.01 x 10 "4 283

Perfluoro-2-(2-ethoxysulfinic Freon 113 T(K) 2.8xlO1 4 exp[-95.1//?7] 304acid) propionyl peroxide

Pivaloyl peroxide Carbon tetrachloride 10 1.9xlO~4 2442-Thenoyl peroxide Carbon tetrachloride 75 2.21 x 10 ~~5 a,mi 2323-Thenoyl peroxide Carbon tetrachloride 75 2.14 x 10 "5 a,mi 232

11 Benzoyl isobutyryl peroxide Acetonitrile 41 4.06 x 10 "4 167Cyclohexane 41 1.63 x lO" 5 167

70 3.05 xlO~4 16740 1.45 x l O - 5 112.5 h,j 16450 5.398 XlO"5 j 16460 1.924 x lO" 4 j 16470 6.872 x lO" 4 j 164

m-Chlorobenzoyl isobutyryl peroxide Acetonitrile 41 1.03 x 10 ~3 167Cyclohexane 40 3.486 x 10 "5 111.3 h,j 164

50 1.362 x lO" 4 j 16441 4.4OxIO-5 167

p-Chlorobenzoyl isobutyryl peroxide Cyclohexane 50 1.029 x 10 ~4 j 16455 1.651 x 10-4 16460 3.21 x 10-4 16465 5.638 x l O - 4 164

p-Fluorobenzoyl isobutyryl peroxide Cyclohexane 55 1.117 x 10 "4 16460 2.038 XlO"4 16465 4.893 x l O - 4 16470 9.603 x lO" 4 164

5-Methyl-bis-2-thenoyl peroxide Carbon tetrachloride 75 2.92 x 10 "5 a 232p-Nitrobenzoyl isobutyryl peroxide Cyclohexane 40 8 .1x l0" 5 164

45 1.336 x lO" 4 16450 2.889 x l O - 4 16455 4.725 XlO ' 4 16460 8.921 x 10 ~4 164

12 P-Allyloxypropionyl peroxide Toluene 70 2.0IxIO"5 a 19180 8.62 x lO" 5 a 19190 2.53 x lO" 4 a 191

p-Xylene 70 2.32 x lO" 5 a 19180 8.88 x lO" 5 a 19190 2.95 x lO" 4 a 191

m-Chlorobenzoyl 2-methyl- Acetic acid 40 1.60 x 10 ~3 256butanoyl peroxide Acetonitrile 40 1.72 x 10 "3 256


Table 4. cont'd


12 (cont'd) m-Chlorobenzoyl 2-methyl- 2-Butanol 40 9.0xl0~ 4 256butanoyl peroxide Carbon tetrachloride 40 1.32 x 10 ~4 256

Cyclohexane 40 6.OxIO"5 256Cyclobutane acetyl peroxide Carbon tetrachloride 65 1.37 x 10 ~5 34

70 2.13,3.08 x 10-5 3475 3.83 x l O - 5 34

Cyclopentane formyl peroxide Carbon tetrachloride 40 1.50 x 10 ~5 3445 2.55 XlO"5 3450 4.96 XlO"5 3455 8.17,7.85 x 10"5 34

Hexanoyl peroxide Toluene 77 1.186 x 10 ~4 2095-Hexenoyl peroxide Toluene 60.1 1.06 x 10 "5 129.3 c 209

70.4 4.15 XlO"5 c 20976.4 8.59 x lO" 5 c 20985.0 2.668 x l O - 4 c 209

4-Methoxybenzoyl isobutyryl- Cyclohexane 55 5.465 x 10 ~5 164peroxide 60 1.024 x lO" 4 164

65 1.876 XlO"4 16470 3.208 XlO"4 164

4-Methylbenzoyl isobutyryl- Cyclohexane 40 9.6IxIO"6 j 164peroxide 50 3.619 x l 0 ~ 5 j 164

60 1.305 XlO"4 j 16470 4.772 x lO" 4 j 164

4-Methyl-2-thenoyl peroxide Carbon tetrachloride 75 2.92 x 10 "5 a,mi 2325-Methyl-2-thenoyl peroxide Carbon tetrachloride 75 4.21 x 10 ~5 ^m 1 232Perfluoro-2-furnanacetyl peroxide Freon 113 T (K) 1.2 x 1011 exp[- 11A/RT] 304Perfluoro-2-propoxypropionyl- Freon 113 T(K) 4.4xlO1 4 exp[- 9Z.5/RT] 304

peroxide perF-ether mix. T (K) 8.9 x 1016 exp[-110.2/RT] 304Perfluoro-2-n-propoxypropionyl- Freon 113 20 4.81 x 10 ~5 100.1 h 283

peroxide 30 1.96 x 10 ~4 28340 7.16 XlO"4 283

Perfluoro-2-iso-propoxypropionyl- Freon 113 20 8.32 x 10 ~5 102.7 h 283peroxide 30 3.43 x 10 ~4 283

40 1.34 x l 0 ~ 3 28314 2-Azidobenzoyl peroxide Benzene 50 2.5 x 10~5 d2 161

80 9.4 XlO"4 d2 161Benzoyl peroxide Acetic acid 75 7.53 x 10 "5 a,r 74

Acetone 50 2.25 x 10 ~6 111.3 a 12670 2.63X10-5 a 12685 1.34 xlO~4 a 126

100 5.83 xlO~4 a 126Acetonitrile 70 1.76 x 10 ~5 tj 124Acetophenone 70 1.15 x 10~5 126.4 a 5

80 4.32xlO-5 a 594.5 2.30xl0~4 a 5

Allyl alcohol 80 3.80 x 10 ~4 a,r 74Anisole 30 1.42 x 10 ~7 a 109Benzaldehyde 80 5.50xl0~5 a,r 74

90 1.71 x 10-4 a,r 74Benzene 25 6.4xlO~5 p2 279

30 4.80 xlO~8 116.3 a 10955 1.14 xlO~6 a,r 7460 2.76 xlO~6 a,r 7460 2 .0xl0~ 6 124.3 m2 1480 2 .5xlO- 5 m2 1470 1.38x10-5 a 21378 2.3OxIO-5 c 23078 1.67x10-5 X9 23079.8 3.48x10-5 17080 4.8x10-5 2066 7.72 x 10 ~6 129.7 a 13172.5 1.87x10-5 a 13178 3.77x10-5 a 13170 1.17x10-5 133.9 a 73

Table 4. cont'd

Number ofC atoms Initiator Solvent J( 0C) kd (s"1) Ea (kj/mol) Notes Refs.

14 (cont'd) Benzoyl peroxide Benzene 75 2.62 x 10 "5 a 7380 4.39 XlO"5 a 7380 3.27 XlO"5 a,b2 34750.8 4.28 XlO"7 123.8 a,t2 6954.9 8.53 x l O - 7 a,t2 6960.9 1.66 x l O - 6 a,t2 6965.6 3.22 XlO"6 a,t2 6971.0 5.94 x l O - 6 a,t2 6975.8 1.19 XlO"5 a,t2 6970 1.27 XlO"5 130 a 33785 8.94 x l O - 5 a 126,337

100 4.96 x l O - 4 a 126,33770 1.03 x l O - 5 a,m2 1670 1.18 XlO"5 t2 12475 1.48 x l O - 5 128.0 1275 1.66 x l O - 5 124.3 m3 1285 4.7 x l O - 5 1285 5.5 XlO"5 m3 12

100 2.28 x l O - 4 12100 2.56 x l O " 4 m3 1279 2.58 x l O - 5 a,t6 12080 3.35 x l O " 5 a 7

Benzyl alcohol 80 4.44 x 10 "4 a,r 74Bromobenzene 80.2 8.15 x l O " 5 231

2.19 x l O " 5 t9 2313.84 x l O - 5 Hi1 2313.55 x l 0 ~ 5 m 3 2314.34 x l O - 5 m 5 231

Butanol 80 6.06 x 10 "4 a,r 74Butanone 80 4.64 x 10 "5 a,r 74Di-n-butyl phthalate 117 2.78 x 10 ~3 120.1 y i 6 236

127 7.44 X lO" 3 236137 1.72 x l O - 2 236147 3.89 X l O " 2 236

Carbon tetrachloride 75 1.07 x 10 "5 a,r 7479 1.69 XlO" 5 t6,a 121

Chlorobenzene 70 1.35 x 10 ~5 I1 12480 4.64 x l O - 5 a,r 7480.2 2.85 x l O " 5 23180.2 2.36 x l O - 5 t9 23180.2 3.52 x l 0 ~ 5 Cm1 23180.2 2.62 XlO" 5 c,m3 23171 1.93 x l O - 5 34491 1.93 x l O " 4 344

113 1.93 XlO"3 344T (K) 6.94 x lO 1 3 exp[- 12235/RT] 344

Chloroform 30 5.47 x 10 ~8 a 109Cumene 80 3.69 x 10 ~5 a,r 74

85 6.39 XlO"5 a,r 7490 1.19 x l O - 4 a,r 7430 7.3OxIO-8 a 10945 1.85 x lO 7 120.5 6760 1.45 x l O - 6 6780 1.70 XlO"5 67

T (K) 1.20 x 1013 exp[- 120.5/RT] 67100 2.5 XlO"4 a,t7 122

Cyclohexane 80 7.72 x 10 ~5 a,r 74Decane 80 2.53 x 10 "5 270Decalin 80 2.26 x 10 "4 a,r 74Dioxane 70 1.30 x 10 "5 ti 74

80 6.72 x l O - 4 a,r 7480 4.2OxIO-4 a,r 680 4.18 x l 0 ~ 5 a,m! 232

Notes page 11-69; References page 11-70

Table 4. cont'd

Number ofC atoms Initiator Solvent T(0C) ^ d ( S 1 ) a (kj/mol) Notes Refs.

14 (cont'd) Benzoyl peroxide Ethanol 25 3.02 xlO~ 8 a 35140 2.77 x l O " 7 a 35150 4.72 x l O - 7 a 351

Ethylbenzene 30 3.61 x 10 "8 a 10975 1.8IxIO-5 a,r 7480 3.33 XlO"5 a,r 7485 5.56 XlO"5 a,r 7490 1.01 x 10-4 a,r 7480 3.15 x l 0 ~ 5 c 239

90% Formic acid 80 6.94 x 10 "4 a,r 74H-Heptane 80 3.11 x 10 ~5 a,r 74

80 2 .7 Ix IO- 5 270130 5.73 XlO"3 z (1500) 377135 1.02 x l O " 2 z (1500) 377140 1.54 x l O - 2 z (1500) 377145 2.25 XlO"2 z (500) 377145 2 .22xlO- 2 z (1000) 377145 2.21 x 10~2 z (1500) 377145 2.12 x l O - 2 z (2000) 377150 3.47 x l O " 2 z (1500) 377155 5.21 x 10-2 z (1500) 377160 7.87 x l O - 2 z (1500) 377

Hexadecane 80 2.51 x 10 "5 270Hexane 80 2.85 x 10 ~5 270Isooctane 80 2.79 x 10 ~5 270

80 2.7OxIO"5 m2 308Isopropylbenzene 80 3.34 x 10~5 c 229Methyl acetate 49.2 6.28 x 10 ~7 123.8 a,t2 69

53.9 1.0 XlO"6 a,t2 69Methylcyclohexane 80 5.25 x 10 ~5 a,r 744-Methyl-2pentanone 80 4.28 x 10 ~5 a,r 74a-Methylstyrene 70 3.02 x 10 "5 a 213Mineral oil 80 2.89 x 10~5 m2 308Neat 105 7.22 x 10 ~3 a 371Nitrobenzene 80 4.58 x 10 ~5 a,r 74

30 6 .6 Ix IO- 8 117.6 a 109PEG 400 25 5 .0 Ix IO- 7 a 351

40 5.73 x l O - 6 a 35150 1.15 x l 0 ~ 5 a 35170 1.15 XlO"4 a 351

90% aq. PEG 400 25 3.65 x 10~7 a 35140 5.35 x l O " 6 a 35150 1.15 x l O - 5 a 35170 1.15 x l O " 4 a 351

80% aq. PEG 400 25 2.77 x 10 ~7 a 35140 3.09 x l O " 6 a 35150 7.29 x l O - 6 a 35170 1.15 x l O - 4 a 352

70% aq. PEG 400 25 1.71 x 10 ~7 a 35140 2 .1 Ix IO- 6 a 35150 5.01 x 10-6 a 35170 1.15 x l O " 4 a 351

rt-Pentanol 80 1.48 x 10 ~4 a,r 74Phenol 80 6.25 x 10 "4 a,r 74Propionic acid 80 3.19 x 10~5 a,r 74Propylene glycol 25 3.25 x 10 ~8 a 351

40 1.51 xlO~ 7 a 35150 3.16 x l O - 7 a 351

Styrene 34.8 3.89 x 10 ~8 a 1049.4 5.28 XlO"7 a 1061.0 2.58 x l O - 6 a 1074.8 1.83 x l 0 ~ 5 a 10

100.0 4.58 x l O " 4 a 10

Table 4. cont'd

Number ofC atoms Initiator Solvent T(0C) ^d(S"1) E a (kj/mol) Notes Refs.

