无皂乳液聚合制备阳离子功能性微示研究

苯乙烯（Ｓｔ）／丙烯酸丁酯（ＢＡ）体系在无乳化剂的条件下分别与少量的自制的Ｎ，Ｎ－二甲基，Ｎ－丁基，Ｎ－甲基丙烯酰氧乙基溴化铵（ＤＢＭＥＡ）、Ｎ，Ｎ－二甲基，Ｎ－丁基，Ｎ－（３－甲基丙烯酰胺基）丙基溴化铵（ＤＢＭＰＡ）进行共聚，难过离子交换－－电导滴定确定了两体系微球表面基团及粒子表面电荷密度，认为微球大小及表面电荷密度主要由引发剂浓度、共聚单体浓度、离子强度、Ｓｔ／ＢＡ主单体比及单体加料方式决定     

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     

P（St－BA）／P（BA－St）胶乳型互穿网络聚合物的研究Ⅱ交联程度对阻尼

考察了交联程度对ＬＩＰＮＰ（Ｓｔ－ＭＡ）／Ｐ（ＢＡ－Ｓｔ）动态力学性能的影响。结果表明，以二乙烯基苯为交联剂，第一组分的交联程度对体系的阻尼性能影响不大，第二组分交联程度增大时可明显提高体系的阻尼性能；以Ｎ－（羟甲基）丙烯酰胺（Ｎ－ＭＡ）为交联剂时，不同的加入方式对体系的阻尼性能影响程度亦有差别。     

WCl_6－Al（i－Bu）_2Cl催化丁二烯－苯乙烯共聚合──丁苯共聚物的结构组成和竞聚率测定

对丁苯共聚物的~１Ｈ－ＮＭＲ谱图进行了归属，并建立了计算其４种结构单元含量的方程式。当Ａｌ（ｉ－Ｂｕ）_２Ｃｌ／ＷＣｌ_６＝６（摩尔比）时，苯乙烯（Ｓｔ）单元含量最低，丁二烯（Ｂｄ）单元含量最高；Ｂｄ单元含量随Ｂｄ／Ｓｔ值的增加而提高，总的Ｓｔ单元含量随Ｂｄ／Ｓｔ值的增加而降低；聚合时间对单元含量的影响与Ｂｄ／Ｓｔ值的影响相似；提高聚合温度，Ｓｔ单元含量降低。用微分法求得转化率低于１０时Ｓｔ的竞聚率为４．７０，Ｂｄ的竞聚率为０．２７。     

P（St—BA）／P（BA—St）胶乳型互穿网络聚络聚合物的研究Ⅱ交联程度对阻尼性...

考察了交联程度对ＬＩＰＮＰ（Ｓｔ－ＭＡ）／Ｐ（ＢＡ－Ｓｔ）动态力学性能的影响。结果表明，以二乙烯基苯为交联剂，第一组分联程度对体系的阻尼性能影响不大，第二组分交联程度增大时可明显提高体系的阻尼性能；以Ｎ－（羟甲基）丙烯酰胺（Ｎ－ＭＡ）为交联剂时，不同的加入方式对体系的阻尼性能影响程度亦有差别。     

苯乙烯—丙烯酸丁酯—丙烯酸羟乙酯共聚物的合成及其与二异氰酸 …

当混合溶剂乙酸丁酯／二甲苯质量比为１：１,过氧化苯甲酰（ＢＰＯ）为１％,苯乙烯（Ｓｔ）／丙烯酸丁酯（ＢＡ）＋丙烯酸羟乙酯（ＨＥＡ）（质量比）为６２：３８,反应温度为１３３℃时,可获得卖座经率为９５．３％,「η」为０．１６ｄＬ／ｇ的Ｓｔ－ＢＡ－ＨＥＡ共聚物。该共聚物（ＨＥＡ的结合量为２－４％）在同一溶剂中加入甲苯二异氰酸酯（ＴＤＩ）或聚醚型二异氰酸酯（ＰＥＤＩ）,当一ＮＣＯ／－ＯＨ摩尔比为１．２－１     

