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2.

Synthesis of Polymers
Hatsuo Ishida Department of Macromolecular Science Case Western Reserve University 2.1. Step Polymerization 2.1.1. Condensation Polymerization 2.1.2. Polyaddition Polymerization 2.2. Addition Polymerization 2.2.1. Free Radical Polymerization 2.2.2. Ionic Polymerization A. Cationic Polymerization B. Anionic Polymerization

2.1.

Step Polymerization

2.1.1. Polycondensation Polymerization Polymeric materials are synthesized from small molecules called monomer with more than two reactive sites on the monomer. There are essentially two types of polymerization reactions. In condensation reaction (or step-growth polymerization), two reactants with degree of polymerization, m and n, combine to form their respective polymer. Polymers such as polyamides and polyesters can be prepared by condensation polymerization where small molecules are eliminated as polymer chains are formed. Condensation polymerization of this type is called polycondensation polymerization. General formula are shown below. or m (X-A-X) + n (Y-B-Y) = -[A-B]m+n- + 2 nXY n X-A-B = -[A]n - + nXY m-mer + n-mer = (m + n) mer Functionality 2 = Linear molecule: thermoplastics >2 = Crosslinkable: gel, thermosets Characteristics Repeat unit often not same as monomer structure Release of small molecules (H2 O, HCl, etc) Gradual growth of molecular weight Successive condensation reactions,coupling Relatively slow reactions Stoichiometric concerns

Examples Polyesters Polyamides Polyethers Polysiloxanes = = = = carboxylic acid + alcohol carboxylic acid + amine dehydration of diols condensation of silanols (SiOH)

Other polymeers made by condensation polymerization

Polycarbonate, polyetheretherketone, Kevlar, polyimides, poly(ethylene 370 6920 [2 [1 ]d gr I 3820 [0 end 0 1 173 1800 1260 3360 2820 1620 3180 2200 3420 2880 4980 4440 5505 2640 3240 4800 4260 3820 2700 5620 2360 5 1088 4 2660 11 3 776 1088 960 1400 3240 2928 2616 2660 1200 2800 3040 2 5560 28 1 DSt I 1080 2640 1260 2820 2200 40 1620 3180 3240 2700 4800 4260 5505 1800 1080 3360 2640 2040 2360 2200 3420 2880 4980 4440 3660 3980 3820 2560 5100 6280 1780 [31 1088 801088 776] 820] I20 1400 776 1400 3240 2616 2928 2800 1088] 1340] 2616] 2660] 3180] 2928] 3820 2 20 Ar 1743 1288 3303 2848 DSt chemdict 2848 3363 2908 4923 4468 5455 3180 5760 [6 1088 826 DSt 1350 3190 2928 2666 2660 3360 11 2697 1137 begin 10 [33 1592 3152 3152 3212 2757 4772 4317 5455 2240 9I 8 2560 1088 SP 826 72800 1350 3190 2666 2928 2420 I 3180 2928 ] ] 391400 DSt Ar /bs[[2 [34 DSt I [12 5100 0 1260 I 2040 2928 1400 1088 DSt1620 [35 DSt I [1 14 62 terephthalate) (PET) %w userdict/chemdict L/gr/grestore L/tr/transform xl pp l SA RA}{6 -1 st}b/OrA{py -8 py np gs fill e o cp 5 a wy dp 0 In x 6 0 2 bW dp/cY g -2 cw -1 CopyRight py 1 ChemDraw dp p cm fill pA sc -1 gr DA}{cw 8 m2 0 pp}{sqrt p 2 o 1 ix dv p l2 r lt{1 mv -9.6 -2 m 2 p s px sc mv cm 180 HA}{dL 0 gr}{pp}{gs -1 dp a}b/PT{8 sm o exec}{al s{dp dv m g dv mv dp rO dv o x -.6 WI py -1 sc exec sm 0 b2 neg lp st 12 xl wF np CA 5 p n 0 mv py 0 at p bd p LB sc 1.2 px gr neg 1986, m a}{ex 7 mv st p 2.25 e Laser 1 p l -9.6 m L/gs/gsave l arcn OA}{1 2 clip}b/Ct{bs p -1 gs ex pp aL p neg}if/py n l L/xl/translate cp np sl gr 0 at mv OB p wy m st}b/HA{lW l 12 0 o mv p 1 3.375 px 1 0 n/ex r 8 ro fill mv n gs 145 90 SA py 16.8 st}{0 np lp l 1987, 1 counttomark{bs Prep s wx ac sg OB/bL aR ix dp bW -1 bd px py sc e 0.3 gr ac px ro DA}{dL 0.6 rad 8 1 fill dict aL at 7 x m1 sc n 0 p cv SA dp end}b/Db{bs{dp DLB 0 eq{DD}{DS}ie py x -1 1 ey L/ie/ifelse Cambridge mt 1.2 gr p m bd ne{bW l 0 120 py 8 x dp rot -9.6 put sc m px DA}{cw m rO l}for m/w mv n/ey rad r -1 180 cm bW -1 ro 1.5 p 2 L/S{sf s p 0 b1 py g 0 CA ac chemdict 0 e dv tr/dy 0 1 l 0 -1 lt{-1 180 sm 21.6 bs 0 p st 2 SA -.6 aA a}ie}b/WW{gs x dp 5 0 a}ie}b/BW{wD py ac px 12 OA}{1 ne{bW 0 ldv}{bd}ie 5 sc np gr}{gs -1 dx rot p e st}{Asc cp L/ix/index m}b/dA{[3 DA}{dL s py m 8 p 6 Scientific 2.2 py m 0 1 x/dx 3 -8 g DLB 5 180 0 r n/dx l -1 g cm 360 a sc -1 2 lp sl dv px -1 0 16 begin/version gs 24.6 type[]type -1 p sqrt 2 4 12 r 2.25 neg}if/px ac gs p sm r arc x mv neg LB r py 0 dv/bd s gi 1 arc o 0 x sc s wF mv 2 0 OB 0 rO 180 0.5 SA CB dp 1 dy 3 gs al -4.8 st}{0 p Computing, 0 0.6 eq{DB}{DS}ie lW 90 L/l/lineto wD S]}b/dL{dA py SA gs e begin m ac 1 w l ac 1 cw pp DA}{2.25 CB 0.5 n/dy rev{neg}if sg 5 px 2 6 r x}if CA lp cW 2 1 sc DA}{cw 2.2 begin 16 px -1 25.8 rO eq{dp e dv -2 o -1 1 x fill sg m 0 py sg np s cX bs OA}{1 a setgray np[{py np 0 r x p wy p dp dv 24 r e fill gr 1 fill dv lp 16 lx 0 bW l mv s cv ne e L/mt/matrix lbs 0 0 o cm 0 wx rlineto cp cm 5 p def/b{bind 0 dp SA arc gr ac g/wb Inc. ly neg gr 0 sc}b/Ov{OrA 0 1 -1.6 n pp}{2 g o e -1 m l 0 rO 16 cm p p px w at sm 1 OA}{1.5 0 sm gs cY g 2 clippath gs ne{bW py sl l mv e sc ac l ac 3 2 eq{gs mt WI div x lp cm sm 27 1 ne 1.5 sc cm st cp px st}{Asc lW 4 m 270 0 bs cm e 1 bL s p ro gi gr}b/OB{/bS neg or{4 dup 1.6 0 fill}b/SA{aF sm w st}{px m py st p sm 0 2 SA l def}bind e L/mv/moveto SA dp tr 0 sm bd al cp p l fill AA}{1 p dv/bd gr put g/bb rO st cp py 27 DA}{270 e 1 wy st 2 l pp gs 1 l mv OA}{1 1 4 fill ZLB st}]e 0 rad neg 0 0.4 gr S r ac lW cm gr rO 0 g m 4.8 -1 a/py setgray o DT}]o 4 lt{pp 0 end px x -1 np setdash}d/cR 1 px x}if o w 2 cpt gs dv ac 1 def/L{load sc p e sm}b/CB{np -1 39 wb eq{dL}if SA 25.8 xl dv m 0 p sc r}if -0.4 xl}{xl ap x x py 0.5 cp gr}b/In{p 0 round CA 2 e 1 sc px 0 l s 4 4 3 lW OA}{1 wx a 180 0 rad L/m/m at mv S}if/lp 1 Bd pp g px st}{1.0 -1 g/cX ix ZLB lW DA}{1 cv sg 1 py -0.4 m/aL nH exec g pp ro}ie a/px gr}b pp 3 0 1 w r 6 AA 8 -2 2 fil ex lp g 3 ix d 1 3 r 0 p 4 n 2 o An xample of polycarbonate formation is shown below. currentpoint C H3 n HO C C H3 bisphenol-A C H3 O C C H3 polycarbonate 2.1.2. Polyaddition Polymerization Same condensation polymerization proceeds without liberating small molecules. This type of condensation polymerization is called polyaddition polymerization. In this type of polymerization, usually active hydrogen transfers from one molecule to the other as shown below in polyurethane reaction. Step polymerixation without elimination of small by-products Examples Polyurethanes = diisocyanates + diol Polyurethanes = diisocyanates + diamines OH + n COCl2 phosgen O O-C n currentpoint . + 2n HCl

