三元偏氯乙烯/丙烯腈/苯乙烯悬浮共聚树脂的合成

以偶氨二异丁腈（ＡＩＢＮ）作引发剂,合成了偏氯乙烯（ＶＤＣ）／丙烯腈（ＡＮ）／苯乙烯（Ｓｔ）三元悬浮共聚树脂。在聚合过程中,压力先逐步升高后下降。当悬浮聚合质量投料比为６０：１５：２５（ＶＣＤ／ＡＮ／Ｓｔ）时,其压力转变点的转化率约为５５％～６５％。聚合得到的三元ＶＤＣ－ＡＮ－Ｓｔ悬浮共聚树脂为球形半透明颗粒,重均粒径约为５０．５６μｍ。合成的悬浮液中存在数量较多的微小粒子,加入ＮａＮＯ２可减少其     

丙烯腈/醋酸乙烯酯/甲基丙烯磺酸钠共聚体系竞聚率的研究

利用核磁共振技术测定共聚物组成,用Ｍａｙｏ－Ｌｅｗｉｓ共聚物组成方程拟合实验数据计算竞聚率。得到的丙烯腈／醋酸乙烯酯（ＡＮ／ＶＡｃ）本体共聚的竞聚率数据用于分析间歇聚合反应试验,理论计算与试验数据吻合。并研究了丙烯腈／醋酸乙烯酯／甲基丙烯磺酸钠（ＡＮ／ＶＡｃ／ＳＭＡＳ）三元水相共聚反应体系的特征,测定了该三元共聚体系表观竞聚率     

偏氯乙烯悬浮共聚过程中蒸汽压变化的研究

研究了ＶＤＣ／ＭＭＡ和ＶＤＣ／ＡＮ悬浮共聚过程中蒸汽压的变化。结果表明：该两个共聚体系的蒸汽压—聚合时间关系可分为三个阶段,第一阶段迅速升压,第二阶段缓慢升压,第三阶段显著降压;由于ＡＮ部分地溶于水,使ＶＤＣ／ＡＮ悬浮共聚的第二阶段压力变化很小;ＶＤＣ／ＭＭＡ悬浮共聚约在转化率为７０％时开始降压;ＶＤＣ／ＡＮ悬浮共聚约在转化率为６５％时开始降压     

甲基丙烯酸季铵盐酯的合成及其共聚物乳液的抗静电性能

用不同碳链长度（Ｃ４，Ｃ８，Ｃ１０，Ｃ１２，Ｃ１６）的溴代正烷烃对甲基丙烯酸Ｎ，Ｎ′－二甲氨基乙酯（ＤＭＡＥＭＡ）进行季铵化，制得了相应的季铵盐（ＣｎＮ＾＋），并用熔点和＾１Ｈ－ＮＭＲ鉴定了它们的纯度；通过与丙烯丁酯（ＢＡ），苯乙烯（Ｓｔ）的无皂乳液共聚，制得了ＢＡ－Ｓｔ－Ｃ１６Ｎ＾＋三元共聚物乳液，织物涂敷试验表明，稀释乳液是一种良好的永久性抗静电剂。     

水相沉淀聚合法合成聚丙烯腈的工艺研究

采用高转化率水相沉淀聚合实验方法，对ＡＮ（丙烯腈）／ＶＡｃ（醋酸乙烯酯）／ＳＳＳ（苯乙烯磺酸钠）三元共聚物进行了研究，重点考察了聚合温度，氧化剂／还原剂比例，反应ｐＨ值等工艺条件对聚合转化率、分子量、共聚物组成的影响，并确定了合适的聚合工艺条件。     

无定形VDC/MMA悬浮共聚树脂的合成研究

用悬浮聚合法合成了无定形ＶＤＣ／ＭＭＡ共聚树脂,研究了单体配比、聚合温度、引发剂浓度等因素对聚合速率、树脂组成和树脂某些特性的影响。结果表明,单体中ＭＭＡ质量分数含量在２０％～４０％范围时,ＶＤＣ／ＭＭＡ悬浮共聚的速率随ＭＭＡ含量的增加而加快,并具有明显的自动加速现象,温度低于６０℃时,自动加速现象较剧烈;高转化率的树脂中ＭＭＡ单元的含量大于初始单体中ＭＭＡ的含量,其玻璃化温度与窄组成分布的ＶＤＣ／ＭＭＡ共聚树脂相近;当初始单体中ＭＭＡ质量分数大于２５％时,用本文悬浮法制得的树脂为无定形ＶＤＣ／ＭＭＡ共聚树脂     

氯乙烯／N—苯基马来酰亚胺／乙烯基单体悬浮共聚速率

根据氯乙烯（ＶＣ）／Ｎ－苯基马来酰亚胺（ＰＭＩ）／乙烯基单体悬浮共聚合工艺的特点，确定了倒加料的聚合工艺，比较了丙烯腈（ＡＮ），甲基丙烯酸甲酯（ＭＭＡ）对ＶＣ／ＰＭＩ聚合速率的影响，研究了ＡＮ的用量和聚合温度对ＶＣ／ＰＭＩ／ＡＮ三元悬浮共聚合速率的影响。     