14 (cont'd) Benzoyl peroxide Poly(styrene) 56.4 3.8 x 10~7 a 1764.6 1.47 x l O - 6 a 1776.7 9.27 x lO" 6 a 1783.4 2.5OxIO-5 a 1798.5 1.41 x lO" 4 a 1770.9 2.86 x l O - 6 a 1580.1 1.11 x l O - 5 a 1589.5 3.33 x l O - 5 a 15

Tetradecane 80 2.64 x 10 ~5 270Tetralin 80 3.72 x 10 "5 a,r 74Toluene 30 4.94 x lO" 8 120.5 a 109

49.0 6.OxIO-7 123.8 a,t2 6955.1 1.31 x 10-6 a,t2 6960.2 2.83 x l O - 6 a,t2 6965.1 5.69 x l O - 6 a,t2 6970.3 1.10 x l O - 5 a,t2 6960.00 2.24 x lO" 6 e,m3 291

Poly(vinylchloride) 64.6 6.3xlO"7 a 1776.7 5.11 XlO"6 a 1783.4 1.44 x lO- 5 a 1798.5 9.33 x lO" 5 a 17

Styrene 50 7 x IO"7 125.7 28760 7.7 x l O - 6 28770 9.9 x lO" 6 287

p-Xylene 80 3.1OxIO-5 c 2293-Bromobenzoyl peroxide Benzene 60 1.1 x 10 "6 116

80 1.22 x l O - 5 11680 2.6OxIO-5 a 7

Dioxane 80 2.57 x 10 ~5 a,mi 6,2324-Bromobenzoyl peroxide Dioxane 80 3.23 x 10 ~5 a,mi 6,2324-terr-Butylbenzoyl peroxide Dioxane 80 6.06 x 10 ~5 a,m 2322-Chlorobenzoyl peroxide Acetophenone 80 3.88 x 10 "4 123.0 a 5

Benzene 80 3.12 x 10 "4 a 73-Chlorobenzoyl peroxide Acetophenone 80 2.85 x 10 ~5 128.4 a 5

Dioxane 80 2.63 x 10 ~5 a,mi 64-Chlorobenzoyl peroxide Acetophenone 80 3.83 x 10 "5 127.2 a 5

Benzene 80 2.17 x 10 ~5 a 750 6.2 x lO" 7 128.9 a 12685 6.64 x l O - 5 a 126

100 3.86 x lO- 4 a 126Dioxane 80 3.62 x 10 "5 ^m 1 6Styrene 34.8 8 .3x l0 - 8 a 10

49.4 8.3 x lO" 7 a 1061.0 3.33 x l O - 6 a 1074.8 2.22 x lO- 5 a 10

100.0 4.17 x lO- 4 a 10Cyclohexane formyl peroxide Benzene 30 9.64 x 10 ~5 84.5 a,h 219

35 1.46 x lO" 4 21940 3.1OxIO-4 21945 5.11xlO"4 21950 7.77 x l O - 4 219

Carbon tetrachloride 35 6.6xlO~~5 14845 2.1IxIO- 4 14850 4.45 xlO~4 14860 1.3OxlO"3 14835 2.87 x lO- 5 3440 5.22,5.29 x 10 "5 3445 9.67 x lO- 5 34

Cyclopentane acetyl peroxide Carbon tetrachloride 65 1.48 x 10"5 3470 3.2OxIO"5 3475 4.97 x lO- 5 34

Diacetylsebacoyl diperoxide Carbon tetrachloride 60 1.04 x 10 ~5 Xi 21573.5 5 .20xl0~ 5 X1 21585 2.3OxIO-4 xi 215


Table 4. cont'd

Number ofC atoms Initiator Solvent J(0C) ^d(S"1) a (kj/mol) Notes Refs.

14 (cont'd) 2,4-Dichlorobenzoyl peroxide Benzene 70 9.7OxIO"5 a,j 1670 1.24 xlO~4 a,k 1650 1.08 xlO~5 117.6 a 126,33770 1.37 xlO~4 a 126,33785 7.69 XlO"4 a 126,337

Styrene 34.8 3.88 x 10 "6 a 1049.4 2.39 x l 0 ~ 5 a 1061.0 7.78 xlO~5 a 1074.8 2.78 xlO~4 a 10

100.0 4.17 x l 0 ~ 3 a 102,2,3,3,4,4,5,5,6,6,7,7-Dodeca- Freon 113 30 1.14 x 10~4 100.6 h 283

fluoroheptanoyl peroxide 40 4.06 x 10 ~4 283Heptanoyl peroxide Toluene 77 1.24 x 10 ~4 a 196-Heptenoyl peroxide Toluene 70 5.33 x 10 ~5 a,k 19

70 5.01 x 10 ~5 a,j 1977 1.07 xlO~4 a,j 1985 2.88 xlO~4 a,k 19

2-Iodobenzoyl peroxide Chloroform 22 1.86 x 10 ~3 822-Iodobenzoyl 4-nitrobenzoyl Acetone 25 3 .0xl0~ 4 78

peroxide Acetonitrile 25 2.1x 10 ~4 78Benzene 25 5.7xl0~ 5 78Carbon tetrachloride 25 3.4xl0~ 5 78Chloroform 25 2.8xlO~4 78Nitrobenzene 25 6.2xlO~4 78

3-Methylbenzoyl peroxide Dioxane 80 4.38 x 10 ~5 a,mi 2324-Methylbenzoyl peroxide Dioxane 80 6.11 x 10 ~5 a,mi 2322-Nitrobenzoyl peroxide Acetophenone 59.3 5.80xl0~5 119.7 a 5

80 1.34 x l 0 ~ 3 a 5Methyl iodide 24.95 1.78 xlO~5 81.2 h 82

45.05 1.50xl0~4 823-Nitrobenzoyl peroxide Acetophenone 80 3 .80xl0" 5 126.4 a 54-Nitrobenzoyl peroxide Acetophenone 80 4.33 x 10 "5 126.8 a 53,5-Dinitrobenzoyl peroxide Acetophenone 80 1.87 x l 0 ~ 5 130.5 a 5Perfluoroheptanoyl peroxide Freon 113 20 3.01 x 10 ~5 98.0 283

30 1.11 xlO~4 28340 4.20xl0~ 4 283

15 Benzoyl phenylacetyl peroxide Benzene 20 1.10 x 10~4 90.8 22225 2.05 xlO~4 22225 3.15 xlO~4 vi 22225 6.38 xlO~4 n 22230 3.88 xlO~4 22235 6.67 xlO~4 222

4-terf-Butylbenzoyl isobutyryl Cyclohexane 55 6.543 x 10 ~5 ti0 164peroxide 60 1.171 x 10~4 tio 164

65 2.663 xlO~4 t10 16470 5.016 xlO~4 tio 164

3-Cyanobenzoyl benzoyl peroxide Dioxane 80 2.73 x 10 ~2 a,m\ 63-Methoxybenzoyl benzoyl peroxide Dioxane 80 4.82 x 10 ~2 a,mi 64-Methoxybenzoyl benzoyl peroxide Dioxane 80 7.57 x 10 ~5 a,mi 64-Methoxybenzoyl 3-bromobenzoyl Dioxane 80 4.43 x 10 ~2 a,mi 6

peroxide4-Methoxybenzoyl-3,5-dinitro- Benzene 51 1.02 x 10 ~5 108

benzoyl peroxide Nitrobenzene 51 9.61 x 10 ~4 10851 1.67 XlO"3 t5 108

4-Methoxybenzoyl 4-nitrobenzoylperoxide Benzene 70 2.08 x 10 ~5 a 89

70 8.03 x l 0 ~ 5 a 8916 3,5-Dibromo-4-methoxybenzoyl

peroxide Benzene 60 9.5 x 10 ~7 9560 6.1 xlO~7 11680 9.4 x 10 ~6 116

Caprylyl peroxide Benzene 50 3.44 x 10 ~6 128.9 a 12670 5.78 x l 0 ~ 5 a 12685 3.78 xlO~4 a 126

Table 4. cont'd


16 (cont'd) Caprylyl peroxide Mineral oil T (K) 9.8 x 1015 exp[- UOA/RT] 1/7-(Chloromethyl)benzoyl peroxide Acetone 70 2.07 x 10 ~5 307

70 1.82 x lO" 5 m7 307THF 70 1.15 XlO"5 307Toluene 70 8 .8x l0" 6 307

3-Cyanobenzoyl peroxide Dioxane 80 1.70 x 10 ~2 a,mi 64-Cyanobenzoyl peroxide Acetophenone 80 2.43 x 10 ~5 a 5

Dioxane 80 2.03 x 10 "5 a,mi 6Cycloheptane formyl peroxide Carbon tetrachloride 35 7.85 x 10 ~5 34

40 1.63,1.34XlO"5 3445 2.02 XlO"4 34

Cyclohexane acetyl peroxide Carbon tetrachloride 65 1.27 x 10 "5 3470 2.76 XlO"5 3475 3.61 x 10 "5 3454.4 3.1 x 10 "6 2464.3 1.19 x lO" 5 2471.8 2.95 XlO"5 24

2-Ethyl-4-methyl-2-pentenoylperoxide Mineral oil T(K) 7 . IxIO 1 6 exp[-138.4//?7] 1

2-Ethylhexanoyl peroxide Mineral oil T(K) 1.2xlO14 exp[- 106A/RT] 12-Ethyl-2-hexenoyl peroxide Mineral oil T (K) 1.6 x 1016 exp[-136.3//?7] 12-Iodophenylacetyl peroxide Acetone 0 2.6OxIO"5 79

Chloroform 0 3.98 x 10 ~5 c,e,q 79Toluene 0 1.3xlO"5 q 79

2-Methoxybenzoyl peroxide Acetophenone 50 6 .0x l0" 5 113.8 a 580 2.15 XlO"3 a 5

3-Methoxybenzoyl peroxide Acetophenone 80 6.42 x 10 "5 120.9 a 5Dioxane 80 5.75 x 10 ~5 a,mi 6

4-Methoxybenzoyl peroxide Acetophenone 80 1.56 x 10 "4 120.1 a 5Dioxane 80 1.18 x 10 ~A a,mi 6

2-Methylbenzoyl peroxide Acetophenone 70 9.02 x 10 "5 126.4 a 53-Methylbenzoyl peroxide Acetophenone 80 4.7OxIO"5 126.4 a 5

Dioxane 80 4.4OxIO"5 a,mi 64-Methylbenzoyl peroxide Acetophenone 80 5.92 x 10 "5 125.1 a 5

Dioxane 80 6.13 x 10~5 a,mi 6Endo-norbornane-2-carbonyl-

peroxide Carbon tetrachloride 44.5 6 . IxIO" 6 j 2353.9 2.83 XlO"5 j 2365.9 1.25 XlO"4 j 23

44.5 9.1 x 10"6 j ,m2 2353.9 4.33 x lO" 5 j , m2 2365.9 1.28 x lO" 4 j ,m2 23

Exo-norbornane-2-carbonyl- Carbon tetrachloride 44.5 4.68 x 10 "5 j 23peroxide 53.9 2.05 x 10 "4 j 23

65.9 8.18 xlO~4 j 2344.5 7.2 XlO"5 j , m2 2353.9 1.6OxIO"4 j ,m2 2365.9 8.48 XlO"4 j , m2 23

Endo-norbornene-5-carbonyl- Carbon tetrachloride 44.5 6.30xl0~5 j 23peroxide 53.9 1.2IxIO"4 j 23

65.9 7.18 x lO" 4 j 23445 2.22 x lO" 5 j ,m2 23

53.9 4.52 XlO"5 j,m2 2365.9 2.37 x lO" 4 j ,m2 23

Exo-norbornene-5-carbonyl- Carbon tetrachloride 44.5 6.58 x 10 "5 j 23peroxide 53.9 1.2IxIO-4 j 23

65.9 8.42 XlO"4 j 2344.5 2.58 xlO~5 j ,m2 2353.9 1.2OxIO"4 j ,m2 2365.9 7.1OxIO-4 j ,m2 23

Dioctanoyl peroxide w-Heptane 70 1.70xl0"5 z (1500) 37780 7.0IxIO- 5 z (500) 37780 6.8OxIO-5 z (1000) 377


Table 4. cont'd

Number ofC atoms Initiator Solvent T(0C) ^ d ( S 1 ) Ea (kj/mol) Notes Refs.

