Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort...

62
Polymer Chemistry 저 저 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY

Transcript of Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort...

Page 1: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

Polymer Chemistry

저 자 : Malcolm P. Stevens

    Professor of chemistry at the university of Hartfort

OXFORD UNIVERSITY PRESS 3rd Ed.(1999)

POLYMER CHEMISTRY

Page 2: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

 

                                                                                                                                                           

                                             

Page 3: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

CONTENTS

PART POLYMER STRUCTURE AND PROPERTIESⅠ

POLYMER CHEMISTRY

1. Basic principles

2. Molecular weight and polymer solutions

3. Chemical structure and polymer morphology

4. Chemical structure and polymer properties

5. Evaluation, characterization, and analysis of polymers

Page 4: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

PART VINYL POLYMERSⅡ

CONTENTS

6. Free radical polymerization

7. Ionic polymerization

8. Vinyl polymerization with complex coordination catalysts

9. Reactions of vinyl polymers

POLYMER CHEMISTRY

Page 5: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

CONTENTS

PART NONVINYL POLYMERSⅢ

10. Step-reaction and ring-opening polymerization

11. Polyethers, polysulfides, and related polymers

12. Polyesters

13. Polyamides and related polymers

14. Phenol-, urea-, and melamine-formaldehyde polymers

15. Heterocyclic polymers

16. Inorganic and partially inorganic polymers

17. Miscellaneous organic polymers

18. Natural polymers POLYMER CHEMISTRY

Page 6: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

Chapter 1. Basic principles

1.1 Introduction and Historical Development

1.2 Definitions

1.3 Polymerization Processes

1.4 Step-reaction Polymerization

1.5 Chain-reaction Polymerization

1.6 Step-reaction Addition and Chain-reaction Condensation

1.7 Nomenclature

1.8 Industrial Polymers

1.9 Polymer Recycling

POLYMER CHEMISTRY

Page 7: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.1 Introduction and Historical Development

Stone age → Bronze age → Iron age → Polymer age

A. Development of civilization

B. Application of polymeric materials

o PE milk bottles

o Polyamide bulletproof vests

o Polyurethane artificial heart

o Fluorinated phosphazene elastomer for arctic environments

POLYMER CHEMISTRY

Page 8: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1. Property difference between polymer and low molecular weight compound

2. Chemistry of polymer synthesis 3. Chemistry of polymer modification

C. The purpose of this book

POLYMER CHEMISTRY

Page 9: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

D. Development of polymer chemistry

POLYMER CHEMISTRY

1833 년 : Berzelius, the first use of terminology, polymer

 1839 년 : Synthesis of polystyrene

1860s  : Poly(ethylene glycol), Poly(ethylene succinate)

1900s : Leo Baekeland, synthesis of phenol formaldehyde resin

1920s : Hermann staudinger

    Structure of polymer(long-chain molecules), Novel Prize (1953 년 )

1939 년 : W.H. Carothers, Nylon synthesis (Du Pont)

