高温本体聚合合成ACS树脂的接枝率研究

研究了聚合条件、配方组成及氯化聚乙烯(CPE)的氯化度对高温本体聚合合成丙烯腈(AN) CPE苯乙烯(St)接枝共聚物（ACS）树脂接枝率的影响。结果表明,本体聚合合成ACS树脂过程中接枝反应主要发生在聚合转化率低于50 %的低转化率阶段;反应温度、引发剂及链转移剂用量是影响本体聚合合成ACS接枝率的主要因素;提高聚合反应温度、增加引发剂和链转移剂浓度均会导致接枝率显著下降;St/AN的质量比、CPE橡胶的含量及氯化度对接枝率的影响较小。     

MMA—St高转化率共聚动力学

在60～90℃范围内,以AIBN、BPO为引发剂进行甲基丙烯酸甲酯(MMA)～苯乙烯(St)本体共聚,研究了高转化率下聚合温度、引发剂浓度及单体配比对共聚速度的影响。结果表明,聚合温度升高、引发剂浓度增大及单体配比中MMA含量增加,均使MMA～St共聚速率增大。但当聚合反应进行到转化率达70%左右时,聚合速率开始显著降低?当转化率达到90%以上时,聚合反应几乎停止。推导并关联了高转化率下共聚动力学模型,在转化率70%以下,模型计算值与实验结果符合很好,该模型为MMA～St共聚生产控制提供了理论依据。     

纳米氧化镁对甲基丙烯酸-丙烯腈共聚体系竞聚率的影响

以偶氮二异丁腈(AIBN)为引发剂,引发甲基丙烯酸(MAA)和丙烯腈(AN)本体聚合。采用滴定法和称重法测定了在低转化率(小于10%)下不同单体配比的共聚物组成,并采用Fineman-Ross法及Kelen-Tudos法计算、作图得到两种单体的竞聚率,它们的最大差值为0.09,说明滴定法和称重法具有一定的可信度。用上述方法测定了反应体系在纳米MgO存在下共聚单体竞聚率的变化,结果表明:加入纳米MgO,MAA和AN的竞聚率均下降。     

本体法合成ABS树脂Ⅱ.预聚合反应动力学研究

采用本体聚合方法,以1,1-二(叔丁基过氧基)环己烷(DP275B)引发苯乙烯、丙烯腈在聚丁二烯橡胶上接枝共聚合.考察了不同聚合工艺条件下丙烯腈-丁二烯-苯乙烯三元共聚物(ABS)预聚合反应动力学行为规律,并求出相应的假一级表观增长反应速率常数.结果表明:不同工艺条件下的动力学曲线均符合一级线性关系;镍系高顺式橡胶BR9004体系的预聚合反应速率最快;增加引发剂DP275B浓度、提高引发温度、降低低顺式聚丁二烯橡胶700A用量和聚合搅拌速率均可加快ABS预聚合反应速率;当w(700A)为5.0%, w(DP275B)为0.021% 时,共聚单体的表观增长反应活化能为10.84 kJ/mol,频率因子为0.12 min-1.     

超声波辅助醋酸乙烯的聚合研究

比较了超声波引发聚合和超声波辅助聚合对醋酸乙烯(VAC)体系的差别,考察了超声波辅助VAC聚合时,单体浓度、引发剂浓度、超声波功率以及反应温度对体系的影响,在较短的时间内,得到了高转化率的稳定聚合物乳液。     

引发剂引发与热引发在苯乙烯本体聚合中的比较

考察了热引发方式和不同种类、浓度下的引发剂引发方式在苯乙烯的本体聚合中对聚合反应速率和产品的分子量及其分子量分布的影响。结果表明：引发剂用于苯乙烯的本体聚合可缩短反应停留时间、提高转化率或提高产品的分子量、使分子量分布变窄，双官能团引发剂的影响更为明显。     

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。     

溶液聚合制备丙烯酸酯橡胶的研究

采用溶液聚合方法,通过改变聚合条件研究丙烯酸酯橡胶聚合转化率随反应时间变化的关系。提高温度有利于聚合速率的提高,但同时会导致单体最终转化率的降低;改变引发剂过氧化苯甲酰（BPO）含量发现,BPO浓度提高聚合反应速率加快,单体转化率差别不大;丙烯酸丁酯（BA）分别与丙烯酸乙酯（EA）、丙烯酸甲酯（MA）共聚,聚合反应速率有所提高,聚合转化率略有降低;改变丙烯酸丁酯与丙烯酸甲酯共聚组成发现,MA作为共聚单体加快了聚合反应速率,对转化率影响不大。     