16 (cont'd) Dioctanoyl peroxide ^-Heptane 80 6.27 x 10~5 z (1500) 37780 6.01 x l 0 ~ 5 z (2000) 37780 5.77xlO- 5 z (2500) 37790 2.13 x lO~ 4 z (1500) 37795 3.8OxIO-4 z (1500) 377

100 6.79 x lO~ 4 z (1500) 377Dioctanoyl peroxydicarbonate Chlorobenzene 63 1.93 x 10 ~5 344

80 1.93 x l O - 4 344100 1.93 x l O - 3 344

T (K) 2.30 x 1015 exp[- 129.05/RT] 344Phenylacetyl peroxide Acetonitrile 20 1.02 x 10 ~3 167

Benzene 20 4.76 x 10 ~4 167Carbon tetrachloride 20 1.86 x 10 ~4 167Cyclohexane 20 1.6OxIO-4 167Styrene 0 7 .8x l0~ 5 316Toluene 0 2.5OxIO-5 96.2 f,u2 59

18 3.34 XlO"4 f,uj 59Triptoyl peroxide Benzene 80 1.42 x 10 ~4 102

80 1.4 x lO~ 4 24418 Apocamphoyl peroxide Benzene 80 2.3 x 10 ~4 102

ds-5-rm-Butylcyclohexylformyl-m-chlorobenzoyl peroxide Acetonitrile 40 5 .9x l0~ 3 256

2-Butanol 40 4.4xlO~ 3 256Carbon tetrachloride 40 6.7 x 10 ~4 256Cyclohexane 40 4.4xlO~ 4 256

fra5-4-^rf-Butylcyclohexylformyl-m-chlorobenzoyl peroxide Acetonitrile 40 4.2xlO~ 3 256

2-Butanol 40 2.8 x 10 ~3 256Carbon tetrachloride 40 6.5 x 10 ~4 256Cyclohexane 40 3.9xlO~4 256

5-terf-Butylthenoyl peroxide Carbon tetrachloride 75 4.03 x 10 ~5 a,mi 232Cinnamoyl peroxide Styrene 50 1.2OxIO-5 316

70 1.67 x l O - 4 316Dibenzoyl succinoyl diperoxide Unknown 70 7.7 x 10 ~6 125.5 X1 214

75 1.42 x l O - 5 xi 21485 5.4 x l O - 5 xi 214

Nonanoyl peroxide Mineral oil T(K) 8.4xlO1 4 exp[-121A/RT] 1Isononanoyl peroxide (3,5,5-

trimethylhexanoyl peroxide) Benzene 50 6 . I x I O - 6 126 a 33770 8.02 x l 0 ~ 5 a 33785 5.3OxIO-4 a 33760 1.9 x l O - 5 a 338

Chlorobenzene 59 1.93 x 10 ~5 34477 1.93 XlO"4 34496 1.93 x l O - 3 344

T (K) 2.84 x 1015 exp[- 128.34/^7] 344n-Heptane 60 5.28 x 10 ~6 z (1500) 377

70 2.06 x l 0 ~ 5 z (1500) 37780 9.53 x l O - 5 z ( l ) 37780 9.1OxIO-5 z (500) 37780 8.62 x l O - 5 z (1000) 37780 8.24 x l O - 5 z (1500) 37780 7.86 x l O - 5 z (2000) 37780 7.46 x l O - 5 z (2500) 37790 2.52 x l O - 4 z (1500) 377

100 8 .8IxIO- 4 z (1500) 377120 6.98 x l O - 3 z (1500) 377125 1.27xl0-2 z (1500) 377130 2.15 XlO"2 z (1500) 377135 2.6OxIO-2 z (1500) 377140 5.7IxIO-2 z (1500) 377145 8.62xl0-2 z (1500) 377150 1.17XlO-1 z (1500) 377

2-Nonenoyl peroxide Mineral oil T (K) 1.6 x 1015 exp[-128.8//?7] 1

Table 4. cont'd

Number ofC atoms Initiator Solvent J( 0C) * d (s"1) E31 (kj/mol) Notes Refs.

18 (cont'd) 3-Nonenoyl peroxide Mineral oil T (K) 3.7 x 1014 exp[- 10S.0/RT] 12-Phenylpropionyl peroxide Cyclohexane 55.8 6.8xlO~6 258

On silica 49.4 7.5 x 10 "5 258Styrene 70 5.5 x 10"5 316

19 Dibenzoyl itaconyl diperoxide Unknown 70 5.63 x 10~4 83.7 X2 2141.87 XlO"5 115.1 X2 214

75 8.63xlO- 4 X2 2143.62 xl0~5 X2 214

85 1.69 X l O " 3 X2 2141.00 X l O - 4 X2 214

Dibenzoyl a-methylsuccinoyl- Unknown 70 2.74 x 10 "4 82.8 X2 214diperoxide 1.26 x l O " 5 116.3 X2 214

75 4.26 X l O " 4 X2 2142.40xl0~5 X2 214

85 9 . 6 O x I O " 4 X2 2148.7 x l O " 5 x2 214

20 Decanoyl peroxide Benzene 60 1.53 x 10~5 127.2 a 126,33770 5.67 XlO"5 a 126,33785 3.8OxIO-4 a 126,337

Chlorobenzene 63 1.93 x 10 "5 34480 1.93 x l O - 4 344

100 1.93 x l 0 ~ 3 344T (K) 3.64 x 1015 exp[- 130.48//?7] 344

Mineral oil T(K) 2 . 7 x l 0 1 5 exp[- 131.9/K7] 1Dioctanoyl a-bromosuccinoyl- Unknown 70 1.52 x 10 ~~4 96.2 X2 214

diperoxide 1.82 x l O " 5 126.4 X2 21475 2.74 XlO"4 X2 214

3.83 xlO-5 X2 21485 6.97 x l O " 4 x 2 214

1.15 X l O " 4 X2 214Dioctanoyl a-chlorosuccinoyl- Unknown 70 2.02 x 10 ~A 95.4 X2 214

diperoxide 2.42 x l O " 5 126.4 X2 21475 3.23 x l O " 4 X2 214

4.83 xlO~5 X2 21485 8 . 5 O x I O - 4 X2 214

Dioctanoyl a-chlorosuccinoyl-diperoxide Unknown 85 1.58 x 10~4 X2 214

4-Ethyl-2-octenoyl peroxide Mineral oil T (K) 8.2 x 101 4 e x p [ - 121A/RT] 121 Dioctanoyl itaconoyl diperoxide Unknown 70 3.23 x 10 ~4 92.9 X2 214

2 . 8 O x I O - 5 127.6 X2 21475 5.47 x l O " 4 X2 214

5 .6OxIO" 5 X2 21485 1.28 x l O " 3 X2 214

1.92 X l O " 4 X2 214Dioctanoyl a-methyl succinoyl- Unknown 70 5.48 x 10 ~4 96.2 X2 214

diperoxide 5.88 x l 0 ~ 5 131.0 x 2 21475 9.58 x l O " 4 X2 214

1.06 x l O " 4 x2 21485 2 .61x l0" 3 x2 214

3.84 x l O " 4 x2 21422 Benzoyl 2-[mms-2-(3-nitrophenyl)- Chlorobenzene 70 1.87 x 10~4 t9 175

vinyljbenzoyl peroxideBenzoyl 2- [frans-2-(4-nitrophenyI)- Chlorobenzene 70 1.18 x 10 "4 t9 175

vinyl]benzoyl peroxide THF 70 6 . 2 x l 0 " 5 t9 175Benzoyl 2-[fras-2-(4-nitrophenyI)- Chlorobenzene 70 1.54 x 10 "5 t9 175

vinyl]-4-nitrobenzoyl peroxideBenzoyl 2-[frans-2-(phenyl)vinyl]- Chlorobenzene 35 9.42 x 10 "5 84.5 h,t9 175

benzoyl peroxide 70 3.02 x 10"3 t9 175Methanol 35 9.77 x 10"4 t9 175

4-Benzylidenebutyryl peroxide Acetophenone 50 7.92 x l O " 5 99.6 13355 1.45 x l O " 4 13365 4.13 x l O " 4 133

T(K) 1.07 x lO 1 2 exp[-99.6//?7] 13355 1.38 x l O " 4 98.7 m2 133


Table 4. cont'd


22 (cont'd) 4-Benzylidenebutyryl peroxide Acetophenone 65 4.02 x 10 "4 m2 133T(K) 7 .14x lO n exp[- 98.1/RT] m2 133

Benzene 50 2.40xl0~5 91.2 h 19460 6.8OxIO-5 19470 1.845 x l O - 4 194

Carbon tetrachloride 60 3.47 x 10~5 112.5 m2 13370 1.06 XlO"4 m2 133

T(K) 1.42xlO13 exp[-112.5 /RT] m2 133Nitrobenzene 60 3.38 x 10~4 133Propylene carbonate 40 7.36 x 10~5 89.5 133

50 2.13 XlO-4 133T (K) 5.93 x 1010 exp[- 89.5/RT] 133

50 2.08 XlO"4 m2 13340 7.23 x l O - 5 82.0 h 19450 2.093 x lO" 4 19460 5.117 x l O - 4 194

Toluene 70 1.64 x 10~4 1334-ter/-Butylbenzoyl peroxide Dioxane 80 6.08 x 10 ~2 a,mi 6cis-4-tert-Butylcyclohexane formyl- Butane 40 1.25 x 10 ~5 z (0.98) 145

peroxide 40 1.69 x lO" 5 z (1010) 145Carbon tetrachloride 40.0 (8.65 0.35) x 10 ~5 76.1 h 35

45.45 (1.32 0.04) x 10-4 3550.7 (2.35 0.05) x 10-4 35

frarcs-4-te7t-Butylcyclohexane formyl- Carbon tetrachloride 40.0 (4.25 0.23) x 10~5 81.6 h 35peroxide 44.7 (7.10 0.38) x 10 ~5 35

48.9 (1.140.04)x 10~4 35fras-4-(4-Chlorobenzylidene)- Benzene 50 2 .10x l0" 5 95.0 h 194

butyryl peroxide 60 6.56 x 10 ~5 19470 1.75 x lO" 4 194

Propylene carbonate 40 5.33 x 10 ~5 19450 1.448 x 10~4 19460 2.791 x 10~4 194

frarcs-4-(4-Fluorobenzylidene)- Benzene 50 2.67 x 10 "5 94.1 h 194butyryl peroxide 60 8.44 x 10 ~5 194

70 2.119 x l O - 4 194Propylene carbonate 40 6.53 x 10 ~5 194

50 1.685 x l O - 4 19460 4.54OxIO-4 194

1-Naphthoyl peroxide Benzene 54.6 1.01 x 10~4 17059.9 1.86 x l O - 4 17064.5 3.OxIO"4 170

4-Nitrobenzoyl-2-[rra5-2-(4-nitro- Chlorobenzene 70 6.06 x 10~5 t9 175phenyl)vinyl] benzoyl peroxide

2-Phenylisovaleryl peroxide Acetonitrile 55.0 2.27 x 10 "5 258Cyclohexane 55.0 6 .4xlO- 6 258On silica 50 2.56 x 10 ~4 n2 258

5-Phenylpenta-2,4-dienoyl-peroxide Styrene 70 2.18 x lO" 4 3165-Phenylpentanoyl peroxide Acetophenone 77 2.37 x 10 ~4 133

Benzene 77 1.054 x lO" 5 127.6 h,m2 194Carbon tetrachloride 70 2.76 x lO" 5 130.1 m2 133

77 7.19 x l O - 5 m2 13385 1.87 x l O - 4 m2 133

T(K) 1.76xlO15 exp[-130.1/i?7] m2 133Propylene carbonate 60 4.41 x 10 ~5 133

60 2.8Ox 10"5 m2 13324 Dibenzoyl 2-bromosebacoyl- Unknown 70 4.80xl0~ 4 87.9 X2 214

diperoxide 3.87 x 10~5 110.8 X2 21475 7.64 x l O - 4 x2 214

7.22 XlO"5 X2 21485 2.0OxIO"3 x2 214

2.02 x l O - 4 X2 214Dioctanoyl 2-bromosebacoyl- Unknown 70 6.46 x 10 ~4 99.6 X2 214

diperoxide 5.23 x 10~5 129.7 X2 21475 1.17IxIO-3 x2 214

Table 4. cont'd

Number ofC atoms Initiator Solvent T(0C) kd(s'1) Ea (kj/mol) Notes Refs.

