顺丁烯二酸二烷基锡聚合物的研究——Ⅳ.聚合动力学的研究

 研究了用过氧化苯甲酰作为引发剂,顺丁烯二酸二丁基锡在苯溶液中的聚合反应.即使引发剂用量达到10％以上,其聚合速率和单体转化率都是低的.通过红外光谱、热重-差热分析和元素分析等对聚合物进行了表征.Poly(DBTM)为白色脆性固体,不溶于普通的有机溶剂.测定了DBTM聚合反应的表观活化能E_c和聚合速率方程.     

4,4′-偶氮二[4-氰基戊酰(对-二甲基氨基)苯胺]引发丙烯酰胺聚合及其动力学研究

以N,N-二甲基甲酰胺(DMF)为溶剂,研究了4,4′-偶氮二[4-氰基戊酰(对-二甲基氨基)苯胺](ACPDA)为引发剂引发丙烯酰胺(AAM)的聚合行为.考察了聚合反应温度、单体浓度和引发剂浓度对聚合物分子量和聚合反应速率的影响,测定了反应级数和聚合反应的活化能.实验结果表明,ACPDA引发AAM的聚合速率方程为Rp=K[AAM]1.03[ACPDA ]0.48,聚合反应的表观活化能(Ea)为126.44kJ·mol-1.     

一种大分子引发剂的引发作用研究

将溶液聚合合成的α-甲基苯乙烯(AMS)和甲基丙烯酸缩水甘油酯(GMA)的低相对分子质量共聚物(计为PAG)作为大分子引发剂,分别研究了PAG引发单体甲基丙烯酸甲酯(MMA)和苯乙烯(St)的本体聚合反应,采用GPC和FTIR等手段对聚合产物进行了表征.研究结果表明,在加热到一定温度时,PAG具有引发作用,可以引发MMA和St进行本体聚合反应;聚合产物具有再引发功能,且其分子量与聚合物产率和聚合反应时间之间均有较好的线性关系.     

新型引发剂引发苯乙烯聚合的动力学

采用过氧化2-乙基己基碳酸叔丁酯为引发剂,研究了苯乙烯自由基本体聚合的动力学过程,考察了引发剂浓度、温度、乙苯质量分数对聚合反应速率和聚苯乙烯分子量的影响.结果表明:在117℃下,聚合速率(Rp)对引发剂浓度的反应级数为0.42,对苯乙烯浓度的反应级数为1,聚合反应的表观活化能为54.8 kJ/mol.引发剂浓度、温度、乙苯质量分数的提高导致聚苯乙烯数均分子量分别下降了约30％、20％和15％,其中引发剂浓度的影响最为显著.     

红外光谱法研究苯乙烯原子转移自由基聚合反应动力学

利用红外光谱法测定反应转化率研究原子转移自由基聚合反应动力学。在环己酮溶液中,以卤代烃为引发剂,过渡金属卤化物与配位剂２,２‘－联吡啶为催化体系,进行了苯乙烯聚合。分别就反应温度,反应物浓度和引发体系对苯乙烯聚合速率的影响进行了动力学测定,证实了原子转移自由基聚合具有活性聚合的特征,同时计算并讨论了苯乙烯原子转移自由基聚合反应的动力学数据。     

4-亚甲基-1,2-氧-异丙叉-3-甲氧基-α-D-呋喃戊糖的合成和聚合

本文报道了4-亚甲基-1,2-氧-异丙叉-3-甲氧基-α-D-呋喃戊糖的合成和在自由基和阳离子引发剂存在下的聚合反应.通过研究聚合物的结构,提出了聚合反应机理.比较了该单体在阳离子和自由基聚合反应中的聚合活性,聚合物的结构和聚合机理上的差别.     

{4-[4-（对硝基苯甲酰基）苯硫基]苯}苯基碘鎓六氟磷酸盐的合成与光引发性能测试

紫外光固化反应按机理分为自由基固化、阳离子固化以及自由基-阳离子混杂固化.自由基-阳离子混杂固化是指在同一体系里同时通过自由基聚合和阳离子聚合而发生的固化[1].混杂聚合结合了各个聚合反应的优点,表现出很好的协同效应.杂化光引发剂被设计成既能引发自由基聚合又能引发阳离子聚合的光引发剂.据报道,目前常见的杂化光引发剂主要有碘鎓盐类和苯基膦二苯甲酮类[2].     