19283746

currentpoint O=C=NC H2 -N=C=O + HO-(CH2)-OH ethyleneglycol O C H2 polyurethane 2.1.3. Carothers Theory Xn = No N where Xn = number average degree of polymerization No = number of molecules present initially N = number of molecules present after time, t N-C-O-(CH 2)2-O H n currentpoint

methylenediphenylisocyanate O C-NH

1928374

For each pair-wise reaction, number of molecules decreases by one: p = extent of reaction at time t = number of functional groups that have reacted = No - N numnber of functional groups present initially No

= probability that any functional group present initially has reacted Rearranging the above equation, No = 1 N 1-p Therefore, Xn = 1 1-p (Carothers Equation)

As p approaches 1 (complete conversion), Xn approaches infinity. For useful high polymer, stoichiometry. Mn = Mo Xn where p> 0.99 !! This demonstrates need for purity, efficiency,

Mo =

molar mass of repeat unit number of monomer units in repeat unit (usually 1 or 2)

For non-stoichiometric reactants Reactant ratio, r r = NA < 1 NB where NA, NB = number of functional groups present initially perfect stoichiometry r = 1

For linear molecule with two functional groups per molecule, No = NA + NB 2 Eliminating NA yields, No = NB(1 + r) 2

It is common to define extent of reaction, p, in terms of the functional group that is in minority (limiting reagent) (A in this case): After time t: number of unreacted A groups = NA - pNA = NA (1 - p) = rNB (1 - p) number of unreacted B groups = NB - pNA = NB (1 - rp) Thus, the number of unreacted molecules after time t is: N = rNB(1 - p) + NB(1 - rp) N (1 + r - 2rp) = B 2 2 NB(1 + r) 2
and

Substituting No = We obtain: Xn = 1+r 1 + r - 2rp (General Carothers Equation) N = NB(1 + r - 2rp) N into X n = o 2 N

If r = 1, Xn = 1 1-p (Carothers Equation)

Molecular weight control/engineering Intentional stoichiometric inbalances Addition of monofunctional compound: adds chain ends Addition of multifunctional compound: molecular weight grows faster with respect to p branched, gels Gel point When first network molecule is formed (or when the molecular weight becomes infinite) A viscous liquid becomes a solid gel (no tendency to flow) Network Forming Polymers (thermosetting resins) Example: phenolic resin, epoxy resin, unsaturated polyester resin Phenolic Resin i) Production of a prepolymer of low molecular weight ii) Prepolymer is forced to flow under elevated temperature and pressure to fill heated mold iii) Heating and/or addition of catalyst couses crosslinking to take place.....rigid polymer Resoles: OH + n HCHO base catalyst C H2OH heat catalyst C H2OH C H2OH OH C H2 OH OH OH C H2OH HOH2C , C H2OH C H2OH C H2OH etc

