化学交联聚氯乙烯树脂的合成和结构

研究了氯乙烯/交联单体悬浮共聚时,交联单体种类、浓度和聚合温度对化学交联聚氯乙烯树脂结构的影响.对于氯乙烯/邻苯二甲酸二烯丙基酯(VC/DAP)悬浮共聚体系,凝胶含量和凝胶交联密度随DAP起始浓度的增加而增大;DAP浓度相同时,凝胶含量和凝胶交联密度随聚合温度上升而下降;当凝胶含量较高时,分子链物理缠结对凝胶交联密度有较大贡献,凝胶交联密度随凝胶含量增加而快速上升.在相同交联单体浓度下,氯乙烯/马来酸二烯丙基酯(VC/DAM)共聚物的凝胶含量最大,VC/DAP共聚物次之,氯乙烯/乙二醇二甲基丙烯酸酯(VC/EGDMA)共聚物最小,这是由于DAM单体的竞聚率小于1,且含有马来酸双键,EGDMA单体的竞聚率远大于1.     

k—型卡接胶／聚乙烯吡咯烷酮共混水凝胶的国徽制备及性质研究

采用辐射技术制备了k-型卡接胶（ＫＣ）／聚乙烯基吡咯烷酮（ＰＶＰ）共混水凝胶,研究了共凝胶内ＫＣ含量、ＰＶＰ的分子量和辐照剂量等对ＫＣ／ＰＶＰ共混水凝胶性质的影响,实验发现,ＫＣ与高分子量的ＰＶＰ（k-90）共混后在一定剂量范围内辐照可得到高强度,高 胀行为的ＫＣ／ＰＶＰ共混水凝胶,随着共混水凝胶内ＫＣ含量的增加,凝胶强度及深胀性能均显著提高,分析表明,ＫＣ与高分子量的ＰＶＰ共混后,在较低剂量下ＫＣ的降解被抑制,从而获得一种由物理交联的ＫＣ和化学交联的ＰＶＰ形成的互穿网络（ＩＰＮ）凝胶。     

交联苯乙烯/丙烯酰胺共聚微球的制备及其C60功能化初探

以二乙烯基苯（ＤＶＢ）为交联剂,利用一次科料分散共聚合的方法合成了交联的苯乙烯（Ｓｔ）／丙烯酰胺（Ａｍ）共聚微球。实验发现,共聚单体Ａｍ的投料量和介质的极性对微球的形态有着显著的影响。在反应过程中并联ＰＳ链段和ＰＡｍ链段发生相分离,使粒子产生异形。随后,通过微球上的酰胺基团与Ｃ６０的反应,将Ｃ６０引入微球表面。初步的光电导性能测试表明,带有Ｃ６０的微球具有较好的光电导性能。     

聚苯胺溶液的凝胶化行为

通过流变学手段对聚苯胺溶液的凝胶化行为研究表明，在室温下，聚苯胺（ＰＡｎ）／Ｎ－甲基－２－吡咯烷酮（ＮＭＰ）溶液有一转折浓度Ｃｇ（０．０５ｇ／ｍＬ），浓度高于此值时，浴液凝胶化速度急剧增大，凝胶速度还与溶剂，ＰＡｎ分子量及溶液的温度有很大关系。溶液中不溶的ＰＡｎ的存在会加速凝胶化过程。ＰＡｎ／ＮＭＰ凝胶的假塑性和触变性明显地反映出ＰＡＶＮＭＰ溶液的凝胶化是溶剂参与的ＰＡｎ分子链间的物理交联过程。     

氯乙烯/邻苯二甲酸二烯丙基酯悬浮共聚特征

对４５℃时的氯乙烯／邻苯二甲酸二烯丙基酯（ＶＣ／ＤＡＰ）的悬浮共聚进行了研究，得到表观竞聚率ｒＶＣ＝０７６９、ｒＤＡＰ＝０３７４．凝胶点对应的ＤＡＰ临界起始浓度在０４６６～０４９３ｍｍｏｌ／ｍｏｌＶＣ之间（聚合转化率为８０～８５％），当ＤＡＰ起始浓度小于临界浓度时，ＶＣ／ＤＡＰ共聚物均为溶胶，溶胶平均聚合度随ＤＡＰ起始浓度和聚合转化率的提高而增大；当ＤＡＰ起始浓度大于临界浓度时，共聚物由溶胶和凝胶组成，凝胶含量随ＤＡＰ浓度和聚合转化率的提高而增加，溶胶聚合度则随ＤＡＰ浓度的提高而减小．在凝胶点前，共聚物的分子量分布随ＤＡＰ浓度的增加而变宽；凝胶点以后，分子量分布随ＤＡＰ浓度的增加而变窄．     

黄原胶以三价铬交联的水凝胶的脱水行为

对黄原胶／三价铬水凝胶在７０，８０和９０℃下的脱水行为进行了研究．脱水与凝胶的交联密度即参与交联反应的三价铬的含量有密切联系．突发脱水之后的过程可以用一级反应动力学描述，反应速度常数随三价铬的浓度和温度的增高而增大，活化能为３４．５ｋｃａｌ／ｍｏｌ．一价盐（ＮａＣｌ）的含量对脱水过程没有影响．     

