Copolymerization

Tra Vinh university – DA09HHTeacher: Luu Thuy Quyen

Group 3Du Hue DungTran Van Hoa

Trương Hoang NamNguyen Thi Cam Nhung

Pham Thi Ngoc QuyenVu Thi Yen

Outline • Kinetics of copolymerization• The Q-e scheme• Commercial• Block copolymers• Graft copolymers• Elastomers• General information on block and graft• Polymer mixture – IPNs, composites, blends, and alloys• Dendrites • Ionmmers• Summary • References

Copolymerization

ABS resins

Copolymerization

• Copolymer is a polymer derived from two (or more) monomeric species, as opposed to a homopolymer where only one monomer is used.

Kinetics of copolymerization

• When having radicals, two reactions occur:R• + M1 M1

•

R• + M2 M2•

• Propagation have four basic equations:M1

• + M1 M1•M1 R11 = k11[M1

•][M1]M1

• + M2 M1•M2 R12 = k12[M1

•][M2]M2

• + M1 M2•M1 R21 = k21[M2

•][M1]M2

• + M2 M2•M2 R22 = k22[M2

•][M2]

Kinetics of copolymerization

• After time is t:– Disapearance of M1:

– Disapearance of M2:

(9.1)

(9.2)

Kinetics of copolymerization

• In steady state: ⇒ The ratio of disappearance of monomers M1/M2

is:

(9.3)

(9.4)

Kinetics of copolymerization

(9.5)

Kinetics of copolymerization

Division by k21:

(9.6)

Kinetics of copolymerization

Substitution of r1 = k11/k12 and r2 = k22/k21 and cancellation of [M2

•]:

(9.7)

Kinetics of copolymerization

(9.8)

Kinetics of copolymerization

(9.9)

n: composition ratio of monomer M1, M2 in copolymer.x = [M1 /M2 ]: composition ratio of monomer in initialr1,r2 : reactivity ratios

M1 M2 R1 r2 r1r2

Acrylamide Acrylic acid 1.38 0.36 0.5

Methyl acrylate 1.30 0.05 0.07

Vinylidene chloride 4.9 0.15 0.74

Acrylic acid Acrylonitrile (500 C) 1.15 0.35 0.40

Styrene 0.25 0.15 0.04

Vinyl acetate (700 C) 2 0.1 0.2

Acrylonitrile Butadiene 0.25 0.33 0.08

Ethyl acrylate (500 C) 1.17 0.67 0.78

Maleic anhydride 6 0 0

Methyl methacrylate 0.13 1.16 0.15

Styrene 0.04 0.41 0.16

Vinyl acetate 4.05 0.06 0.24

Vinyl chloride 3.28 0.02 0.07

Butadiene Methyl methacrylate 0.70 0.32 0.22

Styrene 1.39 0.78 1.08

Table 9.1: Typical Free Radical Chain Copolymerization Reactivity Ratios at 600 C

Kinetics of copolymerization

• Example: copolyrization of acrylic acid and styrene. Composion ratio of this monomers is 1:1.

= 1.09 Product is a acrylic - rich copolymer in which there

would be 12 molecules of acrylic acid to every 11 molecules of styrene in polymer chain.

Kinetics of copolymerization

v Tendencies of copolymer:v r1 < 1 (k11 < k12) or r1 0v r2 < 1 (k22 < k21) or r2 0v r1 = 1v r2 = 1v r1 > 1, r2 < 1: monomer 1 richer than copolymerv r2 > 1, r1 < 1: monomer 2 richer than copolymerv r1 > 1 v r2 > 1

Homopolymers or

Q-e scheme

• Predicting r1 and r2 values for radical copolymerization.

• Be proposed by Alfrey and Price in 1947.• Similar to Hammelt equation, except no limit

to substituted aromatic compounds.

Q-e scheme

• Two factors effect to rate of reaction:- The activity of free radicals.- The polarization of compound in the state

transition.→ Are specific by Q-e scheme.

Q-e scheme

• In Q-e diagram:- P is specific reactivity of free radical- Q is specific reactivity of monomer by

experiment.- Polarization of monomer and free radical is

designed by e.• Styrene, with Q and e values of 1.00 and -8.00,

is used as the comparative standard.