+ H2O

Further crosslinking reactions Novolaks

OH n + m HCHO acid catalyst

OH

C H2

OH

C H2

OH

C H2

OH

Hardners--usually amines Epoxy Resin C H3 C C H3 bisphenol-A O C H2-CHCH2O C H3 C C H3 O OH + ClCH2-CH-CH2 epichlorohydrin OCH2CHCH2O OH n C H3 C C H3 O OCH2CH-CH2 NaOH

HO

epoxy prepolymer, n=0,1,2,... Curing reactions O C H2-CH-CH2 O H2N-R-NH2 C H2-CH-CH2 Further curing reactions C H2 OH + C H2 OH O C H2 The condensation polymerization is the same as ordinary chemical reactions of small molecules except that the reactants have more than one reactive sites. As a result, a long chain or infinite molecular weight cross-linked polymer can be synthesized. If the reactivity of the reacting sites can be assumed equal, then the mole fraction for linear condensation polymers can be calculated. A-A + B-B = A- main chain -A or B-main chain-B A-B + A-B = A-main chain-B C H2 O CH2-CH-CH2 O CH2-CH-CH2 heat catalyst OH C H2 N-R-N C H2 OH C H2 OH OH C H2

Statistical Theory Carothers theory: number average quantities......simple statistics can predict whole picture. Step 1: predict p(x) Let us assume that each of the polymer molecules contains a total of x A groups. Then, we have, 1 unreacted A group at the end and (x-1) reacted A groups. AAAAAAAAAAAA.......AAAAAAAA* probability of finding the reacted A group probability of finding unreacted A* group = p = (1-p)

probability of finding 2 linkages = p2 probability of finding 3 linkages = p3 --------------------------------------------------------------------------probability of finding (x-1) linkages = p(x-1) Thus, the probability of finding the x-mer = (1-p) p(x-1

The probability of finding the x-mer is the same as the mole fraction ,Nx /N,of the x-mer. Nx = p(x-1) (1 - p) [1] N where, N Nx = total number of molecules present in the reaction media. = the number of molecules containing x A groups

Mn = P(x)Mx = xMo (1-p)p(x-1) = Mo (1-p) xp(x-1) Mathematically, it is known that:

xp(x-1)
x=1

= (1-p)-2 for p<1

Thus, Mn = Mo (1-p) (1-p)-2 = Mo (1-p)

Here Xn = Mn Mo Thus, Xn = Mo /(1-p) = 1 Mo (1-p)

This is the same as Carothers theory !! Step 2: find wx wx = = where Nx No Mo total mass of molecules of x monomer units long total mass of all molecules Nx (xMo ) No Mo = number of x-mers = number of total chemical repeat units = mass of one chemical repeat unit

From equation [1], Nx = N(1-p)p(x-1) = No (1-p)2 p(x-1) since Xn = No = 1 N (1-p) The following diagram shows the mole fraction of the x-mers.

The molecular weight of polymers has a profound effect on the physical and mechanical properties. The number average degree of polymerization can be calculated in the following manner. p = No - N = fraction of reacted A groups No By definition, the average degree of polymerization is, Xn = No N From equations [2] and [3], Xn = 1 1-p [4] [3] [2]

With a more involved calculation, the limiting case of the average degree of polymerization can be calculated as follows. Xn = 1 + r 1-r where r = NAo/NBo (stoichiometric ratio) Thus, if the r is 1 (stoichiometric), the polymer would have infinite molecular weight. If r reduces to 0.99 Xn reduces to 199, and for r = 0.95 Xn = 39. It is therefore extremely important for condensation reaction to start with highly purified materials if a large molecular weight is desired. Example Assuming that the polymerization is an irreversible polycondensation of a second-order, obtain the expression for conversion and number average degree of polymerization as a function of time. It is understood that the reactants stoichiometric. Kinetics of Step Polymerization Assumption: Equal reactivity of groups Rate of reaction d[A] d[B] = dt dt makes kinetic expressions simple only one k [5]

Most step polymerization are bimolecular: A + B So, d[A] = k [A][B] dt AB

We assume [A] = [B] = C Then, the above equation is: - dC = k C2 dt Boundary conditions: Co = C at time t Integrating the above differential equation:
C t

Co

- dC = C2

k dt
0

1 - 1 = kt C Co Rearranging yields, Co - 1 = ktC o C Here, Co = No = X n C N From the above two equations, Xn = Co kt + 1 Thus, the number average degree of polymerization increases linearly with time.

2.2.

Addition Polymerization

10

In addition polymerization (chain-growth polymerization), one monomer is added to the growing chain at a time. m-mer + monomer = (m + 1)-mer Characteristics Free radical Ionic: Anionic Cationic Living/Immortal Examples H2=CH2 ethylene H2=CH C H3 propylene F2C=CF2 tetrafluoroethylene C H2=CH styrene C H2=CH Cl vinyl chloride C H2=CH O C=O C H3 vinyl acetate H2C-CH2 n polyethylene H2-CH n C H3 polypropylene F2C-CF2 n polytetrafluoroethylene (Teflon) C H2 - CH

polystyrene C H2 - CH

n Cl poly(vinyl chloride) C H2 - CH O C=O

C H3 poly(vinyl acetate)

11

C H3 C H3 C H2=CH C H2 - CH n C=O C=O O O C H3 C H3 methyl methacrylate poly(methyl methacrylate) 2.2.1. Free Radical Polymerization

