Prof. Jin-Heong Yim

Functional Polymer/1st Semester, 2006Functional Polymer/1st Semester, 2006

History of PolymersHistory of Polymers

Classification of PolymerClassification of PolymerBy Polymerization MechanismBy Polymerization MechanismBy PolarityBy PolarityBy Polymerization ProcessBy Polymerization ProcessBy Recycle AbilityBy Recycle AbilityBy By TacticityTacticity

Interaction of PolymerInteraction of Polymer

Prof. Jin-Heong Yim

History of PolymerHistory of PolymerH. H. StaudingerStaudinger (1881(1881--1965)1965)

고분자설을고분자설을 실험적으로실험적으로 증명증명

천연고무의천연고무의 수소화수소화 실험실험(CH(CH22=CH=CH33CC--CH=CHCH=CH22))

PolystyrenePolystyrene의의 점도가점도가 말단기말단기의의 수가수가 작아짐에작아짐에 따라따라 증가함증가함을을 실험적으로실험적으로 증명증명

1953 1953 Noble PrizeNoble Prize

W.H. W.H. CarothersCarothers (1896(1896--1937)1937)

Nylon Nylon 최초최초 합성합성

19371937년년 DupontDupont社社 상업화상업화

Prof. Jin-Heong Yim

History of PolymerHistory of PolymerK. Ziegler (1898K. Ziegler (1898--1973)1973)

상압상압 폴리에틸렌폴리에틸렌 합성합성

19631963년년 Noble PrizeNoble Prize

G. G. NattaNatta (1903(1903--1979)1979)

Ziegler Ziegler 촉매촉매 이용이용 입체입체규칙성을규칙성을 지닌지닌 폴리프로폴리프로필렌필렌 합성합성

19631963년년 Noble PrizeNoble Prize

P. J. P. J. FloryFlory (1910(1910--1985)1985)

고분자고분자 물리화학의물리화학의 이론이론 집집대성대성

19741974년년 Noble PrizeNoble Prize

A. J. A. J. HeegerHeeger (1936(1936-- ))

반도체반도체//전도성전도성 고분자고분자 발견발견

20002000년년 Noble PrizeNoble Prize

UCSB UCSB 물리학과물리학과 교수교수

Prof. Jin-Heong Yim

PolymerizationPolymerization

Design of monomer

Design of Catalysis

Polymerization Process

General Polymer(LDPE, HDPE, PP, PS, PVC)

Engineering Polymer(PC, PET, PA, POM,m PPO)

Super Engineering Polymer(PI, PSF, PEEK, PTFE)

Radical polymerization

Coordination polymerization

Ionic polymerization

Polycondensation

Bulkpolymerization

Solutionpolymerization

Suspension/Emulsionpolymerization

Gas phasepolymerization

Tailor made control of compound in

the molecular level

Prof. Jin-Heong Yim

C C

H

H

H

CH3

nC C

H

H

H

Hn

C C

H

H

H

nC C

H

H

H

Cn

N

C C

H

H

H

Cln

C O

CH3

CH3

C O

O

n

Sn

C C

OO

O C C

H

H

H

H

O

n

C O

H

H

n

C

O

C

O

NN

H

H

n

C

CH3

CH3

O S

O

O

n

NN

O

O

O

O

n

C C

O

N

O H

N

H

nO O C

O

n

C C

F

F

F

F

n

C C

F

O

F

F

xC C

F

F

F

F

y

CF2CF2OCF2CF2SO3H

General Polymer Engineering Polymer

Super Engineering Polymer

Various PolymersVarious Polymers

Prof. Jin-Heong Yim

Classification by MechanismClassification by Mechanism

Step Polymerization

Chain GrowthPolymerization

Radical Polymerization

Cationic Polymerization

Anionic Polymerization

Coordination Polymerization

Polycondensation

Prof. Jin-Heong Yim

Step PolymerizationStep PolymerizationNylon 66 (PA 66)

