偏氯乙烯/丙烯腈悬浮共聚树脂的粒径及其分布

研究了分散剂浓度、搅拌转速、水油比等因素对偏氯乙烯／丙烯腈悬浮共聚树脂粒径及其分布的影响。结果表明,树脂颗粒的平均粒径随分散剂用量的增加而减少,并趋于平缓;平均粒径受搅拌转速的影响情况与分散剂用量有关,在实验的搅拌转速范围内,分散剂用量高于临界值（约略小于０．４％）时,平均粒径随搅拌转速增加而减小,在低于临界值时,平均粒径随转速增加呈马鞍形变化,平均粒径最低点对应的临界转速约为５００ｒ／ｍｉｎ;平均粒径随水油比的增加而减少,但影响较小。     

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     

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。     

新型氯乙烯非均相聚合动力学和成粒机理

对以正丁烷（But)为反应介质的新型氯乙烯（VC）非均相聚合动力学和成粒机理进行了研究，根据VC-But二元体系气液平衡方程，由聚合过程气相压力或组成变化计算VC聚合转化率，VC非均相聚合的诱导期不明显，自动加速现象一般发生在聚合前、中期，后期聚合速率较小，新型VC非均相聚合PVC树脂的体粒径与悬浮PVC树脂相当，数均粒径较小，PVC颗粒由基本不熔结的初级粒子组成，颗粒内部初级粒子分布密度大，粒径大，孔隙率高；而在颗粒表层初级粒子分布密度高，粒径小，孔隙率低；树脂的增塑剂吸收率远大于悬浮PVC树脂，根据PVC树脂的颗粒特性和PVC与VC／But混合液的溶解度参数差异，推断聚合成粒机理为：PVC分子链在很低转化率时就从聚合介质中沉析出来并聚集形成微区，初级粒子和颗粒；后期成粒过程包括颗粒内部初级粒子的增长和向表层的离心聚集，颗粒对新形成的大分子链及其初级聚集体的捕捉等。     

丙烯腈连续水相沉淀聚合动力学数模

本文研究了丙烯腈（AN）、丙烯酸甲酯（MA）和甲基丙基烯磺酸钾（MAS）在水介质中的沉淀聚合反应。从基本反应和速率方程出发，应用连续搅拌釜（CSTR）的设计方程和聚合物颗粒表面的吸附方程，导出了丙烯腈连续水相沉积聚合的数模。结果表明，由模型算得的反应器出口处单体转化率和产品的平均分子量与实验值相吻合。     

丙烯腈光聚合研究

研究偶氮二异丁腈(AIBN)作光引发剂引发丙烯腈(AN)的光聚合,探讨了单体浓度、引发剂浓度、光照时间和环境温度对单体转化率、聚合物黏均相对分子质量的影响。总结出光引发剂C60-(SR)n(C60负载引发-转移-终止剂)与常规光引发剂AIBN引发AN光聚合的区别。     

无外加表面活性剂的苯乙烯悬浮聚合

针对传统悬浮聚合制备聚苯乙烯颗粒粒径分布宽、有效粒子收率低的问题,采用过硫酸铵/磷酸钙复合分散剂体系,在无外加表面活性剂情况进行苯乙烯悬浮聚合,制备了聚苯乙烯珠粒。通过对聚合稳定性、聚苯乙烯珠粒粒径及分布的测定与分析,考察了磷酸钙、过硫酸铵的用量及比例对悬浮聚合的影响,并分析了过硫酸胺对悬浮聚合的分散稳定机理。结果表明,当过硫酸铵和磷酸钙的用量分别为单体质量的0.01%和1.00%时,悬浮聚合体系稳定,得到的粒子透明性好,平均粒径为1.35 mm,粒径分布窄;通过改变过硫酸铵和磷酸钙的用量,可以调节聚苯乙烯珠粒的平均粒径。     

丙烯腈连续水相聚合的过程分析及控制

简要介绍丙烯腈水相聚合过程的机理及其数学模型，从而导出过程的参变数及对聚合过程目标值的影响。在此基础上，提出丙烯腈水相连续（共）聚合过程的控制方案。     

丙烯腈与衣糠酸在混合溶剂中沉淀共聚合

采用丙烯腈（AN）与衣糠酸（IA）自由基共聚合，以偶氮二异丁腈（AIBN）为引发剂，在二甲基亚砜（DMSO）与H2O的混合溶剂中合成聚丙烯腈（PAN），讨论了反应温度、引发剂质量分数、DMSO与H2O配比、单体质量分数、IA质量分数对转化率的影响。     

聚氯乙烯糊树脂颗粒形态与增塑糊性张关系的研究

用激光散射法对聚氯乙烯糊树脂（PPVC）浆料粒径及其分布和粉料颗粒粒径及其强度进行了测定和研究。结果表明：初级粒子的粒径大小和分布是决定PPVC树脂糊性能的关键因素;在一定范围内（30－60μm）,二次粒子颗粒强度即二次粒子的解碎程度是影响PPVC树脂成糊性能的重要因素之一。     