1963 년 : Ziegler-Natta, stereoregular polymerization

1974 년 : Paul Flory, polymer solution property

1984 년 : Bruce Merrifield, solid-phase protein process

Page 10: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1839      가황 고무 발명 (C. Goodyear) 1868      nitrocellulose 합성 (J.W. Hyatt) 1888      공기 자전거 타이어 발명 (J. B. Dunlop) 1909      phenol-formaldehyde 수지 제조 (L.H. Baekeland)      (1910 한일합병 / 을사보호조약 )       (1919   김성수 , 국민 모금 경성방직 설립 , 무명 옷감 제조 )1922      H. Staudinger의 고분자 개념 제창 . 1927      cellulose actate 와 poly(vinyl chloride) 의 등장 . Buna S (butadiene-styrene 고무 ) 개발 (Bayer Co.) 1928      poly(methyl methacrylate) 상품화 (O. Rohm). 1930      polystyrene 생산 . 1931      Neoprene 고무 생산 (W. H. Carothers, DuPont Co.) 1935      nylon 66 제조 (W. H. Carothers). 1936      PANN, SAN 및 poly(vinyl acetate) 등장 . 1937      polyethylene 합성 ( O. Bayer). 1938      nylon 6 와 epoxy 수지 개발 . LDPE 합성 . 1941      PET 합성 (J.R. Whinfield 와 J.T. Dickinson). 1942      PAN 섬유의 상품화 .      (1945 제 2 차세계대전 종전 / 대한민국 독립 )       (1943   국제고무 " 말표 " 고무신 생산 )      (1946   낙희화학 ( 주 )  PVC 사출 )      (1947   한국나이롱 나일론 66 방적 )1948      ABS 수지 제조 . 1950      한국전쟁 발발 / 자동차 타이어의 노화 원인이 오존인 것을 밝혀내고 antiozonant 의 개발 시작 1952      K. Ziegler 의 ethylene 저압 중합용 촉매 개발 . 1953      H. Schnell 의 poly(ohenylene oxide) 개발 . Hermann Staudinger 노벨상 수상 (Work on macromolecules) 1955      G. Natta 의 Ziegler 형 촉매를 이용한 입체규칙성 고분자 발견 . 1956      poly(phenylene oxide) 개발 (A. S. Hay)        (1957   동신화학 PU 폼 생산 )1958      polyacetal 수지 생산 개시 .             F. Sanger, 펩티드의 아미노산 결합순서 결정 방법 개발로 노벨상 수상 1960     J. D. Watson 과 F. H. C. Crick, DNA 이중나선 구조제안으로 노벨 의학상 수상1962      phenoxy 수지 , EPR 제조 . 1963      Guilio Natta 와 Karl Ziegler 와 노벨상 수상 (Development of catalysts and synthesis of polymers) 1964      EVA, ionomer, polyimide, 변성 PPO 등장 . 1965      polysulfone 제조 .

Page 11: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1968      H. G. Khorana, DNA 의 실험적 합성으로 노벨 의학상 수상1970      열가소성 탄성체 개발 . 1971       한남화학 울산 PS 벌크 중합공장 건설1972      울산석유화학공업단지 / 10 만톤 규모 ( 에틸렌 기준 ) 납사 분해공장 건설 사출성형용 polyamide, 방향족 polyester 제조 .           W. Stein 과 S. Moore, 아미노산 분석기 개발로 노벨상 수상 1974      방향족 poly(aryl sulfone), IPN 개발 . Paul J. Flory 노벨상 수상 (Investigations of polymers) 1979      여천석유화학공단 / 35 만톤 규모 납사 분해공장 건설      (1982. 2   순천대학 (4 년제 단과대학 ) 설립 )1980      W. Gilbert, DNA 염기 서열 결정 방법 개발로 노벨상 수상1983      PEEK, poly(aryl sulfone), IPN 개발 . 1984      Bruce Merrifield 노벨상 수상 (Methods of polypeptide synthesis) 1985      액정고분자 생산 .  1988       대산석유화학공업단지 건설  1991      de Gennes 노벨상 수상 ( 고분자 사슬 운동 ), 메탈로센 고분자의 상업화 (Exxon 회사 )         (1997      한국 /IMF)1995. 6  ' 석유화학강좌 ' 시작 ( 대한화학회 여천지회 )2000      A. J. Heeger, A. G. MacDiarmid, H. Shirakawa 3 인은 전도성 고분자 연구로 노벨상 수상

Page 12: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

W.H. Carothers

(1896-1937) 

1943 년 경 겨울 , 미국의 한 도시 .

술 , 비누 , 휴지 , 면으로 된 기저귀 , 압핀…나일론이 죄다 ' 전쟁에 나가버려 ' 여성들은 인조견과 무명 스타킹을 신었다 .

