Organic Polymer Chemistry

8/11/2019 Organic Polymer Chemistry

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Organic PolymerOrganic PolymerChemistryChemistry

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utl ineutline

I n t r o d c t i o n

C l a s s i f y

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

P r o p e r t i e s

S y n t h e s i s

A p p l i c a t io n





IntroductionIntroduction

p o l y m e r i s a l a r g e m o l e c u l e ( m a c r o m o l e c u l e )

c o m p o s e d o f r e p e a ti n g b a s is m o n o m e r u n i t s





Historyistory

1 8 11 , B r a c o n n o t w o r k e d i n d e r i v a t i v e c e ll u l o s e c o m p o u n d s - t h e e a r l i e s t

i m p o r t a n t w o r k i n p o l y m e r s c i e n c e

! e v e l o p m e n t o f v u l c a n i " a t io n l a t e r i n t h e n i n e t e e n t h c e n t u r y

# n 1 $ % & , ' e o B a e k e la n d c r e a t e d t h e f i r s t c o m p l e t e l y s y n t h e t i c p o l y m e r





Nonmenclatureonmenclature

o n m e n c l ar u r e o f p o l ym e r d e p e n d o n t h e n a m e o f m o n o m e r w i t h t h e

p r e f i * p o l y +

a m p l e t h y l e n e ( p o l y e t h y le n e )





Polymers from substituted derivatives of ethylene containing 2 timesthe original vinyliden name: poly + name substituted vinyliden

. u n c t i o n a l g r o u p p o l y m e r : prefix poly then called f u n c t i o n a l g r o u p n a m e

xample polyester, polyamide, polyuret h an e

CH 2 C

n

CH 2 C

CN

n

polyvinyliden clorua

polyvinyliden xianua

CN

Cl

Cl





Classifylassify

Depend on diferent actorsDepend on origin: natural ( rubber, cellulose, pro de,…) and synthesis ( nylon, te on,…)

Depend onthe composi on

Carbon chainOdd chain: he chain is

ormed rom carbon andsome elements! ",O,#,$

%norganic polymer: &ainchain is orm by inorganicelements





• 'omopolymer: Homopolymeas the polymer is formedfrom a monomer

• Copolymer: Copolymers arepolymers formed from two ormore different monomers.

Depend on the component o the chain





Physical Propertyhysical Property

/ h e m o s t b a s i c p r o p e r t y o f a p o l y m e r i s t h e i d e n t i t y o f i t s

c o n s t i t u e n t m o n o m e r s

s e c o n d s e t o f p r o p e r t i e s , k n o w n a s m i c r o s t r u c t u r e ,

e s s e n t ia l l y d e s c ri b e t h e a r r a n g e m e n t o f t h e s e m o n o m e r s

w i t h i n t h e p o l y m e r





0 o l y m e r s h a v e l a r g e m o l e c u l e w e i g h t

o l u t i o n s o f p o l y m e r h a v e h i g h v i s c o s i t y

o t e /o k n o w t h e p h y s i c a l p r o p e r t y o f p o l y m e r o b v i o u s l y, w e

m u s t u n d e r s t a n d t h e p h a s e b e h a v io r



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2elting pointel t ing point

o t a s o l i d - li 3 u i d p h a s e t r a n s i t i o n b u t a t r a n s i t io n f r o m a c r y s t a l l i n e

p h a s e t o a s o l i d a m o r p h o u s p h a s e - m e l t in g p o i n t , / m

! e p e n d o n / m , w e c l a s s if y p o l y m e r s i n t o t h e r m o p l a s t i c s 4 t h e r m o s e t t i n g

p o l y m e r s






/hermoplastichermoplastic# s a p o l y m e r b e c o m e a l i 3 u id w h e n h e a t e d a n d h a r d

w h e n c o o l e d

5 a n b e e a s i l y r em e l t e d a n d m o u l d e d

r e h i g h - m o l e c u l e w e i g h t p o l y m e r

5 h a i n s a r e a s s o c i a t e d e a c h o t h e r b y 6a l d e r 7 al l

f o r c e s , d i p o l e - d i p o l e i n t e r a t i o n , h y d r o g e n b o n d i n g

