Polymer Chemistry - hxhg.gxu.edu.cnhxhg.gxu.edu.cn/polymerChemistry/uploads/courses/01.pdf · Polymer Chemistry GuangxiUniversity School of Chemistry & Chemical Engineerin g Li Guang

Polymer Chemistry

Guangxi University School of Chemistry & Chemical Engineerin

g

Li Guang Hua (李光华)

Lab：材料楼—409#，321# E-mail : [email protected] phone: 15978133590

mailto:[email protected]

TEXTBOOK & RESULTS

Textbook:

《 Polymer Chemistry》—自编

1. M.P. Stevens, “Polymer Chemistry: an introduction”, Third edition, 1999.

2. G. Odian, “Principles of Polymerization”, Fourth edition, 2003.

3. F.W. Billmeyer, “Textbook of Polymer Science”, Third edition, 1984.

Guangxi University School of Chemistry & Chemical Engineeri

ng

Results:

4. A. Ravve, “Principles of Polymer Chemistry”, Second edition, 2000.

1.考勤：10% (缺勤一次:－2分；迟到3次=缺勤一次；5次以上：F)

2.平时成绩：20% （作业，上课表现）

3.期末考试：70%

1.中文科技期刊数据库，外文科技期刊数据库

2. ACS: 收录 41种期刊 (24种期刊—创刊 ~ 至今)

Databases:

DATABASES & JOURNALS

3. ScienceDirect: 收录 1772种期刊 (1995年 ~至今)—世界最大的电子数据库

Journals:

Hundreds of kinds


ng

4. Wiley InterScience: 收录 479种期刊 (1997年 ~ 至今)

5. SciFinder: 提供科学全领域的文献和专利的题目, 出处和概要.

CONTENTS

1. Basic PrinciplesPrinciples of Polymer Chemistry:

3. Free Radical Polymerization4. Ionic Polymerization

2. Step Polymerization

5. Coordination Polymerization

7. Hydrocarbon Plastics and ElastomersPolymer Materials:


ng

6. Chemical Reactions of Polymers

8. Other Carbon-chain Polymers9. Heterochain Thermoplastic Polymers

10. Thermosetting Resins

5. Coordination Polymerization

CHAPTER 1

1. Introduction

Basic Principles:

2. Definitions 3. Polymerization Processes4. Nomenclature of Polymers5. Molecular Weight


ng(1)

5. Molecular Weight6. Microstructure of Polymers7. Physical State

7.1 Crystalline and Amorphous behavior7.2 Thermal Transitions

8. Industrial Polymers9. Historical Development

1. INTRODUCTION (I)

Three large props of modern civilization

Materials InformationEnergy

Metals CeramicsPolymers

Plastics Fibers Elastomers(Rubbers)

Coatings Adhesives


ng(2)

1. INTRODUCTION (II)

We live in a polymer age


ng(3)

Polymer science

Polymer chemistry

Polymer physics

Research the synthesis and reactions of polymersMechanism; kinetics; influence factor; preparation techniques

1. INTRODUCTION (III)

science

Polymer engineering


ng

Research the relations between polymer structureand properties

Research the principles and technology of polymer molding and engineering of polymerization

(4)

Synthesis Structure(polymer synthesis)

(polymer physics)

1. INTRODUCTION (IV)


ng

PropertyApplication

Direction of the green arrows :

polymer design

(polymer processing)

(5)

1. WHAT IS POLYMER?

A large molecule comprised of repeating units (RU) joined by covalent bonds.

Polymer : “poly” + “mer”

many part/unit

Repeating unitCovalent bond


ng

Covalent bond

Hermann Staudinger (GER) (1953 Nobel prize)In 1926, suggest: Hoch-molekül (巨大分子)

High molecule (UK)

高分子 (JP) 高分子 (CHN)

unifyPolymer

(6)

1. WHAT IS POLYMER?

Small molecule or low molecule < 1,000

High polymer, Polymer = macromolecule高聚物聚合物，高分子大分子

Classification of molecules according to molecular weight:

RU more than one or lack one influence properties.

RU more than one or lack one hardly influence properties.

Oligomer (低聚物 or 齐聚物) 1,000 ~ 10,000

Polymer (聚合物) > 10,000

Ultrahigh molecular weight polymer (UHMWP) > 1,000,000


ng(7)

CH2CH2 n

2. DEFINITIONS (I)

Monomer, polymerization, polymer

CH2 CH2PZN

Polymer

Polymers are synthesized from simple molecules called monomers by a process called polymerization (PZN).

CH2CH

nCl

CH2 CH

Cl

PZN

Monomer

Monomer

Polymer

Polymer


ng

CH2 CHVinyl monomer ( ) Vinyl polymer

Repeating unit (RU)or Structural unit (SU)

(8)

COCH2CH2OC

O

n+ (2n-1) H2O

O

HHO

2. DEFINITIONS (II)

COOH + n HOCH2CH2OHHOOCn

Monomer Monomer

SU SU

RU

PZN

CO

O

n+ (n-1) H2OH OH


ng

COOHHOn

Nonvinyl monomerNonvinyl polymer

MonomerPolymer

RU

RU = SU

(Difunctional compounds)

PZN

(9)

2. DEFINITIONS (III)

Degree of PZN (DP, 聚合度)refers to the total number of structural units (SU)

For vinyl polymers

CH2CH2 n CH2CH

nCl

FDP = n (RU=SU)

MW = n ×M0 = DP ×M0


ng

For nonvinyl polymersF

COCH2CH2OC

O

n

O

HHO DP = 2n (RU = 2SU)

CO

O

nH OH

DP = n (RU=SU)

MW = n×M0 = (DP/2) ×M0

MW = n×M0 = DP ×M0

(10)

2. DEFINITIONS (IV)

End group

CH 2CH 2 nCH3CH 2 CH CH2

The atom or group at the end of a polymer chain.

