NdCl_3·3P350-AlR_3二元催化体系对双烯烃的定向聚合

由氯化稀土的不同种类磷酸酯配合物与三烷基铝组成的Ziegler-Natta催化剂对双烯烃聚合的研究已有报道,其中聚合活性最高的NdCl_3·3P350—AlR_3二元催化体系对丁二烯溶液聚合及异戊二烯本体聚合的详细研究尚未见报道,本文考察了该体系对双烯烃的定向聚合能力,通过二元体系与相应的催化剂活性体聚合规律的对比,提高对稀土催化聚合反应过程的认识。     

稀土定向聚合催化剂及用以聚合的二烯类高聚物的特征

十五年前,我们曾首先报导了用镧系稀土化合物作为丁二稀的定向聚合催化剂,得到了顺-1,4-构型的含量高的聚丁二烯,这在Eiegler-Natta型催化剂中从利用d-轨道成键电子发展f-电子。当时所用催化剂为二元体系,后由Throckmorton改进成三元体系、聚合活性得以提高。之后,我们用三元体系对异戊二烯进行了定向聚合,也得到了顺式含量高的聚异戊二烯。近年来,我们对这类催化体系的定向性、催化聚合活性、聚合反应历程及动力学等方面,以及上述这两种均聚物在结构与性能方面的特点进行了研究。同时还发展了丁二烯和异戊二烯的共聚,两种链节的顺式含量都高,并在催化剂上从三元再发展到新的二元体系,其中一些代表性结果如下。     

二(三氟乙酸)卤化钕催化体系中卤素对催化共轭双烯烃聚合的影响

众所周知,稀土配位催化剂用于共轭双烯的定向聚合,卤素是形成活性中心的必要条件之一。文献上对卤素在稀土催化剂中的作用曾有研究,但报导的都是非均相催化体系和三元催化体系。均相的二元催化体系中的卤素作用尚未见文献报导。鉴于从可溶性(CF₃COO)₂NdClEtOH-Et₃Al体系中分离出含卤素原子的活性体,研究卤素在该体系中的作用,对于活性催化剂的形成条件和催化聚合反应机制的了解都有意义。     

Nd-Al双金属配合物催化双烯聚合反应动力学

以Ｎｄ－Ａｌ双金属配合物为催化剂,考察了丁二烯和异戊二烯聚合反应的动力学,得到稳态聚合速率方程为Ｒｐ＝ｋ〔Ｍ〕〔Ｎｄ〕＾ｎ（ｎ＝１）;丁二烯比异戊二烯有更大的表观增长速率常数ｋ,这些与聚合体系中是否存在过量的烷基铝无关。对多组分稀土催化剂作用下异戊二烯聚合反应动力学方程中出现较高ｎ值的现象进行了初步的探讨。     

三氟甲磺酸稀土催化ε-己内酯开环聚合

采用三氟甲磺酸稀土(镧、钕、铒)作为单组分催化剂催化了ε-己内酯的本体开环聚合反应. 考察了稀土元素种类、催化剂浓度、聚合时间及温度对单体转化率和聚合产物分子量的影响. 该类催化剂在催化聚合过程中具有单一活性中心, 且催化活性较高. 此聚合反应可能是通过阳离子活性末端链聚合机理进行的.     

稀土催化制备窄分子量分布高顺式聚异戊二烯及聚合反应动力学

由稀土羧酸钕盐(Nd)、三异丁基铝(Al)、含氯活化剂(CE)及醇(OH)组成的均相稀土羧酸盐催化体系,用于异戊二烯(Ip)定向聚合,其中含氯活化剂(CE)为氯代烃(CE1)或氯代羧酸酯(CE2).研究了CE和OH的化学结构及Al用量对Ip聚合及聚异戊二烯(PIp)微观结构、分子量及分子量分布的影响,将原位全反射傅立叶红外光谱(in situ ATR-FTIR)技术应用于研究稀土催化Ip配位聚合反应过程及聚合反应动力学,采用FTIR、GPC、NMR及DSC等测试手段表征PIp的微观结构、分子量及其分布、序列分布及热性能.实验结果表明,在稀土催化异戊二烯聚合反应中,少量的CE2和OH有助于提高催化活性、降低分子量分布和提高顺式含量.聚合速率对单体浓度呈现一级动力学关系,表观增长活化能(Ea)为69.5 kJ/mol.通过调节催化剂组分配比及聚合工艺条件,可制备出顺-1,4结构含量可达98%以上、窄分子量分布(Mw/Mn=1.6～2.4)的高顺式聚异戊二烯.     

