非茂钯催化剂催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合的研究
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摘要
本文探索了乙烯/丙烯/极性单体三元共聚物的合成方法.乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚物由于分子中引入了ω-Cl-α-乙烯基极性单体,改变了乙烯丙烯共聚物的化学惰性.我们采用催化剂Cat.L-Pd配位催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合,合成了极性三元无规共聚物.探讨了催化剂结构、聚合条件对三元共聚合行为的影响,并优化了聚合条件.采用红外光谱(FTIR)、核磁共振碳谱(氢谱)(~(13)C(~1H)NMR)、示差扫描量热(DSC)和高温凝胶渗透色谱(GPC)等方法研究了共聚物的结构与性能.FTIR与~(13)C(~1H)NMR结果表明,催化剂Cat.L-Pd能够有效催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合,共聚物中ω-氯代极性单体的插入量达3.6 mol%.极性单体不发生均聚合反应,但能够有效参与乙烯和丙烯的共聚合反应,形成三元无规共聚物.丙烯能够发生均聚合反应,但是不能形成聚丙烯长链段,主要发生乙烯与丙烯共聚合反应.乙烯最易发生聚合反应,并能够形成较长链段的聚乙烯.共聚物的Mw高于2×10~5g/mol.分子量分布在1.6～3.0,说明该类催化剂催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合行为遵循单中心聚合机理.
We investigated the terpolymerization of ethylene/propylene/ω-Cl-α-vinyl monomers to obtain polar terpolymers by non-metallocene catalyst Cat.L-Pd through coordination polymerization directly. The functional ω-Cl-α-vinyl monomer inserted into the polymeric molecules changed the properties of the obtained polymers. The optimum catalyst Cat.L-Pd and polymerization conditions were optimized for the terpolymerization. The structure and properties of the terpolymers were characterized by FTIR,~(13)C(~1H)NMR, DSC and GPC. The optimum incorporation content of11-chloro-1-undecylene within the terpolymer chains is up to 3.58 mol%. The polar monomers did not carry out the homopolymerization itself, but efficiently joined the terpolymerization with ethylene and propylene. Propylene monomer was in favor of the copolymerization with ethylene beside its homopolymerization. But polypropylene segments were not observed within the terpolymer chains. Compared to the polar monomers and propylene, ethylene was the most efficient monomer for joining the terpolymerization of ethylene/propylene/ω-Cl-α-vinyl monomers, and longer segments of polyethylene were produced within the terpolymer chains. Mwup to 2×10~5 g/mol of the terpolymers was obtained by the catalyst system. The terpolymer molecular weight distribution(MWD) was about 2 to 3, implying the terpolymerization behavior followed the single-site mechanism.
We investigated the terpolymerization of ethylene/propylene/ω-Cl-α-vinyl monomers to obtain polar terpolymers by non-metallocene catalyst Cat.L-Pd through coordination polymerization directly. The functional ω-Cl-α-vinyl monomer inserted into the polymeric molecules changed the properties of the obtained polymers. The optimum catalyst Cat.L-Pd and polymerization conditions were optimized for the terpolymerization. The structure and properties of the terpolymers were characterized by FTIR,~(13)C(~1H)NMR, DSC and GPC. The optimum incorporation content of11-chloro-1-undecylene within the terpolymer chains is up to 3.58 mol%. The polar monomers did not carry out the homopolymerization itself, but efficiently joined the terpolymerization with ethylene and propylene. Propylene monomer was in favor of the copolymerization with ethylene beside its homopolymerization. But polypropylene segments were not observed within the terpolymer chains. Compared to the polar monomers and propylene, ethylene was the most efficient monomer for joining the terpolymerization of ethylene/propylene/ω-Cl-α-vinyl monomers, and longer segments of polyethylene were produced within the terpolymer chains. Mwup to 2×10~5 g/mol of the terpolymers was obtained by the catalyst system. The terpolymer molecular weight distribution(MWD) was about 2 to 3, implying the terpolymerization behavior followed the single-site mechanism.