Telechelic polymer (遥爪聚合物 ): containing reactive end groups ( )


ng

Main chain (or backbone)

C C C C C C

H

H H

H H

H H H H

Cl Cl Cl

poly(vinyl chloride)

main chain (主链 )

side group (侧基 )

(11)

2. CLASSIFICATION OF POLYMERS (I)

Based on element forms of main chain

Ø

Ø

Carbon chain polymer (碳链聚合物 ) : single atom C

Heterochain polymer : containing O, N, P, etc. besides C

CH2CH2 n

OO O O

PE

F


ng

Ø Elementary organic polymer (元素有机聚合物 ): containing Si, B, Al, O, N, P etc. without C

COCH2CH2OCn

Si O

R

R n

NH(CH2)6NHC(CH2)4C n

PET Nylon 6,6

Silicone resin

(12)

Based on kinds of monomerØ

Ø

Homopolymer : prepared from a single monomer

Copolymer : prepared from two or more monomers

A A A A A A A A

A B B A B A A B Random copolymer

2. CLASSIFICATION OF POLYMERS (II)

F


ng

A B B A B A A B

A B A B A B A B

A A A A B B B B

A A A A A A A A

B B B B B

Random copolymer(无规共聚物 )

Alternating copolymer(交替共聚物 )

Block copolymer(嵌段共聚物 )

Graft copolymer(接枝共聚物 )

(13)

Based on molecular architectures

2. CLASSIFICATION OF POLYMERS (III)

linear polymer branched polymer network polymer

F

22


ng

star polymer comb polymer ladder polymer

dendrimer (树枝状聚合物)

22

(14)

2. CLASSIFICATION OF POLYMERS (IV)

Linear polymer Branched polymer

network polymercrosslinking

Insoluble (only swelling)Not melt

Soluble in solventsMelt

Process repeatedly Not process repeatedly


ng

Thermosetting Resin(热固性树脂)

Thermoplastics(热塑性塑料)

(15)

2. CLASSIFICATION OF POLYMERS (V)

Based on polymer sourcesØ

Ø

Natural polymer : cotton, wool, silk, protein, etc.

Synthetic polymer : PE, PP, PVC, PET, nylon 6,6, etc.

Based on physical properties or end usePlastics : LDPE, HDPE, PP, PVC, PS, etc.Ø

F

F


ng

Plastics : LDPE, HDPE, PP, PVC, PS, etc.

Ø

Ø

Ø

Ø

Ø

Fibers : PET, nylon 6,6, PAN, PP, etc.

Elastomers (rubbers) : SBR, EPR, PU, etc.

Coatings : styrene-butadiene copolymer, etc.

Adhesives : epoxy resin, etc.

(16)

Suggestion of Carothers (1929)

3. PZN PROCESSES (I)

Polymer

Addition polymer(加聚物)

Condensation polymer

Monomer = RU in composition

Monomer ≠ RU in composition

Addition PZNCH2 CH2n CH2CH2 n


ng

Condensation polymer(缩聚物)

Monomer ≠ RU in composition


COCH2CH2OC

O

n+ (2n-1) H2O

O

HHO

Condensation PZN

(17)

3. PZN PROCESSES (II)

C

O

ROn O R C

O

n

HO R COOHn O R C

O

+ (n-1)H2OnH OH

Addition polymer ?


Addition PZN?

Condensation PZN


ng


Suggestion of Flory (1951)

According to the mechanism of PZN

PZNStep-reaction or step-growth PZN (step PZN) (逐步聚合)

Chain-reaction or chain-growth PZN (chain PZN) (链式聚合 or连锁聚合)

(18)

3. PZN PROCESSES (III)

Step PZN


COCH2CH2OC

O

n+ (2n-1) H2O

O

HHO


ng

Ø No reactive center

Growth occurs by the stepwise reaction between the functional groups of reactants (monomer, oligomer, polymer)

Ø

n

(19)

3. PZN PROCESSES (IV)

monomer + monomer dimer

trimer

tetramer

tetramer

dimer + monomer

dimer + dimer

trimer + monomer

pentamer

pentamer

trimer + dimer

tetramer + monomer

k

k

k

k

k

k


ng

Ø The reaction rate and activation energy of every step are approximately equal.