1940 년 5 월 15 일

Page 13: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

2000 년 노벨화힉상수상자 -   히거 , 맥더미드 , 시라카와

플라스틱 고분자의 전기절연성은 다양한 방면에서 유용하게 사용되는데 , 모든 플라스틱 고분자가 절연체 성질만 갖는 것이 아니라 특별한 조건에서 합성된 고분자를 잘 처리하면 금속 못지 않은 전기전도성을 가질 수 있다는 사실이 1977 년 앨런 히거 (Alan J. Heeger), 앨런 맥더미드 (Alan G. MacDiarmid), 그리고 히데키 시라카와 (Hideki Shirakawa) 에 의해 밝혀졌다 . 그들은 이 놀라운 업적을 인정받아 2000 년 노벨화학상을 수상

Page 14: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

2008 년에 1,650 억 , 향후 5 년간 8,250 억을 투자하는 ‘세계수준의 연구중심대학 (World Class University) 육성 사업

교육과학기술부는 해외학자를 유치하는 해당 대학을 지원하고 국책사업으로서 WCU 사업의 취지를 해외학자에게 적극 홍보

광주과기원 - 히거연구센터 협약체결 부산대 -UCSB 의 글로벌 연구실

향후 5 년간 과학기술부로부터 총 25 억의 연구비와 국내 기업과 해외 기관으로부터 약 15 억의 연구비를 지원받아 ‘신기능의 타이타늄 산화물을 도입한 신개념의 고분자 광전자소자 구현’에 관한 연구를 진행할 계획플라스틱 태양전지 - 광주과학기술원 이광희

Page 15: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.
Page 16: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.
Page 17: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.
Page 18: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

E. Examples of monomers and polymers

POLYMER CHEMISTRY

Monomer Polymer

HOCH2CH2OH

HO CO2H

CH2CH2

CH2CH2O

CH2CH2O

O C

O

CH2 CH2

CH2 CHCl CH2CH2

Cl

H2C CH2

O

Page 19: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.2 Definitions

POLYMER CHEMISTRY

A. According to the amount of repeating units

monomer : one unit

oligomer : few

polymer : many (poly – many, mer – part)

telechelic polymer : polymer containing reactive end group

      (tele = far, chele = claw)

telechelic oligomer : oligomer containing reactive end group

macromer (=macro monomer) : monomer containing long chain

Page 20: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

 The total number of repeating units contained terminal group

C. The kinds of applied monomers

B. DP : Degree of polymerization

One kind : Homopolymer

Two kinds : Copolymer

Three kinds : Terpolymer

1.2 Definitions

POLYMER CHEMISTRY

Page 21: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

D. Types of copolymer

POLYMER CHEMISTRY B-B-B-B-B-

  

Homopolymer : -A-A-A-A-A-A-A-A-

Random copolymer :    -A-B-B-A-B-A-A-B-

Alternating copolymer : -A-B-A-B-A-B-A-B-

Block copolymer :      -A-A-A-A-B-B-B-B-

Graft copolymer :     -A-A-A-A-A-A-A-A-

Page 22: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

E. Representation of polymer types

(a) linear   (b) branch

(c) network

POLYMER CHEMISTRY

Page 23: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

(c)ladder polymer

(b) comb polymer (a) star polymer

(d) semi- ladder (or stepladder) polymer

F. Representation of polymer architectures

POLYMER CHEMISTRY

Page 24: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

F. Representation of polymer architectures

(f) polycatenane (e) polyrotaxane

(g) dendrimer POLYMER CHEMISTRY

Page 25: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

Thermoset   : Network polymer

Thermoplastic : Linear or branched polymer

 

 

G. Thermoplastic and thermoset (reaction to temperature)

POLYMER CHEMISTRY

Page 26: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.3 Polymerization Processes

A. Classification of polymers to be suggested by Carothers

Addition polymers : repeating units and monomers are same

Condensation polymers : repeating units and monomers

are not  equal, to be split out small molecule

POLYMER CHEMISTRY

Page 27: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

Other examples

1. Polyester from lactone (1.7)

from ω-hydroxycarboxylic acid (1.8)

