Chapter 28 785 a, CH,=CHC! b. CHy=CCH, ©. CF)=CF, ¢=0 OCH; Poly(vinyl chloride) would be more apt to contain head-to-head linkages because a chloro substituent is less able (compared with a phenyl substituent) to stabilize the growing end of the polymer chain by resonance. —CH,CH—CHCH,CH,CH—CHCH,CHCH,CH,CH—CHCH,CH,CH— 8 30 HO-OH ——» 2H0- Hols culls —> HO-cH.CH- a a wo-cren CH=CH = HO—CH,CHCH,CH: a a a oa womcinencncn! + CH=CH >= HO~CH;CHCH,CHCH,CH- aoa a a aia Since branching increases the flexibility of the polymer, beach balls are made from more highly branched polyethylene.786 6. Chapter 28 fe —CH,CHCH,CHCH,CCH,CHCH,CH— 00 0 Decreasing ability to undergo cationic polymerization is in the same order as decreasing stability of the carbocation intermediate. (Electron donation increases the stability of the carbocation.) a. CH;=CH CH)=CH CH)=CH > > ICH CH; NO donates electrons withdraws electrons by resonance by resonance q i b. CHy=CHOCCH; > CH;=CHCH,; > CH,=CHCOCH; donates electrons withdraws electrons by resonance by resonance © CH)=CCH; — CH>=CH A tertiary benzylic carbocation is more stable O than a secondary benzylic carbocation. Decreasing ability to undergo anionic polymerization is in the same order as decreasing stability of the carbanion intermediate. (Electron withdrawal increases the stability of the carbanion.) a CHy=CH CH=CH CH,=CH > > NO, CH; CH withdraws electrons donates electrons by resonance by resonance b. CH;=CHC=N > CH)=CHC] > CH,=CHCH, withdraws electrons by resonanceChapter28 787 9, In anionic polymerization, nucleophilic attack occurs at the less substituted carbon because it is the less sterically hindered (Section 12.7). In cationic polymerization, nucleophilic attack occurs at the more substituted carbon, because the ring opens to give the mote stable partial carbocation. p u__ Position of nucleophilic attack DY in cationic polymerization 7 ‘CH; position of nucleophilic attack in anionic polymerization 10. ge a. — RO-CHCO cH, joni > RO-CH:FOCH Co CH, CH, CH GHs Hy CH I I > ROCH,COCH,FOCHSCO™ CH; CH; CH; 3, os CH; FB: —ocH.e— 5 CH; Hy CH; CH; CH, = i a —> FB—ocH,Coct,c— 6: CH; ‘CH; CH; CH;788 11. 12. 13. Chapter 28 oO - 3. CH)=CCH; + BF; © 7\ + CHO CH; a. CH,=¢H + Buli oc: b. CH)=CH + BF; OQ 3,3-Dimethyloxacyclobutane undergoes cationic polymerization by the following mechanism. ee O—BF, >0—CH,CCH,O—BF. wel HC] G ie ° oy — Ws CH HC 6: ss 5 HC r HC wae HAC 7 \ : HC CH; I us —CH,CCH,0CH,CCH,0—BF. Hy JG 2 T 2 2) T 7 q CH. H, x HC Ss, ms HC] ] a HAC c. Si ene eae CH, CH; CH, HC TO14, 15. 16. Chapter 28789 Notice that a branch occurs as a result of nucleophilic attack on C-3 instead of on C-1. al os ROE cu,Lon cHltu, —— > RO-CH,CH=cHCH, RO—CH,CH=CHCH, CH=CH, —> RO-CH,CH=CHCH,CHCH, CH=CH, CH=CH, ROMCH,CH=CHCH,CHCHS cnie“on- cad, CH=CH, \ RO—CH,CH=CHCH,CHCH,CH,CH=CHGH, CH=CH, This polymerization also could take place by a radical mechanism or by a cationic mechanism. i i a, —NHCH,CH,CH,CNHCH,CH,CH,C— ° db. . ‘NH i I i) ti . —NH(CH,),NHCCH,CH,CNH(CH,),NHCCH,CH,C— 9 ° oO il il 1 tl —C(CH;),C-PNH(CH2)gNH—C (CH),C--NH(CH;),NH— nt [ps0 th I + + n HOC(CH,),COH + 1 H3N(CH3)sNH;790 Chapter 28 17. They hydrolyze to give monomers of dicarboxylic acids and diols. ° 9° 9 i Hi 9° AG thon Bloc cto Kodel fron (e) 9° Il n ot Ybor + on noc, )—cH,0H i t i i GD Locrctio L¥ J Hocrcro— Dacron [wow 9 1 Hl n “of V4 y + nm HOCH,CH,OHChapter28 791 18. a. g nt, bu, be Of Omg OE O- Or A, & A, | Altemately add the CHS & phenol and the epoxide. oe 1 A L-cx of 0 Y-octicicn —€_ Voc DS CH, Ou H, 2792 Chapter 28 ° ¥y oob-(Y in @ ccnp v CS OCH, 2 3 OH = H,NCH,CH,NHCH,CH,NH H,NCH,CH,NHCH,CH,NH O CH CH ) ov / ¢ Y ccnp / \ € / oct, CH3 oH J, cH, = CH. Hs 1) I gregh {Y-4C)-congenb>{ 1) -oongren CH, OH on J, CH, OH CH, CH; , ia ie i ww oh Ge CH Hs Hs Ge NHCH,CHCH, ot \--¢_Y-ocnencn — OCH,CHCH:NH ou CH; bu CH; OH 19. Glycerol cross-links 9 ° the polymer chains. I th N CN 'NH—C—OCH,CH,0—C=NI ‘NH- $ CH; CH; CH, CH; i FN Fe ° ° 0 0Chapter28 793 20. Formation of an imine between formaldehyde and one amino group, followed by reaction of the imine with a second amino group, accounts for formation of the linkage that holds the monomers AK HN. tenis HN, UN. _UNH=CH, H,N ON UNH) YY =o formatiog aT - YT No (occurs in sy NaN = 1 See p. 748 of the text.) NH) | NE HN. NHCHNI N._NH, 2 ry i! Y v 2 a dimer of Melmac794 Chapter 28 21. OH Bakelite22. Chapter28 795 a, —CH,GHCH:CHCH.CH— —_chain-growth polymer FOF F >, —CH:CHCH:CHCH,CH— __chain-growth polymer COxH CO;H CO tL tl I & —O(CH,)sCO(CH;);CO(CH);C— _ step-growth polymer il it il —NH(CH,),NHC(CH,),CNH(CH,) NHC(CH,),C— _step-growth polymer 9 i t q q & —OCI NHCOCH,CH,OCNH. .NHCO— Ww step-growth polymer CH; CH; & —CH,CH,OCH,CHN = N— Ryy_f Oe CH; CH, e —¢S-oencn,cn,0-¢_V-w=crcnen— 5 —1{)=cr¥ )— a =796 Chapter 28 24, CH; a. CH;==CHCH,CH; e CH)=CCH=CH, ° 9 U1 vp. ZA f. HO(CH;),COH ‘CH, & CH =CCH; © cwo€_-s0,c1 + HjN(CH;)sNH2 v a. cucu he wocf_\- a,b, d, e, and g are chain-growth polymers. =O Q OH + HOCH,CH,OH ¢,f, and h are step-growth polymers. 25. Whether a polymers isotactic, syndiotactic, or atactic depends on whether the substituents are all on one side of the carbon chain, alternate on both sides of the chain, or are random with respect to the chain, Because a polymer of isobutylene has two identical substituents at each carbon in the chain, different configurations are not possible. GH CHs Gils CH CHE CHE CHAE CHC — CH; CH; CH, CH; polymer of isobutylene 26. a, CHjOCH,CHOCH,CHOCH,CHOCH,CHO— CH; CH, CH; CH; b. CH,CH,CH,CH;CH,CHCH,CHCH,CHCH,CH— a aaaChapter 28797 CH; CH; CH; CH © | —CH,C—CH,C—CH,C—CH,C— NCH; NCH; NCH, NCH; I Il I d. —NH(CH;),CNH(CH,),CNH(CH),C— Depending on the particular Ziegler-Natta catalyst used, the double bonds can be either cis or trans. GHsCH; CH Hs CH CHs —CH,C=CCH,CHj;C=CCH;CHj;C=CCH,— or cnt nonend —CH,C=CCH,CH{C=ECH;CH{C=CCHy— CH, CH CH; £ F,B-CH,CHCH;CHCH,CHCH,CHCH,CH— Gh Gh Gh Cth lh Gi GH: GHz Ha GH CH; CH; CH, CH; CH, 2. a. Because itis a polyamide (and not a polyester), it is a nylon. o 9 i i b. an) —cr, {st and HOC(CH,),COH 28, A copolymer is a polymer composed of more than one kind of monomer. Because the initially formed carbocation can rearrange, two different monomers are involved in formation of the polymer. to 1,2-methyl shift vs = a 21 a 6 %. F)B-CHACHECH, —_—_—_ar FyB—CH,CHECH, CH CH, unrearranged monomer rearranged monomer798 Chapter 28 29. The polymer in the flask that contained a high molecular weight polymer and little material of intermediate molecular weight was formed by a chain-growth mechanism, whereas the polymer in the flask that contained mainly material of intermediate molecular weight was formed by a step-growth mechanism. Ina chain-growth mechanism, monomers are added to the growing end of a chain. This means that at any one time there will be polymeric chains and monomers. Step-growth polymerization is not a chain reaction; any two monomers can react. Therefore, high molecular weight material will be formed by the reaction of two pieces of intermediate molecular weight. 30. a, Vinyl alcohol is unstable, it tautomerizes to acetaldehyde. ge i CH=CH ——> CH;CH vinyl alcohol acetaldehyde b. Itis not a true polyester. It has ester groups as substituents on the backbone of the chain so it does have "polyester" groups, but it does not have ester groups within the backbone of the polymer chain, A true polyester has ester groups in the backbone of the polymer chain. 