Reaction system: a series of different molecular weight speciesØ

(m+n)-merm-mer + n-mer

pentamertetramer + monomer

In general

k

k

(20)

3. PZN PROCESSES (V)

Mol

ecul

ar w

eigh

t

Monomer consumed rapidly while MW increases slowly Ø

Most condensation PZN belong to step PZN


ng

0 20 40 60 80 100

Conversion %

Mol

ecul

ar w

eigh

t

Step PZN

(21)

Chain PZN

3. PZN PROCESSES (VI)

R* R CH2 C*

H

Y

R CH2 C

H

Y

CH2 C*

H

Y

ICH2=CHY CH2=CHY


ng

R CH2 C

H

Y

CH2 C*

H

Ym

CH2 C

H

Y n

termination

Ø Have reactive center R* : cation R+, anion R–, free radical R·

CH2=CHY(m-1)

(22)

3. PZN PROCESSES (VII)

The reaction rate and activation energy of every elementary reaction have relatively larger differences

Ø

Elementary reaction: initiation, propagation, termination, etcØ

Growth occurs by successive addition of monomer to limited number of growing chains

Ø


ng

Monomer consumed relatively slow, but MW increases rapidlyØ

Most addition PZN belong to chain PZN

Reaction system: monomer, polymer, initiatorØ

(23)

3. PZN PROCESSES (VIII)

Mol

ecul

ar w

eigh

t

Chain PZN


ng

0 20 40 60 80 100

Conversion %

Mol

ecul

ar w

eigh

t

Step PZN

(24)

Living PZN

3. PZN PROCESSES (IX)

For anionic PZNF

fast initiation slower propagation no termination

+ CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Y

Nu CH2 C

X

Yn


ng

Ø Linear increase of MW with conversion

fast initiation slower propagation no termination

Living PZN

Control molecular characteristics

MW & its distribution Composition Microstructure Architecture

(25)

3. PZN PROCESSES (X)

Mol

ecul

ar w

eigh

t

Chain PZN

Living PZN


ng

0 20 40 60 80 100

Conversion %

Mol

ecul

ar w

eigh

t

Step PZN

(26)

3. PZN PROCESSES (XI)

Controlled/Living radical PZN

Ø

Ø Stable free radical PZN (SFRP) (1993, Geoges)

Atom transfer radical PZN (ATRP)

TEMPO: 2,2,6,6-tetramethylpiperidinoxy

F

O N.


ng

Ø

Ø(1995, M. Sawamoto; K. Matyjaszewski)

Reversible addition-fragmentation transfer radical PZN (RAFT) (1998, G. Moad)

S

CSZ

R

R–X/CuX/ligand (ex. bipyridine)

RAFT agent: dithioesters（双硫酯）

(27)

Ring-opening PZN (ROP)

C

O

RNHn NH R C

O

nROP

lactamLinear polymerCyclic monomer

polyamide

F

3. PZN PROCESSES (XII)


ng

CH2 CH2

OCH2CH2O n

ROP

ethylene oxide poly(ethylene oxide) (PEO)

F

Ø ROPs usually proceed by the chain PZN mechanism

Ø Many ROPs: MW increases linearly with conversion (living PZN)

(28)

Ø

Ø

Nomenclature based on source (来源基础命名法)

4. NOMENCLATURE OF POLYMERS (I)

Nomenclature

Nomenclature based on structure (结构基础命名法)

Ø IUPAC nomenclature system (系统命名法)

IUPAC: International Union of Pure and Applied Chemistry


ng

Ø Trade name (商品名)

Ø Abbreviations (英文缩写)

IUPAC: International Union of Pure and Applied Chemistry

(29)

4. NOMENCLATURE OF POLYMERS (II)

Vinyl polymers

Nomenclature based on source (来源基础命名法 )

(1) poly + monomer name

CH2 CH2 CH2CH2 npolyethylene

polytetrafluoroethylene

F

CF CF CF CF


ng

polytetrafluoroethylene

CH2 CH CH2CH

n

polystyrene

CF2 CF2 CF2CF2 n

(30)

4. NOMENCLATURE OF POLYMERS (III)

(2) poly (monomer name):more than one word, or have a letter or number before monomer name

CH2 CH CH2CH

nCO2H CO2H

poly(acrylic acid)

CH CH


ng

CH2 C CH2CH

n

CH3 CH3

CH2 CH CH2CH

nCH2CH2CH3 CH2CH2CH3

poly(1-pentene)

poly(α-methylstyrene)

(31)

4. NOMENCLATURE OF POLYMERS (IV)

IUPAC nomenclature system (系统命名法)

(1) The smallest structural repeating unit (CRU) is identified.

F

CRU (constitutional repeating unit) (重复结构单元)

CH2CH2 CH2

RU: CRU: CH2CH2 n


ng

CF2CF2 CF2CF2CF2 n

(2) Substituent groups on the backbone are assigned the lowest possible numbers.

CH2CH

n

CHCH2CRU:

(32)

4. NOMENCLATURE OF POLYMERS (V)

(3) poly(CRU name)

CH CH2CH2CH poly(1-phenylethylene)

CRU:C C

CH2

H

CH2

CH3 nC C

CH2

H

CH2

CH3


ng

22

n

C CCH2

H

CH2

CH3 nC C

CH2

H

CH2

CH3

1 23 4

cis-poly(1-methyl-1-butene-1,4-diyl)

(33)

poly[1-(methoxycarbonyl)-1-methylethylene]

4. NOMENCLATURE OF POLYMERS (VI)

CH3

CH2C

CO2CH3 n

poly(methyl methacrylate)

IUPAC namePolymer structure Source name

CH2CH2 npolyethylene poly(methylene)

CF2CF2 npolytetrafluoroethylene poly(difluoromethylene)


ng

C CCH2

H

CH2

CH3 n

poly(vinyl acetate)

cis-1,4-polyisoprene

poly(1-acetoxyethylene)

cis-poly(1-methyl-1-butene-1,4-diyl)