Nd-AI双金属活性体的活性部位及其对共轭双烯烃聚合机理的研究

<正> 稀土催化剂活性体对双烯烃配位聚合的研究已有很多报道,使用催化剂活性体对双烯烃聚合机理的研究比以前所用的多组分混合物的催化体系显然具有很大的优越性。本文利用NdCl_3·3TBP和Ndel_3·3P_(350)配合物与Al(i-Bu)_3体系所得活性体合成了共轭双烯烃低聚物,用IR、~(13)C-NMR光谱研究了这些低聚物分子的链端结构,从而推测活性体的活性部位组成和聚合机理。     

Nd(naph)3-Al(i-Bu)3体系催化丙烯酸乙酯及丙烯酸亚丁酯聚合

丙烯酸酯类极性单体的聚合反应通常采用自由基型引发剂。过渡金属化合物与烷酸铝所组成的配位催化剂对这类极性单体的催化聚合迄今仍处于研究阶段。我们在稀土催化环氧烷烃聚合的基础上曾研究了稀土钕的磷酸盐体系催化甲基丙烯酸甲酯、正丁酯的聚合。本文研究了环烷酸钕体系催化丙烯酸乙酯及丙烯酸正丁酯的聚合特征。     

稀土膦酸酯盐-烷基铝体系催化正辛基异氰酸酯配位聚合

报道了由稀土膦酸酯盐-烷基铝组成的催化体系在温和条件下催化正辛基异氰酸酯(n-OctNCO)的配位聚合特征. 研究发现, 以Nd(P204)3/Al(i-Bu)3组成的稀土催化体系是正辛基异氰酸酯聚合的良好催化剂. 系统考察了正辛基异氰酸酯在该催化体系下的本体、溶液聚合的聚合规律和溶液聚合反应动力学. 用1H NMR, FTIR, DSC, TGA和GPC等分析测试手段对所得到的聚合物进行了表征.     

FeBr3/Me6TREN催化MMA反向原子转移自由基聚合研究

对FeBr3/Me6TREN催化的反向原子转移自由基聚合进行了研究.在不同的催化剂、引发剂的配比、聚合温度和配体用量等条件下,该催化体系催化的MMA聚合反应动力学为一级反应,聚合物分子量可控,分子量分布很窄,说明该体系催化的聚合反应为活性可控聚合.通过实验计算了反应的活化能,并利用UV光谱对催化剂进行了研究.     

含稀土钛系催化剂的苯乙烯高活性定向聚合研究

本文用新研制的含稀土钕化合物的钛系催化剂(SN-1催化剂)于苯乙烯在苯溶液中进行定向聚合,能同时使产率、等规度、催化效率与聚合速率四项指标得到提高并远超过文献值。研究了各种聚合条件,即催化剂浓度、苯乙烯单体浓度、助催化剂三乙基铝浓度和聚合温度各因素对于催化效率、聚苯乙烯产率、等规度和分子量的影响规律并作讨论。     

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.     