引文
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2 Edson JB,Wang Z,Kramer EJ,Coates GW.J Am Chem Soc,2008,130:4968–4977
3 Rose JM,Cherian AE,Coates GW.J Am Chem Soc,2006,128:4186–4187
4 Makio H,Terao H,Iwashita A,Fujita T.Chem Rev,2011,111:2363–2449
5 Younkin TR,Connor EF,Henderson JI,Friedrich SK,Grubbs RH,Bansleben DA.Science,2000,287:460–462
6 Zhang X,Chen S,Li H,Zhang Z,Lu Y,Wu C,Hu Y.J Polym Sci A,2007,45:59–68
7 Rodriguez BA,Delferro M,Marks TJ.J Am Chem Soc,2009,131:5902–5919
8 Popeney CS,Camacho DH,Guan Z.J Am Chem Soc,2007,129:10062–10063
9 Wang J,Zhang K,Ye Z.Macromolecules,2008,41:2290–2293
10 Zhong L,Li G,Liang G,Gao H,Wu Q.Macromolecules,2017,50:2675–2682
11 Kochi T,Noda S,Yoshimura K,Nozaki K.J Am Chem Soc,2007,129:8948–8949
12 Chen M,Chen C.ACS Catal,2017,7:1308–1312
13 Carrow BP,Nozaki K.J Am Chem Soc,2012,134:8802–8805
14 Chen Z,Liu W,Daugulis O,Brookhart M.J Am Chem Soc,2016,138:16120–16129
15 Zhang D,Chen C.Angew Chem Int Ed,2017,56:14672–14676
16 Li M,Wang X,Luo Y,Chen C.Angew Chem,2017,129:11762–11767
17 Dai S,Chen C.Angew Chem,2016,128:13475–13479
18 Dai S,Sui X,Chen C.Angew Chem,2015,127:10086–10091
19 Chen M,Yang B,Chen C.Angew Chem,2015,127:15740–15744
20 Zhao M,Chen C.ACS Catal,2017,7:7490–7494
21 Guo L,Dai S,Sui X,Chen C.ACS Catal,2016,6:428–441
22 Ota Y,Ito S,Kuroda J,Okumura Y,Nozaki K.J Am Chem Soc,2014,136:11898–11901
23 Yang XH,Liu CR,Wang C,Sun XL,Guo YH,Wang XK,Wang Z,Xie Z,Tang Y.Angew Chem Int Ed,2009,48:8099–8102
24 Johnson LK,Mecking S,Brookhart M.J Am Chem Soc,1996,118:267–268
25 Mecking S,Johnson LK,Wang L,Brookhart M.J Am Chem Soc,1998,120:888–899
26 Zhang J,Guo M,Huang H,Tang Y,Hou L,Sheng J,Liu X.Sci Sin Chim,2014,44:1705–1713(in Chinese)[张京春,郭梅芳,黄红红,唐毓婧,侯莉萍,盛建昉,刘宣伯.中国科学:化学,2014,44:1705–1713]
27 Huang QG,Huang HB,Guo JP.All-heterocyclic non-metallocene catalyst,and preparation method and application thereof.PRC Patent,CN201310108975.1,2013-03-31
28 Wang J,Nan F,Guo J,Wang J,Shi X,Huang H,Huang Q,Yang W.Catal Lett,2016,146:609–619
29 Wang J,He L,Nan F,Wang F,Li H,Wang J,Liu D,Lei M,Li L,Huang Q,Yang W.J Mater Sci,2017,52:5981–5991
30 Wang F,Wang J,He L,Nan F,Li H,Jiang M,Wang J,Yi J,Wang K,Huang Q,Yang W.Mater Lett,2017,209:64–67
31 Wang X,Wang Y,Shi X,Liu J,Chen C,Li Y.Macromolecules,2014,47:552–559
32 Nakano R,Nozaki K.J Am Chem Soc,2015,137:10934–10937
33 Ota Y,Ito S,Kobayashi M,Kitade S,Sakata K,Tayano T,Nozaki K.Angew Chem Int Ed,2016,55:7505–7509
34 Clark KJ,Powell T.Polymer,1965,6:531–534
35 Gates DP,Svejda SA,O?ate E,Killian CM,Johnson LK,White PS,Brookhart M.Macromolecules,2000,33:2320–2334
36 Cheng HN,Lee GH.Polym Bull,1984,12:463–470
37 Ye H,Xu Z,Zhu Q,Yan S,Chen H.Makrom Chem,1988,189:1133–1140
38 Busico V,Cipullo R.Prog Polym Sci,2001,26:443–533