反相悬浮聚合法制备球状卡波树脂的研究

以偶氮二异丁脒盐酸盐(V50)作为引发剂,失水山梨醇硬脂酸酯(Span60)和聚二甲基硅氧烷PEG-7磷酸酯为复合分散剂,蔗糖烯丙基醚和三甲基丙基聚氧乙烯(15)醚三丙烯酸酯为复合交联剂,丙烯酸为单体,正已烷为反应介质,采用反相悬浮聚合方法制备了球状卡波树脂.用光学显微镜和扫描电镜分别对聚合反应的成粒过程和产物的形貌进行了研究.结果表明,聚合体系呈现典型的悬浮聚合相态特征,并获得了堆积密度较高(0.65 g/cm3)的球状卡波树脂.聚合反应动力学研究结果表明,该反相悬浮聚合的聚合速率对单体浓度和引发剂浓度的反应级数分别约为1.36和0.70;聚合反应的表观活化能为78.0 kJ/mol.交联剂对卡波树脂的性能有重要的影响,通过适度交联可提高产物的增稠效率及其抗剪切性能.     

ATRP法制备两亲性嵌段共聚物的研究

以α 溴代丙酸乙酯 (EPN Br)为引发剂、氯化亚铜 (CuCl)和联二吡啶 (bpy)组成的混合体系为催化剂 ,引发苯乙烯聚合 ,得到了端基为卤原子的单分散聚苯乙烯 (PS X)预聚体 .以此PS X为大分子引发剂、CuCl和N ,N ,N′ ,N″ ,N″ 五甲基二亚乙基三胺 (PMDETA) bpy的混合体系为催化剂 ,引发N ,N 二甲基丙烯酰胺(DMAA)聚合 ,得到了分子量分布较窄的聚苯乙烯 b 聚N ,N 二甲基丙烯酰胺 (PS b PDMAA)两亲性嵌段共聚物 .考察了大分子引发剂的分子质量、聚合介质及配位剂等对聚合过程的影响 .并用GPC、IR、1 H NMR等对产物进行了表征 .研究结果表明 ,该聚合反应体系符合原子转移自由基聚合的特征 .     

光引发阳离子聚合反应的研究Ⅲ．硫鎓盐BDS引发环氧化合物光聚合的DSC研究

用改装的国产CDR-1型DSC仪研究了苯基缩水甘油醚(PGE)和环氧树脂(E-51)以双-[4-(二苯硫基)苯基)硫-二-六氟化磷引发的光聚合。研究了引发剂浓度、光强、温度等因素对聚合反应的影响,对于PGE,聚合速率与引发剂浓度的0.90次方、与光强的0.78次方成比例,对于E-51,聚合速率与引发剂浓度的0.87次方成比例,而与光强的关系则比较复杂,温度分别超过70℃(对PGE)或80℃(对E-51)后,对提高聚合反应速率的作用已不明显。作为活性稀释剂,PGE可以较大地提高E-51的聚合速率。     

马来酸二丁基锡的合成及其共聚合

马来酸二丁基锡的合成及其共聚合刘云桥金根河李福绵（北京大学化学与分子工程学院北京１００８７１）关键词马来酸二丁基锡，醋酸乙烯酯，交替共聚物，光聚合关于马来酸酐［１］，马来酰亚胺 Ｎ 取代物［２，３］与富电子烯类单体如苯乙烯，醋酸乙烯酯，乙烯基烷基醚...     

DEPOLYMERIZATION AND KINETICS OF DEPOLYMERIZATION OF POLYETHYLENE TEREPHTHALATE USING DIBUTYLTIN OXIDE CATALYST

Depolymerization of poly（ethylene terephthalate） （PET） was performed in the tubular bomb microreactor which contained the solution of PET in methanol and dibutyltin oxide at the temperature ranging from 433 K to 473 K, the reaction time from 5 to 45 min and the catalyst-to-PET ratio of 0.3%-2% by weight. The optimal condition for PET depolymerization catalyzed by dibutyltin oxide is the temperature of 443-453 K, the reaction time of 20-25 min and 0.8% by weight of catalyst. By using differential methods, the activation energy for the depolymerization process was found to be 154.05 kJ/mol in the temperature range from 433-463 K.     

二烷基锡聚合物的研究——Ⅲ.顺丁烯二酸二丁基锡酯与丙烯酸甲酯、丙烯酸丁酯的共聚合

近年来,新的有机锡聚合物的合成及其在许多领域内的应用研究取得很大的进展,然而,侧链上带有有机锡基团的二烷(芳)基锡聚合物的研究报道较少。众所周知,二烷基锡化合物是一类重要的聚氯乙烯热稳定剂。制备对聚氯乙烯具有改性作用的有机锡共聚合型热稳定剂,以实现聚氯乙烯热稳定剂的高分子化和多功能化,是未来热稳定剂的发展方向之一。我们已研究了顺丁烯二酸二丁基锡酯分别与苯乙烯、甲基丙烯酸甲酯的共聚反应及其共聚物对聚氯乙烯热稳定性的影响。本文报道顺丁烯二酸二丁基锡酯分别与丙烯酸甲酯、丙烯酸丁酯的共聚反应。     

