乙烯/降冰片烯共聚物的合成及其結構

第30卷第5期西安工業(yè)大學(xué)學(xué)報Vol. 30 No, 52010年10月Journal of Xi' an Technological UniversityOct. 2010文章編號: 1673-9965(2010)05-449-05乙烯/降冰片烯共聚物的合成及其結構“李永飛，伍青2(1.西安工業(yè)大學(xué)材料與化工學(xué)院.西安710032;2. 中山大學(xué)化學(xué)與化學(xué)工程學(xué)院,廣州510275)摘要:針對環(huán)烯烴與c烯烴 共聚合而成的熱塑性工程塑料催化劑的選擇,文采用β二亞胺鈦催化劑合成了乙烯與降冰片烯的共聚物,進(jìn)行了其微觀(guān)結構和催化機理研究.研究結果表明，β二亞胺鈦催化劑能夠很好地催化乙烯與降冰片烯的共聚合.通過(guò)對合成的共聚物的徹觀(guān)結構的分析發(fā)現,鈦催化劑合成的乙烯/降冰片烯共聚物以無(wú)規結構為主,共聚物中出現了降冰片烯的二聚和三聚序列結構.共聚合機理的研究也表明該催化劑有利于合成乙烯與降冰片烯的無(wú)規共聚物.關(guān)鍵詞: β二亞胺 鈦;環(huán)烯烴共聚物;共聚物結構;聚合機理中圖號: TH145. 4.文獻標志碼: A .環(huán)烯烴共聚物(COC)是一類(lèi)非常 重要的熱塑的研究上做了大量的工作.對共聚物微觀(guān)結構的分性工程塑料材料,具有很好的透明度、優(yōu)良的熱穩析表明，茂金屬催化體系通常得到的乙烯/降冰片定性和耐化學(xué)侵蝕性,可用于制造各種光學(xué)鏡頭以烯 共聚物中降冰片烯的含量小于50%,共聚物中及取代聚碳酸酯(PC)生產(chǎn)高密度DVD等的材料.降冰片烯單元以孤立的或交替的形式存在[35].另外,COC材料還有非常低的介電常數及很好的文獻[6-7]報道了吡咯亞胺鈦及β-酮胺鈦催化隔潮性能,可用于制造一些電子及電器部件.劑催化乙烯/降冰片烯共聚合.這種[N,N]配位的COC是由環(huán)戊烯、降冰片烯等環(huán)烯烴與乙烯、簡(jiǎn)單配體合成相對簡(jiǎn)單,配體的電子及位阻結構容丙稀或其他-烯烴共聚得到的共聚物.從環(huán)烯烴單易調節,便于研究配體結構對催化劑活性的影響.體的反應機理上,COC的制備方法主要有兩種:開(kāi)我們前期合成了β二亞胺鈦催化劑,并研究了其催環(huán)易位聚合以及乙烯基加成聚合開(kāi)環(huán)易位聚合得化乙烯與降冰片烯的共聚合8.文中研究了鈦催化到的大分子鏈中含有雙鍵,材料的介電常數較高，劑催化合成的乙烯/降冰片烯共聚物的結構,并對抗氧化性及耐化學(xué)腐蝕性較差,限制了材料的用其催化機理進(jìn)行了討論,結果表明這種催化劑得到途".乙烯基加成聚合得到的COC材料中不含雙乙烯與降冰片烯的交替共聚物.鍵，而且保持著(zhù)環(huán)烯烴的環(huán)狀結構,材料的力學(xué)性能很好,是目前在實(shí)驗室中合成CoC材料的主要1實(shí)驗方法.在COC的合成中,催化劑的選擇直接決定著(zhù)1.1原料及試劑合成的COC結構.合成COC常用的催化劑有茂金屬催化劑以及鈦、鋯等金屬為主的過(guò)渡金屬催化甲苯:分析純,廣州化學(xué)試劑廠(chǎng).用前在高純氮劑.環(huán)烯烴單體通常選用價(jià)格相對低的降冰片烯.氣保護下與金屬鈉-起回流6 h以上,蒸餾出使用.Kaminsky等最先報道了茂金屬催化乙烯與降冰片烯(NBE)純度為99% , Aldrich公司生降冰片烯共聚合[2).此后,Fink以及Titto等研究產(chǎn).使用前用金屬鉀在60 C攪拌過(guò)夜,蒸餾出后配小組也在茂金屬催化劑催化乙烯/降冰片烯共聚合成甲中國煤化工YHCNMHG收稿日期:20-04-15資助基金:陜西省教育廳科研專(zhuān)項(07JK273);陜西省自然科學(xué)基金(2007B20);2010年陜西省教育廳科研計劃項目作者簡(jiǎn)介:李永飛(1974-),男,西安工業(yè)大學(xué)副教授,主要研究方向為高分子材料的合成及應用. E-mail:cep03lyf@126. com.450西安工業(yè)大學(xué)學(xué)報第30卷β二亞胺配體及其鈦的配合物的合成,以及助及表征前期已經(jīng)報道過(guò)[8].研究選用降冰片烯單體催化劑甲基鋁氧烷(MAO)的合成見(jiàn)文獻[8].的加入量分別為4 g和10 g,乙烯常壓在40 C聚1.2儀器及測試方法合,得到的乙烯/降冰片烯共聚物中降冰片烯含量18CNMR用UnityINOVA500型核磁共振Xx=0. 25和XN=0.48進(jìn)行聚合物的結構研究.儀測定.聚合物用氘代1,2-二氯苯溶解，以四甲基2.2共聚物的微觀(guān)結構分析硅烷(TMS)作內標.采用二亞胺鈦/MAO催化體系催化乙烯/COC共聚物的分子量及分布是在Varian降冰片烯共聚合,其共聚物的微觀(guān)結構可以通過(guò)INOVA 500-MHz凝膠色譜儀測定.