HN

H(CH2)6 N

H

H+

HO C

O

(CH2)4 C

O

OH-H2O H

NH

(CH2)6 N

H

C

O

(CH2)4 C

O

OH

Hexamethylene diamine Adipic acid

HN

H(CH2)6 N

H

C

O

(CH2)4 C

O

OHH

NH

(CH2)6 NH

H+

-H2O HN

H(CH2)6 N

H

C

O

(CH2)4 C

O H

N (CH2)6 NH

H

Dimer

Dimer Monomer Trimer

n-mer m-mer

(n+m)-mer

-(m+n)/2 H2OH

NH (CH2)6 N

H

C

O

(CH2)4 C

O

OH

H

NH (CH2)6 N

H

C

O

(CH2)4 C

O

OHn m

+

HNH (CH2)6 N

H

C

O

(CH2)4 C

O

OHn+m

Prof. Jin-Heong Yim

Step PolymerizationStep Polymerization

Structural unit Structural unit

Repeating unit

Monomer + Monomer Dimer, Monomer + Dimer Trimer

Monomer + Trimer Tetramer, Dimer + Dimer Tetramer

N-mer + M-mer (N+M)-Dimer

H

NH (CH2)6 N

H

C

O

(CH2)4 C

O

OHn

Prof. Jin-Heong Yim

Chain Growth PolymerizationChain Growth Polymerization

Radical Polymerization

Cationic Polymerization

Anionic Polymerization

Coordination Polymerization

Prof. Jin-Heong Yim

InitiationInitiationGeneration of active initiatorGeneration of active initiatorReaction with monomer to form growing chainsReaction with monomer to form growing chains

PropagationPropagationChain extension by incremental monomer additionChain extension by incremental monomer addition

TerminationTerminationConversion of active growing chains to inert Conversion of active growing chains to inert polymerpolymer

Chain TransferChain TransferTransfer of active growing site by terminating one Transfer of active growing site by terminating one chain and reinitiating a new chain. chain and reinitiating a new chain.

Chain Growth PolymerizationChain Growth Polymerization

Prof. Jin-Heong Yim

Radical PolymerizationRadical Polymerization

C

O

O O C

O Heat or LightC

O

O2 .

I 2 Rokd

initiation

C

O

O. +H2C CHC

O

O .H2C CH

Ro + M R1ki

initiation

Prof. Jin-Heong Yim

Radical PolymerizationRadical PolymerizationH2C CHC

O

O . + H2C CHH2C

HCC

O

OH2C CH.

R1 + M R2kp

propagation

H2C

HCC

O

OH2C CH.

n-1+ H2C CH

H2C

HCC

O

OH2C CH.

n

Rn + M Rn+1kp

propagation

Prof. Jin-Heong Yim

Radical PolymerizationRadical PolymerizationH2C

HCC

O

OH2C CH.

n-1+ H2C CH

H2C

HCC

O

OH2C CH2

n-1+ H3C CH.

Rn + M kc

Chain transferPn + R1

H2C

HCC

O

OH2C CH.

n-1CH2

HC C

O

OH2CHC.+

H2C

HCC

O

OH2C CH

n-1CH2

HC C

O

OH2C

HCRn + Rn

kt

TerminationPn

Prof. Jin-Heong Yim

Cationic PolymerizationCationic Polymerization+ H2C CHB+X-

H2C C+B X-

H2C C+B X- + H2C CH CH2 C+HB X-CH2CH

CH2 C+HB X-CH2CHn-1

+ H2C CH CH2 C+HB X-CH2CHn

Prof. Jin-Heong Yim

Anionic PolymerizationAnionic Polymerization+ H2C CH

H2C C-A M+

H2C C-A M+ + H2C CH CH2 C-HA M+CH2CH

CH2 C-HA M+CH2CHn-1

+ H2C CH CH2 C-HA M+CH2CHn

M+A-

Prof. Jin-Heong Yim

Coordination PolymerizationCoordination PolymerizationMetallocene Activation & insertion

Prof. Jin-Heong Yim

Classification by PolarityClassification by Polarity전기음성도의전기음성도의 정의정의: : 공유공유 결합에서결합에서 전자쌍을전자쌍을끌어끌어 당기는당기는 힘의힘의 크기크기