壳聚糖/聚乙烯醇/三聚磷酸钠三元复合微球的制备及表征

由壳聚糖（ＣＳ）、聚乙烯醇（ＰＶＡ）和三聚磷酸钠（ＴＰＰ）制备了壳聚糖／聚乙烯醇／三聚磷酸钠三元复 合微球,探讨了体系中壳聚糖含量对复合微球的影响,以及离子种类及浓度和ｐＨ值对复合微球溶胀度的影 响。采用ＸＲＤ、ＦＴＩＲ和ＳＥＭ等测试技术对微球的组分、结构和形貌进行了表征。结果表明,ＣＳ和ＰＶＡ具有良好的相容性,随着ＣＳ含量的增加,ＰＶＡ的结晶性逐渐降低,复合微球的粒径约为４００～９５０ μｍ,表面较为粗糙;随着ＣＳ添加量的增加,凝胶平衡溶胀度先增大再减小,ＣＳ／ＰＶＡ／ＴＰＰ复合微球在ｐＨ值为３～8的溶胀度最大,且在同一种溶液中,随着离子浓度的增加,其溶胀度明显降低;复合微球具有溶胀 收缩可逆性,显示ＣＳ／ＰＶＡ／ＴＰＰ复合微球是ｐＨ／离子敏感型凝胶,可为药物缓释系统提供实验和理论依据。     

起始共聚物的结构对超高交联聚苯乙烯的结构和抗溶胀破碎性能的影响

本文以凝胶型低交联聚苯乙烯为起始共聚物，合成了各种超高交联聚苯乙烯，研究了起始共聚物的化学交联和物理缠结对合成的超高交联聚苯乙烯的表面和孔道结构的影响。此外，本文还以干态超高交联聚苯乙烯加入液体介质中时的碎球率为指标，考察了起始共聚物的结构对合成的超高交联聚苯乙烯机械性能的影响。     

PVC／PE交联共混体系的动态力学研究

在ＰＶＣ／ＰＥ共混体系中加入交联剂和引发剂能产生ＰＶＣ－ＣＯ－ＰＥ共聚物，这种共聚物在共混物中可起到增容剂的作用。通过动态力学分析和扫描电镜研究了ＰＶＣ／ＰＥ交联共混体系的相容性。发现引发剂、交联剂、稳定剂和增塑剂等对共混物中的交联反应均有较大的影响。     

自由基交联共聚合体系凝胶点和凝胶形成机理

通过分析几个有代表性的单烯／二烯自由基交联模型的计算机模拟结果，认为凝胶点判据和凝胶形成机理是两个相互联系但决不相同的概念。将体系中首次出现分子平均交联密度等于１／ＤＰｐｗ的分子作为凝胶点判据。凝胶形成过程可分为成核与生长两个阶段，成核条件为溶胶分子平均交联密度等于１／ＤＰｐｗ。     

离子交联聚氯乙烯的结构与性能

由氯乙烯/丙烯酸悬浮共聚合成了不同羧基含量的PVC树脂,采用溶液反应和熔融加工法制备离子交联PVC,对其结构和性能进行了研究.结果表明,共聚物中羧基主要以二聚体形式存在,用金属离子中和能形成部分络合结构;用Ca²⁺、Mg²⁺离子络合的羧基含量较高的VC/AA共聚物存在离子对聚集态结构;离子对含量、金属离子种类和增塑剂浓度影响离子聚集相的比例和稳定性,离子聚集具有热可逆性;离子交联使PVC的T_g、熔体粘度和回弹性提高.     

聚氯乙烯的热可逆共价交联

利用环戊二烯 (CPD)在常温下自动二聚形成双环戊二烯 (DCPD)、在高温下DCPD又可解聚成CDD的热可逆Diels Alder反应 ,合成了DCPD二羧酸衍生物 ,并将其引作聚氯乙烯 (PVC)的共价交联 ,研究了交联剂种类和用量对交联程度、力学性能和流动特性的影响及交联产物的热可逆转化行为 ,制得了力学性能和耐热性均有所提高的热可逆共价交联PVC     

KINETICS OF VINYL CHLORIDE (CO) POLYMERIZATION AT HIGH CONVERSION

This paper provides a summarized review on the kinetics of vinyl chloride homopolymerization inthe absence and presence of chain transfer agents, of VC/DAP(diallyl phthalate) copolymerization with chainextension and/or slightly crosslinking functions, and of vinylidene chloride/VC random copolymerization.Models of rate, degree of polymerization or molecular weight, copolymer composition, gel fraction andcrosslinking density were proposed and interpreted mechanistically.     

