[N,P]型非茂过渡金属催化剂合成PE-b-P(E/P)多嵌段共聚物的研究
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摘要
采用2种结构不同的配体,与过渡金属Ti、Zr、Ni、Pd的氯化物反应得到8种[N,P]型非茂过渡金属催化剂.通过研究配体结构、中心金属原子及主要聚合条件对乙烯/丙烯共聚合行为的影响,优化出催化剂Cat.L2-Ti,其催化乙烯/丙烯共聚合的活性高,所得共聚物中丙烯插入量达11.5 mol%,共聚物Mw高达2.75×105 g/mol.由核磁共振(13C-NMR)、示差扫描量热法(DSC)与广角X射线衍射(WAXD)结果表明共聚物分子链是以乙烯单元为主,乙烯单体一部分以聚乙烯长链段存在,一部分与丙烯单体无规共聚生成了乙烯/丙烯无规共聚物;同时FTIR表明聚丙烯长链段对应的红外特征峰没有出现,DSC结果也表明聚丙烯链段对应的熔点也没有出现,说明丙烯单元未形成聚丙烯长链段. DSC分析表明随着共聚物中丙烯单体插入量增加,聚乙烯长链段显示的熔点渐渐降低,当丙烯插入量达11.5 mol%时,共聚物的熔融峰不明显. WAXD分析表明即使丙烯插入量达11.5 mol%时,没有聚丙烯长链段的结晶衍射峰,但是聚乙烯长链段的结晶衍射峰强度随丙烯插入量增加而减弱.当丙烯插入量达11.5 mol%时,共聚物的结晶衍射峰明显变弱.这些结果证实[N,P]型非茂过渡金属配合物催化乙烯、丙烯共聚可获得PE-b-P(E/P)多嵌段共聚物.
Eight[N,P]-type non-metallocene catalysts were synthesized successfully via the reaction between two kinds of ligands carrying different electronic effect groups and chloride compounds of transition metals Ti,Zr,Ni and Pd.Catalyst Cat.L2-Ti exhibited the highest catalytic activity toward ethylene/propylene copolymerization thanks to the combined effects exerted by ligand structure,central atomic species,and polymerization conditions on copolymerization behavior of ethylene with propylene.The copolymer product achieved a high Mw up to 2.75×10~5 g/mol as measured by GPC,and ~(13)C-NMR test suggested that the content of propylene insertion within copolymer backbone reached 11.5 mol%.Characterization with ~(13)C-NMR,DSC,and WAXD demonstrated that macromolecular chains of the obtained copolymer were composed mainly of ethylene units existing as long-chain segments,while some other ethylene units formed random segments with copolymerized propylene monomers.Melting point of the copolymer decreased along with the increasing amount of propylene insertion,and so did the peak intensity in crystal diffraction of polyethylene segments.At the greatest insertion amount of propylene of 11.5 mol%,the melting peak could hardly be noted on DSC curve,and the peak intensity in crystal diffraction weakened markedly as well.Moreover,neither the characteristic peak in FTIR spectra nor the diffraction peak on WAXD patterns showed up for the long segments of polypropylene.Together with the missing melting peak of isotactic polypropylene on DSC curve,it was inferred that polypropylene hardly existed in the long-chain form basically.All these results confirmed the effective role played by[N,P]-type non-metallocene catalysts in the preparation of multi-block copolymers PE-b-P(E/P).
Eight[N,P]-type non-metallocene catalysts were synthesized successfully via the reaction between two kinds of ligands carrying different electronic effect groups and chloride compounds of transition metals Ti,Zr,Ni and Pd.Catalyst Cat.L2-Ti exhibited the highest catalytic activity toward ethylene/propylene copolymerization thanks to the combined effects exerted by ligand structure,central atomic species,and polymerization conditions on copolymerization behavior of ethylene with propylene.The copolymer product achieved a high Mw up to 2.75×10~5 g/mol as measured by GPC,and ~(13)C-NMR test suggested that the content of propylene insertion within copolymer backbone reached 11.5 mol%.Characterization with ~(13)C-NMR,DSC,and WAXD demonstrated that macromolecular chains of the obtained copolymer were composed mainly of ethylene units existing as long-chain segments,while some other ethylene units formed random segments with copolymerized propylene monomers.Melting point of the copolymer decreased along with the increasing amount of propylene insertion,and so did the peak intensity in crystal diffraction of polyethylene segments.At the greatest insertion amount of propylene of 11.5 mol%,the melting peak could hardly be noted on DSC curve,and the peak intensity in crystal diffraction weakened markedly as well.Moreover,neither the characteristic peak in FTIR spectra nor the diffraction peak on WAXD patterns showed up for the long segments of polypropylene.Together with the missing melting peak of isotactic polypropylene on DSC curve,it was inferred that polypropylene hardly existed in the long-chain form basically.All these results confirmed the effective role played by[N,P]-type non-metallocene catalysts in the preparation of multi-block copolymers PE-b-P(E/P).