Addition polymerization can be initiated by free radicals. Free radicals are the molecules with unshared electrons. Well-known free radicals are by fragmentation molecules 285 4480 [2 [1 ]d gr [0 end 0 1 39 1125 3105 1515 2335 5485 5875 660 2640 5020 820 1270 3250 5630 2800 5180 5 1040 4 32 3 1040 1300 780 940 1040 1300 28 2 3420 1 40 I 820 2800 1515 2335 5180 5875 1125 820 1270 2800 3250 5180 5630 1125 3105 5485 1420 2460 5780 80 1040 780 780] 20 1300 780 820 1300] 1300 1040 780] 1300] 1040] 2 20 1096 Ar 3076 1565 2385 5456 5925 DSt chemdict 1096 2698 3076 5078 5456 /bs[[2 830 [6 830 940 11 1040 1250 847 0 2827 1565 2385 5207 5925 begin 10 660 830 9 1213 2827 3193 5207 5573 1040 8 830 820 SP 7 ] produced I1040 1250 ]2800 820 ]1300 1300 718 DSt [14 1040 Iof 1420 847 1250 1040 ]DSt [15 I 24 333 4780 [3 [1 ]d gr [2 end 2 31 1 1640 1540 2860 6160 6060 I 2040 1540 32 2400 2120 2420 2140 96 3880 2260 40peroxide 1830 1540 2860 6350 6060 80 2040 DSt 20 [3 2400] 2260] 2300] 2420] 2280] 2 20 I Ar 2860 chemdict /bs[[3 2300 2begin 2960 DSt [5 SP 2420 Iby 6060 3150 2280 2420] DSt 0 1 4 3{bs e g Db such as benzoyl and azobisisobytylnitrile homolytic scission (homolysis) of Bd}repeat a %w userdict/chemdict L/gr/grestore L/tr/transform xl pp l SA RA}{6 -1 st}b/OrA{py -8 py np gs fill e o cp 5 a wy dp 0 In x 6 0 2 bW dp/cY g -2 cw -1 CopyRight py 1 ChemDraw dp p cm fill pA sc -1 gr DA}{cw 8 m2 0 pp}{sqrt p 2 o 1 ix dv p l2 r lt{1 mv -9.6 -2 m 2 p s px sc mv cm 180 HA}{dL 0 gr}{pp}{gs -1 dp a}b/PT{8 sm o exec}{al s{dp dv m g dv mv dp rO dv o x -.6 WI py -1 sc exec sm 0 b2 neg lp st 12 xl wF np CA 5 p n 0 mv py 0 at p bd p LB sc 1.2 px gr neg 1986, m a}{ex 7 mv st p 2.25 e Laser 1 p l -9.6 m L/gs/gsave l arcn OA}{1 2 clip}b/Ct{bs p -1 gs ex pp aL p neg}if/py n l L/xl/translate cp np sl gr 0 at mv OB p wy m st}b/HA{lW l 12 0 o mv p 1 3.375 px 1 0 n/ex r 8 ro fill mv n gs 145 90 SA py 16.8 st}{0 np lp l 1987, 1 counttomark{bs Prep s wx ac sg OB/bL aR ix dp bW -1 bd px py sc e 0.3 gr ac px ro DA}{dL 0.6 rad 8 1 fill dict aL at 7 x m1 sc n 0 p cv SA dp end}b/Db{bs{dp DLB 0 eq{DD}{DS}ie py x -1 1 ey L/ie/ifelse Cambridge mt 1.2 gr p m bd ne{bW l 0 120 py 8 x dp rot -9.6 put sc m px DA}{cw m rO l}for m/w mv n/ey rad r -1 180 cm bW -1 ro 1.5 p 2 L/S{sf s p 0 b1 py g 0 CA ac chemdict 0 e dv tr/dy 0 1 l 0 -1 lt{-1 180 sm 21.6 bs 0 p st 2 SA -.6 aA a}ie}b/WW{gs x dp 5 0 a}ie}b/BW{wD py ac px 12 OA}{1 ne{bW 0 ldv}{bd}ie 5 sc np gr}{gs -1 dx rot p e st}{Asc cp L/ix/index m}b/dA{[3 DA}{dL s py m 8 p 6 Scientific 2.2 py m 0 1 x/dx 3 -8 g DLB 5 180 0 r n/dx l -1 g cm 360 a sc -1 2 lp sl dv px -1 0 16 begin/version gs 24.6 type[]type -1 p sqrt 2 4 12 r 2.25 neg}if/px ac gs p sm r arc x mv neg LB r py 0 dv/bd s gi 1 arc o 0 x sc s wF mv 2 0 OB 0 rO 180 0.5 SA CB dp 1 dy 3 gs al -4.8 st}{0 p Computing, 0 0.6 eq{DB}{DS}ie lW 90 L/l/lineto wD S]}b/dL{dA py SA gs e begin m ac 1 w l ac 1 cw pp DA}{2.25 CB 0.5 n/dy rev{neg}if sg 5 px 2 6 r x}if CA lp cW 2 1 sc DA}{cw 2.2 begin 16 px -1 25.8 rO eq{dp e dv -2 o -1 1 x fill sg m 0 py sg np s cX bs OA}{1 a setgray np[{py np 0 r x p wy p dp dv 24 r e fill gr 1 fill dv lp 16 lx 0 bW l mv s cv ne e L/mt/matrix lbs 0 0 o cm 0 wx rlineto cp cm 5 p def/b{bind 0 dp SA arc gr ac g/wb Inc. ly neg gr 0 sc}b/Ov{OrA 0 1 -1.6 n pp}{2 g o e -1 m l 0 rO 16 cm p p px w at sm 1 OA}{1.5 0 sm gs cY g 2 clippath gs ne{bW py sl l mv e sc ac l ac 3 2 eq{gs mt WI div x lp cm sm 27 1 ne 1.5 sc cm st cp px st}{Asc lW 4 m 270 0 bs cm e 1 bL s p ro gi gr}b/OB{/bS neg or{4 dup 1.6 0 fill}b/SA{aF sm w st}{px m py st p sm 0 2 SA l def}bind e L/mv/moveto SA dp tr 0 sm bd al cp p l fill AA}{1 p dv/bd gr put g/bb rO st cp py 27 DA}{270 e 1 wy st 2 l pp gs 1 l mv OA}{1 1 4 fill ZLB st}]e 0 rad neg 0 0.4 gr S r ac lW cm gr rO 0 g m 4.8 -1 a/py setgray o DT}]o 4 