e m a i n m a n y s h a p e s

5 a n b e b r a n c h o r s t r a i g h t c i r c u i t






o m e t h e r m o p l a s t i c d o n o t c r y s t a l l i" e ( f o r m a m o r p h o u s p l a s t i c )

l e s s c h e m i c a l r e s i s t a n t

/ h e r m o p l a s t i c w i l l c r y s t a l l i " e t o a c e r t a i n e t e n t ( s e m i - c r y s t a l l i n e )

m o r e r e s i s t a n t t o s o l v e n t s a n d o t h e r c h e m i c a l s






1ome thermoplasticsome thermoplastics

0 p o l y a m i d e

0 o l y a c r y l a t e

0 B ! p o l y b u t a d ie n e

0 p o l y e t h y l e n e

0 p o l y s t y r e n e

0 6 p o l y v i n y l a c e t a t e






/hermosettinghermosetting7 h e n h e a t e d b e c o m i n g h a r d e r






5haracteristicsharacteristics5 a n n o t b e r e m e l t e d o r r e m o u l d e d

5 e r t a i n r e g u l a r s h a p e

9 i g h h a r d n e s s d u e t o c r o s s - l in k

l m o s t h a r d n e s s a n d b r i t t l e

stress

thermosetting Cross-link






Boiling pointoiling point

/ b s t r o n g l y d e p e n d e n t o n c h a i n l e n g t h

9 i g h p o l y m e r s d o n o t e h i b i t a b o il in g p o i n t b e c a u s e t h e y d e c o m p o s e

b e f o r e r e a c h i n g t h e o r e t i c a l b o i l i n g t e m p e r a t u r e s

. o r s h o r t e r o l i g o m e r s , / b m a y b e o b s e r v e d a n d w i l l i n c r e a s e r a p id l y a s

c h a i n l e n g t h i s i n c r e a s e d






: lass transition temperaturelass transition temperature/ h e t e m p a t w h i c h p o l y m e r s c h a n g e f r o m a c r y s t a l li n e s o l i d t o a

b r i t t l e , g l a s s y a m o r p h o u s s o l i d - / g






(1)- Crystalline material(2)-Polymer






1trength

• 5ritical length needed beforestrength increases

•9ydrocarbon polymers averageof 1%% repeating units necessarybut only ;% for nylons

• /ensile strength measures the

forces needed to break apolymer






5hemical properties of polymerhemical properties of polymer

e a c t i o n m a i n t a i n p o l y m e r c i r c u it

Polivinyl alcolPVA






e a c t i o n c u t s p o l y m e r c i r c u i t

9ydrolysis polyester

9ydrolysis polypeptide or polyamide

0yrolysis polysterene

Q





5 i r c u i t c o n n e c t i o n r e a c t i o n

6ulcani"ation rubber << << <<

Bakelide resin

Q





1ynthesisynthesis

r e a c t i o n i n w h i c h m a n y m o n o m e r u n i t s

c o m b i n e d i n t o a l a rg e m o l e c u l e

n = ( ) n =

Polymerization





. ree radical polymeri"ationree radica l polymeri"ation

r e a c t i o n t o f o r m p o l y m e r f r o m m o n o m e r s th a t c o n t a i n d o u b l e b o n d ( 5 > 5 )

2 e c h a n i s m

# n i t i a t io n ? @

: r o w c h a i n

? 2 2

?

/ e r m i n a t i o n 2 ? 2 2 - 2

2

?

2 -

?