2 3 n

CH2CH

OCCH3

O n

CH2CH

N

poly(2-vinylpyridine) poly[1-(2-pyridinyl)ethylene]

(34)

Nonvinyl polymersNomenclature based on source (来源基础命名法)Cyclic monomer or single monomer :

F

4. NOMENCLATURE OF POLYMERS (VII)

nylon 6

NHO

nNH(CH2)5C

O

n

poly + monomer name or poly + (monomer name)


ng

polycaprolactam (or nylon 6)caprolatam

O

O

n OCH2CH2C

O

n

poly(3-propiolactone)3-propiolactone

HOCH2CH2OHn CH2CH2O npoly(ethylene glycol) (PEG)ethylene glycol

β-propiolactone Poly(β-propiolactone)

(35)

Nomenclature based on structure (结构基础命名法)FTwo different monomer： poly (name of the structural group)

4. NOMENCLATURE OF POLYMERS (VIII)

COOH + n HOCH2CH2OHHOOCnC

O

n

O

OCH2CH2OC

poly(ethylene terephthalate) terephthalic acid ethylene glycolPET, polyester


ng

NH(CH2)6NHC(CH2)4C

O

n

O

poly(hexamethylene adipamide)hexamethylene diamine

n H2N(CH2)6NH2 + n HOOC(CH2)4COOH

adipic acid

的确良, 涤纶PET, polyester

Nylon 6,6, polyamide

尼龙 6,6

(36)

IUPAC nomenclature system (系统命名法)

(1) The smallest structural repeating unit (CRU) is identified.F

4. NOMENCLATURE OF POLYMERS (IX)

poly(β-propiolactone)Ex.,

OCH2CH2C

O

OCH2CH2C

O

OCH2CH2C

O

OCH2CH2C

O


ng

OCH2CH2C

O

n CH2CH2CO

O

n

OCCH2CH2

O

n

CH2COCH2

O

n

COCH2CH2

O

n

(37)

(3) Substituent groups on the backbone are assigned the lowest possible numbers.

4. NOMENCLATURE OF POLYMERS (X)

(2) The order of decreasing priority for heteroatom(s) is

O > S > N > P > C.

OCH2CH2C

O

n OCCH2CH2

O

n


ng

possible numbers.

(4) poly(CRU name)

OCCH2CH2

O

n

poly[oxy(1-oxopropane-1,3-diyl)] OCCH2CH2

O

n

(38)

4. NOMENCLATURE OF POLYMERS (XI)

CH2CH2On

CH2 CH2

O

HOCH2CH2OH

CH2CH2On

poly(ethylene glycol)ethylene glycol

poly(ethylene oxide)

poly(oxyethylene)

poly(oxyethylene)

Source nameIUPAC nameMonomer

Polymer structure(polyethers)


ng

CHO

CH3 n

CH2 CH2 nethylene oxide poly(oxyethylene)

CH3CHO polyacetaldehydepoly(oxyethylidene)acetaldehyde

CH2O nHCHO polyformaldehyde

poly(oxymethylene)formaldehyde

(39)

O

O

OCH2CH2C

O

Source or common nameIUPAC nameMonomer

Polymer structure(polyesters)

poly(3-propiolactone)poly[oxy(1-oxopropane-1,3-diyl)]

3-propiolactone

4. NOMENCLATURE OF POLYMERS (XII)

O poly(10-decanoate)


ng

OCH2CH2OC

O

C

O poly(ethylene terephthalate)poly(oxyethyleneoxytere-

phthaloyl)

HOCH2CH2OH

CO2HHO2C

+

terephthalic acid

HO(CH2)9CO2H10-hydroxydecanoic acid O(CH2)9C

O poly(10-decanoate)poly[oxy(1-oxodecane-1,10-diyl)]

(40)

NH(CH2)5C

ONHO poly(caprolactam) or nylon 6

poly[imino(1-oxohexane-1,6-diyl)]caprolactam

4. NOMENCLATURE OF POLYMERS (XIII)

Source or common nameIUPAC nameMonomer

Polymer structure(polyamides)

O poly(11-undecanoamide) or nylon 11


ng

NH(CH2)6NHC(CH2)4C

O O poly(hexamethylene aidpamide)poly(iminohexane-1,6-diylimino-

adipoyl)

H2N(CH2)6NH2

HO2C(CH2)4CO2H+

H2N(CH2)10CO2HNH(CH2)10C

O poly(11-undecanoamide) or nylon 11

11-aminoundecanoic acid poly[imino(1-oxoundecane-1,11-diyl)]

hexamethylene diamine

adipic acid

(41)


Commonly used polymer abbreviations

ABS Acrylonitrile–butadiene–styrene copolymer PF Phenol–formaldehyde polymer

EPR (or EPM) Ethylene–propylene rubber PMMA Poly(methyl methacrylate)

HDPE High–density polyethylene PP Polypropylene

LCP Liquid crystal polymers PPO Poly(phenylene oxide)

LDPE Low–density polyethylene PS Polystyrene


ng

LDPE Low–density polyethylene PS Polystyrene

LLDPE Linear low–density polyethylene PTFE Polytetrafluoroethylene

MF Melamine–formaldehyde polymer PVAc Poly(vinyl acetate)

PAN Polyacrylonitrile PVC Poly(vinyl chloride)

PC Polycarbonate SBR Styrene–butadiene rubber

PEO Poly(ethylene oxide) UF Urea–formaldehyde polymer

PET Poly(ethylene terephthalate) UP Unsaturated polyester

(42)

In general, the source or common name is used for the common polymers.