lt{pp 0 end px x -1 np setdash}d/cR 1 px x}if o w 2 cpt gs dv ac 1 def/L{load sc p e sm}b/CB{np[{[{C -1 39 wb eq{dL}if SA 25.8 xl dv m 0 p sc r}if -0.4 xl}{xl ap x x py 0.5 cp gr}b/In{px 0 round CA 2 e 1 sc px 0 l s 4 4 3 lW OA}{1 wx a 180 0 rad L/m/mul at mv S}if/lp 1 Bd pp g px st}{1.0 -1 g/cX ix ZLB lW DA}{180 cv sg 1 py -0.4 m/aL nH exec g pp ro}ie}b/ a/px gr}b/w pp 3 0 1 w r 6 AA}{1 8 -2 2 fill exec}b lp gs 3 ix -1 def}b 1 360 rO 0 pp}if 4 n 24.6 o x o/c x sc -1 12 dv ac s{n gr Ac gr} p gi x p xl 1 o wb dx sc a lp L L a single bond by heat as shown below. %w userdict/chemdict L/gr/grestore L/tr/transform xl pp l SA RA}{6 -1 st}b/OrA{py -8 py np gs fill e o cp 5 a wy dp 0 In x 6 0 2 bW dp/cY g -2 cw -1 CopyRight py 1 ChemDraw dp p cm fill pA sc -1 gr DA}{cw 8 m2 0 pp}{sqrt p 2 o 1 ix dv p l2 r lt{1 mv -9.6 -2 m 2 p s px sc mv cm 180 HA}{dL 0 gr}{pp}{gs -1 dp a}b/PT{8 sm o exec}{al s{dp dv m g dv mv dp rO dv o x -.6 WI py -1 sc exec sm 0 b2 neg lp st 12 xl wF np CA 5 p n 0 mv py 0 at p bd p LB sc 1.2 px gr neg 1986, m a}{ex 7 mv st p 2.25 e Laser 1 p l -9.6 m L/gs/gsave l arcn OA}{1 2 clip}b/Ct{bs p -1 gs ex pp aL p neg}if/py n l L/xl/translate cp np sl gr 0 at mv OB p wy m st}b/HA{lW l 12 0 o mv p 1 3.375 px 1 0 n/ex r 8 ro fill mv n gs 145 90 SA py 16.8 st}{0 np lp l 1987, 1 counttomark{bs Prep s wx ac sg OB/bL aR ix dp bW -1 bd px py sc e 0.3 gr ac px ro DA}{dL 0.6 rad 8 1 fill dict aL at 7 x m1 sc n 0 p cv SA dp end}b/Db{bs{dp DLB 0 eq{DD}{DS}ie py x -1 1 ey L/ie/ifelse Cambridge mt 1.2 gr p m bd ne{bW l 0 120 py 8 x dp rot -9.6 put sc m px DA}{cw m rO l}for m/w mv n/ey rad r -1 180 cm bW -1 ro 1.5 p 2 L/S{sf s p 0 b1 py g 0 CA ac chemdict 0 e dv tr/dy 0 1 l 0 -1 lt{-1 180 sm 21.6 bs 0 p st 2 SA -.6 aA a}ie}b/WW{gs x dp 5 0 a}ie}b/BW{wD py ac px 12 OA}{1 ne{bW 0 ldv}{bd}ie 5 sc np gr}{gs -1 dx rot p e st}{Asc cp L/ix/index m}b/dA{[3 DA}{dL s py m 8 p 6 Scientific 2.2 py m 0 1 x/dx 3 -8 g DLB 5 180 0 r n/dx l -1 g cm 360 a sc -1 2 lp sl dv px -1 0 16 begin/version gs 24.6 type[]type -1 p sqrt 2 4 12 r 2.25 neg}if/px ac gs p sm r arc x mv neg LB r py 0 dv/bd s gi 1 arc o 0 x sc s wF mv 2 0 OB 0 rO 180 0.5 SA CB dp 1 dy 3 gs al -4.8 st}{0 p Computing, 0 0.6 eq{DB}{DS}ie lW 90 L/l/lineto wD S]}b/dL{dA py SA gs e begin m ac 1 w l ac 1 cw pp DA}{2.25 CB 0.5 n/dy rev{neg}if sg 5 px 2 6 r x}if CA lp cW 2 1 sc DA}{cw 2.2 begin 16 px -1 25.8 rO eq{dp e dv -2 o -1 1 x fill sg m 0 py sg np s cX bs OA}{1 a setgray np[{py np 0 r x p wy p dp dv 24 r e fill gr 1 fill dv lp 16 lx 0 bW l mv s cv ne e L/mt/matrix lbs 0 0 o cm 0 wx rlineto cp cm 5 p def/b{bind 0 dp SA arc gr ac g/wb Inc. ly neg gr 0 sc}b/Ov{OrA 0 1 -1.6 n pp}{2 g o e -1 m l 0 rO 16 cm p p px w at sm 1 OA}{1.5 0 sm gs cY g 2 clippath gs ne{bW py sl l mv e sc ac l ac 3 2 eq{gs mt WI div x lp cm sm 27 1 ne 1.5 sc cm st cp px st}{Asc lW 4 m 270 0 bs cm e 1 bL s p ro gi gr}b/OB{/bS neg or{4 dup 1.6 0 fill}b/SA{aF sm w st}{px m py st p sm 0 2 SA l def}bind e L/mv/moveto SA dp tr 0 sm bd al cp p l fill AA}{1 p dv/bd gr put g/bb rO st cp py 27 DA}{270 e 1 wy st 2 l pp gs 1 l mv OA}{1 1 4 fill ZLB st}]e 0 rad neg 0 0.4 gr S r ac lW cm gr rO 0 g m 4.8 -1 a/py setgray o DT}]o 4 lt{pp 0 end px x -1 np setdash}d/cR 1 px x}if o w 2 cpt gs dv ac 1 def/L{load sc p e sm}b/CB{np[{[{C -1 39 wb eq{dL}if SA 25.8 xl dv m 0 p sc r}if -0.4 xl}{xl ap x x py 0.5 cp gr}b/In{px 0 round CA 2 e 1 sc px 0 l s 4 4 3 lW OA}{1 wx a 180 0 rad L/m/mul at mv S}if/lp 1 Bd pp g px st}{1.0 -1 g/cX ix ZLB lW DA}{180 cv sg 1 py -0.4 m/aL nH exec g pp ro}ie}b/ a/px gr}b/w pp 3 0 1 w r 6 AA}{1 8 -2 2 fill exec}b lp gs 3 ix -1 def}b 1 360 rO 0 pp}if 4 n 24.6 o x o/c x sc -1 12 dv ac s{n gr Ac gr} p gi x p xl 1 o wb dx sc a lp L L a Initiator (formation of free radicals) currentpoint O O O 2 CO OC CO currentpoint 192837465