Q-e scheme

• Higher Q values indicate greater resonance stability.

• Higher e values (less negative) indicate greater electron-withdrawing power of the alpha substituent on the vinyl monomer.

Q-e scheme

• Example: Butadiene has Q value is 2.08 more reactive

than Styrene that has 1.00 of Q value.

Monomer Q e

Benzyl methacrylate 3.64 0.36

Methacrylic acid 2.34 0.65

Isopropyl methacrylate 1.20 -0.15

P-Nitrostyrene 1.04 -0.32

Styrene 1.00 -0.80

m- Methylstyrene 0.91 -0.72

Methyl metharcrylate 0.74 0.40

Vinyl Chloride 0.044 0.20

Vinyl acetate 0.026 -0.22

Table 1. Typical Q and e values for monomer

Q-e scheme• The Alfrey- Price equation: k11 = P1Q1 e-e

12

k12 = P1Q2e-e1e2

Therefore: r1 = (k11/k12) = (Q1/Q2)e-e1(e1-e2). K22= P2Q2e-e

22

k21= P2Q1e-e1e2

r2 = (k22/k21) = (Q2/Q1)e-e2(e2-e1)

r1.r2 = e-(e1-e2)2

Q-e scheme

Meaning of equation:• Indicate the relationship of reactivity and

resonance effect of free radical M1•.• Composition of copolymer formed is

influenced by the polarization of two monomer M1 and M2.

Q-e scheme • Example: Predicting the ability copolymer of acrylonitrile and

methyl methacrylate? Calculate r1 and r2 of two couple: Styrene-acrylonitrile and styrene-

methyl methacrylate.ü Styrene-acrylonitrile: Q1=1, e1=-0.8; Q2=0.6, e2= 1.20 → r1 =

0.33.ü Styrene-methyl methacrylate: Q1=1, e1=-0.8; Q2=0.74, e2=0.4 →

r2 = 0.46.► Alternating copolymer.

Commercial copolymer

• Vinylite: Copolymer of vinyl chloride and vinyl acetate.

• Vinoflex: Copolymer of vinyl chloride vinyl isobutyl ether.

• Vinyon: Copolymer of vinyl chloride and acrtlonitrile.

• Pliovic: Copolymer of vinyl chloride and vinylidene chloride.

Commercial copolymer

• Saran: Copolymer of vinylidene chloride and vinyl chloride.

• SBR: Copolymer of styrene and butadien.• EPMs: ethylene-propylene copolymer.• EPDMs: Polymerizing ethylene, propylene

and small amount (3-9%) of Ziegler-Natta catalysts.

Driving force

• Various contributing especially to tertiary and quaternary.

• Major factors appear to be combinations of phillic and phobic forces and periodicity.

• By varying the nature of the partical blocks, combination of coils, chain-extended or chain-folded crystallites and double helices achieved.

Miscibility Mixing

• Mixing that is generally driven by entropy factors.

• Example: The miscibility of multicomponent systems

decrease as rigidity of one of the components increases.

Miscibility Mixing

• Enthalpy effects is only overcome when entropy are sufficient to overcome this tendency of a molecule to associate with itself.

Block copolymers

• Are one of types of copolymers.• Don’t occur naturally.• Have been synthesized by all know

polymerization techniques.

Block copolymers

Block copolymers

Block copolymers

• Consisting of hydrophilic and lyophilic segments• Being an excellent surfactant.

C C O

H

H

H

H

* C C O

H

H

C H 3

H

C C O

H

H

H

H

*

2 0 + 2 0 + 2 0 +

A B A c o p o ly m e r o f e th y le n e o x id e a n d p ro p y le n e o x id e

Block copolymers

Micelle

Hydrophilic portions

Hydrophobic

portions

Spandex• Soft segment is composed of poly(ethylene oxide)

chains – contains 2 hydroxyl groups chain. • Hard segment is derived from the reaction of the

diisocyanate with the hydroxyl end groups forming polar urethane linkages.