Source or common name:Simple and convenient

Abbreviations:Simple and convenient


ng

The IUPAC system is generally used for all except the common polymers.

IUPAC system:Strict and complicated

Simple and convenientThe abbreviations are used in journal, articles

and trade.

(43)

5. MOLECULAR WEIGHT (I)

Molecular weight (MW)

C

Mec

hani

cal s

tren

gth Critical point or

Entanglement MWLimitimg value

5,000 ~ 10,000Difficult to synthesize & process

Dependence of mechanical strength on polymer MW


ng

MW

A

B

Mec

hani

cal s

tren

gth

M0 Ms

≥ 1,000

M0 : MW for emerging strength; Ms : MW for saturation strength

(44)

Ø

5. MOLECULAR WEIGHT (II)

M0 & MS : related to intermolecular forces

Crystalline polymer (M0 and MS ) < amorphous polymer

Polar polymer (M0 and MS ) < non-polar polymer

Ø The higher the MW, the tougher the polymer

MW, M and M of commonly used polymers


ng

M0 (×10-4) MS(×10-4) MW (×10-4)

PlasticsPS 6 30 10 ~ 30

HDPE 2.8 – 6 ~ 30

FiberPET 0.8 3.0 1.8 ~ 2.3

Nylon 6,6 0.6 2.4 1.2 ~ 1.8Rubber SBR – – 15 ~ 20

MW, M0 and MS of commonly used polymers

(45)

Wei

ght f

ract

ion,

wx Polymer: in general, the mixtures of molecules

of different MW

5. MOLECULAR WEIGHT (III)


ng

Wei

ght f

ract

ion,

MW

Molecular weight distribution (MWD)

MW was described by average molecular weight

(46)

5. MOLECULAR WEIGHT (IV)

F Number-average MW (Mn)

Molecular weight: M1, M2, … Mx

Number of molecules : N1, N2, … Nx

Weight of molecules : W1, W2, … Wx

∑= xNN

∑=∑= NMWW


ng

∑=∑= xxx NMWW

∑=

x

xx N

Nn

xNW

∑ x

xx

NMN

∑∑

∑ xx MnMn = = =

Mole fraction of Mx

(47)

Ø

5. MOLECULAR WEIGHT (V)

Methods of measurement:

Colligative properties of solution

¹ Vapor pressure lowering ( < 1 ~ 1.5万)

¹ Freezing point depression ( < 0.1 ~ 1万)

¹ Osmotic pressure ( 2万 ~ 50万)


ng

Ø End group analysis

¹ 1H-NMR

¹ -COOH/KOH (titration)< 2.0万

(48)

5. MOLECULAR WEIGHT (VI)

F Weight-average MW (Mw)

= xWw Weight fraction of M

x

xx

WMW

∑∑

xx

xx

MNMN

∑∑ 2

∑ xx MwMw = = =


ng

Ø

∑=

xW

xxw Weight fraction of Mx


Light scattering method (光散射法) > 5千 ~ 1.0万

(49)

5. MOLECULAR WEIGHT (VII)

F Viscosity-average MW (Mv)

Mv = =[ ] αα /1∑ xx Mwαα /11

∑∑ +

xx

xx

MNMN

Dependent on the hydrodynamic volume of polymers(constant)


ng

Dependent on the hydrodynamic volume of polymers(constant)α

α: Variation with polymer, solvent, temperature

Mark-Houwink equation αη vKM=][

(50)

Intrinsic viscosity

Methods of measurement : Viscometer

5. MOLECULAR WEIGHT (VIII)

00rel t

t==

ηη

η

1relsp −=ηη

Csp

redη

η =

Relative viscosity

Specific viscosity

Reduced viscosity


ng

Ubbelohde viscometer(乌氏黏度计)

capillary

C

Crel

inhlnη

η =Inherent viscosity

inhη

redη

][η

C

×

×

××

×

× ××

(51)

5. MOLECULAR WEIGHT (IX)

F Molecular weight distribution (MWD)

Wei

ght f

ract

ion,

wx

Mn

MvMw

lower MW fraction

higher MW fraction


ng

MW

Wei

ght f

ract

ion,

MWD or polydispersity index (PDI)n

wM

M=


Ø GPC (Gel Permeation Chromatography, 凝胶色谱仪)

Ø MALDI-TOF or MALDI-MS (基质辅助激光解吸离子化质谱)(matrix-assisted laser desorption ionization mass spectrometry)

(52)

5. MOLECULAR WEIGHT (X)

F GPC

Solvent bottle

Pressurepump

Sampleinjection

Column.….….….…

Injection valve(loaded onto loop)

MWDRelative Mn & Mw


ng

Solvent bottle

DetectorRecorder

Solvent : THF, toluene, DMF, chloroform, H2O

Detector :UV detectorRI (refractive index) detectorViscosity detector

(53)

5. MOLECULAR WEIGHT (XI)

F MALDI-MS

Polymer + solid matrixlaser pulse

Vaporized polymer with attached metal ions


ng

MWDAbsolute Mn & Mw

(54)

