SYNTHESIS OF A COMB GRAFT COPOLYMER VIA RING OPENING METATHESIS POLYMERIZATION CATALYZED BY SUPPORTED RHUTHENIUM CARBENE COMPLEX

5－Chloromethyl-2-norbornene was synthesized via Diels-alder reaction of cyclopentadiene and allyl chloride using a polymer supported boron trifluoride as the catalyst,and was then lithiated and used to initiate a livcing anionic polymerization of styrene to prepare a macromonome,5-polystryl-2-norbornene NB-PS,Comb graft copolymer PNB-g-PS was synthesized via ring opening metathesis polymerization of the macromonomer under the catalysis of ruthenium carbene complex RuCl2(PPh3)2(=CCHtBu)and its polymer supported correspondent.Experimetal results showed that the behavior of both the supported boron and supported ruthenium catalysts are superior to their unsupported counterparts.The possible promotion mechanism of the tailor-made supports is discussed.     

载体化络合催化开环歧化聚合合成梳形接枝共聚物研究

由环戊二烯（CPD）及烯丙基氯（AC）经聚合物支载三氟化硼催化的Diels-Alder反应合成了5-氯甲基-2-降冰片烯（NB-CH2Cl),锂代后用以引发甲基丙烯酸甲酯（MMA）及苯乙烯（S）的活性阴离子聚合,合成了带聚合物取代基的降冰片烯大分子单体NB-PMMA及NB-PS。在聚合物支载钌卡宾络合物催化作用下进行所合成大分子单体的开环歧化聚合反应（ROMP）,合成了二种接枝于开环歧化聚降冰片烯（PNB）主链的梳形接技共聚物PNB-g-PMMA及PNB-g-PS。实验结果表明所研制聚合物支载硼、钌络合物催化性能明显优于对应非支载活性种。     

TAILORING POLYMERS WITH NOVEL STRUCTURES VIA RING OPENING METATHESIS POLYMERIZATION

ThisProjectwassupportedby"NationalNaturalScienceFoundationofChina(projectapprovalnumber29474160)"and"FOundationofStateKeyLaboratoryofFunctionalPolymericMaterialsforAdsorptionandSeparation,NankaiUniversity(kf035)".ThisisalsoaninvitedlecturegivenattheChemistryDepartmentofSophiaUniversity,Japan,onJan.14,1998.ReceivedMay5,1998##D1NTRODUCTIONInrecentyearssomedramaticadvancesinthefieldofROMPhaveattractedgreatinterestandattentionofscientistsengagedinthedesignandtailoringofmolecularstr…     

活性开环歧化合法合成带羧酸酯基功能高分子

由石油化工C5馏分提取得到的粗产品双环戊二烯(DCPD,83.9%)经精馏制成高纯度双环戊二烯(98.9%),解聚后制成环戊二烯(CPD).以CPD、丙烯酸叔丁酯(tBA)为原料经Diels-Alder反应合成得到了一种带叔丁氧羰基的降冰片烯衍生物-2-叔丁氧羰基-5-降冰片烯(BOCN).以钌卡宾络合物RuCl2(PCy3)2(=CHPh)为引发剂进行所合成降冰片烯基单体BOCN的活性开环歧化聚合(ROMP)反应,合成得到一种具有受控分子量及窄分子量分布的带羧酸酯基的反应性高分子.     