以二氯苯為溶18C NMR譜圖進(jìn)行研究.降冰片烯含量XN=0.25劑,110 C柱溫.分子量以聚苯乙烯為標準處理.的乙烯/降冰片烯共聚物的C NMR譜圖如圖21.3乙烯與降冰片烯 共聚合所示.主要的吸收峰為降冰片烯交替結構(ENEN)在帶有電磁攪拌的50 mL的玻璃聚合反應瓶以及孤立的降冰片烯(ENEE)序列(如圖3所示).中,加入232 mg固體MAO,用注射器加入10 mL譜圖上29. 9 ppm以下以及35~41 ppm范圍內沒(méi)降冰片烯的甲苯溶液及19 mL甲苯,通人乙烯氣有吸收峰,表明共聚物中沒(méi)有降冰片烯的嵌段結構至常壓.反應體系在聚合溫度充分攪拌均勻后繼續出現.因為在這些區域應該是降冰片烯二聚或三聚攪拌10 min,加入催化劑的甲苯溶液1 mL,調節乙序列的吸收峰出現的區域10].圖2上出現的吸收烯的壓力為常壓，聚合反應開(kāi)始.在聚合過(guò)程中保峰的歸屬見(jiàn)表1.持乙烯的壓力為常壓不變.聚合反應0.5 h后停止乙烯的通人.向反應器加入鹽酸/乙醇終止反應.將得到產(chǎn)物經(jīng)乙醇浸泡，過(guò)濾用無(wú)水乙醇洗滌數次后,將聚合物在60 C真空干燥箱內千燥至恒重.共聚物中降冰片烯的含量(Xw)的計算方法為XN=[(Iq/q, +Iq/q +2I, )/3Ian ]J9]人其中Iq.c/q.Ic,以及l(fā)ay分別為共聚物"C54:40353NMR譜中C/C .C/C、C的積分,Iay,為Cs/Cppm以及乙烯的CH2在"C NMR譜圖上的總積分.圈2乙烯/降冰片 烯的共聚物的2結果與討論IC NMR譜團(XN=0.25)Fig.2 3C NMR spectrum of the ethylene2.1乙烯 與降冰片烯的共聚合norbormene copolymer (XN =0.25).實(shí)驗所用β二亞胺鈦配合物結構如圖1所示.F,CC/ CF,交替等規交替間規.. I號()(um1)，CCF，F,C -Isolated NBE中國煤化工烯單元的圖1 β二亞胺鈦配合物結構Fig.1 Titanium complex bearing f-dikeiminate ligand.MH.CNMH(G結構Fig.3 ivIcrostrUcture oI etnylene/ norbomene copolymer大位阻的β-二亞胺配體及鈦的配合物的合成with alternating and isolated norbornene unit.第5期李永飛等:乙烯/降冰片烯共聚物的合成及其結構51表1乙烯/降冰片烯共聚物的"C NMR譜歸屬的引發(fā)主要是主催化劑在MAO的作用下形成MTab.1 Chemical shifts assignment in BC NMR-R鍵,單體插人M- R鍵形成活性種.由于有兩spectrum of ethylene/ norbormene copolymer種單體,因此活性中心可能不止一種. Titto認為化學(xué)位移(ppm)微觀(guān)結構茂金屬Zr催化乙烯/降冰片烯共聚合在鏈的引發(fā)30. 06.交替間規C/Gq可能形成Zr+-E以及Zr+-N活性種,但是動(dòng)力30. 58C/C:/C./Cp學(xué)的研究表明活性種以Zr+ - N為主，前者對鏈轉31. 10 .交替等規C/Gq33.27交替/孤立的C移以及鏈增長(cháng)速率的貢獻大[0. Fjuita通過(guò)端基分41. 85交替間規/孤立的G/C析認為雙-(吡咯亞胺)鈦催化乙烯/降冰片烯共聚42. 37交替間規C/C合的活性種是Ti-N-CHs,而Ti-E- p活性種47. 40交替間規/孤立的C/G出現在鏈增長(cháng)過(guò)程中(6].由于雙-(β-二亞胺)鈦催48. 12交替等規的C/Gs化劑得到的乙烯/降冰片烯共聚物的微觀(guān)結構以交隨著(zhù)共聚物中降冰片烯含量的增加,共聚物替或孤立結構為主,因此其活性種也應該是以2的"C NMR譜圖也有所變化.降冰片烯含量為48為主(圖5).因此反應將主要沿著(zhù)3-4-7-4的mol%的共聚物的"C NMR譜圖如圖4所示.與圖順序進(jìn)行.由于共聚物結構分析表明含有孤立的降2相比,圖4在28. 5,31. 6 ppm附近出現了蜂,而冰片烯單元，因此鏈增長(cháng)過(guò)程也有順著(zhù)3-4-6這些位置的峰通常認為是Cs/Cs以meso-或race-進(jìn)行的.降冰片烯也能進(jìn)- - 步插人鏈增長(cháng)種3使得mic-ENNE順序排列的降冰片烯二聚(D)序列1.鏈得到增長(cháng).但是由于降冰片烯結構的空間位阻作圖4還在34~41 ppm.43.4 ppm以及48. 9~51用，使得形成NN降冰片烯二聚序列的結構5變ppm處都出現了明顯的吸收峰.說(shuō)明共聚物中包得閑難了.