单一化学交联与物理化学复合交联高吸油树脂的比较

提出在单一化学交联吸油树脂中引入物理交联的设想，并采用悬浮聚合法了单一化学交联和物理－化学复合交联的聚丙烯酸酯系高吸油树脂，对两种不同树脂的吸油速率，低亲油性单体树脂的吸油性能，最佳单体配比以及化学交联剂含量的影响进行了比较，结果表明物理交联的引入加快了树脂的吸油速率，提高低亲油性单体树脂的吸油能力，并且还使最佳单体配比中低亲油性单体含量增加，同时表明部分物理交联吸油树脂有一最佳化学交联剂含量区。     

Mechanistic discussion of cationic crosslinking copolymerizations of 1,2‐epoxycyclohexane with diepoxide crosslinkers accompanied by intramolecular and intermolecular chain transfer reactions

Our previous mechanistic discussion of the free‐radical crosslinking monoallyl/diallyl copolymerizations was extended to the cationic crosslinking monoepoxide/diepoxide copolymerizations, typically including 1,2‐epoxycyclohexane (ECH) as a monoepoxide and bis[3,4‐epoxycyclohexylmethyl] adipate (BECHMA) as a diepoxide crosslinker. In the cationic polymerization, oligomer is usually obtained because of the occurrence of characteristic chain‐forming reactions. Therefore, cationic crosslinking monoepoxide/diepoxide copolymerizations could be in the category of the network formation through free‐radical crosslinking monoallyl/diallyl copolymerizations. Thus, the gelation behavior was discussed by comparing the actual gel points with the theoretical ones; the greatly delayed gelation from theory was observed. Then, the resulting network polymer precursors (NPPs) were characterized by SEC‐MALLS‐viscometry to clarify the cationic crosslinking ECH/BECHMA copolymerization mechanism. Notably, the correlation lines of molecular weight versus elution volume were specific for the NPPs obtained at a high conversion close to the gel point as compared with those obtained by the free‐radical crosslinking monoallyl/diallyl copolymerization. This may be ascribed to the occurrence of intramolecular and intermolecular chain transfer reactions characteristic of cationic polymerization; the chain transfer reactions involve the intramolecular and intermolecular nucleophilic attack of ether oxygen or terminal hydroxyl oxygen in the NPPs to a terminal growing cation that leads to the formation of not only the loop‐ but also the crosslink‐structures containing NPPs, providing fragile ultrahigh‐molecular‐weight NPP in the SEC columns. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Radiation crosslinking of elastomers. I. Polybutadienes

The chemical and physical crosslink densities of irradiated polybutadiene were determined using a precise and consistent method. This method included the use of a statistical theory of crosslinking modified to include chain reactions and the use of Langley's theory for calculating the number of trapped chain entanglements. The number of crosslinks formed per unit radiation dose, G(X), was measured for a series of polybutadienes containing various isomeric forms of unsaturation. The physical crosslink density and the molecular weight between entanglements were determined from measurements of the compression modulus of swollen samples.     

利用聚乙烯醇结晶辅助制备多重交联的高强度聚丙烯酰胺水凝胶

在表面带有C=C双键的乙烯基杂化二氧化硅纳米颗粒(vinyl hybrid silica nanoparticle,VSNP)上接枝丙烯酰胺(AM),所得到的纳米刷状凝胶因子通过聚丙烯酰胺(PAM)间的氢键形成物理交联点,则多官能化的VSNP可作为拟共价交联点构筑双重交联的单一网络纳米复合物理水凝胶(nanocomposite physical hydrogel,NCP gel),表现出较高的强度和超拉伸性.为了进一步提高凝胶的强度和韧性,将少量PVA和PAM/VSNP纳米刷混合制成凝胶,通过冷冻-融化处理,使与PAM分子链相互缠绕并形成氢键作用的PVA结晶,形成新的交联点进一步交联PAM NCP gel,得到多交联的PAM NCP gel体系.通过拉曼光谱和示差扫描量热分析,证明凝胶中的PVA通过氢键既可以与PAM相互作用,又形成微晶为新交联点,大大增强了NCP gel的力学性能,与PAM NCP gel相比,凝胶的拉伸强度和断裂能分别从313 k Pa和1.41×104 J/m~2提高到了557k Pa和4.65×104 J/m~2.     

Synthetic thermally reversible gel systems. VIII. Poly(vinyl chloride)–dioxane

When interpreted by network theory, equilibrium swelling measurements on poly-(vinyl chloride) (PVC) film in dioxane and moduli measurements on the equilibrium swelled films yield values for the approximate molecular weight between thermally reversible crosslinks and for the number of these crosslinks per polymer chain. These values are in reasonable agreement with the thermodynamic analysis of PVC–dioxane gels by Takahashi, Nakamura, and Kagawa and with the premise that three-dimensional network formation in these gels occurs by crystallization of a very limited number of syndiotactic sequences per chain having a sequence length of between 8 and 10. Failure to observe fusion endotherms by DTA on PVC–dibutyl phthalate gels supports the view that PVC gels have a low crystalline crosslink density and a low heat of crosslinking. The heat of crosslinking obtained by the method of Eldridge and Ferry shows only moderate agreement with expectations based on the heat of fusion of PVC and the number of repeating units per PVC chain passing through a crystalline crosslink in a PVC–dioxane gel.