双环戊二烯开环歧化聚合反应催化体系的配位体效应研究

用WCl6－Et2AlCl催化体系进行双环戊二烯的开环歧化聚合反应，考察了催化体系的配体效应。实验结果表明在催化体系中添加位阻酚—2．6-二叔丁基-对甲苯酚（DTBC）能明显提高聚合反应的转化率和合成聚合物的机械性能（如冲击强度、拉伸强度等）。利用位阻高分子酚──线形酚醛树脂（LPF）作为配体也得到类似的结果。     

LIGAND EFFECT OF CATALYTIC SYSTEM WCl_6-Et_2Al FOR RING OPENING METATHESIS POLYMERIZATION OF DICYCLOPENTADIENE

INTRODUCTIONInrecentyearsresearchprojectsonROMPofcycloolefinshavebeenattractingattentionofscientistsengagedinthesynthesisanddesignofnewpolyTneric'AprojectsupportedbytheNationalNaturalSCienceFoundationofChina(projectapprovalnumber:29474160).'-Correspondingauthormaterials,amongthemROMPsofnorbornene,norbornenederivativesandDCPDhavefoundgrowingfavourinthechemists,.y.,LI--4].Acrosslinkedpolarer(PDCPD),anewplastic,possessingexcellentmechanicalproperties(highNIS,TSetc)a-ndgoodthermal…     

环状碳酸酯低聚物的合成及其开环聚合的研究

环状碳酸酯低聚物的合成及其开环聚合的研究陈雨萍魏玮李革（中国科学院化学研究所工程塑料国家重点实验室北京１０００８０）关键词环状碳酸酯低聚物，聚碳酸酯，开环聚合环状单体的开环聚合在合成高聚物方面具有突出的优点，即在聚合过程中没有副产物、热效应低、聚合...     

双环戊二烯开环歧化聚合反应及合成聚合物性能研究

采用WCl6－ArOH／Et2AlCl（ArOH：2，6-二叔丁基对甲苯酚）催化体系进行了双环戊二烯的开环歧化聚合反应，考察了单体纯度以及催化体系支载化对聚合反应和合成聚合物性能的影响。在极限聚合浓度下，研究了单体与主、助催化剂摩尔比等因素对聚合反应及合成聚合物性能的影响。实验结果表明：单体纯度越高所得聚合物的机械性能越好；催化体系经聚合物支载化后能显著提高催化体系的催化聚合活性及合成聚合物的机械性能。     

二(叔丁基环戊二烯基)钕甲基配合物催化ε-己内酯开环聚合

二（叔丁基环戊二烯基）钕甲基配合物催化ε 己内酯开环聚合罗云杰姚英明沈琪（苏州大学化学化工学院苏州２１５００６）关键词开环聚合，ε 己内酯，茂基稀土甲基配合物聚ε 己内酯（Ｐｏｌｙｃａｐｒｏｌａｃｔｏｎｅ，ＰＣＬ）是一种生物降解材料，有良好的相...     

SYNTHESIS OF NOVEL BI-FUNCTIONAL COPOLYMER BEARING STERICALLY HINDERED PHENOL AND HINDERED AMINE GROUPS VIA RING-OPENING METATHESIS POLYMERIZATION

Norbornene derivatives exo,endo-2-[2-(3,5-di-tert-butyl-4-hydroxyphenoxy)-acetoxy]methyl-5-norbornene(M1) and 3,3,5,5-tetramethyl-4-piperidinyl 5-norbornene-exo,endo-2-carboxylate(M2)were synthesized and polymerized by RuCl_2(=CHPh)(PCy_3)_2 to prepare a novel kind of bi-functional polymer bearing sterically hindered phenol(SHP)and hindered amine(HLAS)groups via ring-opening metathesis polymerization(ROMP).The resulting copolymers were characterized by gel permeation chromatography(GPC),~1H-NMR and diffe...     

双金属氰化物络合物催化环氧烷烃开环聚合的特征

合成了Co Zn双金属氰化物 (DMC)络合物催化剂 ,以X 射线衍射、元素分析、红外光谱等手段进行了表征 ,考察了该催化体系下环氧丙烷开环聚合的反应特性 ,并初步探讨了聚合反应的机理 .研究发现 ,Co Zn双金属氰化物催化剂具有很高的催化活性 ,适合于中高分子量聚醚的合成 ,但是碱性起始剂起阻聚作用 ;在该催化体系下聚合物分子量可控 ,不饱和度很低 (<0 .0 14meq g) ,分批加料聚合所得到的聚合物分子量分布较窄 (Mn Mw <1.4 ) ,而一步加料聚合所得到的聚合物分子量分布变宽 ;1 3C NMR分析表明聚合物主链具有无规立构分布的特点 ,且链节分布几乎都为头 尾方式 .聚合过程中活性链与非活性链之间可能存在一个交换反应 ;虽然聚合反应有终止 ,但与聚合物链长没有关系 ,聚合物链的终止是可逆的 .     