同樣原因,形成降冰片烯三聚序列NNN含有更長(cháng)的降冰片烯均聚序列結構[2]. Fink、Shio-的9可能性更加小了.因此共聚物結構中含有降冰no等研究認為這些新的共振峰主要是共聚物中的片烯二聚以及三聚序列的含量較少.降冰片烯二聚(D)以及三聚(T)序列[1014].通過(guò)與L,TKCI相關(guān)文獻[ 10-14]中碳的化學(xué)位移的對比,可分別MAO|對這些區域的降冰片烯的二聚以及三聚序列結構L,Ti -CH,旦只"三只。進(jìn)行歸屬.L,Ti CH, LTi,/ L.T息。ITi-EEN)56MD56RDMRTI pLti日LT(c/C,C/C，C， CJC.&CH(Ti-NEN)" LTIJIL_ RDl_(Ti-ENN)55 5043530 25ppm日L,TiR圈4乙烯/降冰片烯的共聚物的同N目|(Ti-NNN)HC NMR譜團(XN=0.48)r-NFig. 41C NMR spectra of the ethyleneP:聚合物鏈E: IInorbornene copolymer (XN =0.48).-(A-亞映)針健化劑健化乙烯/降冰片烯2.3共聚合機理中國煤化工機理由前面對乙烯/降冰片烯共聚物的微觀(guān)結構的THC N M H Gain itiation分析可以推斷出這種雙-(β二亞胺)鈦催化劑催化and the propagation in ethylene/ norbomene∞opolymerization乙烯/降冰片烯共聚合的可能機理如圖5所示.鏈with bis-(Bdiketiminato) titanium complexes452西安工業(yè)大學(xué)學(xué)報第30卷文獻[3-4]等的研究結果表明，降冰片烯最后4] Tritto I, Boggioni L, Ferro D R Alternating lsotactic插人的鏈增長(cháng)種B要比乙烯最后插人的鏈增長(cháng)種Ethylene- Norbornene Copolymers by C - SymmericA穩定得多,主要是因為B難以發(fā)生p-H轉移,而Metallocenes: Determination of the CopolymerizationParameters and Mechanistic Considerations on theA則容易發(fā)生鏈轉移反應,形成乙烯基端基的聚合Basis of Pentad Analysis[J]. Macromolecules, 2004,物鏈如圖6所示.另外,由于共聚物的分子量分布37 :9681.比較寬(Mm/M,~ 2. 5),說(shuō)明還存在向烷基鋁的鏈[5] McKnight A L,Waymouth R M. Group 4 ansa-.Cyclo-轉移反應.pentadienyl- Amido Catalysts for Olefin Polymeriza-βH刷單體.tion[J]. Chem Rev, 1998,98:2587.的轉移[ALF-CH,6] Yoshida Y, Mohri J I, Ishii S I,et al Living Copoly-[Al)merization of Ethylene with Norbornene Catalyzed byBis(Pyrrolide-lmine) Titanium Complexes with MAOL,Ti AL,Ti'-R[].J Am Chem Soc,2004,126; 12023.LTi-CH,_7] Li X,Dai K, Ye W,et aL. New Titanium Complexeswith Two β-Enaminoketonato Chelate Ligands: Syn-- LTitheses, Structures, and Olefin Polymerization Activi-B[AL-CH, .ties[J]. Organmaeallics,2004,23: 1223.[AI][8] li Y,Gao H, Wu Q Homo and Copolymerization of圖6雙-(β二亞胺)鈦催化劑催化乙烯/Ethylene and Norbormene with Bis( b- diketiminato)降冰片烯共聚合的鏈轉移反應Titanium Complexes Activated with Methylaluminox-Fg 6 Chain transfer in ethylene/ norbormene copolymerizationane[J].J Polym Sci; Part A: Polym. Chem, 2008,46;with bis(j-diketiminato) titanium complexes93.9] Tritto I,Boggioni L,Sacchi M C,et aL Ethylene.Nor-3結論bornene Copolymers Prepared with Metallocene -Based Catalysts: New Sequence Assinments by 1Cβ二亞胺鈦催化劑/MAO體系能夠有效催化NMR[J]. Macromol Rapid Commun, 1999 ,20:279.