24 (cont'd) Dioctanoyl 2-bromosebacoyl- Unknown 1.08 x 10 "4 X2 214diperoxide 85 3.0OxIO"3 X2 214

3.72 x l 0 ~ 4 X2 214Lauroyl peroxide Benzene 30 2.56 x 10 "7 a 99

40 4.91 x 10~7 6850 2.19 x l O - 6 6860 9.17 xlO~6 6870 2.86 x l O - 5 6860 1.51 x 10~5 127.2 a 126,33770 5.58 x l 0 ~ 5 a 126,33785 3.75 x l O - 4 a 126,33770 4.33 x l O - 5 a,j 16

Carbon tetrachloride 40 2.91 x 10 ~7 6850 1.15 XlO"6 6860 4.75 x l O - 6 6870 1.87 xlO~5 68

Chlorobenzene 61 1.93 x 10 ~5 34479 1.93 x l O - 4 34499 1.93 XlO"3 344

T (K) 3.92 xlO1 4 exp[- 12337/RT] 344Ethyl acetate 40 6.03 x 10 ~7 68

50 2.7OxIO-6 6861 1.05 x l 0 ~ 5 6870 3.99 x l 0 ~ 5 68

Ethyl ether 30 1.97 x 10 "6 a 99Mineral oil T (K) 2.2 x 1016 exp[- 137.9/RT] 1Styrene 34.8 2.06 x 10 ~7 a 10

49.4 2.25 x lO" 6 a 1061.0 1.42 x l 0 ~ 5 a 1074.8 1.00 x l O - 4 a 10

100.0 2.39 x l O - 3 a 1050 3.1 x 10"6 121.1 28760 1.2OxIO-5 28765 2.22 x l O - 5 28770 4.32 x l O - 5 287

rraw5-4-(4-Methoxybenzylidene)- Benzene 50 2.03 x 10 ~4 194butyryl peroxide

frarcs-4-(4-Methylbenzylidene)- Benzene 50 6.58 x 10 ~5 90.4 c,h 194butyryl peroxide 60 1.815 x 10 ~4 c 194

70 4.729 x lO" 4 c 19426 2-Phenoxybenzoyl peroxide Acetophenone 65 8.18x10 ~5 121.3 a 528 Myristoyl peroxide Benzene 70 3.38 x 10 ~5 a 1636 Menthylphthaloyl peroxide Dioxane 55 1.15 x 10~4 65x Aliphatic polymeric Chlorobenzene 75 9.04 x 10 ~5 Vu 302

diacyl peroxide 75 9.00 x 10 "5 Vi5 30280 1.720xl0"4 V15 302

TABLE 5. HYDROPEROXIDES AND KETONE PEROXIDES

Number ofC atoms Initiator Solvent T(0C) fcd (s"1) Ea (kj/mol) Notes Refs.

4 sec-Butyl hydroperoxide Toluene 172.0 2.65 x 10 ~5 199182.3 4.9 XlO"5 199

ter/-Butyl hydroperoxide Benzene 130 3 x 10 ~7 138 a 337145 1.6 XlO"6 a 337160 6.6 x l O - 6 a 337154.5 4.29 XlO"6 170.7 h 76161.7 9.27 x l O - 6 76169.3 2.OxIO-5 76174.6 4.OxIO-5 76


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Front MatterTable of ContentsII. Polymerization and DepolymerizationDecomposition Rates of Organic Free Radical InitiatorsA. IntroductionB. Tables of Decomposition Rates of Organic Free Radical InitiatorsTable 1. AzonitrilesTable 2. Miscellaneous Azo-derivativesTable 3. Alkyl PeroxidesTable 4. Acyl PeroxidesTable 5. Hydroperoxides and Ketone PeroxidesTable 6. Peresters and PeroxycarbonatesTable 7. Miscellaneous Initiators

C. NotesD. References

Propagation and Termination Constants in Free Radical PolymerizationTransfer Constants to Monomers, Polymers, Catalysts and Initiators, Solvents and Additives, and Sulfur Compounds in Free Radical PolymerizationPhotopolymerization ReactionsFree Radical Copolymerization Reactivity RatiosQ and e Values for Free Radical Copolymerizations of Vinyl Monomers and TelogensPatterns of Reactivity (U,V) Parameters for the Prediction of Monomer Reactivity Ratios and Transfer Constants in Radical PolymerizationCopolymerization Parameters of Metallocene-catalyzed CopolymerizationsRates of Polymerization and Depolymerization, Average Molecular Weights, and Molecular Weight Distribution of PolymersHeats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer Concentrations, and Polymerizability of Heterocyclic CompoundsActivation Energies of Propagation and Termination in Free Radical PolymerizationActivation Volumes of Polymerization ReactionsActivation Enthalpies and Entropies of Stereocontrol in Free Radical PolymerizationsProducts of Thermal Degradation of PolymersRadiation Chemical Yields: G Values

Index

Polymer_Handbook/Polymer Handbook/66286_03b.pdfTable 4. cont'd

Number ofC atoms Initiator Solvent T(0C) kd(s'1) Ea (kj/mol) Notes Refs.

24 (cont'd) Dioctanoyl 2-bromosebacoyl- Unknown 1.08 x 10 "4 X2 214diperoxide 85 3.0OxIO"3 X2 214

3.72 x l 0 ~ 4 X2 214Lauroyl peroxide Benzene 30 2.56 x 10 "7 a 99

40 4.91 x 10~7 6850 2.19 x l O - 6 6860 9.17 xlO~6 6870 2.86 x l O - 5 6860 1.51 x 10~5 127.2 a 126,33770 5.58 x l 0 ~ 5 a 126,33785 3.75 x l O - 4 a 126,33770 4.33 x l O - 5 a,j 16

Carbon tetrachloride 40 2.91 x 10 ~7 6850 1.15 XlO"6 6860 4.75 x l O - 6 6870 1.87 xlO~5 68

Chlorobenzene 61 1.93 x 10 ~5 34479 1.93 x l O - 4 34499 1.93 XlO"3 344

T (K) 3.92 xlO1 4 exp[- 12337/RT] 344Ethyl acetate 40 6.03 x 10 ~7 68

50 2.7OxIO-6 6861 1.05 x l 0 ~ 5 6870 3.99 x l 0 ~ 5 68

Ethyl ether 30 1.97 x 10 "6 a 99Mineral oil T (K) 2.2 x 1016 exp[- 137.9/RT] 1Styrene 34.8 2.06 x 10 ~7 a 10

49.4 2.25 x lO" 6 a 1061.0 1.42 x l 0 ~ 5 a 1074.8 1.00 x l O - 4 a 10

100.0 2.39 x l O - 3 a 1050 3.1 x 10"6 121.1 28760 1.2OxIO-5 28765 2.22 x l O - 5 28770 4.32 x l O - 5 287

rraw5-4-(4-Methoxybenzylidene)- Benzene 50 2.03 x 10 ~4 194butyryl peroxide

frarcs-4-(4-Methylbenzylidene)- Benzene 50 6.58 x 10 ~5 90.4 c,h 194butyryl peroxide 60 1.815 x 10 ~4 c 194

70 4.729 x lO" 4 c 19426 2-Phenoxybenzoyl peroxide Acetophenone 65 8.18x10 ~5 121.3 a 528 Myristoyl peroxide Benzene 70 3.38 x 10 ~5 a 1636 Menthylphthaloyl peroxide Dioxane 55 1.15 x 10~4 65x Aliphatic polymeric Chlorobenzene 75 9.04 x 10 ~5 Vu 302

diacyl peroxide 75 9.00 x 10 "5 Vi5 30280 1.720xl0"4 V15 302

TABLE 5. HYDROPEROXIDES AND KETONE PEROXIDES


4 sec-Butyl hydroperoxide Toluene 172.0 2.65 x 10 ~5 199182.3 4.9 XlO"5 199

ter/-Butyl hydroperoxide Benzene 130 3 x 10 ~7 138 a 337145 1.6 XlO"6 a 337160 6.6 x l O - 6 a 337154.5 4.29 XlO"6 170.7 h 76161.7 9.27 x l O - 6 76169.3 2.OxIO-5 76174.6 4.OxIO-5 76


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TABLE 5. cont'd

Number ofC atoms Initiator Solvent T(0C) #d ( s 1 ) Ea (kj/mol) Notes Refs.

4 (cont'd) tert-Butyl hydroperoxide Benzene 172.3 1.09 xlO" 5 199182.6 3.1 x 10~5 199

Chlorobenzene 171 1.93 x 10~5 344199 1.93 xlO" 4 344231 1.93 xlO" 3 344

Cumene 182.6 8.1 x 10"5 c 199Cyclohexane 100 1.2xlO-? 199

172 1.4IxIO-4 c 199Dodecane 86.1 1.32 xlO~6 128.4 b 41

98.5 5.55 x lO- 6 b 41Heptane 172 1.41 x 10"4 199w-Octane 149.8 8x lO" 6 163.2 f 118

159.9 2.5 XlO"5 f 118169.6 6.9 x l0~ 5 f 118179.6 1.82 x l0~ 5 118

Toluene 100 5 .7xl0" 8 199172.5 9.2 xlO" 6 199181.5 2.69 XlO"5 199192.6 8.3 xlO" 5 199204.5 1.52 XlO"4 c 199214.9 3.24 xlO~4 199

Vapor 570 3.4XlO1 188670 4.95 188773 8.4XlO1 188873 5.66 x 102 188973 2.58 x 103 188

tert-Butyl hydroperoxide/cobalt Chlorohenzene 0 1.01 x 10"3 1902-Ethyl hexanoate 0 8.29 x 10 ~5 Vi0 190

0 5.4OxIO"4 V7 19025 2.3 XlO"3 19825 1.1 x lO" 3 V1 198

tert-Butyl hydroperoxide/cobalt 45 1.4xlO"3 198stearate 45 l.OxlO"3 Vi 198

Methyl ethyl ketone peroxides Benzene 100 1.3 x 10 "5 101 a 337115 4.80xl0" 5 a 337130 1.60xl0"4 a 337

Ethyl acetate 70 1.28 x 10~6 135 tert-Amyl hydroperoxide Chlorobenzene 153 1.93 x 10 "5 344

190 1.93 x lO" 4 344228 1.93 x lO" 3 344

6 Acetone cyclic diperoxide Benzene 135.5 6.25 xlO" 7 147.1 h 286145.5 2 .09xl0- 6 286165.0 1.41 x 10"5 286

Toluene 165.0 1.37 xlO" 5 2863,3,6,6-Tetramethyl-1,2,4,5- Benzene 135.5 6.25 x lO" 7 373

tetroxane 140.5 1.19 x 10~6 373145.5 2.09 x lO" 6 373150.5 2.83 XlO"6 373165.0 1.41 x 10"5 373

Toluene 165.0 1.37 xlO" 5 373Vapor 130.1 1.8 x lO" 6 365

150.1 3.4xlO-6 365170.1 3 .5x l0- 6 365177.1 4.6x10-6 365185.1 1.3 x l0~ 5 365194.1 2.4 x lO- 5 365207.1 8.5 xlO" 5 365215.1 1.66 xlO" 4 365250.1 4.88 x lO- 4 365

Cyclohexyl hydroperoxide Benzene 70 0 a 91Benzene/styrene (50/50) 70 1.27 x 10~3 a 91Cyclohexane 130 2.38 x l0~ 3 a 91

140 1.16 x lO- 2 a 91150 3.20xl0"2 a 91

TABLE 5. cont'd


6 (cont'd) Cyclohexyl hydroperoxide Benzene 80 Reaction order 119varies from1.5 to 2.0