DIBUTYLTIN DILAURATE-CATALYZED DIISOCYANATE COUPLING—GRAFTING OF POLY(ETHYLENE GLYCOL) ONTO NANO-SILICA SURFACE THROUGH A ONE-STEP PROCEDURE

Grafting polymer glycols onto nano-silica surface through one-step procedure was investigated. The major characteristic of this procedure is that all the materials and reagents (silica, PEG, TDI, DBTDL, solvent) required for grafting were added simultaneously into the reaction vessel. TDI and DBTDL were used as coupling agent and catalyst, respectively.The products were characterized by FTIR, TGA, elemental analyses and TEM, giving evidence for successful grafting of PEG. Possible mechanism of this grafting was studied and two grafting processes were proposed. The process through which the grafting proceeds depends on the reaction temperature. Effect of molecular weight of PEG on grafting was also investigated.     

二烷基锡聚合物的研究——Ⅲ.顺丁烯二酸二丁基锡酯与丙烯酸甲酯、丙烯酸丁酯的共聚合

Benzoyl peroxide (BPO) was used for initiator in copolymerization of dibutyltin maleate (DBTM, M₂) with methyl acrylate (MA, M₁) in benzene and the reactivity ratios of copolymerization r1 and r2 were found to be 12.67 and 0.03, respectively. But in copolymerization of DBTM (M₂) with butyl acrylate (BA, M₁) r1 and r2 were 11.1 and 0> respectively. The cc-polymerization conditions, such as amount of initiator, ratios of monomers and addition method of initiator were examined. Copolymers were characterized by ¹H-NMR,IR,elemental and TG analyses. MA-DBTM copolymer is a white and brittle solid, while BA-DBTM copolymer is a transparent elastomer at room temperature.     

DIBUTYLTIN DILAURATE-CATALYZED DIISOCYANATE COUPLING- GRAFTING OF POLY(ETHYLENE GLYCOL) ONTO NANO-SILICA SURFACE THROUGH A ONE-STEP PROCEDURE

Grafting polymer glycols onto nano-silica surface through one-step procedure was investigated. The major characteristic of this procedure is that all the materials and reagents (silica, PEG, TDI, DBTDL, solvent) required for grafting were added simultaneously into the reaction vessel. TDI and DBTDL were used as coupling agent and catalyst, respectively.The products were characterized by FTIR, TGA, elemental analyses and TEM, giving evidence for successful grafting of PEG. Possible mechanism of this grafting was studied and two grafting processes were proposed. The process through which the grafting proceeds depends on the reaction temperature. Effect of molecular weight of PEG on grafting was also investigated.     

STRUCTURAL STUDIES OF DICHLORO-(4,7-DIPHENYLPHENANTHBOLINE)DIBUTYLTIN(Ⅳ) ETHANOL SOLVATE,[SnBu_2Cl_2(DPphen)]·C_2H_5OH

<正> C34H40N2OCl2Sn,Mr=682.3, triclinic, P1, a = 10.082(1),b= 10.932(1), c=15.666(2) A,α= 79.85(1),β=84.19(1),γ=84.92(1)°;V =1686.5 A3,Z = 2,Dc = 1.344 g.cm-3,μ(MoKα) = 9.5 cm-1, T=294(1)K. The coordination of tin is essentially octahedral, with the nitrogen atoms from bidentate ligand DPphen and cis-chlorine atoms lying in the equatorial plane and the two carbon atoms from trans-butyl groups in the axial positions. The average Sn-N distance of 2.39A happens to be in the shortest limit for this kind of complexes exhibiting antitumor activity.     

STRUCTURE OF BIS(QUINOLINE-8-OLATO)DIBUTYLTIN(IV)[Sn(C4H9)2(C9H6NO)2]

<正> INTRODUCTION. Studies of six-coordinated diorganotin(Ⅳ) compounds with octahedral geometry have been widely made, which indicate that the transor distorted trans [SnR_2] unit is common for the dialkyltin(Ⅳ) species     

水中高锰酸盐指数测量不确定度的评定

对GB 11892 - 1989《水质　高锰酸盐指数的测定》中酸性高锰酸钾氧化法测定水中高锰酸盐指数的测量不确定度进行了评定。通过对测量重复性、滴定管、移液管、标准溶液浓度等影响测量结果的不确定度分量的分析和量化 ,求得水中高锰酸盐指数测定结果的相对合成标准不确定度为 1.10× 10 -2 。