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     

Acrylonitrile/ammonium itaconate aqueous deposited copolymerization

Acrylonitrile/ammonium itaconate [AN/(NH₄)₂IA] aqueous deposited polymerizations were studied in this work. It shows that the polymerizations were influenced by various factors, especially the water solubility of AN. In the polymerization process, the system was as separated monomer and water phases, and AN transferred from monomer phase to water phase until the monomer phase disappeared. Because of the solubility of AN in water, the reactivity ratios of monomer calculated by Kelen‐Tudos method were different in various monomer contents. Although (NH₄)₂S₂O₈ was a water‐soluble initiator, there was a short amount of polymer formed in monomer phase. To inhibit the polymerization in monomer phase, two additives were used in the polymerization and experiment data indicated that the two inhibitors exert inhibitory role effectively in monomer phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 904–908, 2006     

Room temperature initiated and self-heating polymerization via concentrated emulsions: application to acrylonitrile based polymers

Summary A novel concentrated emulsion polymerization procedure, in which the polymerization is initiated at room temperature and the heat generated by the reaction accelerates the process, is proposed. The polymerization of acrylonitrile (AN) and its copolymerization with vinylidene chloride (VDC) are used as examples. AN (alone or with a comonomer) containing an oxidant was first dispersed in water to generate a concentrated emulsion. The polymerization of the monomers was initiated at room temperature by introducing an aqueous solution containing a mixture of reductants (ferrous sulfate and sodium metabisulfite) into the concentrated emulsion. The heat generated in the system increased its temperature and accelerated the polymerization. The polymerization was completed in one hour with conversions higher than 90%. The small volume of the continuous phase in a concentrated emulsion constitutes an advantage of the procedure, since only a small amount of the produced heat is used for its heating. In addition, because the reductant, which is present in the water phase, together with the oxidant, which is present in the oil phase, constitute the initiator, the large oil-water interfacial area of the concentrated emulsion constitutes an additional advantage.     

原位乳液聚合制备丙烯腈聚合物/纳米氧化硅复合粒子

利用2,2'-偶氮(2-脒基丙烷)二氯化氢(AIBA)引发剂与纳米氧化硅粒子的静电作用而使AIBA吸附在纳米氧化硅表面,进而引发丙烯腈-甲基丙烯酸甲酯(AN-MMA)原位乳液聚合.考察了AIBA浓度和反应温度对AN-MMA原位乳液聚合动力学的影响以及氧化硅含量对AN-MMA共聚物/纳米氧化硅复合乳胶粒径分布和形态的影响.结果表明:聚合速率随AIBA浓度和聚合温度的升高而增大; AIBA浓度相同时,原位乳液聚合速率小于普通乳液聚合;AN-MMA共聚物/纳米氧化硅复合粒子粒径随纳米氧化硅含量增加而增大;原位乳液聚合得到的复合胶粒表面粗糙,当纳米氧化硅质量分数为10%时,纳米氧化硅与聚合物乳胶粒子复合良好;当纳米氧化硅质量分数为20%和30%时,有部分纳米氧化硅粒子与乳胶粒子分离而分散在连续相中.     

Porous acrylonitrile/itaconic acid copolymers prepared by suspended emulsion polymerization

Porous acrylonitrile (AN)/itaconic acid (IA) copolymers were successfully prepared by suspended emulsion polymerization for the first time, with potassium peroxydisulfate (KPS) as an initiator, poly(vinyl alcohol) (PVA) as a dispersant agent, and Span80 as an emulsifier. The effects of the water/monomer mass ratio, agitation conditions, KPS concentration, PVA concentration, Span80 concentration,s and IA concentration on the average particle size and size distribution, particle morphology, and porosity of the AN/IA copolymers were investigated. The results show that the final AN/IA copolymers formed with agglomerates of primary particles had a porous structure, low particle density, and uniform particle size and did not agglomerate easily between the particles. The preparation conditions for the AN/IA copolymers were optimized as follows: (1) the water/monomer mass ratio was 0.3 : 1; (2) the concentrations of KPS, IA, PVA, and Span80 were 0.5, 12.4, 0.1, and 0.5 wt %, respectively, based on the weight of AN separately; (3) the agitation rate was 400 rpm; (4) the polymerization temperature was 70°C; and (5) the reaction time was 3 h. The size of the final AN/IA copolymer particles was in the range 200–400 μm. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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。     

pH值对超声辐照下聚乙烯醇-丙烯腈体系共聚反应影响的研究

<正>聚乙烯醇(PVA)是制造维纶纤维的原料.维纶是棉型纤维,具有高强、耐磨和高吸湿性特点,但是染色性差,回弹性低.腈纶具有高回弹性和优良染色性,素有合成羊毛之称,但是强度较低,吸湿性差.通过嵌段共聚可使腈纶和腈纶在分子基础上结合,制得兼具维纶和腈纶优异性能的新型合成纤维.有关在超声辐照下PVA与丙烯腈(AN)的嵌段共聚反应已有报道,为进一步提高共聚反应速率、共聚物产率及共聚物中AN含量,本文对体系PH值的影响进行了研究.     

氯乙烯/N-苯基马来酰亚胺/丙烯腈三元悬浮共聚三元悬浮共聚

从氯乙烯/N-苯基马来酰亚胺/丙烯腈三元悬浮共聚的技术特点出发,研究了加料方式对聚合工艺及产物颗粒特性的影响,并在此基础上考察了引发剂体系的影响,确定了适宜的引发剂种类及用量。     

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。