Cyclohexane 80 Reaction order 119varies from1.5 to 2.0

Cyclohexene 80 Reaction order 119varies from1.5 to 2.0

Dimethylheptadiene 80 Reaction order 119varies from1.5 to 2.0

1-Octene 80 Reaction order 119varies from1.5 to 2.0

7 Benzyl hydroperoxide Styrene 60 9 x l O ~ 6 C3 27660 1.8 x l O - 5 C4 276

8 1,4-Dimethylcyclohexane- 1,4-Dimethylcyclohexane 120 1.4xlO"5 137.2 c 224hydroperoxide

1,1,3,3-Tetramethylbutyl-hydroperoxide Benzene 130 1.7xlO~5 134 a 337

145 7.41 x 10-5 a 337160 2.83 XlO"4 a 337

Chlorobenzene 135 1.93 x 10 ~5 344153 1.93xlO-4 344173 1.93 x l O - 3 344

2,5-Dimethyl-2,5-di(hydro-peroxy)hexane Benzene 130 2.7xlO~6 113 a 337

145 1.0 x l O - 5 a 337160 3.16 x l O - 5 a 337

n-Octyl hydroperoxide White oil 150 9.29 x 10 ~5 112.5 a 1772,4,4-Trimethylpentyl- White oil 150 9.29 x 10 "5 112.5 a 177

2-hydroperoxide(S)x Poly(phenyleneethyl hydro- Chlorobenzene 26 2.0OxIO-4 46.0 t3 212

peroxide)/manganese resinate 30 2.75 x 10"4 t3 21235 3.67 XlO"4 t3 212

9 Cumene hydroperoxide Benzene 115 4 x l O " 7 122 a 337130 1.7 x l O - 6 a 337145 6.6 x lO~ 6 a 337

Chlorobenzene 159 1.93 x 10 ~5 344193 1.93 x l O " 4 344253 1 .93xl0- 3 344

Cumene 110 2.742 x 10 ~6 367120 5.194 x l O - 6 367132 9.305 x l O - 6 367

T(K) 2.1OxIO11 exp[- S0.0/RT] 367Mesitylene 98.7 58Styrene 101.3 58Toluene 125 9 x l O ~ 6 199

139 3 x l O - 5 199182.3 6.45 x l O " 5 199

White oil 150 1.34 x 10~4 121.3 a 177Cumyl hydroperoxide Acetone-d6 -33 .0 7 .0x l0~ 5 62.0 264

-23.0 2.28 XlO"4 264-12 .0 1.2IxIO-3 264-18 .0 8.3 x l O - 5 110.2 t u 264

- 8 . 0 4.23 x l O - 4 tM 264

- 3 . 0 1.65xlO-3 t u 26410 p-Cymene hydroperoxide /?-Cymene 110 5.50OxIO"6 367

120 1.20OxIO-5 367132 2.089 XlO"5 367

T(K) 1.23 xlO 1 2 exp[-85.48//?71 367


TABLE 5. cont'd

Number ofC atoms Initiator Solvent T(0C) ^d(S"1) a (kj/mol) Notes Refs.

10 (cont'd) Decalin hydroperoxide Acetic acid 130 5.5xl0~ 4 228Chlorobenzene 130 10% in 3 h 228Decalin 130 1.4IxIO-5 124.3 2281,2-Dichlorobenzene 130 4.48 x lO" 5 176.4 228Ethylene glycol 130 1.65 x 10 ~4 117.2 228Nitrobenzene 130 4.73 x 10 ~5 228Pyridine 130 (2.31-2.89) x 10 ~4 228

Pinane hydroperoxide Benzene 130 7.08 x 10 "6 123.8 a 18145 2.72 x l 0 ~ 5 a 18160 9.17 x l O - 5 a 18

2-Phenylbutyl 2-hydroperoxide sec-Butylbenzene 110 2.944 x 10 ~6 367120 6.61IxIO-6 367132 1.089 XlO"5 367

T(K) 4.06 xlO1 2 exp[-87.15//?7] 367l-Phenyl-2-methylpropyl- Benzene 133.8 3.18 x lO" 6 122.2 h 76

hydroperoxide 143.9 8.95 x 10 "6 76153.9 2.OxIO"5 76163.7 4.03 XlO"5 76174 9.77 x lO" 5 76

l-Phenyl-2-methylpropyl-2- Benzene 144.2 5.04 x 10 "6 125.5 h 76hydroperoxide 154.5 1.21 x IO"5 76

165.6 2.92 x lO" 5 76176.0 6.97 XlO"5 76

Tetralin hydroperoxide Poly(butene) 170 2.17 x lO" 3 78.2 t3 71n-Butyl stearate 170 1.47 x lO" 4 125.5 t3 712-Ethyl-l-hexene 130 1.08 x lO" 4 82.8 e,t3 71

170 1.26 x lO" 3 t3 711-Hexadecene 170 7.92 x lO" 4 117.2 t3 71Mineral oil 135.6 4.2 x lO" 5 131.4 t3 71

150.6 1.00 XlO"4 e,t3 71170 4.82 x l O - 4 t3 71

/i-Octadecane 170 2.54 x 10~4 119.2 t3 71Isooctane 170 1 31 x 10"4 t3 71Octyl ether 170 1.45 x l 0 ~ 3 121.3 t3 71Poly(propylene) 170 2.5OxIO"3 t3 71-Tetradecane 170 2.32 x 10~4 t3 71Tetralin T(K) 2.27 x 109 exp[-102.1 /RT] 1122,2,4-Trimethyl-l-pentene 170 1.67 x 10~3 t3 71white oil 150 1.34 x 10~4 121.3 177

(1O)n Poly(cumyleneethylhydroperoxide) Toluene 130 2.79 x 10"5 210(MWIlOO) 140 4.OxIO-5 210

150 5.78 XlO"5 21011 2,2-Bis(terf-butyldioxy)propane Cumene 90 2.16 x 10~6 361

100 9.14 x lO" 6 361110 2.97 XlO"5 361120 9.56 x lO" 5 361

l-Methoxy-l-(terf-butylperoxy) Cumene 80 4.79 x 10 ~6 348cyclohexane 90 1.898 x 10 ~5 348

100 6.57 x l 0 ~ 5 348110 2.139 x l O - 4 348

sc-Butyltoluene hydroperoxide ^c-Butyl toluene 100 4.11IxIO-6 367110 8.194 XlO"6 367120 1.9555 x l O - 5 367

T(K) 1.02 xlO16 txp[-\W2/RT] 36712 2,2-Di-(tert-butylperoxy)butane Chlorobenzene 98 1.93 x 10 ~5 344

116 1.93 x lO- 4 344136 1.93 xlO"3 344

T(K) 9.3OxIO16 exp[-154.08/^7] 3442,2-Bis(ter/-butyldioxy)butane Cumene 100 1.84 x 10 ~5 361Diisopropylbenzene Chlorobenzene 150 1.93XlO"5 344

monohydroperoxide 182 1.93 x 10 ~4 344218 1.93 x l O - 3 344

l-Methoxy-l-(terr-amylperoxy) Cumene 80 7.82 xlO~6 348cyclohexane 90 3.07 x 10 "5 348

TABLE 5. cont'd

Number ofC atoms Initiator Solvent T(0C) A:d (s"1) Ea (kj/mol) Notes Refs.

12 (cont'd) l-Methoxy-l-(te/Y-amylperoxy) Cumene 100 1.058 xlO~4 348cyclohexane 110 3.450 x 10 "4 348

13 l-Methoxy-l-(terf-hexylperoxy) Cumene 80 8.34 x 10~6 348cyclohexane 90 3.17 x lO" 5 348

100 1.12Ox 10"4 348110 3.653 x l O - 4 348

U-Bis(tert-butylperoxy)- Cumene 80 4.98 x lO" 6 349,364cyclopentane 90 1.80xl0~5 349,364

100 6.67 x lO" 5 349,364110 2.17 XlO"4 349,364

2,2-Bis(terf-butyldioxy)-3-methyl- Diphenylmethane 90 1.08 x 10 ~5 358butane 100 3.75 x 10 ~5 358

110 1.29 XlO"4 358120 4 .1IxIO- 4 358

Cumene 100 3.17 x lO" 5 36114 U-Bis(terf-butylperoxy)- Cumene 80 3.47 x 10~6 349,350

cyclohexane 90 1.45 x 10 ~5 349,350100 5.06 x lO" 5 349,350110 1.62 XlO"4 348,349,350

Chlorobenzene 94 1.93 x 10 "5 344113 1.93 x lO" 4 344134 1.93 x l 0 ~ 3 344

T (K) 3.47 x 1015 exp[- 142A/RT] 344w-Dodecane 100 3.51 x 10 ~5 364n-Hexadecane 100 3.15 x lO" 5 364H-Hexane 100 3.82 x 10 "5 364n-Nonane 100 3.62 x 10 ~5 364

l,l-Bis(terr-butylperoxy)-2-methyl- Cumene 80 1.55 x 10~5 349cyclopentane 90 5.82 x 10~5 349

100 1.85 x lO" 4 349110 6.0OxIO"4 349

1,1-Diphenylethyl hydroperoxide Chlorobenzene 90 2.OxIO"9 374110 1.007 XlO"6 374130 1.034 XlO"6 374150 1.223 XlO"6 374

T (K) 1.38 x 108 exp[- 105A/RT] 37415 l-Methoxy-l-(rm-octylperoxy)- Cumene 70 5.9xlO~6 348

cyclohexane 80 2.3OxIO"5 34890 8.18 x lO" 5 348

100 2.84OxIO"4 348U-Bis(^-butylperoxy)-2-methyl- Cumene 80 1.29 x 10~5 349

cyclohexane 90 4.51 x 10 "5 349100 1.43 XlO"4 349110 4.58 x lO" 4 349

16 U-Bis(terf-amylperoxy)- Cumene 80 5.34 x lO" 6 348cyclohexane 90 2.02 x 10 "5 348

100 7.32 x lO" 5 348110 2.44 XlO"4 348

l,l-Bis(terf-butylperoxy)- Cumene 90 1.11 x 10 "5 364cyclooctane 100 4.15 x 10~5 364

110 1.36 x l O - 4 364120 4.24 xlO~4 364

17 l,l-Bis(^rr-butylperoxy)-2-n-propyl- Cumene 80 1.2OxIO-5 349cyclohexane 90 4.19 x 10 "5 349

100 1.38 XlO"4 349l,l-Bis(terf-butylperoxy)- Cumene 70 2.59 x 10"5 349

2-isopropylcyclohexane 80 4.86 x 10 ~5 34990 1.98 x lO" 4 349

100 7.46 XlO"4 349l,l-Bis(ferf-butylperoxy)- Cumene 80 3.82 x 10~6 349,364

3,3,5-trimethylcyclohexane 90 1.50 x 10 "5 349,364100 5.31 x 10 "5 349,364110 1.75 XlO"4 349,364


TABLE 5. cont'd

Number ofC atoms Initiator Solvent J(0C) kd (s"1) Ea (kj/mol) Notes Refs.