5. MOLECULAR WEIGHT (XII)

Typical ranges of Mw/Mn in synthetic polymers

Polymer Range

Living polymers 1.01 ~ 1.05

Addition polymer, terminated by coupling 1.5


ng

Addition polymer, terminated by disproportionation 2.0

high conversion vinyl polymers 2 ~ 5

branched polymers 20 ~ 50

Condensation polymers 2.0

(55)

6. MICROSTRUCTURE OF POLYMERS (I)

Positional Isomerism (结构[位置]异构)

CH2 CHR CH2 CH

R

CH2 CH

R

CH2 CH

R

n CH CH2

R

Head tail head tail head tail tail head

head-to-tail tail-to-tail

predominant


ng

The different spatial arrangements that cannot change from one to the other or such a change requires the breaking of chemical bonds

Configuration Isomerism (构型异构)

Stereoisomerism (立体异构)

Geometric isomerism (cis-trans isomerism) (几何异构(顺反异构))

predominant

Configuration ?

(56)

F Stereoisomerism

CCH2

RH

CH2

CRH

CH2

CRH

CH2

CRH

CH2

CRH

CH2 CH

R

n

Isotactic (等规)

6. MICROSTRUCTURE OF POLYMERS (II)


ng

CCH2

RH

CH2

CR H

CH2

CRH

CH2

CR H

CH2

CRH

CCH2

HH

CH2

CRH

CH2

CR H

CH2

CRH

CH2

CRH

Syndiotactic (间规)

Atactic (无规)

(57)

F Geometric Isomerism (cis-trans Isomerism)

6. MICROSTRUCTURE OF POLYMERS (III)

CHCH

CH2 CH CH CH2n CH CH CH2CH2 n

1,3-butadiene polybutadiene


ng

trans-polybutadiene

C CCH2

H

CH2

H n

C CCH2

HCH2

H n

cis-polybutadiene

(58)

7. PHYSICAL STATE OF POLYMERS (I)

The different arrangements of atoms and substituents of the polymer chain brought about by rotations about single bonds.

Conformation ?

fully extended chain random coil folded chain helical chain

Ø


ng

extended chain random coil folded chain helical chain

For solid polymers:

Morphology(形态)

Crystalline: the ordered regions of polymer chains(结晶)

Amorphous: the disordered regions of polymer chains(无定形)

(59)

7. PHYSICAL STATE OF POLYMERS (II)

F

Crystalline & Amorphous Behavior

Fringed-micelle model (缨状微束模型) (1930s)

Crystalline regionCrystallite (微晶)


ng

Amorphous region

Ø

Ø

Crystallites imbedded in a disordered, amorphous polymer matrix

Polymer molecules pass through several different crystalline region

Crystalline and amorphous regions can be not separated

(60)

7. PHYSICAL STATE OF POLYMERS (III)

F Folded-chain lamella model (折叠链晶片模型) (1950s)

Single crystal:

Length of polymer chain > 100 nm

Crystalline and amorphous regions can be separatedThickness of lamella : 10 nm


ng

10nm

Adjacent reentry model(近邻松散折叠)

Switchboard model(跨层折叠)

(61)

7. PHYSICAL STATE OF POLYMERS (IV)

Thermal Transitions

Crystalline melting temp. (Tm):

Glass transition temp. (Tg):

the melting temp. of the crystalline domains

the temp. at which the glass transition of the amorphous domains occurs


ng

Exot

herm

al

TTg Tm

For semicrystalline polymer (DSC curve)

Crystallization temp. (Tc)

(62)

Tm : The ceiling temp. of crystalline polymers for application

Tg : The ceiling temp. of amorphous polymers for application

Polymer materials:

Tm, Tg : Important targets of heat resistance of polymers

Influence Factor of Tm, Tg :F

F

7. PHYSICAL STATE OF POLYMERS (V)


ng(63)

Influence Factor of Tm, Tg :F

Molecular symmetry

Structural rigiditySecondary attractive forces of polymer chains

21

≈m

g

TT

32

≈m

g

TT

(symmetrical molecules)

(asymmetrical molecules)

Polymer Repeating Unit Tg (oC) Tm (oC)

Polydimethylsiloxane —OSi(CH3)2— -127 -40Polyethylene —CH2CH2— -125 137Polyoxymethylene —CH2O— -83 181Polyisobutylene —CH2C(CH3)2— -73 44Polypropylene —CH CH(CH )— -13 176

7. PHYSICAL STATE OF POLYMERS (VI)

Thermal transitions of polymers


ng(64)

Polypropylene —CH2CH(CH3)— -13 176

Poly(vinyl acetate) —CH2CH(OCOCH3)— 32 -

Poly(ε-caprolactam) —(CH2)5CONH— 40 223

Poly(hexamethylene adipamide) —NH(CH2)6NHCO(CH2)4CO— 50 256

Poly(ethylene terephthalate) —OCH2CH2OOC—Ø—CO— 61 270Poly(vinyl chloride) —CH2CHCl— 81 273

Polystyrene —CH2CH (C6H5)— 100 250

Poly(methyl methacrylate) —CH2C(CH3)(CO2CH3)— 105 220

8. INDUSTYIAL POLYMERS (I)

Plastics, Fibers, Elastomers (rubbers), Coatings, Adhesives

Stress (σ)