苯乙烯热引发本体聚合的动力学研究 Ⅱ 数均分子量

基于提出的自由基本体聚合三段聚合模型以及双分子热引发机理,进一步导得了苯乙烯热引发本体聚合时数均分子量的计算方程。同时,通过对已有文献中的数据进行关联,获得了不同聚合温度条件下聚苯乙烯数均分子量的通用计算方程。分析获得的方程,可以认为,对于自由基本体聚合,由低转化阶段至凝胶效应阶段,链增长反应速率常数kp和向单体的链转移反应速率常数krt.m或向单体的链转移常数Cm维持不变,且Cm与聚合反应温度无关。此外,结果表明,在低转化阶段,数均分子量不随转化率改变,仅与聚合反应温度有关。但在凝胶效应阶段,分子量随转化率改变而变化,且反应温度越高,变化越显著。     

引发剂体系对AN-MAA本体共聚合的影响

以聚合热力学为基础,研究了引发剂体系对丙烯腈(AN)-甲基丙烯酸(MAA)本体共聚合的影响.不同活性的偶氯二异丁腈(AIBN)和偶氮二异庚腈(ABVN)单独引发AN-MAA共聚合时,不能消除暴聚现象.采用AIBN/ABVN复合引发剂且复合引发剂半衰期为63,4～117.1 h、总用量为0.12～0.24 phr、聚合温...     

丙烯腈与丙烯酸的共聚合及表征

以偶氮二异丁腈为引发剂 ,研究了丙烯腈与丙烯酸在二甲基亚砜中的自由基溶液共聚合反应。考察了单体浓度 ,引发剂浓度 ,反应温度和时间等对共聚反应的影响。分别用称重法和乌氏粘度计测定了反应的转化率和产物的相对分子质量。用 IR,DSC和 TG对产物的结构和性能进行了表征。研究结果表明 ,最佳的反应条件是 :总单体浓度 2 2 % ,AIBN占总单体浓度 1 % ,反应温度和时间为 6 0℃和 2 4h     

丙烯腈与丙烯酸共聚合

以偶氮二异丁腈为引发剂,研究了丙烯腈与丙烯酸在环己烷中的自由基溶液共聚合反应。探讨了单体质量分数,引发剂质量分数,反应温度等对共聚反应的影响。用乌式粘度计测定了产物的相对分子质量。用IR和TG对产物的结构和性能进行了表征。研究结果表明,最佳反应条件是:总单体质量分数30%,AIBN占总单体质量分数5%,反应温度为70℃,反应时间为4 h。     

Radiation-initiated graft copolymerization of individual monomer and comonomer onto polyethylene and polytetrafluoroethylene films

Preparation and some properties of the graft copolymers obtained by radiation-induced graft polymerization of methacrylic acid (MAA) and (acrylonitrile/MAA) comonomer onto polyethylene and polytetrafluoroethylene films, were investigated. The effect of reaction conditions, solvent, monomer, and inhibitor concentration, comonomer composition, and comonomer concentration, on the graft copolymerization process was studied. The grafting process was enhanced in the presence of comonomer (AN/MAA) as compared with individual grafting of MAA or acrylonitrile (AN). The optimum comonomer composition, at which the highest grafting yield was obtained, was found to be (80/20) wt % of (AN/MAA) comonomer. The graft copolymerization of (AN/MAA) comonomer was enhanced in presence of AN due to its higher polarity strength. The electrical and swelling properties of the graft copolymers were greatly affected by the contents of PAN and PMAA graft chains. Mechanical properties of the graft copolymers were significantly changed with the grafting yield.     

高单体进料浓度下丙烯腈连续水相沉淀共聚的研究Ⅱ聚合物颗粒形态

以ＫＰＳ－ＮａＨＳＯ３－Ｆｅ２＋ 为引发体系,在５ 升ＣＳＴＲ 中进行了高单体进料浓度（＞ ２８％ ）的丙烯腈（ＡＮ）－丙烯酸甲酯（ＭＡ）－苯乙烯磺酸钠（ＳＳＳ）三元连续水相沉淀共聚,系统考察了搅拌条件、单体进料浓度、引发剂浓度及配比、ｐＨ 值、平均停留时间和聚合温度等工艺因素对聚合物颗粒形态的影响。结果表明,有利于提高聚合反应速率的因素,包括提高单体进料浓度、引发剂浓度、ｐＨ值和聚合温度等均有利于改善颗粒形态,其中搅拌强度和单体进料浓度影响最明显。适当延长平均停留时间也对颗粒形态稍有改善。     

Preparation of nanometer‐sized poly(methacrylic acid) particles in water‐in‐oil microemulsions

