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Polymerization Reactions

Polymerization = Reaction to convert monomers to a polymer. Two types of polymerization reaction: Step-Growth Polymerization (Old = Condensation Polym.) applies to monomers with functional groups such as: -COOH, -COOR, -COOOC-, -COCl, -OH, -NH2, -CHO, -NCO, epoxy. Chain Polymerization (Old = Addition Polym.) applies to monomers having double bonds or ring structure. Both classes of reaction can lead to the formation of either linear polymers or polymer networks. Whether the linear chains or polymer networks are obtained only depends on the number of reactive entities per monomer.

Molar Mass Distribution

Molar Mass Average and Molar Mass Distribution depend on the type of polymerization reaction. Step-Growth Polymerization Mn < 30,000 usually Mw / Mn 2 Chain Polymerization Mn > 50,000 usually Mw / Mn = 1.01 50

Step-Growth Polymerization:
Basic Reactions
Condensation: coupling reaction with loss of small molecule example: (with monofunctional molecules) CH3-NH2 + HOOC-CH2-CH3 Amine + Acid = CH3-NH-CO-CH2-CH3 + H2O Amide + Water

Addition: coupling reaction without loss of small molecule example: (with monofunctional molecules) CH3-N=C=O + HO-CH2-CH3 Isocyanate + Alcohol = CH3-NH-CO-O-CH2-CH3 Urethane

Step-Growth Polymerization:
In step-growth polymerization, a linear chain results from the stepwise condensation or addition of reactive groups of bifunctional monomers. A A+B A B B ( ( D D )n )n

Polyesters: D = -COOA = -COOH, -COCl, -COOR, -COOOC- and B = -OH Polyamides: D = -CONHA = -COOH, -COCl, -COOR, -COOOC- and B = -NH2 Polyurethanes: D = -NHCOOA = -NCO and B = -OH

Step-Growth Polymerization:
The step-growth reaction proceeds through formation of dimers, trimers, tetramers, etc, reactions that are identical in rate and mechanism.

Since these reactions are equilibrium reactions, high molecular weight polymer chains will be obtained if the equilibrium is displaced towards the formation of products. This can be achieved by stripping through distillation the low molecular weight condensation products that may form during the reaction (H2O, CH3OH, etc,...).

Relation Between Chain Length and Extent of Reaction

W.H. Carothers determined a relationship between xn the number average chain length (number of repeat units) and the extent of reaction, p for step-growth polymerization reactions. Consider the polymerization of A-X-B, assuming N0 molecules at t = 0, then the extent of reaction at time t is defined by: p = (N0-N)/ N0 where N is the number of molecules at time t. Since xn is given by xn = N0/N (number of monomers per molecule), then the Carothers equation is written as: Note for the case of HOOC-(CH2)5-NH2 p = 0.9 xn= 10 Mn = 1,310 g.mol-1 p = 0.95 xn = 50 Mn = 6,550 g.mol-1 p = 0.99 xn = 100 Mn = 13,100 g.mol-1 p = 0.999 xn = 1000 Mn = 131,000 g.mol-1

xn = 1/(1-p) Mn = M0 xn

Step-Growth Polymerization:
Similar treatment can be applied to the polymerization of A-X-A with B-Y-B. One must now consider that the initial number of molecules is 2N0. (N0 of A-X-A and N0 of B-Y-B). The same Carothers equation applies. If the molar mass is to be controlled very accurately, one needs to work with extremely pure monomers and add either monofunctional groups or an excess of one of the monomers. This can be expressed by an extension of Carothers equation: xn = (1+r) / (1+r-2rp) where r is the ratio of the number of molecules of the reactants. For a reaction with p = 0.999 and r = N(A-X-A)/N(B-Y-B) = 1/1.05 Therefore xn = 39 (as opposed to xn = 1000 if r = 1.0)

Step-Growth Polymerization:
Variation in xn with p

Variation in xn with the stoichiometric ratio r for p = 1.0 and p = 0.998

Number and Weight Fraction Distribution During Step-Growth Polymerization

1) p = 0.96 2) p = 0.9875 3) p = 0.9950

Mn = M0/(1-p) Mw = M0 (1+p)/(1-p) Mw/ Mn = 1+p

Step-Growth Polymerization
+ Thermosetting Polymers: one of the monomers has a functionality higher than 2 !!

+ F=3 F=2

Commercial Step-Growth Polymers

Polycaprolactam: Nylon-6 Poly(decamethylene carboxamide): Nylon-11 Poly(hexamethylene adipamide): Nylon-6,6 Poly(p-phenylene terephthalamide): KevlarTM Poly(ethylene terephthalate): PET: MylarTM Poly(ether ether ketone): PEEK: VictrexTM Polyurethane: PellethaneTM Poly(ether imide): ULTEMTM Epoxy, Silicone, Polycarbonate, Polyurea, Polyanhydride, etc.