引文
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2 Fang Yuanyuan(方园园),Yu Luqiang(于鲁强),Li Ruxian(李汝贤).Petrochemical Technology(石油化工),2014,43(8):861-869
3 Kuang Xiao(匡晓),Liu Guoming(刘国明),Wen Tao(文韬),Zhang Xiuqin(张秀芹),Dong Xia(董侠),Wang Dujin(王笃金).Acta Polymerica Sinica(高分子学报),2013,(5):679-687
4 Arriola D J,Carnahan E M,Hustad P D,Kuhlman R L,Wenzel T T.Science,2006,312(5774):714-719
5 Dow Global Technologies Inc.US patent.20120083575.2012-04-05
6 Hustad P D,Kuhlman R L,Arriola D J,Carnahan E M,Wenzel T T.Macromolecules,2007,40(20):7061-7064
7 Tian J,Hustad P D,Coates G W.J Am Chem Soc,2001,123(1):5134-5135
8 Kojoh S,Matsugi T,Saito J,Mitani M,Fujita T,Kashiwa N.Chem Lett,2001,30(8):822-823
9 Furuyama R,Mitani M,Mohri J,Mori R,Tanaka H,Fujita T.Macromolecules,2005,38(5):1546-1552
10 Weiser M S,Thomann Y,Heinz L C,Pasch H,Mülhaupt R.Polymer,2006,47(13):4505-4512
11 Sakuma A,Weiser M S,Fujita T.Polym J,2007,39(3):193-207
12 Mitani M,Furuyama R,Mohri J,Saito J,Ishii S,Terao H,Nakano T,Tanaka H,Fujita T.J Am Chem Soc,2003,125(14):4293-4305
13 Saito J,Mitani M,Mohri J,Yoshida Y,Matsui S,Ishii S,Kojoh S,Kashiwa N,Fujita T.Angew Chem Int Ed,2001,40(15):2918-2920
14 Mitani M,Mohri J,Yoshida Y,Saito J,Ishii S,Tsuru K,Matsui S,Furuyama R,Nakano T,Tanaka H,Kojoh S,Matsuqi T,Kashiwa N,Fujita T.J Am Chem Soc,2002,124(13):3327-3336
15 Yamahiro M,Mori H,Nitta K,Terano M.Macromol Chem Phys,1999,200(1):134-141
16 Yamahiro M,Mori H,Nitta K,Terano M.Polymer,1999,40(19):5265-5272
17 Mori H,Yamahiro M,Prokhorov V V,Nitta K,Terano M.Macromolecules,1999,32(19):6008-6018
18 Exxon Chemical Patents Inc.US patent,9504248.1995-04-06
19 Exxon Chemical Patents Inc.US patent,9504250.1995-04-06
20 Yang Bingxin(杨炳忻).China Basic Science(中国基础科学),2014,(2):9-13
21 Xiao A,Wang L,Liu Q,Yu H,Wang J,Huo J,Tan Q,Ding J,Ding W,Amin A.Macromolecules,2009,42(6):1834-1837
22 Zhang C,Dong J.J Macromol Sci,Pure Appl Chem,2010,47(4):324-328
23 Liu W,Wang W J,Fan H,Yu L,Li B G,Zhu S.Eur Polym J,2014,54(1):160-171
24 Liu W,Zhang X,Bu Z,Wang W J,Fan H,Li B G,Zhu S.Polymer,2015,72:118-124
25 Mohammadi Y,Ahmadi M,Saeb M R,Khorasani M M,Yang P,Stadler F J.Macromolecules,2014,47(14):4778-4789
26 Guo Y,Cheng Z,Song S,Weng Y,Wu A,Xu J,Fu Z,Fan Z.J Polym Sci,Part A:Polym Chem,2017,55:2725-2729
27 Ahmadi M,Rashedi R,Ahmadjo S,Karimi M,Zahmaty M,Mortazavi S M M.J Therm Anal Calorim,2018,131(3):2523-2533
28 Leone G,Mauri M,Bertini F,Canetti M,Piovani D,Ricci G.Macromolecules,2015,48(5):1304-1312
29 Ma L,Liu W,Yi J,Wang H,Huang Q,Gao K,Yang W.J Appl Polym Sci,2015,120(6):3171-3179
30 Sheng Y,Huang H,Yu M,Zhang X,Cheng L,Liu Z,Liu W,Huang Q,Yi J,Yang W.J Ind Eng Chem,2014,20(2):419-425
31 Huang Q,Huang H,Guo J,Fan M,Li F,Cheng L,Liu Z,Liu W,Yang W.CN patent,201310108975.1.2013-03-31
32 Wang J,Nan F,Guo J,Wang J,Shi X,Huang H,Huang Q,Yang W.Catal Lett,2016,146:609-619
33 Dasari A,Rohrmann J,Misra R D K.Met Sci J,2003,19(9):1298-1308
34 Zhu X,Yan D,Yao H,Zhu P.Macromol Rapid Commun,2000,21(7):354-357
35 Li Sanxi(李三喜),Ma Ruichun(马瑞春),Zhang Fan(张帆).Chinese Journal of Magnetic Resonance(波谱学杂志),1998,(2):109-116
36 Feng Y,Hay J N.Polymer,1998,39(26):6723-6731