A water‐in‐oil microemulsion, water‐in‐cyclohexane stabilized by poly(ethylene glycol) tert‐octylphenyl, was developed to prepare poly(methacrylic acid) (PMAA) particles. Up to 100% conversion of the amphiphilic monomer, methacrylic acid (MAA), which could not be converted to the polymer efficiently in a dioctylsulfosuccinate sodium salt/toluene microemulsion, was achieved. The viscosity‐average molecular weight of the PMAA prepared was 1.45 × 10⁵ g/mol. The effects of some polymerization parameters, including the reaction temperature and the concentrations of the initiator and the monomer, on the polymerization of MAA were investigated. The results showed that the polymerization rate of MAA was slower than that of acrylamide in the microemulsions reported in the literature. The degree of conversion increased with the initiator concentration, reaction temperature, and monomer concentration. However, the stable microemulsions became turbid during the polymerization when the reaction temperature was at 70°C or at a high monomer concentration (40 wt %) The synthesized PMAA particles were spherical and had diameters in the range of ～50 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2497–2503, 2006     

偏氯乙烯/丙烯腈/苯乙烯悬浮共聚合动力学

本文研究了偏氯乙烯（ＶＤＣ）／丙烯腈（ＡＮ）／苯乙烯（Ｓｔ）三元悬浮共聚合体系的聚合机理、共聚速率、非聚物组成及其特性粘度的影响因素。实验表明随着投料配比的改变，可分成四个不同聚合机理区域。Ｓｔ对ＶＤＣ／ＡＮ／Ｓｔ三元悬浮共聚有缓聚作用。ＶＤＣ三元悬浮共聚速率可用半经验模型，ｄＣ／ｄｔ＝αＣ＾β「Ⅰ」ｏ＾γｅｘｐ（－γｋｄｔ）描述，由实验得到模型参数γ值为２．２４，模型参数α、β是聚合温度与引发剂浓度的函数。ＶＤＣ－ＡＮ－Ｓｔ三元悬浮共聚物存在着较宽的ＶＤＣ组成分布，并受到单体ＡＮ水溶性的影响，经ＡＮ动态相平衡校正后，可预测ＶＤＣ三元共聚物组成。ＶＤＣ－ＡＮ－Ｓｔ共聚物的特性粘度随着转化率的升高而增大。在相同引发剂用量下，高转化率ＶＤＣ－ＡＮ－Ｓｔ共聚物特性粘度的对数与温度的倒数成线性关系。     

聚丙烯腈原丝纺丝溶液的合成

以偶氮二异丁腈 (AIBN)为引发剂 ,研究了丙烯腈与丙烯酸甲酯在二甲基亚砜溶剂中的自由基均相溶液共聚合反应。考察了单体浓度、引发剂浓度、单体配比 ,反应温度和时间等对共聚反应的影响。分别用称重法和乌氏粘度计测定了反应的转化率和产物的相对分子质量。研究结果表明 ,制备高性能聚丙烯腈纺丝溶液最佳的反应条件是 :总单体浓度2 5 % ,AIBN占总单体浓度 1% ,反应温度为 6 0℃ ,时间为 30h     

Kinetics studies on copolymerization of acrylonitrile vinyl acids by solvent–water suspension polymerization

Polyacrylonitrile is an important polymer that is widely used in the manufacture of synthetic fibers, particularly for applications in apparel. Although a vast amount of literature is available on the polymerization process of acrylonitrile (AN) with other monomers, there are few reports of studies on polymerization in a mixed solvent of water with an organic solvent. It is conceivable that this method could combine the advantages of the solution and suspension polymerization methods. Synthesis of AN copolymers with two vinyl acids, methacrylic acid (MAA) and itaconic acid (IA), is carried out by solvent–water suspension polymerization. The polymerizations are performed with an equal ratio mixture of dimethylformamide as a solvent and water as a nonsolvent at 60°C using α,α‐azobisisobutyronitrile as an initiator. The kinetics of polymerization are studied by plotting the conversion versus reaction time for different mole ratios of AN with vinyl acids. Copolymers are characterized by FTIR and capillary viscometery. The results show that IA depresses the rate of polymerization more than MAA in this reaction medium, and this effect becomes more significant at higher vinyl acid mole ratios. High conversion in a short reaction time is obtainable for copolymers with a low vinyl acid mole fraction. However, for mole ratios of more than 93:7, the rate of the reaction is drastically reduced and low conversion (<60%) results, even after 8 h. The intrinsic viscosities of all cases are surprisingly high. Although they are reduced with increasing acidic comonomer mole fraction, this reduction is more significant for IA compared to MAA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1284–1291, 2005