RING OPENING POLYMERIZATION OF PROPYLENE SULFIDE BY RARE EARTH COORDINATION CATALYSTS*

Ring opening polymerization of propylene sulfide using rare earth coordination catalysts has been investigated for the first time. It has been found that trinary rare earth coordination catslysts composed of rare earth compounds of phosphonate, naphthenate or acetylacetonate, trialkyl sluminum and water are effective catalysts for the polymerization of propylene sulfide. The polymerization in toluene is a homogeneous reaction. High molecular weight as high as several million poly(propylene sulfide) with high yield can be prepared by these catalysts. Kinetic studies showed that the polymerization rate is of first order with respect to both monomer concentration and catalyst concentration. The activation energy of the polymerization reaction is 61.4 k fJ/mol. The structure of the polymers so obtained has also been characterized by ~(13)C NMR spectroscopy, X-ray diffraction, gel permeation chromatography and differential scanning calorimetry.     

肌酐乳酸胍催化L-丙交酯活性开环聚合反应研究

合成了一种新型有机胍化合物即肌酐乳酸胍(CGLA),并将其应用于L-丙交酯(LLA)的开环聚合反应.聚合反应动力学研究表明,CGLA引发的LLA开环聚合反应具有典型活性聚合反应特征,ln[M]0/[M]t-t、Mn-Conversion关系均呈准直线关系.同核去偶1H-NMR法对产物立构规整度的表征证明所合成PLLA具有较高等规度(76%).聚合反应的添加剂效应研究证明了大分子活性物种的非自由基及非离子性本质.以1H-NMR法对聚合反应的跟踪和增长大分子物种结构的表征证明了增长大分子活性端为肌酐胍-烷氧结构(CG-OR),在实验研究的基础上推断CGLA引发的丙交酯开环聚合反应遵循配位插入增长机理.     

可修饰的内酯，α-氯甲基-α-甲基-β-丙内酯的合成和聚合

可修饰的内酯，α－氯甲基－α－甲基－β－丙内酯的合成和聚合＊王明霞李子臣贺晓晖杨丽＊＊李福绵（北京大学化学系北京１００８７１）关键词α－氯甲基－α－甲基－β－丙内酯，开环聚合＊１９９５－０２－２０收稿；１９９６－０３－１２修回：自然科学基金课题；＊＊...     

二(芳氧基)稀土(Ⅱ)配合物催化ε-己内酯开环聚合

系统地研究了二（２，６ 二叔丁基 ４ 甲基酚基）钐［（ＡｒＯ）２Ｓｍ（ＴＨＦ）４］催化ε 己内酯的开环聚合，发现它具有很高的催化活性并显示“活性”聚合的特点，在甲苯中，当［Ｍ］／［Ｉ］＝２０００（摩尔比），６０℃，１ｈ，转化率可达９８％．并比较了不同的两价稀土化合物的催化活性．通过核磁分析末端基结构的方法，研究了（ＡｒＯ）２Ｓｍ催化己内酯开环聚合的引发机理，发现催化剂首先与己内酯反应，生成三价烯醇式稀土化合物，后者引发己内酯聚合．     

聚乙二醇-聚苯乙烯接枝共聚物的合成及其接肽反应性能

本文应用环氧乙烷在羟乙基树脂上的开环聚合方法,合成了凝胶和大孔型聚乙二醇-聚苯乙烯接枝共聚物(简称PEG树脂)。对不同类型载体的接肽反应动力学性能研究表明,在PEG树脂载体上的反应速度是在氯甲基化树脂上的三倍,与在溶液中进行的接肽反应速率相当。此外,还对载体性能与树脂交联度、骨架结构之间的关系进行了初步探索。     