Il (cont'd) U-Bis(tert-butylperoxy)- Chlorobenzene 85 1.93 x ICT5 3443,3,5-trimethylcyclohexane 105 1.93 x 10 ~4 344

128 1.93 XlO- 3 344T (K) 7.59 x 1013 exp[- 127.52/RT] 344

rc-Butyl 4,4-di-(terf-butylperoxy) Chlorobenzene 102 1.93 x 10 "5 344valerate 121 1.93 x 10 ~4 344

143 1.93 XlO- 3 344T(K) 1.91 x 1015 exp[- 143.51/RT] 344

18 l,l-Bis(terr-hexylperoxy)- Cumene 80 5.38 x 10~6 348cyclohexane 90 2.06 x 10 ~5 348

100 7.48 XlO"5 348110 2.48 XlO- 4 348

20 U-Bis(tert-butylperoxy)- Cumene 90 8.14 x l O " 6 364cyclododecane 100 3.22 x 10~5 364

110 9.93 XlO"5 36422 U-Bis(tert-octylperoxy)- Cumene 80 1.513 x 10~5 348

cyclohexane 90 5.62 x 10 ~5 348100 1.983 XlO- 4 348110 6.26 x l O - 4 348

31 2,2-Bis[4,4-di-(tert-butyl- Chlorobenzene 87 1.93 x 10 ~5 344peroxycyclohexyl)propane 106 1.93 x 10 ~4 344

128 1.93 x l O - 3 344T(K) 8.79 x lO 1 4 exp[-135.56//?7] 344

TABLE 6. PERESTERS AND PEROXYCARBONATES


4 Dimethyl peroxalate Pentane 25 1.7xlO~5 2035 tert-Butyl percarbamate Chlorobenzene 90 6.6xlO"6 141

tert-Butyl performate Chlorobenzene 130.8 5.43 x 10 ~5 159.0 h 218140.8 1.7OxIO-4 218140.6 1.8OxIO-4 m2 218140 2.12 XlO"3 64.0 V8 218140 5.06 x lO- 4 V1 218

4-Chlorotoluene 140.6 1.61 x 10~4 218140 1.62 x lO- 3 v8 218

Cumene 140.6 1.77 x 10~4 b 218140 1.02 XlO"3 b,v6 218

6 Isobutyl peracetate a-Methylstyrene 79.5 1.36 x lO" 5 115.2 25388.4 3.61xl0"5 25392.8 5.58 x lO- 5 253

tt-Butyl peracetate a-Methylstyrene 64 ~ 9 . 6 x l 0 ~ 3 g2,vi6 25364 8.2 x lO- 3 g2,vi7 25364 6.5 x lO- 4 g2,vi8 25364 1.2 x lO- 3 g2,vi9 25379.6 1.57 x lO- 5 101.0 25387.8 3.27 x lO- 5 25392.6 5.38 x lO- 5 253

sec-Butyl peracetate a-Methylstyrene 88.2 1.79XlO"5 104.3 25392.8 3.19 x lO- 5 25399.4 5.37 x lO- 5 253

terr-Butyl peracetate terf-Amyl alcohol 75 2.8 x 10 "6 193Benzene 85 1.2xlO~6 193

85 2.18 x lO- 6 151.9 a 126,337100 1.54 x 10-5 a 126,337115 1.02 XlO"4 a 126,337130 5.69 x lO- 4 a 126,337

n-Butanol 75 2.65 x 10 ~5 193

TABLE 6. cont'd

Number ofC atoms Initiator Solvent T (0C) d (s"1) E31 (kj/mol) Notes Refs.

6 (cont'd) rm-Butyl peracetate 2-Butanol 75 1.13 x 10"4 c 19375 5.3 XlO"5 t7 19375 4 x l O - 7 m3 193

Chlorobenzene 60 2 .3IxIO" 8 159.0 a,h 81100 1.93 XlO"5 344119 1.93 XlO"4 344139 1.93 x l O " 3 344

T (K) 1.57 x 1016 exp[- 149.36/RT] 344Decane 100 1.5 x IO"5 134 337

115 7 .9 Ix IO- 5 337125 2.45 XlO"4 337100 1.95 x 10-5 270

Dodecane 100 1.78 x 10 ~5 270Hexadecane 100 1.55 x 10 "5 270Hexane 130.1 5.08 x 10~4 169Octane 100 2.07 x 10 ~5 270Paraffin 130.1 3.13 x 10~4 169Tetradecane 100 1.55 x 10 ~5 270

rm-Butyl trichloroperacetate Chlorobenzene 60 1.19 x 10 "5 125.9 a,h 8166.8 2.75 x l O - 5 126.8 h 2877.0 1.00 XlO"4 28

Diethyl peroxydicarbonate terr-Butanol 45 1.25 x 10 "5 133.9-138.1 c 1855 5.7 x l 0 ~ 5 c 18

2,2'-Oxydiethylene 40 6.94 x l O " 6 127.2 a 90bis(allyl carbonate) 50 2.86 x 10 "5 a 90

60 1.28 x l O - 4 a 90Diethyl peroxalate Pentane 25 2 .6x lO" 5 203

7 ten-Amyl peracetate Chlorobenzene 90 1.93 x 10 "5 344108 1.93 x l O " 4 344129 1.93xl0-3 344

T(K) 4.13 xlO 1 5 exp[-141.1/#n 344tert-Butyl methoxyperacetate Ethylbenzene 40.0 2 .2x lO" 4 104.7 a,h 315

39.6 1.94 x l O - 4 103.9 h 32850.2 8.24 x l O - 4 32860.1 2.35 x l O - 3 328

terf-Butyl peracrylate Benzene 90 1.12 x l O " 5 86.2 a 211100 1.5IxIO-5 a 211110 4.85 x l O - 5 a 211

terr-Butylperoxy isopropyl Chlorobenzene 98 1.93 x 10 "5 344117 1.93 XlO"4 344137 1.93 x l O - 3 344

T(K) 2.49 x lO 1 6 exp[-150.15//?7] 344terr-Butyl perpropionate Benzene 80 1.53 x 10~6 a 213

carborate 90 6.04 x 10 "6 a 213Decane 100 1.82 x 10 ~5 270Dodecane 100 1.78 x IO"5 270Hexadecane 100 1.58 x 10 ~5 270a-Methylstyrene 70 3.02 x 10~7 a 213

90 4.85 x l O " 6 a 213Octane 100 2.03 x 10 ~5 270Tetradecane 100 1.68 x 10 ~5 270

8 rm-Butyl 2-acetoxyperacetate Ethylbenzene 91.8 2.73 x 10 ~5 b 328tert-Buty\ cyclopropane-

percarboxylate -Dodecane 113.0 5.48 x 10 ~5 255rc-Hexadecane 102.6 1.28XlO"5 153.8 h 255

113.0 4.92 x l O - 5 2552,2,4-Trimethyl- 102.6 1.7IxIO-5 146.2 h 255

pentane 113.0 6.19 x 10~5 255120.4 1.505 XlO"4 255

ferf-Butyl ethoxyperacetate Ethylbenzene 40.0 2.96 x 10 ~4 105 a 31540.6 2.89 x l O - 4 102.7 m2,h 32846.0 5.58 x l O - 4 32855.6 1.94 XlO"3 328


TABLE 6. cont'd


8 (cont'd) tert-Butyl heptafluoroperoxy- Benzene 65.0 1.56 x 10 "5 v24 370butyrate 70.0 3.09 x 10 ~5 V24 370

75.0 5.27 XlO"5 V24 37080.0 9.08 x lO" 5 V24 37060.0 9.5 x lO" 6 V25 37065.0 1.61 x 10~5 V25 37070.0 2.7OxIO-5 V25 37075.0 5 .23xl0- 5 V25 37080.0 9.18 x l 0 ~ 5 V25 37060.0 9.6 XlO"6 V26 37065.0 1.93 x l O - 5 V26 37070.0 3.57 XlO"5 V26 37075.0 6.35 x l 0 ~ 5 V26 370

Methanol 10.0 7.19 x 10~5 36915.0 9.37 x l 0 ~ 5 36919.6 1.304 x l O - 4 36930.0 2.604 x l O - 4 369

Methoxybenzene 55.0 5.01 x 10 ~5 37060.2 8.56 x lO" 5 37065.0 1.378 x l O - 4 37070.0 2.444 XlO"4 370

Nitrobenzene 40.0 3.26 x 10 ~5 37045.0 6.36 x lO" 5 37050.0 9.31 x 10 "5 370

Octane 85.0 5.1 x 10 ~6 37090.0 9.5 xlO~6 37095.0 1.75 x lO- 5 370

100.0 3.41 x 10 "5 370Pyridine 30.0 2.74 x 10 "5 370

40.0 7.66 x lO" 5 37050.0 1.868 x lO" 4 370

Toluene 65.0 1.88 x 10 "5 36975.0 4.66 XlO"5 36980.0 7.06 x lO" 5 36985.0 1.203 x lO" 4 369

terf-Butyl methoxyperpropionate Ethylbenzene 40.3 4.30xl0~3 328terr-Butyl perisobutyrate Benzene 78 3.77 x 10~5 a 37

70 6.69 x lO" 5 140.6 a 126,33785 5.33 x lO- 5 a 126,337

100 3.5OxIO-4 a 126,337Bulk 70 4.12 XlO"5 a 37Chlorobenzene 90.6 8.13 x 10"5 140.6 h 136

100.7 2.75 x lO" 4 136110.0 8.92 x lO" 4 13679 1.93 xlO~5 34498 1.93 x lO- 4 344

118 1.93 x lO" 3 344T(K) 2.07 xlO1 5 exp[-135.16/,RrI 344

Cumene 90.6 6.9 x lO" 5 133.1 h 136100.7 2.35 x lO" 4 136110.0 6.57 x lO" 4 136

Decane 70 4.7 x lO" 6 122 a 33785 2.6 x l O - 5 a 337

100 1.55 x lO" 4 a 337100 1.46 x lO" 4 270

Dodecane 100 1.56 x 10 "4 270Hexadecane 100 1.47 x 10 "4 270Iso-octane 103.4 2.16 xlO~4 251Nujol 103.4 2.23 x lO" 4 251Octane 100 1.59 x 10 ~4 270Tetradecane 100 1.52 x 10 "4 270

terf-Butyl percrotonate Benzene 100 2.5xlO"5 138 a 337115 1.5OxIO-4 a 337130 7.39 x lO- 4 a 337

TABLE 6. cont'd

Number ofC atoms Initiator Solvent T(0C) ^d(S"1) E2, (kj/mol) Notes Refs.

8 (cont'd) tert-Butyl permaleic acid Acetone 70 2.7xlO~6 113 a 33785 1.6 x lO" 5 a 337

101 6.77 xlO" 5 a 337tert-Butyl permethacrylate Benzene 90 1.92 x l O ' 5 137.0 a 211

100 7.66 XlO-5 a 211110 1.92 x lO" 4 a 211

tert-Butyl peroxyisopropyl carbonate Benzene 90 6.64 x 10 "6 a 9100 2.21 x 10~5 a 9110 6 .87xl0- 5 a 9

Cyclohexyl peracetate a-Methylstyrene 88.6 1.63 x lO" 5 109.4 25393.0 2 .30xl0" 5 25399.3 4.75 XlO"5 253

Diisopropyl peroxalate Pentane 25 6.0xl0~5 203Diisopropyl peroxydicarbonate Benzene 54.0 5 .0x l0" 5 ni2 60

Di-rc-butyl phthalate 77 1.39 x 10 ~3 yi6 23687 4.09 x lO" 3 yi6 23697 1.25 x lO" 2 y16 236

107 3 .54xl0- 2 yi6 236117 7.98 xlO" 2 y !6 236

Decane 35 6.3 x lO" 6 113 a 33745 2.7xlO- 5 a 33760 1.85 x lO" 4 a 337

Ethylbenzene 54.3 4.5 x 10 "5 6054.3 5.2x10-5 m2 60

Mineral spirits 30 2 x l O " 6 113 a 33745 1.8xl0-5 a 33760 1.28 XlO"4 a 33775 7.55 x lO" 4 a 337

2,2/-Oxydiethylene- 40 6.39 x 10~6 117.6 a 90bis(allyl carbonate) 50 2.28 x 10 "5 a 90

60 9.44xlO-5 a 90Toluene 50 3.03 x 10 "5 a 90

Ethyl tert-butyl peroxalate Benzene 45 4.48 x 10~5 112.5 c,h 3155 1.63 x lO" 4 3165 5.93 x lO" 4 31

9 tert-Butyl 2-acetoxyperpropionate Ethylbenzene 91.4 3.6OxIO"4 328ter/-Butyl 5-bromo-2-perthenoate Carbon tetrachloride 99.2 2.24 x 10 "6 143.5 a 176

112.0 1.18x10-5 a 176124.5 4.30x10-5 a 176

tert-Butyl 5-chloro-2-perthenoate Carbon tetrachloride 99.2 2.29 x 10 "6 143.5 a 176112.0 9.56 XlO"6 a 176124.5 4.42x10-5 a 176

tert-Butyl cyclobutane-percarboxylate n-Hexadecane 102.6 4.33 x 10~5 255

2,2,4-Trimethyl- 92.9 1.2IxIO-5 150.4 h 255pentane 102.6 4.84 x 10 "5 255

113.0 1.668 XlO"4 255ter/-Butyl 2,2-dimethyl-

3-bromoperpropionate Cyclohexane 55 9.50xl0~6 118.2 h,t6 32065 3.58xl0- 5 t6 32075 1.23 x lO" 4 t6 320

tert-Butyl 2,2-dimethyl-3-chloroperpropionate Cyclohexane 55 3.55 x 10"6 128.6 h,t6 320

65 1.48x10-5 t6 32075 5.65x10-5 t6 320

tert-Butyl 2,2-dimethyl-3-iodoperpropionate Cyclohexane 55 2.91 x 10"5 116.9 h,t6 320

75 3.76 x lO- 4 t6 320tert-Butyl isopropoxyperacetate Ethylbenzene 40.0 4.8 x 10~4 100.6 a,h 315

39.9 4.22 x lO- 4 98.9 h,m2 32849.9 1.39 x 10 "3 32855.3 2.68 x lO" 3 328


TABLE 6. cont'd

Number ofC atoms Initiator Solvent T(0C) * d (s"1) a (kJ/mol) Notes Refs.