31. Each of the five carbocations shown below can add the growing end of the polymer chain. 1,2-hydride 1,2-hydride CH —cH.6H anit, —CHCHCH —Suft__ —CHCH,CH G+ CH, GHCH, CHs GHcHs cH, Oh 1,2-methyl shift CH3 —1,2-hydride ily —CH:CHsCHCH shift —cH,CH,CCH,CH, CH, 32. Because 1,4-divinylbenzene has substituents on both ends of the benzene ring that can engage in polymerization, the polymer chains can become cross-linked, which increases the rigidity of the polymer.Chapter 28 799 CH=CH, 1,4-divinylbenzene CH=cR, —CH—CH,—CH—CH,—CH—CH;~-CH—CH;—CH— SSS SS — CH—-CH;— CH—CH;~ CH—CH,— CH— CH,—CH—CH soo 00 Glyptal gets its strength from cross-linking. f i i t rf — CS -Locu,encn,ot-€_\-bocrntncaot 9 | I i ; COCH,CHCH,OC— oe ¢=0 ° 9 c=0 CH. J 20 e 9 oO I oe TL v0ek\—Locastrcrot— o-0-9-0—-{ & ©800 Chapter 28 35. Both compounds can form esters via intramolecular or intermolecular reactions. The product of the intramolecular reaction is a lactone; the intermolecular reaction leads to a polymer. 5-Hydroxypentanoic acid reacts intramolecularly to form a six-membered-ring lactone, whereas 6-hydroxyhexanoic acid reacts intramolecularly to form a seven-membered-ring lactone. ° oO I) HOCH,CH,CH,CH,COH = ——> CY S-hydroxypentanoic acid o 1 HOCH,CH,CH,CH,CH,COH = ——> oO 6-hydroxypentanoic acid ‘The compound that forms the most polymer will be the one that forms the least lactone, because the two reactions compete with one another. The six-membered-ring lactone is more stable and so is the transition state for its formation, compared to a seven-membered ring lactone. Since it is easier for 5-hydroxypentanoic aci to form the six-membered ring lactone, than for 6-hydroxyhexanoic acid to form the seven- membered ring lactone, 6-hydroxypentanoic acid will form more polymer.Chapter 28 801 36. Rubber contains cis double bonds. Ozone, which is present in the air, oxidizes double bonds to carbonyl groups, destroying the polymer chain, Polyethylene does not contain double bonds, so itis not air-oxidized. oY = AL 37. The plasticizer that keeps viny! soft and pliable can vaporize over time, causing the polymer to become brittle. For this reason, high boiling materials are preferred over low boiling materials as plasticizers. 38. a, Because the negative charge on the propagation site can be delocalized onto the carbonyl ‘oxygen, the polymer is best prepared by anionic polymerization. cH, cH. fe oN OT (CO ze CHy=C_7 CH; ECH CHCH,CH,CH,SLi G=0. cog 5 coo" / NO, NO, CH, CH, I I - ge oe —CH,GHCH,CHCH,CHCH,CH— oe —CH,CHCH,CHCH,CHCH,CH— x coo coo coo coo-802 Chapter 28 b. The carboxyl substituent is in position to remove a proton from water, making water a stronger nucleophile. (See page 1013 of the text.) oF neni —CHGHCH,CHCH,PHCH,CH— c=0 cH. c=0 coo I 0 ° nfo NO, NO, 39, Hydrolysis converts the ester substituents into alcohol substituents, which can react with ‘ethylene oxide to graft a polymer of ethylene oxide onto the backbone of the random polymer of styrene and vinyl acetate. —CH,CHCH,CHCH;CHCH,CHCH,CHCH,CHCH,CH— ° ° g o=€ o=¢ oe CH CH, CH, wf —CH,CHCH,CHCH,CHCH,CHCH,CHCH,CHCH,CH— bn “Co "aA ethylene oxide41. Chapter 28 803, —CH,CHCH,CHCH;CHCH,CHCH,CHCH;,CHCH,CH— Bay p ml i fe fs oO Oo O Edy bes oa Fae Gite Oo oO oO ge fs ys GRe GAs Ge Oo oO ° I | The desired polymer is an alternating copolymer of ethylene and 1,2-dibromoethylene. CH)=CHy cu=¢H Br Br a. . H H H H wed * odd a oh a ok a odd H H | H H i HO—CH,—O—CH,—O—CH,—0—CH,—O—CH,— Delrin b. Delrin is a chain-growth polymer,