Polymerization of acetylenes with rare earth coordination catalysts

The polymerization of acetylene and its derivatives by rare earth coordination catalysts and the characterization of the polymers so obtained in our laboratory are reviewed. Because of the metallic conductivity possessed by doped polyacetylene and the unique properties such as conductivity (semiconductivity), paramagnetism, migration and transfer of energy and chemical reactivity and complex formation ability often shown by acetylenic polymers, which seem promising as specialty polymers, there has been considerable interest in the polymers of acetylene and its derivatives. A wide variety of catalyst systems have been developed for the polymerization of acetylenes. But there has been no information concerning the use of rare earth compounds as catalysts in the polymerization of acetylene and its derivatives. We for the first time in 1981 have succeeded in the polymerization of acetylene with rare earth coordination catalysts, which in turn is a development based upon earlier work on the diene polymerization using rare earth coordination catalysts(Ref. 1). Using rare earth catalysts, acetylene can be polymerized conveniently into high cis polyacetylene films with metallic sheen at room temperature and phenylacetylene can also be polymerized into high molecular weight, high cis polyphenylacetylene films at ambient temperature. Thus new varieties of polyacetylenes have been developed and a novel family of coordination catalysts consisting of a rare earth compound plus trialkyl aluminum for the polymerization of acetylenes has been exploited. This article reviews our studies on the polymerization of acetylene and its derivatives with rare earth coordination catalysts and on the characterization of the polyacetylenes prepared.     

多核Nd-Al双金属配合物对丁二烯的聚合——Ⅰ.聚合物的分子量与微观结构间的关系及其聚合机理的讨论

在从均相稀土催化剂中分离出有聚合活性的Nd-Al双金属配合物的基础上,利用该配合物可单独引发丁二烯聚合的特点,较详细地研究了活性体浓度,外加烷基铝浓度,单体浓度以及聚合温度等因素对聚合产物分子量及微观结构的影响,确认二者之间存在着一定的内在联系,即分子量越高,顺式含量也越高;反之,分子量越低,顺式含量也越低。对此,本文提出了增长链对聚合过程起反作用的观点,从聚合机理的角度给予了解释。     

RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE USING LANTHANIDE TRIS(N-PHENYL-3,5-DI-T-BUTYLSALICYLALDIMINATO)S AS SINGLE COMPONENT CATALYST

Ring-opening polymerization of ε-caprolactone has been carried out by using rare earth Schiff base complexes:lanthanide tris(N-phenyl-3,5-di-t-butyisalicylaldiminato)s [Ln(OPBS)3]as single component catalyst for the first time.The influences of different rare earth elements,monomer and catalyst concentration as well as reaction time on the polymerization were investigated.Mechanism studies showed that monomer inserts into the active site with the acyl-oxygen bond scission rather than the break of alkyl-oxygen bond.     

RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE USING LANTHANIDE TRIS（N-PHENYL-3,5-DI-T-BUTYLSALICYLALDIMINATO）S AS SINGLE COMPONENT CATALYST

Ring-opening polymerization ofε-caprolactone has been carried out by using rare earth Schiff base complexes: lanthanide tris(N-pheny1-3,5-di-t-butylsalicylaldiminato)s[Ln(OPBS)_3]as single component catalyst for the first time.The influences of different rare earth elements,monomer and catalyst concentration as well as reaction time on the polymerization were investigated.Mechanism studies showed that monomer inserts into the active site with the acyl-oxygen bond scission rather than the break of alkyl-oxygen bond.     

多核Nd－Al双金属配合物对共轭双烯烃的聚合Ⅲ．溶剂等因素的影响

报道了多核Nd-Al双金属配合物活性体对共轭双烯烃的溶液聚合.结果表明,适宜的振荡时间有利于提高活性体的催比活性;通过外加AlEt₃,验证了聚合体系的纯度和活性体的稳定性,溶剂类型对活性体催比活性和聚合物分子量影响较大,活性次序为甲苯≥环己烷>正己烷;对产物[η]的影响则相反:甲苯《环己烷<正己烷.不同单体的定向聚合性能有差别,聚丁二烯的顺1,4含量较低,且易受反应条件的影响.     

稀土催化四氢呋喃开环聚合

1937年Meerwein首次发现Et_3O~(+BF)可催化四氢呋喃(THF)开环聚合。到目前为止,发现能使THF开环聚合的催化剂有质子酸、Lewis酸、洋离子、正碳离子等。1990年吴健等将(Acac)_3Nd-(i-Bu)_3Al-H_2O-环氧氯丙烷催化体系应用于THF聚合,发现它和(i-Bu)_3Al-H_2O-环氧氯丙烷体系具有相同的活性,这说明稀土配合物没有参与活性中心的形成。本工作发现(CF_3CO-2)3Ln(Ln=Y,La,Ce,