benzoyl peroxide 103 2200 gr end 23 4120 47 currentpoint 189 1200 40 4120 80 20 2 20 Ar /bs[]d chemdict Db begin SP (CH3)2- C N=N C-(CH3)2 + N2 2 (CH3)2- C %w userdict/chemdict L/gr/grestore L/tr/transform xl pp l SA RA}{6 -1 st}b/OrA{py -8 py np gs fill e o cp 5 a wy dp 0 In x 6 0 2 bW dp/cY g -2 cw -1 CopyRight py 1 ChemDraw dp p cm fill pA sc -1 gr DA}{cw 8 m2 0 pp}{sqrt p 2 o 1 ix dv p l2 r lt{1 mv -9.6 -2 m 2 p s px sc mv cm 180 HA}{dL 0 gr}{pp}{gs -1 dp a}b/PT{8 sm o exec}{al s{dp dv m g dv mv dp rO dv o x -.6 WI py -1 sc exec sm 0 b2 neg lp st 12 xl wF np CA 5 p n 0 mv py 0 at p bd p LB sc 1.2 px gr neg 1986, m a}{ex 7 mv st p 2.25 e Laser 1 p l -9.6 m L/gs/gsave l arcn OA}{1 2 clip}b/Ct{bs p -1 gs ex pp aL p neg}if/py n l L/xl/translate cp np sl gr 0 at mv OB p wy m st}b/HA{lW l 12 0 o mv p 1 3.375 px 1 0 n/ex r 8 ro fill mv n gs 145 90 SA py 16.8 st}{0 np lp l 1987, 1 counttomark{bs Prep s wx ac sg OB/bL aR ix dp bW -1 bd px py sc e 0.3 gr ac px ro DA}{dL 0.6 rad 8 1 fill dict aL at 7 x m1 sc n 0 p cv SA dp end}b/Db{bs{dp DLB 0 eq{DD}{DS}ie py x -1 1 ey L/ie/ifelse Cambridge mt 1.2 gr p m bd ne{bW l 0 120 py 8 x dp rot -9.6 put sc m px DA}{cw m rO l}for m/w mv n/ey rad r -1 180 cm bW -1 ro 1.5 p 2 L/S{sf s p 0 b1 py g 0 CA ac chemdict 0 e dv tr/dy 0 1 l 0 -1 lt{-1 180 sm 21.6 bs 0 p st 2 SA -.6 aA a}ie}b/WW{gs x dp 5 0 a}ie}b/BW{wD py ac px 12 OA}{1 ne{bW 0 ldv}{bd}ie 5 sc np gr}{gs -1 dx rot p e st}{Asc cp L/ix/index m}b/dA{[3 DA}{dL s py m 8 p 6 Scientific 2.2 py m 0 1 x/dx 3 -8 g DLB 5 180 0 r n/dx l -1 g cm 360 a sc -1 2 lp sl dv px -1 0 16 begin/version gs 24.6 type[]type -1 p sqrt 2 4 12 r 2.25 neg}if/px ac gs p sm r arc x mv neg LB r py 0 dv/bd s gi 1 arc o 0 x sc s wF mv 2 0 OB 0 rO 180 0.5 SA CB dp 1 dy 3 gs al -4.8 st}{0 p Computing, 0 0.6 eq{DB}{DS}ie lW 90 L/l/lineto wD S]}b/dL{dA py SA gs e begin m ac 1 w l ac 1 cw pp DA}{2.25 CB 0.5 n/dy rev{neg}if sg 5 px 2 6 r x}if CA lp cW 2 1 sc DA}{cw 2.2 begin 16 px -1 25.8 rO eq{dp e dv -2 o -1 1 x fill sg m 0 py sg np s cX bs OA}{1 a setgray np[{py np 0 r x p wy p dp dv 24 r e fill gr 1 fill dv lp 16 lx 0 bW l mv s cv ne e L/mt/matrix lbs 0 0 o cm 0 wx rlineto cp cm 5 p def/b{bind 0 dp SA arc gr ac g/wb Inc. ly neg gr 0 sc}b/Ov{OrA 0 1 -1.6 n pp}{2 g o e -1 m l 0 rO 16 cm p p px w at sm 1 OA}{1.5 0 sm gs cY g 2 clippath gs ne{bW py sl l mv e sc ac l ac 3 2 eq{gs mt WI div x lp cm sm 27 1 ne 1.5 sc cm st cp px st}{Asc lW 4 m 270 0 bs cm e 1 bL s p ro gi gr}b/OB{/bS neg or{4 dup 1.6 0 fill}b/SA{aF sm w st}{px m py st p sm 0 2 SA l def}bind e L/mv/moveto SA dp tr 0 sm bd al cp p l fill AA}{1 p dv/bd gr put g/bb rO st cp py 27 DA}{270 e 1 wy st 2 l pp gs 1 l mv OA}{1 1 4 fill ZLB st}]e 0 rad neg 0 0.4 gr S r ac lW cm gr rO 0 g m 4.8 -1 a/py setgray o DT}]o 4 lt{pp 0 end px x -1 np setdash}d/cR 1 px x}if o w 2 cpt gs dv ac 1 def/L{load sc p e sm}b/CB{np[{[{CS} -1 39 wb eq{dL}if SA 25.8 xl dv m 0 p sc r}if -0.4 xl}{xl ap x x py 0.5 cp gr}b/In{px 0 round CA 2 e 1 sc px 0 l s 4 4 3 lW OA}{1 wx a 180 0 rad L/m/mul at mv S}if/lp 1 Bd pp g px st}{1.0 -1 g/cX ix ZLB lW DA}{180 cv sg 1 py -0.4 m/aL nH exec g pp ro}ie}b/AA a/px gr}b/wD pp 3 0 1 w r 6 AA}{1 8 -2 2 fill exec}b/C lp gs 3 ix -1 def}b/d 1 360 rO 0 pp}ifels 4 n 24.6 o x o/cX x sc -1 12 dv ac s{nH gr Ac}{0 gr}ie} p gi x p xl 1 o wb dx sc ac lp L/n LB ap aL l gs CA sg lt{e arc -1 px cm al r p 3 d/ w 0 2 9 n p 5 s x 1 m C N C N C N currentpoint 192837465