&

O R C

O

O C

O

R

(1.7)

(1.8)OH R CO2H O R C

O

+ H2O

POLYMER CHEMISTRY

Page 28: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

Other examples

2. Polyamide from lactam (1.9), and from ω-aminocarboxylic acid (1.10)

(1.9)

NH C NH R C

O

R

O

H2N R CO2H NH R C

O+ H2O (1.10)

POLYMER CHEMISTRY

Page 29: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

3. Polyurethane from diisocyanate and dialcohol(1.11) and from diamine and bischloroformate(1.12):

Other examples

OCN R NCO + HO R' OH

CNH R NHCO R' O

H2N R NH2 + ClCO R' OCCl

CNH R NHCO R' O + 2HCl

O O

O O

O O

(1.11)

(1.12)

POLYMER CHEMISTRY

Page 30: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

Other examples

4. Hydrocarbon polymer from ethylene (1.13), and from α,ω-dibromide (1.14)

FUNCTIONAL POLYMERS LAB

(1.13)

(1.14)

CH2 CH2 CH2CH2initiator

BrCH2(CH2)8CH2Br CH2CH2 5+ 2NaBr

2Na

POLYMER CHEMISTRY

Page 31: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

POLYMER CHEMISTRY

Chain growth polymerization : Addition polymerization         molecular weights increase successively,  one by one monomer Ring-opening polymerization may be either step or chain reaction

1.3 Polymerization Processes B. Modern classification of polymerization according to    polymerization mechanism   Step growth polymerization : Polymers build up stepwise

Page 32: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.4  Step-reaction Polymerization

A. Monomer to have difunctional group

1. One having both reactive functional groups in one molecule

A R B R X

(1.8)HO R CO2H O R C

O

+ H2O

H2N R CO2H NH R C

O+ H2O (1.10)

POLYMER CHEMISTRY

Page 33: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

2. Other having two difunctional monomers

A R A + B R' B R X R' X

OCN R NCO + HO R' OH

CNH R NHCO R' O

H2N R NH2 + ClCO R' OCCl

CNH R NHCO R' O + 2HCl

O O

O O

O O

(1.11)

(1.12)

POLYMER CHEMISTRY

Page 34: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

B. Reaction : Condensation reaction using functional group

Example - Polyesterification

n HO CO2H O C

O

n+ nH2O

nHO2C CO2H + nHOCH2CH2OH

C

O

COCH2CH2O

O

n + 2nH2O

(1.3)

(1.4)

POLYMER CHEMISTRY

Page 35: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

C. Carothers equation

P = NO N

NO

Or N = NO(1 P)

( NO : number of molecules N : total molecules after a given reaction period. NO – N : The amount reacted P : The reaction conversion )

( DP is the average number of repeating units of all molecules present)

DP = NO/N

DP = 1

1 - P

For example At 98% conversion

DP = 1

1- 0.98 POLYMER CHEMISTRY

Page 36: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B(d)

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B(a)

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

(b)

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

A

B

(c)

(A) Unreacted monomer

(B) 50% reacted, DP = 1.3

(C) 75% reacted, DP = 1.7

(D) 100% reacted, DP = 3

Step-Reaction Polymerization

Page 37: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.5 Chain-reaction Polymerization

A. Monomer : vinyl monomer                χCH2=CH2

B. Reaction : Addition reaction initiated by active species

C. Mechanism :  

Initiation        R + CH2=CH2 → RCH2CH2  

Propagation

       RCH2CH2 + CH2=CH2 → RCH2CH2CH2CH2

.

. .

.