乙烯與降冰片烯的共聚合,合成COC材料.催化劑[10] Amdt M,Engehausen R, Kaminsky W,et al. Hydrooli-的活性及共聚物分子量都隨著(zhù)共聚單體中降冰片gomerization of Cylolefins -a View of the Microstrur-烯投料量的增加而下降.實(shí)驗通過(guò)'CNMR研究ture of Polynorbomene[J]. J Mol Catal A: Chem,了乙烯/降冰片烯共聚物的微觀(guān)結構,發(fā)現合成的1995,101:171.共聚物中降冰片烯以交替或孤立鏈節結構為主,在[11] Hasan T, Ikeda T, Shiono T. Ethene- Norbormene降冰片烯含量高的共聚物中出現了降冰片烯的二Copolymer with High Norbornene Content Produced聚和三聚序列結構.對共聚合機理的探討表明共聚by ansa - Fluorenylamidodimethyltitanium Complex有利于乙烯的插人,影響了共聚物中降冰片烯含量Using a Suitable Activator [J]. Macromolecules,2004 ,37 :8503.的提高.[12] McKnight A L, Waymouth R M Ethylene/Nor-參考文獻:bormene Copolymerizations with Titanium CpA Cat-alysts[J]. Macromolecules, 1999，32:2816.[1] Luo X,Wu Q Vinyl Polymerzation of Cyelic Olefins[13] Wendt A R, Fink G. Ethene norbormene Copolymeri-[]. Petrol Chem Ind,2001,30<7):567.zations Using Two Different Homogeneous Metallo-[2] Kaminsky W. New Polymers by Metallocene Catalysiscene Catalyst Systems and Investigations of the Co-[J]. Micromol. Chem. Phys, 1996, 197 :3907.polymer Microstructure[J].J Mol Catal Part A:[3] Ruchatz D, Fink G. Ethene- Norbormene Copolymeri-zation withHomogeneous Metallocene and Half -中國煤化工Sandwich Catalysts ; Kinetics and Relationships be[14]=et al Ethylene nor-MYHcNMHGreAsmeandtween Catalyst Structure and Polymer Structure 3Advances Based on Assignments of 13C NMR Spec-Copolymerization Parameters and Copolymerizationtra[J]. Macromoleue2000.33.8931.Diagrams[J]. Macromolecules, 1998,31 :4681.第5期李永飛等:乙烯/降冰片婼共聚物的合成及其結構453Synthesis and Structure of Cyclic Olefin CopolymerLI Yong feil.2 ,WU Qing2(1. School of Materials and Chemical Engineering, Xi' an Technological University,Xi' an 710032,China;2. Institute of Polymer Science,School of Chenistry and Chemical Enineering,Sun Yat-Sen University,Guangzhou 510275,China)Abstract:The importance role of choosing suitable catalysts in preparing thermoplastic cyclic olefincopolymer (COC) is emphasibed. The paper studies the copolymerization of ethylene with norbornenecatalyzed