. . .

azoisobutylnitrile (AIBN) Or redox reactions...single electron transfers (used at low temperatures) C H3 C OOH + C H3 cumyl hydroperoxide Fe
2+

ferrous ion

C H3 C O C H3

+ OH Fe3+

If the initiator molecule is represented as I, the initiator undergoes first-order decomposition with the rate kd. currentpoint kd I 2 R currentpoint 192837465 [11]

Initiation The free radical is very reactive and attacks a monomer with a double bond as shown below. Two possibilities

12

+ C H2

..

CH X

R C H2 -CH X

This reaction is preferred since steric hindrance produces more stable free radical. Or, R C H -CH2 X

.
(short lived)

Initiator efficiency (wastage)...not every I* starts a new chain 2 O recoupling C-O O O C-O O-C O C-O 2 O O C-O O-C Propagation This process is repeated many times and each time the polymer free radical grows by one monomeric unit. If the newly formed polymer free radical is expressed as Pn , the propagation process is expressed as: Pn + O C-O + O C-O + CO 2

+ M

kp

Pn+1

.
C H2-CH X

[12]

Termination These polymer free radicals can also react each other rather than with the monomer. The termination reaction (combination reaction) can be expressed as follows. C H2-CH X

..

+ CH-CH2 X

CH-CH2 X

This chemical reaction can be expressed as:

13

Pn

+ Pm

kt c

Pn + m

[13]

Polystyrene terminates predominantly by combination. As is obvious from the above equation, the molecular size grows upon combination reaction. Another termination reaction is the hydrogen extraction by the free radical and is called disproportionation reaction. C H2-CH X

..

+ CH-CH2 X

C H2-CH2 + CH=CH X X

This reaction is expressed as: ktd Pn + Pm

Pn

+ Pm

[14]

Poly(methyl methacrylate) terminates predominantly by disproportionation, due to the steric hindrance of the methyl methacrylate group. 2.2.2. Kinetics of Free Radical Polymerization Kinetics of free radical polymerization can be expressed as follows. The rate of initiation The rate of propagation Ri = 2fkd[I]

Rp = kp[M][Pn ]

The rate of terminationRt = 2kt[Pn ]2 where kt = ktc + ktd

[15] [16] [17]

Under the steady state assumption, the rate of initiation and the termination is equal. Thus, Ri = Rt From the above equations, 2fkd[I] = 2kt[Pn ]2 Thus, the polymer radical concentration is, [Pn ] =

[18]

fkd[I] kt

1 2

[19]

Inserting equation [19] into equation [16] yields,

14

Rp = kp fkd 2 [I]2 [M] = K[I]2 [M] kt where K is constant. The kinetic chain length, , is defined as the ratio of the rate of propagation against the rate of initiation. = Rp = Ri kp [M] 2(fkdkt )2 [I]2
1 1

Therefore, the number average molecular weight of polymers by free radical polymerization is, Xn = Xn = 2 Increase [M] Increase [I ] Autoacceleration The expression of Rp is quite valid at the beginning of the reaction. However, as p increases, there is often a shrat increase in Rp . This is called Trommsdorff-Norrish effect (or autoacceleration, or gel effect) termination by disproportionation termination by combination Rp Rp , Xn , Xn

15

100% (pure monomer) 80% 60% % Conversion 40% 10% solution

Time Autoacceleration is due to the increased viscosity. Long, growing chains have great difficulty diffusing and finding each other to terminate. Sharp reduction of kt On the other hand, small monomer molecules can diffuse and find the polymer free radicals to grow. Exothermic Reactions Heat must be controlled Explosive reactions How one can control the reactions.....Use dilute solutions However, the probability of chain transfer increases What is Chain Transfer? Reactions in which dead polymer molecules are created, but new growing chains are initiated stop of the growth of molecular weight in a termination reaction, all free radicals are killed Pn-T + A

Pn + T-A where

16

T-A T A Rp Xn

= chain transfer agent (monomer, initiator, solvent) inter- and intromolecular chain transfer = often hydrogen, halogen, or stable radical = new radical, can start new chain

not significantly affected chains are shortened, thus if there is chain transfer, we must take into account when analysing Xn . moles of monomer consumed in time, t moles of polymer chains formed in time, t kp [M][M] ktc[M]2 + 2ktd[M]2 + ktrM[M][M] + ktrI[M][I] + ktrS[M][S]

Xn = =

Using steady state assumption for [M], and rearranging: 1 = kt Rp + CM + CI [I] + CS [S] 2 Xn [M] [M] k2 p [M] where CM, CI, and CS are transfer constants Transfer agent can be added on purpose to tailor-make a certain Xn Intramolecular Charge Transfer (backbiting) A growing chain can charge transfer on its own chain by forming a quasi-six membered ring. As a result, short branching such as ethyl and buthyl branches are formed. H CH C H2 C H2

C H

CH
C H2 C H2 C H2=CH2 CH C H2

C H3 C H2

C H2

C H2 - CH2

C H2 C H2 C H3

butyl branch

17

C H2 CH C H2 CH C H2 C H3 C H2

C H2 C H3

CH C H2 CH

C H2 C H3 ethyl branch

Intermolecular Charge Transfer C H3 O C=O C H2 - C + H C H3 O long branching C=O C H2 - C +