POLYMER CHEMISTRY

Page 38: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

TABLE 1.1 Comparison of Step-Reaction and Chain-Reaction Polymerization

Step Reaction Chain Reaction

Growth occurs throughout matrix by

reaction between monomers, oligomers,

and polymers

DPa low to moderate

Monomer consumed rapidly while

molecular weight increases slowly

No initiator needed; same reaction

mechanism throughout

No termination step; end groups still reactive

Polymerization rate decreases steadily as

functional groups consumed

Growth occurs by successive addition of

monomer units to limited number of

growing chains

DP can be very high

Monomer consumed relatively slowly, but

molecular weight increases rapidly

Initiation and propagation mechanisms different

Usually chain-terminating step involved

Polymerization rate increases initially as

initiator units generated; remains relatively

constant until monomer depleted

aDP, average degree of polymerization..

Page 39: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.6 Step-reaction Addition and Chain-reaction Condensation

A. Step-reaction Addition.

(CH2)6+

O

O

(CH2)6

O

O

(1.15)

POLYMER CHEMISTRY

Page 40: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

B. Chain-reaction Condensation

(1.16)

CH2N2 CH2 + N2

BF3

1.6 Step-reaction Addition and Chain-reaction Condensation

POLYMER CHEMISTRY

Page 41: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

A. Types of Nomenclature a. Source name : to be based on names of corresponding monomer        Polyethylene, Poly(vinyl chloride), Poly(ethylene oxide)    b. IUPAC name : to be based on CRU, systematic name       Poly(methylene), Poly(1-chloroethylene), Poly(oxyethylene)   c. Functional group name : According to name of functional group in the polymer backbone       Polyamide, Polyester  

1.7 Nomenclature

POLYMER CHEMISTRY

Page 42: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

d. Trade name : The commercial names by manufacturer Teflon, Nylon

e. Abbreviation name : PVC, PET   

f. Complex and Network polymer : Phenol-formaldehyde polymer   

g. Vinyl polymer : Polyolefin

1.7 Nomenclature

POLYMER CHEMISTRY

Page 43: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.7.1 Vinyl polymers

A. Vinyl polymers

a. Source name : Polystyrene, Poly(acrylic acid),

                  Poly(α-methyl styrene), Poly(1-pentene)  

b. IUPAC name : Poly(1-phenylethylene), Poly(1-carboxylatoethylene)

            Poly(1-methyl-1-phenylethylene), Poly(1-propylethylene)

CH2CH

Polystyrene        Poly(acrylic acid)

Poly(α-methylstyrene)  Poly(1-pentene)

CH2C

CH3

CH2CH

CO2H

CH2CH

CH2CH2CH3 POLYMER CHEMISTRY

Page 44: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

B. Diene monomers

Source name : 1,2-Poly(1,3-butadiene)    1,4-Poly(1,3-butadiene)

IUPAC name : Poly(1-vinylethylene)      Poly(1-butene-1,4-diyl)  

cf) Table 1.2

CH2CH

HC CH2

1,2-addition 1,4-addition

POLYMER CHEMISTRY

1.7.1 Vinyl polymers

CH2CH CHCH2

Page 45: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.7.2 Vinyl copolymer

Systematic

Poly[styrene-co-(methyl methacrylate)] Poly[styrene-alt-(methyl methacrylate)]

Polystyrene-block-poly(methyl methacrylate) Polystyrene-graft-poly(methyl methacrylate)

Concise Copoly(styrene/methyl methacrylate) 

Alt-copoly(styrene/methyl methacrylate) Block-copoly(styrene/methyl methacrylate) Graft-copoly(styrene/methyl methacrylate)

POLYMER CHEMISTRY

Page 46: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.7.3 Nonvinyl Polymers

O CCH2CH2

O

O CH2CH2 O C C

oxy 1-oxopropane-1,3-diyl

oxy ethylene oxy terephthaloyl

POLYMER CHEMISTRY

Page 47: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

* Representative Nomenclature of Nonvinyl Polymers

Poly(hexamethylene   Poly(iminohexane- sebacamide) or Nylon6,10  1,6-diyliminosebacoyl)

Monomer          Polymer            Source or          IUPAC name structure          repeating unit       Common Name