PVF2／P（MM—St）共混体系的结晶性能和相容性的研究

用示差量热法（ＤＳＣ）、动态力学分析法（ＤＭＡ）和悬浮法测密度法研究了聚偏氟乙烯（ＰＶＦ２）／甲基丙烯酸甲酯与苯乙烯的无规共聚和［Ｐ（ＭＭＡ－Ｓｔ）］的共混体系的相容性和结晶性能。结果发现ＰＶＦ２／Ｐ（ＭＭＡ－Ｓｔ）共混体系是部分相容体系,其结晶性能随共混物中Ｐ（ＭＭＡ－Ｓｔ）的含量而变化,并就模压成型的热历史对该共混体系相容性的影响进行了讨论。     

Iniferter BDC的合成及引发St、MMA光聚合

合成Ｎ,Ｎ’－二乙基二硫代氨基甲酸苄酯（ＢＤＣ０。以ＢＤＣ作为ｉｎｉｆｅｒｔｅｒ引发Ｓｔ、ＭＭＡ光聚合,单体Ｓｔ和ＭＭＡ的转化率随光照时间的增加而增加,但没有呈现出线性关系。此外,反应环境温度高,单体转化率增加;ＰＳ和ＰＭＭＡ的粘均分子量则随光照时间的增加而呈现线性增加的关系;所得聚合物的分子量分布较宽;ｉｎｉｔｅｒｔｅｒ ＢＤＣ可以进行分子设计,合成Ｐ（Ｓｔ－ｂ－ＭＭＡ）嵌段共聚物,表现为“准活     

阳离子P（BA—St—MBDM）共聚物乳液的合成及其抗静电性能

以丙烯酸丁酯（ＢＡ）、苯乙烯（Ｓｔ）和甲基丙烯酰氧乙基，二甲基，丁基溴化铵盐（简称ＭＢＤＭ、（ＣＨ２＝ＣＣＨ３－ＣＯＯＣＨ２Ｎ（ＣＨ３）２－ｎＣ４Ｈ９）＾＋Ｂｒ＾－）为共聚单体，Ｎ－甲基－Ｎ－十六烷基吗啉硫酸甲酯盐作乳化剂进行自由基型乳液聚合，研究了影响聚合速度、共聚物［η］和乳液稳定性的因素，合成了一系列稳定的阳离子共聚物乳液。所得乳液经稀释后对不同织物进行处理，处理后的织物具有良好的抗静电性和     

丙烯腈水溶性对偏氯乙烯/丙烯腈/苯乙烯三元悬浮共聚合成粒机理的影响

本文研究了以偶氮二异丁腈（AIBN）引发的偏氯乙烯（VDC）－丙烯腈（AN）－苯乙烯（St）悬浮聚合颗粒的粒径及其分布。实验发现在该体系中存在两种成粒机理：单体液滴的珠状成粒和水相聚合沉淀成粒。水相聚合是由于AN的水溶性增加了AIBN在水中的溶解度所致。加入亚硝酸钠（NaNO2）可以有效减少水相聚合生成物,使悬浮颗粒的粒径分布变窄。     

PMI-St-AN耐热改性剂的合成及应用

以提高聚氯乙烯(PVC)的耐热性能为目的,用悬浮聚合的方法,合成了N-苯基马来酰亚胺-苯乙烯-丙烯腈三元共聚物型耐热改性剂。通过差热分析、元素分析、凝胶渗透色谱分析等手段对共聚物的玻璃化转变温度、组成及其分布、分子量及其分布进行了表征。初步考察了丙烯腈的加入对N-苯基马来酰亚胺-苯乙烯交替共聚体系共聚合规律的影响。将合成的耐热改性剂用于PVC共混改性,取得了较好的效果。     

偏二氯乙烯-丙烯腈悬浮共聚动力学

研究了单体配比、引发剂浓度、聚合温度、转化率等因素对偏二氯乙烯(VDC)-丙烯腈(AN)悬浮共聚树脂的组成、相对分子质量和聚合速率的影响,建立了动力学模型,讨论了AN的水溶性对树脂组成的影响,提出了相对分子质量与聚合温度及引发剂浓度关系的模型。     

Effects of water solubility of acrylonitrile on vinylidene chloride/acrylonitrile/styrene suspension polymerization

The water solubility of acrylonitrile (AN) and its effects on vinylidene chloride/acrylonitrile/styrene (VDC/AN/St) suspension copolymerization were investigated in this study. It shows that the VDC/St ratio and the presence of suspending agent have no obvious influences on AN phase partition between the monomer and aqueous phases, whereas the water solubility of AN increases as temperature increases. Polymerization in the aqueous phase occurs extensively with azobis(isobutyronitrile) (AIBN) as initiator, whereas with lauryl peroxide (LPO) as initiator, polymerization in the aqueous phase is negligible. Theoretical analysis and experimental results indicate that transport of the monomer molecule is possible during polymerization. Both VDC and AN transfer from the monomer phase to the aqueous phase when AIBN is used as initiator. AN transfers from the aqueous phase to the monomer phase for the polymerization system initiated by LPO. Sodium nitrite (NaNO₂), but not sodium sulfide (Na₂S), can be used to effectively inhibit polymerization in water and exerts less influence on the polymerization in the monomer phase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1431–1438, 2001     