+ C H2 - CH C=O O C H3 Inhibitors/ Retarders

C H2 - CH2 + C=O O C H3

Inhibitors are low concentration radical scavengers that prevent polymerization initiation until all the scavenger is consumed. Redarder is a compound that slows down the rate of reaction. Oxygen is both inhibitor and retarder Nitrobenzene is retarder (charge transfer agent that produces less reactive free radical) reduced Rp and Xn

18

without additives

% Conversion

retarder

inhibitor

induction time 2.2.2. Ionic Polymerization

Time

Active center is ionic charge instead of free radical. Therefore, ionic polymerization is more monomer specific than free radical. Only monomers that can sufficiently stabilize positive or negatic charge will undergo ionic polymerization. + C H2 - CH e X _ C H2 - CH X _ donating delocalize + charge

withdrawing

delocalize - charge

Therefore, most monomers cannot be polymerized by ionic polymerization. Characteristics of Ionic Polymerization i) Ionic polymerization is faster than free radical polymerization (generally) [M*] = concentration of propagating chain is higher [M+], [M-] = 104 - 106 [M]

ii) Counter ion of opposite charge

19

Degree of association inluences rate and steretchemistry of propagation Thus, polarity of solvent, ability to solvate counter ion significantly affect

iii) Termination cannot occur between two growing chains (coupling) Active centers are of the same charge and the same chage repel each other so that coupling cannot take place

A. Cationic Polymerization I. Initiation Creation of + active centers: Monomer + electrophiles, R+. a) Protonic acids, H2 SO4 + perchloric acid, HClO4 involve addition of H+ to monomer b) Hydrogen halide acids, Hcl------not suitable because Cl- recombines. c) Lewis acids + co-catalyst such as water, acid, organic halide Boron trifluoride, BF3 Aluminum chloride, AlCl3 Tin tetrachloride, SnCl4 First step BF3
+

H2O (trace)

H+ (BF3OH)R+ (AlCl4)-

AlCl3 + RCl Second Step H+ (BF3OH)R+Ainitiator II. Propagation R +


+

CH2=CR1R2

C H3- C+R1R2 (BF3OH)R-CH2- C+R1R2Aelectrophile, R


+

CH2=CR1R2

counter ion, A

C H2- C+R1R2A- + CH2=CR1R2

C H2-CR1R2-CH2- C+R1R2A-

Propagation step is similar to free radical Predominantly head-to-tail Used for making stereospecific polymers

20

III. Termination a) Unimolecular rearrangement of ion pair: R C H2- C+R1R2AR


+ CH=CR 1R2 + H A

b) Chain transfer to monomer is usual C H2- C+R1R2A- + CH2=CR1R2 C H2=CR1R2 + CH3- C+R1R2Anew chain dead polymer

chain transfer to colvent, impurities, H2 O, polymer (branching) are all common. Kinetics: Specific to actual monomer, solvent, initiator........ General, Practical Considerations: Side reactions are many, and likely. Sub-zero temperatures are often necessary for high molecular weight polymers If water is co-=catalyst, it must by stoichiometric H2 O is good charge transfer agent Rigorously dried, purified Rapid; complete conversion in seconds Problem: heat transfer non-steady state conditions! Only Commercially Noteworthy Example: Synthesis of butyl rubber by copolymerization of isobytylene with small amount of isoprene at -90o C using Lewis acid initiator (ALCl3 ) in chlorinated solvents such as chloromethane. Solvent/ Counter Ion Effects: Mn-A covalent Mn+Acounter ion pair Mn+ / / Asolvent separated ion pair Mn+ + Afree ions

Very polar solvents (dichloromethane) separate ions and large, bulky counter ions (SbCl6 -) weakly associated-----faster B. Anionic Polymerization Absence of an inherent termination process Ion pair rearrangement involves elimination of a hydride ion, H-.....highly unfavorable.

21

Alkali metal counter ions, +, have no tendency to recombine with active, growing centers to form dead polymer.

Thus, without chain transfer, there is no tendency to create unreactive polymer! Polymer chains that permanently retain their active centers and grow as long as there is monomer -----Living Polymerization Example: Polymerization of styrene in liquid ammonia (one of first examples of anionic polymerization) I. Initiation KNH2 potassium amide NH2- + CH2=CH K+ + NH2amide ion H2NCH2-CH-

II. Propagation H2N(CH2-CH)n-1C H2-CH- + C H2=CH H2N(CH2-CH)nC H2-CH-

III. Chain Transfer H2N(CH2-CH)nC H2-CH- + NH3 H2N(CH2-CH)nC H2-CH2 + NH-

solvent Common Initiator Systems Organolithium compounds: Buthyl lithium

dead polymer

new chain

very reactive used with non-polar hydrocarbon solvents with low Cs constants -----living polymerization Electron transfer initiation involves donation of a single electron to form radical anion radical anions then couple to form dianione

22

example ether Na + Na + + _

green ion

C H2=CR1R2

C H2- C-R1R2 Na + + Na +R2R1C--CH2-CH2- C-R1R2 Na + red ion

coupling

propagation Molecular Weight Distribution without termination----Poisson distribution MW = 1 + 1 Mn Xn as Xn is close to infinity, PDI approaches 1

If ki > kp , narrow distribution standards can be obtained Termination of the Propagating Ions Add alcohols C H2- C-R1R2 Na + + ROH Add acids C H2- C R1R2 Na O C H2-CH2
+ - + C H2-CHR1R2 + RO M

C O2

O acid + C H2- C R1R2-CO Na


-

O C H2- C R1R2-COH carboxylic acid


-

C H2-CR1R2-CH2C H2O Na Solvent/ Counter Ion Effects M+ counter ions are smaller than Atighter bound

acid C H2-CR1R2-CH2C H2OH alcohol

23

propagation 102 - 104 times slower than cationic using polar solvents help solvate and activate ion pairs

If propagation is slow compared with ki, broad molecular weight distribution results Practical Considerations High reactivity Low concentration of reacting species purity, dryness, inert gases (H2 O, CO2 , O2 all kill growing chains) despite difficulties: very narrow PDIs block copolymers of defined length

24