O

H2C CH2

HOCH2CH2OH

H2N(CH2)6NH2 NH(CH2)6NHC(CH2)8C

O O

HO2C(CH2)8CO2H

Poly(ethylene oxide)

Poly(ethylene glycol) Poly(oxyethylene)

Poly(oxyethylene) CH2CH2O

CH2CH2O

cf) Table 1.3

POLYMER CHEMISTRY

Page 48: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.7.4 Nonvinyl copolymers

POLYMER CHEMISTRY

a. Poly(ethylene terephthalate-co-ethylene isophthalate)

OCH2CH2O C

O

C

O

OCH2CH2OC

O

C

O

b. Poly[(6-aminohexanoic acid)-co-(11-aminoundecanoic acid)]

NH CH2 C

O

NH CH2 C

O

5 10

Page 49: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.7.5 End Group

H OCH2CH2 OH

α-Hydro-ω-hydroxypoly(oxyethylene)

POLYMER CHEMISTRY

Page 50: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.7.6 Abbreviations

   

PVC Poly(vinyl chloride)

HDPE High-density polyethylene LDPE Low-density polyethylene PET Poly(ethylene terephthalate)

POLYMER CHEMISTRY

Page 51: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

a. The world consumption of synthetic polymers    : 150 million metric tons per year.

1) Plastics : 56%

2) Fibers  : 18%

3) Synthetic rubber : 11%

4) Coating and Adhesives : 15%

b.Styrene-butadiene copolymer  

Synthetic rubber,   PET  Fiber (polyester)

                      Latex paint           Plastic (bottle)

1.8 Industrial Polymers

POLYMER CHEMISTRY

Page 52: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1) Commodity plastics     LDPE, HDPE, PP, PVC, PS   cf) Table 1.4

2) Engineering plastics     Acetal, Polyamide, Polyamideimide, Polyarylate,     Polybenzimidazole, etc.   cf) Table 1.5

3) Thermosetting plastics  Phenol-formaldehyde, Urea-formaldehyde, Unsaturated polyester, Epoxy, Melamine-formaldehyde    cf) Table 1.6

4) Functional plastics     Optics, Biomaterial, etc.

1.8.1 Plastics

POLYMER CHEMISTRY

Page 53: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

TABLE 1.4 Commodity Plastic

Type Abbreviation Major Uses

Low-density polyethylene

High-densityPolyethylene

Polypropylene

Poly(vinyl chloride)

Polystyrene

LDPE

HDPE

PP

PVC

PS

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

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

Automobile and appliance parts, furniture, cordage, webbing, carpeting, film packaging

Construction, rigid pipe, flooring, wire and cable insulation, film and sheet

Packaging (foam and film), foam insulation appliances, housewares, toys

POLYMER CHEMISTRY

Page 54: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

TABLE 1.5 Principal Engineering Plastics

Chapter Where DiscussedType Abbreviation C

Acetala

Polyamideb

PolyamideimidePolyarylatePolybenzimidazolePoltcarbonatePolyeseterc

PolyetheretherketonePolyetherimidePolyimidePoly(phenylene oxide)Poly(phenylene sulfide)Polysulfoned

POM

PAI

PBIPC

PEEKPEIPIPPOPPS

11131312171212111113111111

POLYMER CHEMISTRY

Page 55: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

TABLE 1.6 Principal Thermosetting Plastics

Chapter WhereDiscussed

Phenol-formaldehyde

Urea-formaldehyde

Unsaturated polyester

Epoxy

Melamine-formaldehyde

Electrical and electronic equipment, automobile parts, utensil handles, plywood adhesives, particle board binderSimilar to PF polymer; also treatment of textiles, coatingsConstruction, automobile parts, boat hulls, marine accessories, corrosion-resistant ducting, pipe, tanks, etc., business equipmentProtective coatings, adhesives, electrical and electronics applications, industrial flooring highway paving materials, compositesSimilar to UF polymers; decorative panels, counter and table tops, dinnerware