WCl6—Al（i—Bu）2Cl催化丁二烯—苯乙烯共聚合：丁苯共聚物的结构组…

对丁苯共聚物的＾１Ｈ－ＮＭＲ谱图进行了归属，并建立了计算其４种结构单元含量的方程式。当Ａｌ（ｉ－Ｂｕ）２Ｃｌ／ＷＣｌ６＝６（摩尔比）时，苯乙烯单元含量最低，丁二烯单元含量最高；Ｂｄ单元含量随Ｂｄ／Ｓｔ值的增加而提高，总的Ｓｔ单元含量随Ｂｄ／Ｓｔ值的增加而降低；聚合时间对单元含量的影响与Ｂｄ／Ｓｔ值的影响相似；提高聚合温度，Ｓｔ单元含量降低。用微分法求得转化率低于１０％时Ｓｔ的竞聚率为４．７０，Ｂｄ     

聚丙烯酸丁酯-丙烯酸/苯乙烯辐射接枝共聚物粘接性能的研究

采用过氧化预辐射法将生产高分子特效膜残留下的废苯乙烯（Ｓｔ）与聚丙烯酸丁酯－丙烯酸（ＰＢＡ－ＡＡ）接枝，制得ＰＢＡ－ＡＡ／Ｓｔ接枝共聚物。比较了辐射法和化学法所制接枝共聚物的粘接性能，考察了Ｓｔ含量、丙烯酸丁酯（ＢＡ）／ＡＡ共聚物特性粘度、ＡＡ用量、ＢＡ和Ｓｔ预辐射剂量对接枝共聚物粘接性能的影响。结果表明，采用辐射法所制接枝共聚物的粘接性能优于化学法所制接枝共聚物的粘接性能；废Ｓｔ比纯Ｓｔ效果好；当Ｓｔ含量为３３％、ＢＡ／ＡＡ共聚物特性粘度适中、ＡＡ用量为５．５份（ＢＡ用量固定为１００份）、ＢＡ预辐射剂量为１６．０ｋＧｙ、Ｓｔ预辐射剂量为３２．０ｋＧｙ时，制得的接枝共聚物的粘接性能最为理想     

聚烯烃用SBS四元接枝改性粘合剂的研究

研究了以丙烯酸（ＡＡ）为功能性单体,与ＳＢＳ和甲基丙烯酸甲酯（ＭＭＡ）、丙烯酸丁酯（ＢＡ）进行四元接枝共聚反应,着重探讨了ＭＭＡ／ＢＡ配比、ＡＡ用量和加入方式及固化时间对粘接性能的影响,所得四元接枝胶对聚烯烃的粘接强度及室温固化性能优于 ＳＢＳ－ ｇ－ ＭＭＡ－ ｇ－ ＢＡ三元接枝胶,尤其与异氰酸酯配合使用时,其效果更佳。     

橡胶粒子的粒径及粒径分布对ABS性能和结构的影响

采用种子乳液聚合技术在聚丁二烯（ＰＢ）和丁苯胶乳（ＳＢＲ）乳胶粒上接枝共聚苯乙烯（Ｓｔ）和丙烯腈（ＡＮ）,分别合成了橡胶含量为２０％的ＡＢＳ共聚物,并研究了ＡＢＳ的力学性能和形态结构。结果表明,在两种ＡＢＳ中橡胶粒子都比较均匀地分散在ＳＡＮ基体中,其橡胶粒子直径分别为０．０５μｍ（ＳＢＲ０和０．２５μｍ（ＰＢ）左右,并且在ＰＢ橡胶粒子中含有大量的结构－－ＳＡＮ次级粒子,其冲击强度值分别为１５Ｊ／ｍ     