HO OH O C N R N C O

O

C N R N C

O

O

Flexiblepolyester orpolyether Diisocyanate

Flexible block copolymer

Block copolymers

Poly(ethylene oxide)• Made from ethylene oxide through a base

catalyzed ring-opening polymerization.• Uses:

§ In manufacture of polyurethane products§ Using as a surfactant, functional fluid,

thickener, lubricant, and plasticizer§ Used to make circuit boards

Block copolymers

Block copolymers

C

C

SiO*

C

CH3

SiO

C

C

SiO

CH3

CH3

SiO O

C

C

Si O *

CH3

Si O

CH3

CH3

Si O

nn n n n n

A

B C

A

BC

S iH O

C H 3

S i

O H

C H 3

C H 3

p-b is(d im ethy lhydroxysily l)benzene

S i O H

C H 3

C H 3

H O

n

+

po lyd im ethy lsiloxane

S i*

C H 3

C H 3

S i O S i O

C H 3

C H 3

n

C H 4

m

n-hexy lam ine-2 -e thy lhexoa te

Block copolymers

Block copolymers

Other siloxane block copolymer have made form:• Polysiloxanes and polyalkylene ethers• Polysiloxanes and polyarylene ethers• Polysiloxanes and polyvinyl compounds

Block copolymers

• The mechanical or ultrasonic degradation of a mixture of two or more polymersM1M1

. + M2M2. à M1 – M2

n m n + mMacroradical Macroradical BlockFrom Elastomer from copolymerMolecule plastic molecule

CC C C C C C C*

H

H

H

H

H H H

H

H

H

HH

n n

n

CC C C C C C C*

H

H

H

H

H H H

H

H

H

HH

n n

nH H

Block copolymers

Graft copolymers

The major difference is the position of chain extension.

Block copolymer Graft copolymer

Graft copolymers

Prepared by:• The reaction of ethylene oxide with these

polymers.• Polymerizing styrene by using Lewis acid in

the presence of poly-p-methoxystyrene.

Graft copolymers

H2C CH

styrene

C C C C

H

H

H

Cl

H

H

H

Cl

AlCl3C C C C

H

H

H

Cl

H

H

H

CH2HC

Graft copolymers

C C

Cl

Poly p-chlorostyrene

HH

HC

CHH2C

N

Acrylonitrile

Na

C C

HH

H

C

HCH2C

N

Graft copolymers

C C C C

H

H

H H H

H

H2C CH

CH3

Propylene

C C C C

H

H

H H H

H

H2CHC

CH3

Al(H)(C2H5)2

TiCl3

Graft copolymers

O

O

C CH

CH

C O

O

CH2

*

2

H2C CH

R .

O

O

C C C C O

O

CH 2

*

2

H 2 CHC

H H

H

ELASTOMERS

• Highly amorphous.• Highly random orientation.• High elongation.• There are 2 types: Thermoplastic elastomers (TPE). Thermoset elastomers (TSE).

TPE

• High copolymer.• Resiliency• Plasticity.• If heat was increase, It will be transfer from

hard to soft.

HARD SOFTheat

cool

TPE

• Some kind of TPE:ØSBS (Poly(styrene-butadiene-styrene)).ØPE (Poly Ethylene)ØPVC (Poly Vinyl chloride)ØPP (Poly Propylene)ØBR (Butadiene Rubber).

SBS ELASTOMER

• SBS is poly(styrene-butadiene-styrene).• Its hard rubber.• It’s a type of copolymer, a block tripolymers.• Its backbone chain make up three segment.

SBS ELASTOMER

SBS ELASTOMER

SBS ELASTOMER

THERMOSET ELASTOMERS

• The 3D structure polymer.• High copolymer.• Resiliency.• Plasticity.

THERMOSET ELASTOMER

• Polyester.• Silicone.• Melamines• Ureas • Phenolic.

Silicone

S O

C

C

H H

H H

H

H H

H

RECYCLING

• Thermoset elastomers are difficult to recycle.• Recycling can be accomplished thermoplastic

elastomers, rubber.

ELASTOMER PROCESSING

• Performing.• Molding.• Dipping.

Elastomers Processing

General information on block and graft copolymers

• Can not separated into components.• Each segment of the chain exhibit its own

characteristic properties.• Elastomeric fibers and thermoplastic

elastomers have been produced by controlling the size and flexibility of the domains in block and graft copolymers.