Type Abbreviation Typical Uses

PF

UF

UP

-

MF

14

14

14

11

12

Page 56: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1) Cellulosic :

Acetate rayon, Viscose rayon

2) Noncellulosic : Polyester, Nylon(Nylon6,6, Nylon6, etc) Olefin (PP, Copolymer(PVC 85%+PAN and others 15%; vinyon))

3) Acrylic :

Contain at least 80% acrylonitrile     (PAN 80% + PVC and others 20%)        

1.8.2 Fibers

POLYMER CHEMISTRY

Page 57: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1) Natural rubber : cis-polyisoprene

2) Synthetic rubber :

Styrene-butadiene, Polybutadiene,    Ethylene-propylene(EPDM), Polychloroprene, Polyisoprene,

   Nitrile, Butyl, Silicone, Urethane

3) Thermoplastic elastomer :

Styrene-butadiene block copolymer    (SB or SBS)

1.8.3 Rubber (Elastomers)

POLYMER CHEMISTRY

Page 58: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

TABLE 1.7 Principal Synthetic Fibers

Description

Cellulose acetateRegenerated cellulose

Principally poly(ethylene terephthalate)Includes 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, or vinylidene chloride (copolymers consisting of more than 85% vinyl chloride are called vinyon fibers)Contain at least 80% acrylonitrile; included are modacrylic fibers comprising acrylonitrile and about 20% vinyl chloride or vinylidene chloride

Type

Cellulosic Acetate rayon Viscose rayonNoncellulosic Polyester Nylon Olefin

Acrylic

Page 59: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

1.8.4 Coating and Adhesives

1) Coating :

Lacquer, Vanishes, Paint (Oil or Latex), Latex

2) Adhesives :

Solvent based, Hot melt, Pressure sensitive, etc.     Acrylate, Epoxy, Urethane, Cyanoacrylate

POLYMER CHEMISTRY

Page 60: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

TABLE 1.8 Principal Types of Synthetic Rubber

Type

Styrene-butadiene

Polybutadiene

Ethylene- propylene

Polychloroprene

PolyisopreneNitrileButyl

Silicone

Urethane

Description

Copolymer of the two monomers in various proportions depending on properties desired; called SBR for styrene-butadiene rubberConsists almost entirely of the cis-1,4 polymer

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

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

Mainly the cis-1,4 polymer; sometimes called “synthetic natural rubber”Copolymer of acrylonitrile and butadiene, mainly the latterCopolyner of isobutylene and isoprene, with only small amounts of the LatterContains inorganic backbone of alternating oxygen and methylated silicon atoms; also called polysiloxane (Chap. 15)Elastomers prepared by linking polyethers through urethane groups (Chap. 13)

Page 61: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

a. Durability of polymer property

1) Advantage : Good materials for use

2) Disadvantage : Environmental problem  

b. Treatment of waste polymer : Incinerate, Landfill, Recycling

ex) Waste Tire : Paving materials     Waste PET : To make monomer ( hydrolysis )                   To make polyol ( glycolysis )

1.9 Polymer Recycling

POLYMER CHEMISTRY

Page 62: Polymer Chemistry 저 자 : Malcolm P. Stevens Professor of chemistry at the university of Hartfort OXFORD UNIVERSITY PRESS 3rd Ed.(1999) POLYMER CHEMISTRY.

TABLE 1.9 Plastics Recycling Codea

Number

1

2

3

4

5

6

7

Letters

PETEb

HDPE

V or PVC

LDPE

PP

PS

OTHER

Plastic

Poly(ethylene terephthalate)

High-density polyethylene

Poly(vinyl chloride)

Low-density polyethylene

Polypropylene

Polystyrene

Others or mixed plastics

aAdopted by the Society of the Plastics lndustry (SPI).bPET is the more widely accepted abbreviation.

POLYMER CHEMISTRY