9 (cont'd) tert-Butyl 1-methylcyclopropyl- 2,2,4-Trimethylpentane 102.6 2.30 x 10 "5 133.7 h 255percarboxylate 113.0 7.47 x lO" 5 255

Di-(tert-butylperoxy)-carbonate Chlorobenzene 99.95 6.72 x 10~5 133.1 27110.1 2.13 xlO~4 27120.1 6.05X10-4 27

1,2-Dichlorobenzene 120.1 5.98 x 10 ~4 27Cumene 99.95 6.72 x 10 "5 27Isopropyl ether 99.95 2.76 x 10 ~4 27

terf-Butylperoxy isopropyl Benzene 85 3.3xlO"6 138 a 337carbonate 100 2.2xlO"5 a 337

115 1.36xlO-4 a 337terf-Butyl perpivalate Benzene 50 9.77 x 10 "6 119.7 a 126,337

70 1.24X10-4 a 126,33785 7.64X10-4 a 126,33750 1.03 XlO"5 35955 1.94 XlO"5 35960 3.92 x l 0 ~ 5 35965 7.31 x 10~5 35970 1.30x10-4 359

Chlorobenzene 48.9 8.4xlO"6 k 24958.6 3.35xlO-5 125.5 h 2864.3 7.0IxIO-5 2857 1.93 x l 0 ~ 5 34475 1.93xlO-4 34494 1.93 x lO" 3 344

T(K) 7.09 XlO14 exp[- 123.59/RT] 34474.8 2.79xlO-4 2860 3.85 XlO"5 128.0 a,h 8160.6 4.0OxIO-5 t9 15674 1.93X10-4 t9 156

Cumene 45 3.53 x 10 ~6 106.7 h 16055 1.73 x lO" 5 16060 2.95 XlO"5 36265 4.53 x lO- 5 16064.6 5.8IxIO-5 115.5 15975.6 2.1OxIO-4 15984.6 5.94 xlO" 4 15970.3 1.11 x lO- 4 267

Cyclohexane 55 1.03 x 10 ~5 122.8 h 32065 4.02 x lO- 5 32075 1.45 x lO- 4 320

Decane 50 4 . IxIO" 6 117 a 33770 5.52 XlO"5 a 33780 2.18 x lO- 4 270

Dioxane/water (90/10) 60.6 6.26 x 10~5 t9 156Dodecane 80 2.38 x 10 ~4 270Hexadecane 80 2.39 x 10 "4 270Hexane 55 8.42 x 10 '6 359

60 1.59 XlO"5 35965 3.39 x lO- 5 35970 6.19 XlO"5 358

Heptane 80 2.33 x 10 ~4 270Isooctane 60.6 1.97 x 10 ~5 t9 165

73.9 8.82 xlO" 5 t9 165Mineral spirits 55 1.01 x 10 ~5 359

60 2.15 x l0~ 5 35965 4.14 x lO- 5 35970 7.58 XlO"5 35975 1.47X10-4 359

T (K) 3.56 x 1014 exp[- 123/RT] 376Octane 80 2.34 x 10 ~4 270Tetradecane 80 2.27 x 10 ~A 270

tert-Buty\ perpivalate-d6 Chlorobenzene 60.6 3.24 x 10~5 t9 15674.0 1.57 xlO~4 t9 156

TABLE 6. cont'd


9 (cont'd) tert-Butyl perpivalate-d6 Dioxane/water (90/10) 60.6 5.05 x 10"5 t9 156Isooctane 60.6 1.62 x 10~5 t9 165

73.9 8.82 x l O - 5 t9 165tert-Butyl 2-perthenoate Carbon tetrachloride 99.2 3.3 x 10 "6 147.3 m2 176

112.0 1.66 x l 0 ~ 5 m2 176124.5 6.87 x l O - 5 m2 176

tert-Butyl 1-pyrollidine-percarboxylate Chlorobenzene 90 7.59 x 10 ~5 141

tert-Butyl Af-succinimido-percarboxylate Acetonitrile 100 9.9xlO~4 142

Benzene 100 3.79 x 10~5 113.4 h,m2 142Chlorobenzene 90 1.32 x 10 ~5 141

100 4 .9IxIO- 5 m2 142Cumene 90 3 . 3 x l 0 - 6 141Cyclohexane 100 1.10 x 10~5 t9 142Cyclohexene 100 9.OxIO-6 142Methanol 100 6 .00xl0" 3 142Methylene chloride 90 9.24 x 10 ~5 141Nitrobenzene 100 3.4IxIO- 4 m2 142

10 tert-Amyl perpivalate Benzene 51 1.9XlO"5 a 338Chlorobenzene 55 1.93 x 10 ~5 344

72 1.93 x l O - 4 34491 1.93 x l O - 3 344

T (K) 4.12 x 1015 exp[- 121J6/RT] 344Cumene 50 1.05 x 10 ~5 362

60 3.5IxIO- 5 36270 1.309 XlO"4 36280 4.239 XlO"4 362

Di-(sec-butyl)peroxy- Decane 35 6.9xlO~6 113 a 337dicarbonate 45 2.6xlO"5 a 337

60 1.8OxIO-4 a 337Chlorobenzene 47 1.93 x 10 ~5 344

63 1.93 XlO"4 34482 1.93 XlO"3 344

T(K) 3.19 xlO1 5 exp[-123.85//?7] 344Mineral spirits 30 2 x l O " 6 113 a 337

40 1.0 x l O - 5 a 33760 1.34 x l O - 4 a 337

Di-w-butyl peroxydicarbonate Chlorobenzene 49 1.93 x 10 "5 34465 1.93 x l O - 4 34483 1.93 XlO"3 344

T (K) 7.00 x 1015 exp[- 126.65/RT] 344tert-Butyl 2-acetoxy-2- Ethylbenzene 74.7 1.98 xlO~4 m2 328

methyl perpropionate 80.7 4.37 x 10 "4 32890.8 1.25 x l O - 3 328

tert-Butyl tert-butoxyperacetate Ethylbenzene 40.3 2.91 x 10 "4 328tert-Butyl 4-carbomethoxy- Cumene 99.8 1.65 x 10 ~5 151.3 h 257

perbutyrate 116.6 1.38 x 10~4 257129.9 6.83 x l O - 4 257

tert-Butyl cyclopentyl-percarboxylate n-Hexadecane 113.0 3.02 x 10 ~4 255

2,2,4-Trimethyl- 92.9 2.47 x 10 ~5 140.8 h 255pentane 102.6 8.87 x 10 "5 255

113.0 2.89 x l O - 4 255tert-Butyl peroxydiethyl acetate Chlorobenzene 75 1.93 x 10 "5 344

93 1.93 x l O - 4 344113 1.93 x l 0 ~ 3 344

T (K) 2.45 x 1015 exp[- 134.00/RT] 344tert-Butyl 2,2-dimethylperbutenoate Cumene 42.42 9.04 x 10 ~5 100.7 h 274

50.30 2.349 x l 0 ~ 5 27457.95 5.66OxIO-5 274

tert-Butyl 2,2-dimethylperbutyrate Cumene 44.85 1.874 x 10 ~5 27450.10 3.609 x l O - 5 27460.20 1.306 x l O - 4 274


TABLE 6. cont'd


10 (cont'd) Di(tert-butylperoxy)-oxalate Benzene 35.0 6.77 x 10"5 106.7 c,h 3045.0 2.6IxIO"4 c 3055.0 9.3 XlO"4 c 30

tert-Butanol 25.0 1.83 x lO" 5 197Decane 41 1.75 x 10 "4 270Dodecane 41 1.81 x 10"4 270Octane 41 1.79 x 10 "4 270n-Pentane 37.8 1.01 x 10"4 197Tetradecane 41 1.71 x 10~4 270Styrene 35 5 .5x l0" 5 75.3 215

45 1.71 x 10"4 21555 6.0IxIO"4 215

tert-Butyl 5-methyl-7-perthenoate Carbon tetrachloride 99.2 4.6xlO~6 137.7 a,m2 176112.0 1.94 x l 0 ~ 5 a,m2 176124.5 7.95 XlO"5 a,m2 176

P-Methyl-P-phenyl-P-peroxy- Carbon tetrachloride 106.8 5.65 x 10 "6 131.8 h,v9 195propiolactone 126 4.59 x 10 "5 195

134 9.71 x 10"5 c,v9 195Bis(2-nitro-2-methylpropyl)-peroxy- Toluene 50 2.22 x 10 ~5 a 90

dicarbonate1-Phenylethylperacetate Benzene 100 1.14 x lO" 4 138.7 h 259

11 tert-Butyl 4-chloroperbenzoate Phenyl ether 100.0 3.89 x 10 ~6 164.4 a 53110.1 1.85 x l 0 ~ 5 a 53120.2 6.39 XlO"5 a 53130.9 2.42 xlO~4 a 53

Carbon tetrachloride 80 4.2xlO~7 354tert-Butyl-JV-(2-chlorophenylperoxy)- Toluene 87.0 3 .5x l0" 5 157.3 h 36

carbamate 95.5 1.48 x 10 ~4 36103.3 3.3 XlO"4 36

tert-Butyl-AK3-chlorophenylperoxy> Toluene 78.0 2.6 x lO" 5 115.5 h 36carbamate 87.0 7 .8x l0" 5 36

96.6 2.03 xlO~4 36102.7 4.62 XlO"4 36

tert-Butyl-AH4-chlorophenylperoxy)- Toluene 73.0 5.57 x 10 ~5 119.7 h 36carbamate 78.5 1.42 x 10 ~4 36

87.0 2.75 xlO~4 3692.5 5.37 x lO" 4 36

tert-Butyl cyclohexylperoxy- -Hexadecane 92.9 6.70xl0~5 136.6 h 255carboxylate 102.6 2.046 x 10 ~4 255

2,2,4-Trimethyl- 82.2 1.57 x lO" 5 135.8 h 255pentane 92.9 6.13 x l 0 ~ 5 255

102.6 2.046 xlO~4 255113.0 6.58 x lO" 4 255

tert-Butyl-iV-(2,5-dichlorophenyl- Toluene 88.0 2.75 x 10 ~5 128.9 h 36peroxy) carbamate 95.0 5.58 x 10 ~5 36

103.3 1.48 xlO~4 36114.5 4.82 xlO~4 36

tert-Butyl 2,2-dimethylperpentanoate Cyclohexane 55 1.66 x 10 ~5 120.7 h 32065 6.31 x 10~5 32075 2.23 xlO~4 320

Cumene 45 6.2xlO~6 105.4 h 16055 2.15 x l 0 ~ 5 160

tert-Butyl 5-ethyl-2-perthenoate Carbon tetrachloride 99.2 5.39 x 10 ~6 130.5 176112.0 2.12 x l 0 ~ 5 176124.5 7.91 x 10~5 176

tert-Butyl 2-iodoperbenzoate Chlorobenzene 85.0 4.02 x 10 ~5 134102.4 2.58 xlO~4 134118.8 1.32 xlO~3 134

tert-butyl 4-nitroperbenzoate Phenyl ether 110.1 7.56 x 10 "6 172.8 53120.2 3.19 x l 0 ~ 5 53130.9 1.11 xlO~4 53141.5 3.92 xlO~4 53

Carbon tetrachloride 80 2.9xlO~7 354tert-Butyl 3,5-dinitroperbenzoate Carbon tetrachloride 80 1.1 x 10 ~7 354

TABLE 6. cont'd

Number ofC atoms Initiator Solvent T(0C) A:d (s"1) E2, (kj/mol) Notes Refs.