Prof. Jin-Heong Yim

Polar PolymerPolar Polymer

H

NH (CH2)6 N

H

C

O

(CH2)4 C

O

OHn

-+

-+ -

+-+

H: 2.2, N: 3.0C: 2.5, O: 3.4

H2C C

H

Cl

**n-

+C: 2.5, Cl: 3.2

Prof. Jin-Heong Yim

NonpolarNonpolar PolymerPolymer

C C

H

CH3

**n

H

H

C C

H

H

**n

H

H

C C

H

**n

H

H

H: 2.2, C: 2.5

C C

F

F

**n

F

F

-+

-

-+

-

C: 2.5, F: 4.0

Prof. Jin-Heong Yim

By ProcessBy Process

Removal of additivesRemoval of additivesCoagulation neededCoagulation neededLatex stabilityLatex stability

High High RRpolypolyLow TemperaturesLow TemperaturesHigh Mol. Wt.High Mol. Wt.High surface area latexHigh surface area latex

EmulsionEmulsion

Removal of additivesRemoval of additivesLow viscosityLow viscosityDirect bead formationDirect bead formation

SuspensionSuspension(Pearl)(Pearl)

Lower mol. Wt.Lower mol. Wt.Low Low RRpolypolySolvent RecoverySolvent Recovery

Good mixingGood mixingReady for applicationReady for application

SolutionSolution

Heat buildupHeat buildupGel effectGel effectBranched or Branched or crosslinkedcrosslinked productproduct

Simple equipmentSimple equipmentRapid reactionRapid reactionPure polymer isolatedPure polymer isolated

Bulk (Neat)Bulk (Neat)DisadvantagesDisadvantagesAdvantagesAdvantagesMethodMethod

Prof. Jin-Heong Yim

By Recycle AbilityBy Recycle Ability

Thermoplastic: Thermoplastic: polymers that flow when heatedpolymers that flow when heatedeasily reshaped and recycledeasily reshaped and recycleddue to presence of long chains with limited or no due to presence of long chains with limited or no crosslinkscrosslinkspolyethylene, polyvinylchloridepolyethylene, polyvinylchloride

Prof. Jin-Heong Yim

Thermosetting: Thermosetting: decomposed when heateddecomposed when heatedcan not be reformed or recycledcan not be reformed or recycledpresence of extensive presence of extensive crosslinkscrosslinks between long between long chains chains epoxy and polyestersepoxy and polyesters

By Recycle AbilityBy Recycle Ability

Prof. Jin-Heong Yim

ElastomersElastomers: : intermediate between thermoplastic and intermediate between thermoplastic and thermosetting polymers thermosetting polymers some some crosslinkingcrosslinkingcan undergo extensive elastic deformationcan undergo extensive elastic deformationnatural rubber, siliconenatural rubber, silicone

By Recycle AbilityBy Recycle Ability

Prof. Jin-Heong Yim

Structural CharacteristicsStructural Characteristics

Prof. Jin-Heong Yim

By By TacticityTacticity• Polymers can be either amorphous or semi-crystalline

• Tacticity, i.e. arrangements of substituents around the backbone, determines the degree of crystallinity

• Atactic polymers are amorphous

• Isotactic and syndiotactic may crystallize

• Crytallinity depends on:–size of side groups (smaller, ↑crystallinity)–regularity of chain

• Increased crystallinity enhances mechanical properties

Prof. Jin-Heong Yim

By By TacticityTacticity

Prof. Jin-Heong Yim

Primary Bond

Secondary Bond Ionic Bond

Hydrogen Bond

Dipole-dipole interaction

Van der Waals interaction

Covalent Bond

Interaction of PolymerInteraction of Polymer

200-500

10-20

3-7

1.5-3

0.5-1

BE (KJ/mol)

Prof. Jin-Heong Yim

Interaction of PolymerInteraction of PolymerH2C CH

COOH

H2C

HC

COOH

**n

H2C

HC

COO-

*H2C

HC

COO-

H2C

HC

COO-

H2C

HC

COO-

*

H2CCH

COO-

*H2CCH

COO-

H2CC

H

COO-

H2CCH

COO-

*

Ca2+ Ca2+

H

NH (CH2)6 N

H

C

O

(CH2)4 C

O

OHn

H

N (CH2)6 N

H

C

O

(CH2)4 C

O

HHOn

H2C

HC

C N

H2C

HC

C N

H2C

HC

C Nn

H2C C

H

CNH2C C

H

CNH2C C

H

CN

n

Ionic Bond

Hydrogen Bond Dipole-dipole interaction

+

+

-

-

+

+

-

-

-

-

+

+

-

-

+

+

+

+

+

+

+

+-

- -

- -

-