-





Synthesis PMMASynthesis PMMA

# s a c l e a r A p l as t i c , u s e d a s a s h a t t e r p r o o f r e p l a c e m e n t f o r g l a s s

0 2 2 i s m o r e t r a n s p a r e n t t h a n g l a s s





8eaction


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Mechanism

Initiators: V59 -2,2'-Azodi(2-methylbutyronitrile )WWW.FACEBOOK.COM/DAYKEM.QUYNHON WWW.DAYKEMQUYNHON.UCOZ.COM




Emulsion polymerizationEmulsion polymerization

' a t e i s t h e s t a b l e d i s p e r s i o n ( e m u l s i o n ) o fp o l y m e r m i c r o p a r t i c l e s in a n a 3 u e o u sm e d i u m

' a t e i s u s e d i n c o a t i n g s a n d g l u e s b e c a u s et h e y s o l i d i f y

b y c o a l e s c e n c e o f t h e p o l y m e r p a r t i c l e s a s t h ew a t e r

e v a p o r a t e s , a n d t h e r e f o r e c a n f o r m f i lm sw i t h o u t r e l e a si n g p o t e n t i a ll y t o i c o r g a n i cs o l v e n t s i n t h e e n v i r o n m e n t





m o n o m e r i s d i s p e r s e d o r A e m u l s if i e d A in a s o l u t i o n o f s u r fa c t a n t

a n d w a t e r f o r m i n g r e l a t iv e ly l a r g e d r o p l e t s o f m o n o m e r i n w a t e r

c e s s s u r f a c t a n t c r e a t e s A m i c e l l e s A i n t h e w a t e r

m a l l a m o u n t s o f m o n o m e r A d i ff u s e At h r o u g h t h e w a t e r t o t h e

m i c e l l e

w a t e r -s o l u b l e i n i t i a t o r i s i n t r o d u c e d i n t o t h e w a t e r p h a s e

w h e r e i t r ea c t s w i t h m o n o m e r i n t h e m i c e l le s

Theory





2 e c h a n i s me c h a n i s m





Copolymerizationopolymerization

5 o p o l y m e r i " a t io n i s a p o l y m e r i " a t io n

o f t w o o r m a n y d i f fe r e n t m o n o m e r s

/ h e r e a c t i o n i s u s e f u l f o r im p r o v i n g

p r o p e r t i e s o f p o l y m e r w i t h u s a g e

p u r p o s e





5opolymeri"ation of 1B8opolymeri"ation of 1B8' i m i t 0 i s s t a b l e w i t h h i g h t e m p b u t it i s b r i t t l e a n d h a r d l y d y e

v e r c o m e ! e c r e a s e b r i t t l e p r o p e r t y, w e c o p o l y m e r i " a t i o n t y r e n e w i t hB u t a d i e n e





!efinit ionefinition

2 a n y s m a l l m o l e c u l e s ( m o n o m e r s ) a re c o m b i n e d w i t h e a c h o t h e r t o

f o r m l a r g e r m o l e c u l e s a n d l i b e ra t i o n w a t e r v a p o u r

a c h s m a l l m o l e c u l e h a s t o c o n t a i n a t l e a s t d i f f e r e n t t w o f u n c t i o n a l

g r o u p s


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1ome e)amples aboutome e)amples aboutcondensation reactionsondensation reactions

Zerol resin

axit ε-aminocaproicNilon – 6 (capronsilk

!akelide resin





5ommon characteristicsommon characteristics

b t a i n e d p o l y m e r s h a v e h i g h # p f a c t o r ( h i g h d i s p e r s i o n )

5 a n b e b r a n c h o f f o r t h r e e - d i r e c t i o n a l

5 o n t a i n f u n c t i o n a l g r o u p s a t t w o s i d e s o f c i r cu i t





5lassificationlassification

/ wo - d i r e c t i o n c o n d e n s a t i o n , t h r e e d i r e c t i o n ( m o r e t w o f u n c t i o n a l

g r o u p s )

9 o m o g e n e o u s a n d u n - h o m o g e n e o u s c o n d e n s a t i o n ( t w o t y p e o f

m o n o m e r s s o l u b l e e a c h o t h e r )

5 o n d e n s a t io n b e t w e e n t w o t y p e s o f m o n o m e r s e a c h o t h e r