W (cont'd) /m-Butyl-AH3-nitrophenylperoxy)- Toluene 78.0 8.4 x lO" 6 133.1 h 36carbamate 88.7 2.43 x 10 "5 36

98.0 1.01 x 10-4 36106.0 2.36 x lO" 4 36

fm-Butyl-AK4-nitrophenylperoxy)- Toluene 73.0 6.4xlO~6 113.8 h 36carbamate 87.0 3.11 x 10~5 36

98.0 8.75 x lO" 5 36106.0 2.38 xlO~4 36

terf-Butyl perbenzoate Acetic acid 100.0 3.83 x 10 ~5 130.1 a 56110.0 1.14 x 10~4 a 56

Benzene 100 1.07 x KT5 145.2 a 126,337115 6.22 x l 0 ~ 5 a 126,337130 3.5OxIO-4 a 126,337110.0 3.50xl0"5 144.3 a 56119.4 1.04 XlO"4 a 56130.0 3.30xl0~4 a 56

Bromobenzene 119.4 1.37 x 10 ~4 a 56rc-Butanol 90.0 9.27 x 10 "5 120.5 a 56

100.0 2.7OxIO-4 a 56-Butyl acetate 110.0 1.06 x 10~4 123.4 a 56

119.4 2.67 x lO" 4 a 56110.0 3.6IxIO-5 148.5 a,m2 56

1194 1.10 xlO~4 a,m2 56tert-Butylbenzene 119.4 1.03 x 10 ~4 a 56w-Butyl ether 100.0 7.8OxIO-5 99.2 a 56

110.0 1.80 XlO"4 a 56Carbon tetrachloride 80 8 .8xl0" 7 354Chlorobenzene 110.0 3.83 x 10~5 141.8 a 56

119.4 1.11 x lO" 4 a 56120 1.3IxIO-4 m2 22135 6.74 x lO- 4 m2 22150 3.12 x lO- 3 m2 22103 1.93 XlO"5 344122 1.93 x l O - 4 344142 1.93 x lO" 3 344

T(K) 2.23 xlO1 6 exp[- 151.59/RT\ 3444-Chlorotoluene 110.0 3.25 x 10 "5 144.3 c 55

119.4 9.80xl0" 5 c 55130.0 3.06 x lO- 4 c 5560 3.85 XlO"7 140.2 a,h 81

Cumene 79.6 7.21 x 10 ~5 27285.0 1.320xl0"6 34599.3 9.37 x l O - 6 345

115.0 5.8IxIO-5 345130.2 3.24 x lO" 4 345

Decane 100 1.4xlO-5 134 a 337115 8.05 XlO"5 a 337130 3.56 x lO- 4 a 337115 6.77 XlO"5 270

Dodecane 115 6.44 x KT5 270Ethylbenzene 119.4 1.07 x 10~4 a 56Heptane 115 7.21 x 10~5 270Hexadecane 115 5.97 x 10 ~5 270Methyl benzoate 119.4 7.8OxIO"5 a 56Octane 115 7.06 x 10 "5 270Phenyl ether 100.0 6.94 x 10 ~6 156.9 a 53

110.1 2.28 x lO" 5 a 53120.2 9.0OxIO-5 a 53130.9 2.92 x lO" 4 a 53

Tetradecane 115 6.03 x 10 ~5 270Trimethylbenzene T (K) 2.62 x 1016 exp[-152.0/RT] 376Xylene 119.4 1.09 x 10~4 141.4 a 56

130.0 3.42 x l O - 4 a 56


TABLE 6. cont'd


11 (cont'd) terf-Butyl-AK4-bromophenylperoxy)- Toluene 70.8 3.32 x 10 "5 177.6 h 36carbamate 79.8 1.04 x 10 ~4 36

84.0 1.75 x l O - 4 3696.0 7.70xl0~4 36

tert-Butyl percarboxycyclohexane Chlorobenzene 100.1 2.75 x 10 ~4 131.0 h 181111.4 9.65 XlO-4 181120.0 2.39 XlO-3 181

Cumene 79.6 1.86 x lO" 5 z (1) 16379.6 1.42 x l 0 ~ 5 z (2030) 16379.6 1.15xl0-5 z (4050) 163

tert-Butyl per-2-methylphenylacetate Isooctane 60.6 6.60 x 10 ~5 ni2 16573.9 3.233 x l O - 4 m2 165

tert-Butyl-N-(phenylperoxy) Toluene 51.2 3 .4xlO- 6 139.7 h 36carbamate 67.7 2.31 x 10 "5 36

77.7 1.15 x l O - 4 3690.7 6.41 x 10 ~4 36

Chlorobenzene T(K) 1.51 x 1016 exp[- 136.0/RT] 40tert-Hexyl peroxypivalate Cumene 40 2.39 x 10 ~6 362

50 8.83 x l O - 6 36260 3 .37xl0- 5 36270 1.226 x l O - 4 36280 4.166 x l O - 4 362

1,1,2-Trimethylpropyl perpivalate Cumene 40 3.6xlO"6 36250 1.59x10-5 36260 5.14x10-5 36270 1.921 x 10-4 362

Cumyl peracetate Carbon tetrachloride 100 4.68 x 10 "5 c 271Toluene 100 3.43 x 10 ~5 p 271

12 tert-Amyl peroxybenzoate Chlorobenzene 99 1.93 x 10 ~5 344118 1.93 x 10~4 344139 1.93 x l O - 3 344

T (K) 8.38 x 1015 exp[- 147.02/RTl 3444-Bromocumyl perpropionate Benzene 70 1.48 x 10 "6 129.7 a 213

80 5.73 x l O - 6 a 21390 1.8IxIO-5 a 213

oc-Methylstyrene 70 1.99 x 10~6 121.3 a 21380 4.93 x l O - 6 a 21390 1.55x10-5 213

tert-Butyl bicyclo[2.2.1]lheptane- Cumene 85 1.16 x 10~6 155.2 h 1602-percarboxylate 100 1.02 x 10 ~5 160

110 3.76xlO-5 160110 4.6x10-5 150.2 h 223120 1.56 XlO"4 223130 4.99 x lO" 4 223

terf-Butyl endo-bicyclo[2.2.1]- Chlorobenzene 94.0 1.75XlO"5 137.2 h 147heptane percarboxylate 101.9 6 .20xl0" 5 147

109.6 1.7 x l O - 4 147120.5 5.72 x l O - 4 14794.5 9.69x10-5 147

101.9 1.96xlO-5 182111.9 6.53x10-5 182100.1 4 .6IxIO- 5 149.0 h 181111.4 1.96 xlO~4 181120.0 5.4OxIO-4 181

Cumene 94.0 1.87 x lO" 5 154.0 h 147101.9 5.3OxIO-5 147109.6 1.10 x lO" 4 147120.3 4.3 x l O - 4 14794.5 5 .27xl0- 5 130.1 h 182

101.9 1.12 x l O - 4 182111.9 3.57 x l O - 4 182

terf-Butylexo-bicyclo[2.2.11]- Chlorobenzene 94.5 8.86 x 10 ~5 182heptane-2-percarboxylate 101.9 2.28 x 10 ~4 182

112.1 8.85 x l O - 4 182

TABLE 6. cont'd

Number ofC atoms Initiator Solvent T(0C) d (s"1) Ea (kj/mol) Notes Refs.

12 (cont'd) 96.0 1.33 x 10"4 147100.1 1.90xl0"4 129.3 h 181111.4 6.79 xlO"4 181120.0 1.64 xlO"3 181

Cumene 84.4 2.19 xlO"5 129.3 h 14794.7 7.29 x l0~ 5 147

100.1 1.37 xlO~4 147108.6 3.6 XlO"4 147113.5 6.19 XlO"4 14794.5 6.05 x lO" 5 131.4 h 182

101.9 1.53 x lO" 4 182112.1 4.72 XlO"4 182

tert-Butyl endo-bicyclo[2.2.1]-hept- Cumene 94.5 3.11 x lO" 5 136.4 h 1825-ene-2-percarboxylate 101.9 7.35 x 10 ~5 182

112.0 2.48 x lO" 4 182tert-Butyl exo-bicyclo[2.2.1]-hept- Chlorobenzene 94.5 5.59 x lO" 5 182

5-ene-2-percarboxylate 101.9 1 25 x 10"4 182112.1 5.0OxIO"4 182

Cumene 94.5 4.48 x lO" 5 138.1 h 182101.9 1.18 x l O - 4 182112.1 3.97 x lO" 4 182

tert-Butyl 4-bromophenoxyperacetate Ethylbenzene 70.5 2.6xlO~4 a 315tert-Butyl 4-chlorophenoxyperacetate Ethylbenzene 70.5 2.9xlO~4 a 315tert-Butyl 3-chlorophenylperacetate Chlorobenzene 79.6 4.05 x 10 ~5 123.0 h 178

90.7 1.44 x l O - 4 178100.5 4.38 x lO" 4 178

Cumene 79.6 2.98 x 10 "5 z (0.98) 20779.6 1.99 x lO" 5 z (6090) 207

tert-Butyl 4-chlorophenyl peracetate Chlorobenzene 79.6 8.44 x 10 "5 117.2 h 17890.7 2.95 x l O - 4 178

100.5 8.19 x lO" 4 178Cumene 79.6 6.54 x 10 "5 z (0.98) 207

79.6 4.45 x 10 "5 z (6090) 207tert-Butylcycloheptyl percarboxylate rc-Hexadecane 92.9 1.801 x 10 "4 121.5 h 255

102.6 5.17 x lO" 4 2552,2,4-Trimethylpentane 92.9 1.703 x 10 "4 125.7 h 255

102.6 5.07 x lO" 4 255tert-Butyl 2,4-dichlorophenoxy- Ethylbenzene 70.5 9.4xlO"5 a 315

peracetatetert-Butyl 2,2-diethyl perbutyrate Cumene 45 1.23 x 10 "5 100.3 h 160

55 4.92 x lO" 5 16065 1.46 x l O - 4 160

tert-Butyl per-2-ethylhexanoate Benzene 72 1.9xlO"5 a 338Chlorobenzene 72 1.93 x 10 ~5 344

91 1.93 x lO" 4 344113 1.93xl0-3 344

T(K) 1.54 xlO1 4 exp[- 124.90/RT] 344tert-Butyl 2-methoxy-2-methyl- Chlorobenzene -14.0 2.05 x 10 "5 86.3 m2 275

perpropionate -7 .0 6.73 x 10"5 m2 275-1 .0 1.67 XlO"4 m2 27515.0 1.28 XlO"3 m2 275

tert-Butyl 4-methoxyperbenzoate Phenyl ether 100.0 1.07 x 10 "5 149.8 a 53110.1 4.17 x lO" 5 a 53120.2 1.28 x l O - 4 a 53130.9 4.28 x lO" 4 a 53

tert-Butyl peroxy-2-methyl- Chlorobenzene 96 1.93 x 10 "5 344benzoate 115 1.93 x 10 "4 344

136 1.93 x lO" 3 344T (K) 8.56 x 1015 expr[- 145.97/RT] 344

tert-Butyl 4-methoxyperbenzoate Carbon tetrachloride 80 l.OxlO"6 354tert-Butyl 4-methylperbenzoate Phenyl ether 100.0 9.42 x 10 "6 151.0 a 53

110.1 3.19 XlO"5 a 53120.2 1.06 XlO"4 a 53


TABLE 6. cont'd

Number ofC atoms Initiator Solvent T(0C) ^d(S"1) E2, (kj/mol) Notes Refs.

12 {cont'd) terr-Butyl 4-methylperbenzoate Phenyl ether 130.9 3.25 x 10~A a 53rm-Butyl 2-methyl-2-terf- Benzene 9.0 6.66 xlO~5 78.8 m2 275

butylperoxyperpropionate 19.0 1.99 x 10 ~4 27530.0 6.94 xlO~4 27542.0 2.43 x l 0 ~ 3 275

terf-Butyl 2-methylsulfonyl Chlorobenzene 105 6.68 x 10 ~6 22perbenzoate 120 5.57 x 10~5 22

135 2.76 xlO~4 22150.6 2.05 x l 0 ~ 3 22

tert-Butyl 2-(methylthio)perbenzoate Chlorobenzene 60 8.08 x 10~A 95.0 a,h 9739.4 2.59 x lO- 5 b 13450.1 2.42 XlO-4 c 13450.2 1.88 x l O - 4 m2 13469.8 1.96 XlO"3 134

tert-Butyl 4-(methylthio)perbenzoa

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