Flexible plastics

Rigid plastics

Fiber


ng

Strain (ε)

Elastomer

Modulus (E, 弹性模量)

Rigid plastics > Fiber > Flexible plastics > Elastomer

Ø

(65)

8. INDUSTYIAL POLYMERS (II)

Features of Polymers :FLow density (light weight) (0.83 ~ 2.2 g/cm3)

High specific strength & specific modulus (σ/ρ, E/ρ)

Good processability

Corrosion resistanceEasy coloring


ng

Easy coloringPoor electric & thermal conductivity

56% 18% 11% ~15%

Synthetic polymers : ~1.5 亿吨 /年 (late 1990’s)

Plastics, Fibers, Elastomers (rubbers), Coatings & Adhesives

Inexpensive price

(66)

8. INDUSTYIAL POLYMERS (III)

Thermolplastics

Plastics1980s: the volume of plastics > steel & iron

Commodity plastics(通用塑料)

Engineering plastics(工程塑料)

high volume, low cost

higher cost, lower volumesuperior mechanical propertiesgreater durability


ng(67)

Thermosetting plastics

(工程塑料) greater durabilitygood heat resistance

Crosslinked polymers

Thermoplastics : Thermosetting plastics ≈ 6 : 1

8. INDUSTYIAL POLYMERS (IV)

Commodity Plastics

Type Abbreviation Major Uses

Low-densitypolyethylene LDPE

Packaging film, wire and cable insulation, toys, flexible bottles, housewares, coatings

High-densitypolyethylene HDPE

Bottles, drums, pipe, conduit, sheet, film, wire and cable insulation


ng(68)

polyethylene cable insulation

Polypropylene PPAutomobile and appliance parts, furniture, cordage,

webbing, carpeting, film packaging

Poly(vinyl chloride) PVCConstruction, rigid pipe, flooring, wire and cable

insulation, film and sheet

Polystyrene PSPackaging (foam and film), foam insulation,

appliances, housewares, toys

8. INDUSTYIAL POLYMERS (V)

Principal Engineering Plastics

Type Abbreviation Type Abbreviation

Acetal a POM Polyetheretherketone PEEK

Polyamide b — Polyetherimide PEI

Polyamideimide PAI Polyimide PI


ng(69)

Polyarylate Poly(phenylene oxide) PPO

Polybenzimidazole PBI Poly(phenylene sulfide) PPS

Polycarbonate PC Polysulfone —

Polyester c —a Common name for polyformaldehyde. Abbreviation refers to poly(oxymethylene)b Principally nylon 6 and 6,6c Principally poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT)

8. INDUSTYIAL POLYMERS (VI)

Principal Thermosetting Plastics

Type Abbreviation Typical Uses

Phenol-formaldehyde PF

Electrical and electronic equipment, automobile parts, utensil handles, plywood adhesives, particle board binder

Urea-formaldehyde UF

Similar to PF polymers; also treatment of textiles, coatings


ng(70)

formaldehyde UF coatings

Unsaturated polyester UP

Construction, automobile parts, boat hulls, marine accessories, corrosion-resistant ducting, pipe, tanks, etc., business equipment

Epoxy—

Protective coatings, adhesives, electrical and electronics applications, industrial flooring, highway paving materials, composites

Melamine-formaldehyde MF

Similar to UF polymers; decorative panels, counter and table tops, dinnerware

8. INDUSTYIAL POLYMERS (VII)

Fibers

High strength & modulusGood elongationGood thermal stability (withstand ironing)SpinnabilityDyeability (可染性)Chemical resistance

Requirements


ng(71)

Synthetic Fibers

Natural Fibers

Natural fibers : Synthetic fibers ≈ 1 : 1

Chemical resistance Insect & mildew (霉) resistance

Cotton

Silk (丝绸)

Polysaccharide celluloseWool Protein

Protein Fibers

8. INDUSTYIAL POLYMERS (VIII)

Principal Synthetic Fibers

Type Description

CellulosicAcetate rayonViscose rayon

Cellulose acetateRegenerated cellulose

NoncellulosicPolyester Principally poly(ethylene terephthalate)


ng(72)

Nylon

Olefin

Acrylic

Principally poly(ethylene terephthalate)Include nylon 66, nylon 6, and a variety of other aliphatic and

aromatic polyamidesIncludes polypropylene and copolymers of vinyl chloride,

with lesser amounts of acrylonitrile, vinyl acetate, orvinylidene chloride (copolymers consisting of more than 85% vinyl chloride are called vinyon fiber)

Contain at least 80% acrylonitrile; included are modacrylicfibers comprising acrylonitrile and about 20% vinyl chloride or vinylidene chloride

8. INDUSTYIAL POLYMERS (IX)

Elastomers (弹性体)

Rubber (橡胶)

Rubber (Elastomers)

Naturally occurring polymer

Synthetic polymer 可混用

Resilience (回弹性)Requirements Network structure

Chemical crosslinking


ng(73)

Crosslinking Non-network structure


Physical crosslinking


PS clusterPBD

Physical crosslinking (SBS)

8. INDUSTYIAL POLYMERS (X)

Principal Synthetic Rubber Type Description

Styrene-butadiene Copolymer of the two monomers in various proportions depending on properties desired; called SBR