Basic type of reactionsasic type of reactions

. o r m i n g c o - p r o d u c t s r e a c t i o n k i n d m a k e s c h a n g e m o l e c u l a r

s t r u c t u r e

9 @ ( 5 9 @ ) 5 9 ? 9 9 ( 5 9 @ ) 5 9

9 @ ( 5 9 @ ) n = 5 = = ( 5 9 @ ) n = 5 9 ? 9 @

e a c t i o n f o r m s 0 o l y a m i d e " H





Reaction to form PET ( PolyethyleneTerephthalate





o t f o r m i n g c o - p r o d u c t s n o t m a k e s c h a n g e m o l e c u l a r s t r u c t u r e

n 9 ( 5 9 @ ) ; 9 ? > 5 > ( 5 9 @ ) C > 5 >

- - ( 5 9 @ ) ; = 5 = = ( 5 9 @ ) C = = 5 - -

y n t h e s i s r e a c t i o n s f r o m c o m b i n e f r e e o r i g i n s

? =< <

< <

n

"H H"n





1wellwell

w e l l i s p r o c e s s t h a t s o l v e n t p e n e t r a t e s i n t o p o l y m e r s

/ wo s w e l l c r i t i c a l s w e l l , n o n c r i t i c a l s w e l l


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.actors affect to swell andactors affect to swell andsolubili ty of polymerolubili ty of polymer

a t u r e o f p o ly m e r a n d s o l v e n t

0 l a s t i c it y o f p o l y m e r s

/ e m p e r a t u r e

2 o l e c u l e w e i g h t

5 r o s s l i n k





5ondensation reaction occurondensation reaction occuron the surface divided phasen the surface divided phase

2 o n o m e r s i s n o t s o l u b l e e a c h o t h e r

5 o - p r o d u c t s e s c a p e a n d d i s p e r s e i n t o w a t e r e n v i ro n m e n t

0 o l y m e r i s s e l e c t e d d i r e c t l y f r o m r e a c t i o n m e d i u m

c c u r r i n g 3 u i c k l y, r o o m t e m p


0reparation between copolymer andreparation between copolymer andWWW.DAYKEMQUYNHON.COM



0reparation between copolymer andreparation between copolymer andcondensation reactionondensation reaction

Copolymer

Concentration of monomers

red#ce $rad#ally d#rin$ reaction.

%olymers is esta&lished instantly

and ' w little chan$e in reaction.he lon$er reaction time spends)

the hi$her efficiency is o&tained.

Components only contain

monomers) polymers.

%rod#cts do not contain water.

Need a$ent to create free

elements

Condensation

'onomers do not maintain at

first period of reaction.

' w increases with reaction time.

*eaction need stretch.

Components contain many

types of different intermediate

molec#les.

%rod#cts contain water.

+o not need.





Block average moleculelock average moleculeweighteight

' n ,Σ Ni.' i

Σ Ni

i ,Ni.' i

Σ Ni. i

' w , Σi.' i

p ,' w

' n

p coefficient/ Characteristic for dispersi&ility of polymeWWW.FACEBOOK.COM/DAYKEM.QUYNHON WWW.DAYKEMQUYNHON.UCOZ.COM




Application of polymerpplication of polymer






Application ofWWW.DAYKEMQUYNHON.COM



Application ofThermoplastics






A li i f Elli ti f El tWWW.DAYKEMQUYNHON.COM



Application of Elastomerspplication of Elastomers






Application of Thermosetspplication of ThermosetsWWW.DAYKEMQUYNHON.COM



Application of Thermosetspplication of Thermosets





rganic 0olymer chemistry

1ummary

Preparation methods

ppl icat ionsonmenclature

2odern f ield in thefuture

Characteristics

0hysicalpropert ies





8eferenceseferencesD B E 9 3 u o c g i a /0 9 5 2 - 9 o a 9 o c v a 9 o a ' y 0 o ly m e r

w w w g o o g l e t h e r m o p l a s t i c c o m

w w w g o o g l e t h e r m o s e t t i n g c o m

w w w g o o g l e t h e r p l a s t i c a n d t h e r m o s e t t i n g c o m

w w w g o o g l e c o n d e n s a t i o n r e a c t i o n c o m

w w w g o o g le c h e m i c a l p r o p e r t i e s p o ly m e r c o m





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Organic Polymer Chemistry

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