by bis(β diketiminato) titanium complex/ MAO. The microstructure of CoC obtained and thecopolymerization mechanism are investigated. The results indicate that bis (β- diketiminato) titaniumcomplex is a good catalyst for catalyzing copolymerization of ethylene with norbornene in the presence ofMAO. The obtained polymers are an alternative copolymer with norbornene dimer and trimer.Additionally, the mechanism analysis shows that the titanium complex is favorable to produce randomethylene norbornene copolymer.Key words: bis(β diketiminato) titanium; cyclic olefin copolymer; structure of COC;polymerization mechanism(責任編輯、校對張立新)(上接第448頁(yè))[3]胡添元,余雄慶. 基于CATIA二次開(kāi)發(fā)的飛翼外形HU Ting. Technological Basis of CATIA Secondary參數化建模[]飛機設計,2007 ,27(6):10.Development[M]. Electronic Industry Press, 2006.HU Tian-yuan, YU Xiong-qing. A Parametric Model-(in Chinese)ing of Flying wing Configuration Using API in CAT-[5]劉程鵬.基于CATIA軟件對VBA的支持進(jìn)行曲面IA[J]. Aircraft Design,2007 ,27(6):10.設計[J].貴州大學(xué)學(xué)報,2007,24(5):495.LIU Peng cheng. Using VBA to Design Curved Sur-[4]胡挺. CATIA二次開(kāi)發(fā)技術(shù)基礎[M].北京:電子工face Based on CATIA Software [J]. Journal of業(yè)出版社,2006.Guizhou University ,2007 ,24(5) :495. (in Chinese)A Method of Surface Reconstruction in ReverseEngineering Based on CATIA VBAXIAO Jiang -chao(School of Mechatronic Engineering,Xi' an Technological University,Xi' an 710032 ,China)Abstract: The algorithm of surface reconstruction in reverse engineering based on the secondarydevelopment of CATIA is proposed as a solution to the problem that the generation of the splines ofsections needs many surface point coordinates, which is prone to error because of heavey workload.Firstly,the control points are read by using VBA program, and the splines of former sections aregenerated automatically in the generative shape design of CATIA. Then, the design of surfacereconstruction is finished by“l(fā)oft”command of CATIA,aIrfaces model inreverse engineering based on CATIA VBA. The experiment中國煤化工hod can ahievethe surface reconstruction.:TYHCNMHGKey words: reverse engineering; splines;CATIA; surface reconstruction; VBA(責任編輯、校對魏明明)