Chain Polymerization
Polymer chains can also be formed by simple addition of monomers having double bonds. These monomers are also bifunctional but the mechanism of polymerization is very different from that encountered in step-growth processes. Chain polymerization proceeds by the succession of three steps: Initiation: The first active center (radical, anion or cation) is formed and the growth of the chain is initiated. C = C C+ - C- C - C. Propagation: Growth of the polymer chain occurs by the successive addition of monomers to the active center at the end of the chain. Termination: Growth is terminated by either neutralization or transfer of the active center.

Chain Polymerization Mechanism

I J* (radical, cation, anion) J* + H2C = C(RR) J-CH2-C*(RR)

J-CH2-C*(RR) + H2C = C(RR) J-CH2-C (RR)-CH2-C*(RR) J-[CH2-C (RR)]n-CH2-C*(RR) + H2C = C(RR) J-[CH2-C (RR)]n+1-CH2-C*(RR)

--- CH2 - C*(RR) + C*(RR) - CH2 ---a) --- CH2 - C (RR) - C (RR) - CH2 ---b) --- CH = C (RR) + HC(RR) - CH2 ---Combination Rxn. Disproportionation Rxn.

Whether the polymerization of a given monomer proceeds by the free radical, anionic or cationic mechanisms, depends on the chemical structure of the monomer (steric and electronic effects).

Molar Masses and Distributions

Chain polymerization potentially leads to very high molar mass polymers (up to 107 g/mol). Molar mass builds up very fast once a chain is initiated. At any time during polymerization, there is coexistence of high molar mass polymer and monomers. There is steady decrease in monomer concentration during polymerization. There is no typical molar mass distribution as in the case of stepgrowth. Anionic can (when living) give rise to very narrow molar mass distribution (Mw/Mn ca. 1.02 - 1.10). Cationic generally leads to broader molar mass distributions. Radical processes generally lead to polydispersity index (Mw/Mn) around. 2.0 or greater, except for recently unveiled radical living processes.

Chain Polymers
High Density Polyethylene: HDPE Low Density Polyethylene: LDPE Linear Low Density Polyethylene: LLDPE Constrained Geometry Catalyst Polyethylene: CGC PE Isotactic Poly(propylene): It-PP Ethylene/Vinyl Acetate Copolymers Poly(vinyl chloride): PVC Polystyrene: PS Poly(methyl methacrylate): PMMA Poly(vinyl acetate): PVAc Poly(acrylonitrile): PAN Polybutadiene Polyisoprene Polychloroprene Styrene-Butadiene-Styrene: SBS Polytetrafluoroethylene: PTFE Poly(oxymethylene): POM Poly(ethylene oxide): PEO Poly(tetramethylene oxide): PTMO

Commercial Polymers
U.S. Production in 1990 : (from Chemical & Enginnering News, 06/24/91) Plastics: A. Thermoplastic Resins B. Thermosetting Resins Synthetic Fibers: A. Cellulosics B. Non-cellulosics Synthetic Rubbers:

46.3 billion lbs 6.4 billion lbs

0.5 billion lbs 8.2 billion lbs 4.7 billion lbs

Important Monomers
Ethylene: 37.5 billion lbs @ $0.23 = $8.6 billions 80% used for PE, PVC and PE copolymers, cracking of hydrocarbons Propylene: 22.1 billion lbs @ $0.18 = $4 billions 28% for it-PP, P(EP), PP copolymers 16% for acrylonitrile synthesis (PAN) 14% for propylene oxide synthesis (PPO) Vinyl Chloride: 10.7 billion lbs @ $0.24 = $2.6 billions oxychlorination of ethylene >90% polymer production (PVC and copolymers) Styrene: 8.0 billion lbs @ $0.41 = $3.2 billions Dehydrohalogenation of ethylbenzene. >90% polymer production (a-PS) Terephthalic Acid: 7.7 billion lbs @ $0.41 = $3.2 billions (tires, clothing, films, bottles) oxidation of p-xylene. >95% used for PET

Packaging accounts for a third of thermoplastics use

Exports 12% Transp. Equip. 4%

Others 14%

Packaging 32%

Furniture, Furnish. Electrical Consumer Equip. 5% Products 6% 13%

Building 14%

1989 sales and captive use: 46.3 billion lbs

Building and construction account for two thirds of thermosets use.

Consumer Electrical Prod. Equip. Others 4% 11% 4% Adhes., Inks, Coatings 4% Transp. 8% Building 69%

1989 sales and captive use: 6.3 billion lbs

Summary: Polymerization Reactions

Chain Growth Addition Rapid addition of monomers to a small number of active centers. Decreases slowly during reaction. Step-Growth Rapid coupling of any two species (monomer, oligomer, polymer). Decreases rapidly before any high polymer is formed. Present at low Is only present at very conversion. high conversion. May be very high Is usually low (102-105) (<103) Initially, rises to a Is maximum as the start maximum, remains and decreases continously constant, then drops. till p reaches its maximum.

Monomer Concentration High MW Polymer Mean Degree of Polymerization Polymerization Rate