SYNTHESIS AND ANIONIC POLYMERIZATION OF 2-METHYL-2-METHOXY CARBONYL-5-METHYLENE-1, 3-DIOXOLAN-4-ONE

A new cyclic monomer, 2-methyl-2-methocycarbonyl-5-methylene 1,3-dioxlan-4-one,wassynthesized successfully. The monomer and intermediate were characterized by ~1H NMR,~(13)C NMR, INEPT (Intensive Nuclei Enhanced by Polarization Transfer) technique, IR andelemental analysis. Anionic polymerization of the monomer was carried out in anhydrous THF at.70℃, and 9-fluorenyllithium was used as initiator. The polymer strucure was determined byIR, NMR and elemental analysis. Molecular weight of the polymer was estimated by viscositymeasurement in DMSO at 30℃.     

阴离子聚合制备聚乙烯-g-聚氧化乙烯接枝共聚物

聚烯烃 (聚乙烯 ,聚丙烯等 )的化学改性一直是科学研究和实际生产的一个热点 ,改性过的聚烯烃可以广泛应用到高分子共混物和复合材料中 .在众多聚烯烃中 ,聚乙烯产量最大 ,但因其惰性也最难于化学改性 .我们采取的改性方法是在聚合物中引入反应性基团 ,可以在温和条件下进行有选择的而且高效的化学改性 .由于两亲性共聚物可用作乳液聚合和悬浮聚合中的表面活性剂及稳定剂 ,塑料的表面改良剂和聚合物的共混相容剂等[1,2 ] ,因此人们对该共聚物的研究越来越多 .过去 ,多数两亲性共聚物的研究局限于聚苯乙烯 (ＰＳ)和聚氧化乙烯 (ＰＥＯ)接枝共…     

四氢呋喃开环均聚以及四氢呋喃和环硫氯丙烷共聚新催化体系

研究发现无水稀土氯化物 ５０％发烟硫酸体系是四氢呋喃（ＴＨＦ）均聚和四氢呋喃与环硫氯丙烷（ＣＭＴ）共聚合的优良新催化体系．考察了ＴＨＦ均聚反应特征，在合适条件下，ＴＨＦ聚合以６５％转化率制得粘均分子量达１０，０００～１５，０００的白色聚四氢呋喃（ＰＴＨＦ）固体．端羟基分析法测得聚合物的分子链两端均为羟基．考察了影响ＴＨＦ ＣＭＴ共聚合反应诸因素，如聚合温度和时间、两单体的比例等，制得数均分子量为１，０００左右的淡黄色粘性固体共聚物．     

SYNTHESIS OF ABA TYPE TRIBLOCK COPOLYMERS BY RADICAL POLYMERIZATION WITH 1,4-BIS(p-TERTBUTYLPHENYLSELENOMETHYL) BENZENE AS A PHOTOINIFERTER

1,4-Bis(p-tert-butylphenylselenomethyl)benzene was used as a bifunctional photoiniferter for the polymerization of methyl methacrylate (MMA). Both the polymer yields and the number average of molecular weights ([Mbar]_n) of polymers increased with the polymerization time and the [Mbar]_n linearly increased with polymer yield. The addition of MMA to the poly(MMA) with irradiation increased the [Mbar]_n of the polymer. Photoirradiation of telechelic polystyrene having phenylseleno groups at both ends as polymeric photoiniferter in the presence of MMA or p-chloromethylstyrene afforded effectively corresponding to the ABA type triblock copolymers. On the other hand, photopolymerization of p-methylstyrene with ABA type triblock copolymer of styrene and p-chloromethylstyrene as polymeric photoiniferter afforded to multiblock copolymer of styrene and p-substituted styrenes.