Polybutadiene Consists almost entirely of the cis-1,4-polymerEthylene-propylene Often abbreviated EPDM for ethylene-propylene-diene monomer;

made up principally of ethylene and propylene units with small amounts of a diene to provide unsaturation


ng(74)

Polychloroprene Principally the trans-1,4 polymer, but also some cis-1,4 and 1,2 polymer; also known as neoprene rubber

Polyisoprene Mainly the cis-1,4 polymer; sometimes called “synthetic natural rubber”

Nitrile Copolymer of acrylonitrile and butadiene, mainly the latterButyl Copolymer of isobutylene and isoprene, with only small amounts

of the latterSilicone Contains inorganic backbone of alternating oxygen and methylated

silicon atoms; also called polysiloxaneUrethane Elastomers prepared by linking polyethers through urethane groups

8. INDUSTYIAL POLYMERS (XI)

Natural varnish (天然清漆)

Paint (色漆)

Coatings & Adhesives

Used for portrait, landscape

Used for decorative coating

Coatings (涂料)F

Lacquer (真漆) Cellulose nitrate


ng(75)

Interior latex wall paint

Exterior latex paint Recent

Styrene-butadiene copolymer

Poly(vinyl acetate)/poly(acrylic ester)

Synthetic paint, synthetic varnish (醇酸树脂清漆)

Development of synthetic polymers

8. INDUSTYIAL POLYMERS (XII)

Natural gum (天然树胶) Bitumen (沥青)

Coatings & Adhesives

Adhesives (黏合剂)F

StarchCellulose nitrate


ng(76)

Phenol-formaldehyde (酚醛树脂)

Urea-formaldehyde (脲醛树脂)

Development of synthetic polymers

Cellulose nitrate

Epoxy resin (环氧树脂)

Used for wood industry

Cyanoacrylate (氰基丙烯酸酯)

9. HISTORICAL DEVELOPMENT (I)

1839: Vulcanized rubber (硫化橡胶) was discovered by CharlesGoodyear (US)。

The concept of large molecules began in the 1920s, while the application of polymers was earlier than it.

Ø

Ø 1868: Celluloid (赛璐珞), cellulose nitrate plasticized with camphor, was prepared by A. Parks (UK)


ng

Ø

Ø 1920: The macromolecular concept was formulated by Hermann Staudinger. (received the Nobel Prize in 1953)。

1907: First synthetic polymer—phenolic resin (Bakelite, 酚醛树脂) was synthesized by Baekeland (BE).

was prepared by A. Parks (UK)。

(77)

Ø 1930s:

¹ Many addition polymers were commercialized via free radical polymerization.

9. HISTORICAL DEVELOPMENT (II)

¹Wallace Carothers studied polycondensation reactions, synthesized nylon 6,6 and polychloroprene.


ng

Ex., PVC, PMMA, PS, PVAc, LDPE

¹ The theory about polymer solutions and the methods of measurement of molecular weight were established. (Flory received the Nobel Prize in 1974)

(78)

Ø 1950s: The catalysts of coordinate PZN were discovered by

9. HISTORICAL DEVELOPMENT (III)

Ø 1940s: World War II has promoted the development of polymer materials, and many important elastomers and plastics were synthesized.

Ex., SBR (丁苯橡胶), NBR (丁腈橡胶), butyl rubber (丁基橡胶),

PTFE (有机氟材料), PET (涤纶树脂)，ABS


ng

Ø

Ø

1950s: The catalysts of coordinate PZN were discovered by Ziegler and Natta, and HDPE and isotactic PP were synthesized. (Ziegler and Natta received the Nobel Prize in 1963)

1956: Michael Szwarc (US) discovered living anionic PZN. This technique permitted the preparation of narrow MWD and ‘exact’ di- and tri-block copolymers, which pioneered polymer designs.

(79)

9. HISTORICAL DEVELOPMENT (IV)

Ø After the 1960s: Special polymers and functional polymers were developed.

Ø The late 1950s ~ 1960s: Many engineering plastics come out.

Ex., POM (聚甲醛)，PC (聚碳酸酯)，Polysulfone (聚砜)，

PPO (聚苯醚)，Polyimide (聚酰亚胺)


ng

¹ Functional polymers：分离材料(离子交换树脂、分离膜等)，导电高分子，感光高分子，

高分子催化剂，高吸水性树脂，医用高分子，药用高分子，高分子液晶等。

¹ Special polymers：

高模量高强度，耐高低温，耐辐射，高频绝缘，半导体等。

(80)

Ø After the 80s: The new PZN methods and polymers with new structure have constinuously appeared and developed.

¹ New PZN methods：Living cationic PZN, GTP (基团转移聚合)，living radical PZN plasma PZN (等离子体聚合)

9. HISTORICAL DEVELOPMENT (V)


ng

¹ Polymers with new structure：Block copolymer，graft copolymer，star polymer，dendrimer，hyperbranched polymer, etc.

(81)

Hermann Staudinger (1881—1965)


ng

H.W.Review exercises : 2, 3, 5, 6, 7, 8, 10

(81)

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Polymer Chemistry - hxhg.gxu.edu.cnhxhg.gxu.edu.cn/polymerChemistry/uploads/courses/01.pdf · Polymer Chemistry GuangxiUniversity School of Chemistry & Chemical Engineerin g Li Guang