丙烯腈、偏二氯乙烯水相沉淀共聚的研究

讨论了丙烯腈(AN)、偏=氯乙烯(VDC)水相沉淀共聚合过程中的反应条件、助溶剂及第三单体甲基丙烯磺酸钠等对总单体转化率、共聚体中VDC含量及共聚体相对粘度(ηγ)的影响。结果表明:提高总单体浓度和引发剂用量能显著地提高总单体转化率和共聚体中VDC的含量。但共聚体ηγ随之下降;在相同反应条件下,与甲醇相比,采用乙醇作助溶剂能获得更高的总单体转化率和共聚体中的VDC含量;采用甲基丙烯磺酸钠作第三单体能提高总单体转化率以及共聚体中的VDC含量和ηγ。     

Studies on the development of branching in ATRP of styrene and acrylonitrile in the presence of divinylbenzene

Branching atom transfer radical polymerization (ATRP) of styrene and acrylonitrile was attempted in the presence of divinylbenzene targeting toward soluble branched copolymer. The kinetics and the development of branching with monomer conversion were studied in detail. Gas chromatography (GC), gel permeation chromatography (GPC) coupled with multi-angle laser light scattering (MALLS), proton nuclear magnetic resonance (¹H NMR) spectroscopy and intrinsic viscosity determination were used to monitor the polymerization process and characterize the obtained copolymer. Analysis of conversion of reactants, the growth manner of molecular weight with monomer conversion and GPC traces proved that the primary chains with low polydispersity formed mainly at the early stage and then were linked in a statistical manner to start the branching at the middle or late stage. The more the branching agent was used, the earlier the branching occurred, and too much higher level of branching agent resulted in gelation. For the selected ratio of [t-BBiB]/[DVB]/[St]/[AN] = 1/0.9/15/15, with monomer conversion less than 40%, primary chains with low polydispersity formed from the polymerization of St, AN and DVB, and only a part of the primary chains contained pendent vinyl group. When monomer conversion was up to 40%, the pendent vinyl groups participated in polymerization, resulting in the linking of the primary chains statistically to start the branching. The branching became significant at monomer conversion up to 50%, giving rise to a steep increase in molecular weight and width in molecular weight distribution. As the polymerization proceeded, the polymer composition gradually approached the feed composition, identifying the obtained branched copolymer provided some gradients are in its primary chains. Finally, branched copolymer bearing about six primary chains was prepared at monomer conversion near to 80%, its absolute weight average molecular weight was about 8.87 × 10⁴.     

Kinetics of heterogeneous polymerization of vinylidene chloride. I. Mechanism and modeling

The similarities and differences between the heterogeneous polymerization of vinylidene chloride (VDC) and vinyl chloride (VC) were compared and analyzed. The effect of the poly(vinylidene chloride)(PVDC) crystal morphology on the kinetics of VDC polymerization was discussed. Based on the assumption that polymerization occurs in the monomer phase and on the edges of the PVDC lamellar crystals, a mechanism of VDC polymerization is proposed and then a kinetic model for VDC bulk/suspension polymerization is developed according to the elementary reactions. The model can be used to predict polymerization rate and conversion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2576‐2581, 2004     

N-苯基马来酰亚胺与苯乙烯共聚物乳液的研究

采用种子乳液聚合法制备了N-苯基马来酰亚胺(NPMI)与苯乙烯(St)共聚物乳液,讨论了单体配比对共聚物乳液的聚合稳定性、转化率、流变性、表面张力、粒径大小及分布的影响。结果表明:随着混合单体中NPMI含量的增加,NPMI与St混合单体的转化率降低,聚合物乳液的凝胶量增大,聚合稳定性减弱,黏度逐渐增加。所得共聚物乳液粒径为70~80nm,粒径分布均匀。     

VTMS/MMA/St三元共聚物的合成与表征

以甲基丙烯酸甲酯（MMA）、苯乙烯（St）、乙烯基三甲氧基硅烷（VTMS）为单体通过乳液聚合制备了含有机硅氧烷的三元共聚物乳液；研究了单体配比与转化率之间的关系．并表征了共聚物的结构，测试了共聚物的热性能。结果表明，共聚物中成功地引入丁有机硅链节．聚合过程中部分硅氧烷部分发生水解，共聚物的热稳定性和玻璃化温度有一定提高。     

偏氯乙烯-氯乙烯悬浮共聚树脂的分子质量及分布

在5L聚合釜中合成了偏氯乙烯(VDC)-氯乙烯(VC)悬浮共聚树脂,研究了聚合温度、转化率、单体配比和助剂对分子质量及分布的影响．结果表明,共聚树脂的分子质量与聚合温度的关系符合Arrhenius方程,其综合活化能为-32．877kJ／mol;聚合物的特性黏数在高转化率阶段基本不变;分子质量随着单体配比中VC含量的增加而降低、分子质量分布也有一定的波动;聚合前加入助剂对共聚树脂的分子质量及分布影响不大。