• Some of these high performance plastics are graft copolymer.

Polymer mixtures

• Polymer blends• IPNs• Composites• Alloys

• Polymers can be mixed and allowed to solidify.

• The mixing can give materials with properties similar to short sequenced copolymers or quite different.

• Compatible blends exist in a single phase and incompatible blends exist as two phases.

• At constant temperature: Gm = Hm + T Sm

Polymer Blend

• Immiscible polymer: Inability of a mixture to form a single phase.

• Miscible polymer: Capability of a mixture to form a single phase over certain ranges of temperature, pressure, and composition.

Polymer Blend

IPNs

• IPNs, interpenetrating polymer networks, are described by Sperling.

• An intimate combination of two polymers, both in network form.

• Where at least one of the two polymers is synthesized or/and crosslinked in the immediate presence of the other.

• But not covalently bonded to each other and cannot be separated unless chemical bonds are broken

IPNs

Similar a sponge cake soaking in warm ice and refreezing the ice cream, resulting in a desert.

Composites

• Consist of a continuous phase and a discontinuous phase.

• Consider as mixture on a macroscopic level.• Example :

Fiber – reinforced materials are the major type of commercial composite.

Plywood is a commonly encountered composite material.

Polymer alloys

• Polymeric material, exhibiting macroscopically uniform physical properties throughout its whole volume, that comprises a compatible polymer blend, a miscible polymer blend, or a multiphase copolymer

DENDRITES

Polymer type structure exists in the form of dendrites. These molecules act as buffers and building blocks of the copolymer varies depending on the uses for which synthesis.

DENDRITES

While some make adistinetion between dendrimers and hyperbranched polymer :

F Hyperbranched form under conditions that give variety but different structures.

F Dendrimers form one step at time giving afairly homogeneous product.

DENDRITES

• Dendrites are highly branched, usually curves, the structure, a branch exists a functional group to the molecule can react further. Dendrites have more unoccupied space so the application as adhesives, catalysts

DENDRITES

DENDRITES

The growth of dendrimer structure divided into two groups:

F Growth occurred outward from an inner core molecule. F Growth based on convergent.

DENDRITES

• Polymer spherical dendrites, different properties compared to other macromolecules. Denndrimer acts as a balloon no longer wiring harness. In the solution, viscosity increases as molecular weight increases to a point decreased viscosity but molecular weight increases

DENDRITES

Dendrites have a complex structure called a "star". We can develop a "star" based on chlorosilanes, example development on “star”: 3,12,18…

DENDRITES

The length can control when matter control is

added to react and properties hydrophobic / hydrophilic of system

IONOMERS

• Ionomer is a form of polymer containing 90% ethylene unit and remaining acrylic acid. These ions crosslinking by the metal atoms. Ionomer treated with thermoset, thermoplastic modified as they can through heat and pressure.

IONOMERS

• As with all polymer properties depend on the synthesis and catalytic materials: location, amount, nature and distribution of metal. industry has produced not been oxidation, where in addition to simple metal by heating preionomer

IONOMERS

Ionomer can sufonate formed rubber, hight melt viscosities, abrasion corrosion should be applied in many industries: cars, shoes, golf balls, electronic hardware…

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References

• http://140.138.140.197/991%E5%84%80%E5%99%A8%E5%88%86%E6%9E%90%E5%A0%B1%E5%91%8A/%E9%AB%98%E5%88%86%E5%AD%90%E7%89%A9%E6%80%A72/Synthesis%20and%20characterization%20of%20ABA%20block%20copolymer-based%20polymer%20electrolytes.pdf

• http://www.google.com/search?ds=i&pq=dimethyl+siloxane+structure&hl=vi&sugexp=kjrmc&cp=6&gs_id=17&xhr=t&q=ABA%20block&um=1&gs_sm=&gs_upl=&bav=on.2,or.r_gc.r_pw.,cf.osb&biw=1366&bih=667&wrapid=tljp1318759537157012&ie=UTF-8&sa=N&tab=iw

• http://plc.cwru.edu/tutorial/enhanced/files/polymers/struct/struct.htm

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