中空聚合物微球的制备——种子及核乳胶粒的制备

为了制得具有中空结构的聚合物微球,首先以十二烷基苯磺酸钠(SDBS)为乳化剂,在其用量低于CMC的条件下,进行甲基丙烯酸甲酯(MMA)、甲基丙烯酸(MAA)和丙烯酸丁酯(BA)的乳液聚合,制备了带羧基的种子乳胶粒.然后采用MMA、MAA和二乙烯基苯为单体进行种子乳液聚合,制备了轻度交联的带羧基的核乳胶粒.该核乳胶粒经过核-壳乳液聚合和适当的碱处理工艺就可成为具有中空结构的聚合物微球.采用粒度仪测定了乳胶粒的直径及其分布,采用TEM对乳胶粒结构形态进行了表征.研究了种子及核乳胶粒制备过程中单体加料方式、乳化剂用量及羧基单体种类等因素对聚合稳定性、乳胶粒直径及其分布以及最终的中空聚合物微球结构形态的影响,确定了制备种子及核乳胶粒的最佳工艺条件.在制备种子阶段,SDBS用量为单体总量的0.5%,采用一次性加入单体的进料工艺;在核乳胶粒制备阶段,以MAA为羧基单体,所有单体采用"饥饿式"加料,半连续补加乳化剂并使乳化剂用量为核单体总量的0.15%时可保持聚合稳定性并保证无新乳胶粒生成.     

St-BA-BVP无皂共聚物阳离子乳胶粒大小及形态研究

合成阳离子共单体 1-丁基 ,4 -乙烯吡啶溴化铵 ( BVP) ,并以偶氮二异丁基咪盐酸 ( A IBA)作引发剂 ,制备苯乙烯 /丙烯酸丁酯 ( St/ BA )共聚物乳液 ,通过 TEM研究改变 BVP的浓度、St/ BA主单体的配比及单体加料方式对 P( St/ BA / BV P)乳胶粒大小形态的影响 ,结果表明批量法和单体全滴加法制备的乳胶粒形状规则、分布均匀、半连续法制备的乳胶粒子呈多分散分布 ,粒径相差很大 ,且 P( St) / P( BA)得到的乳胶粒呈明显的核壳结构。     

用阴离子Gemini 9 B-6-9 B乳化剂合成苯乙烯-丙烯酸丁酯共聚物纳米乳液

以壬基酚、1,6-二溴己烷、氯磺酸为主要原料合成的阴离子Gemini磺酸盐表面活性剂9 B-6-9 B为乳化剂,苯乙烯(St)、丙烯酸丁酯(BA)为单体,合成了乳胶粒径小于100 nm且分布均匀的苯乙烯-丙烯酸丁酯共聚物纳米乳液,考察了聚合温度、乳化剂用量、引发剂用量、单体配比、单体含量对乳液的影响,探讨了乳胶粒子成核机理。结果表明,随着温度的升高,乳胶粒子的平均粒径减小,转化率与凝胶率增大;随着乳化剂或引发剂用量的增加,乳胶粒子的平均粒径和凝胶率减小,转化率增大;随着软单体比例的增加,乳胶粒子的平均粒径与转化率增大,粒径分布变宽,凝胶率减小;单体用量增大,乳胶粒子的平均粒径与凝胶率增大,转化率降低;乳胶粒子的粒径呈单峰分布,可能是按胶束成核机理形成的。     

Preparation of monodispersed hollow polymer particles by seeded emulsion polymerization under low emulsifier conditions

In a low emulsifier system, the MMA‐BA‐MAA copolymer emulsions were prepared as seed latices and the seeded emulsion polymerization of MMA‐MAA‐DVB was consequently carried out to prepare carboxylated core particles. The hydrophobic shell was then synthesized onto the core using styrene, acrylonitrile, and divinylbenzene as comonomers. The hollow latex particles were obtained by alkalization treatment of the core‐shell latex particles. The effects of the feeding rate of monomer mixture, contents of emulsifier SDBS and crosslinking agent DVB, and ratio of the monomers during the core stage and shell stage on the morphology and volume expansion of the latex particles were investigated. The results show that the monodispersed hollow latex particles with large size can be obtained when the feeding rate is 0.1 g/min, SDBS content is 0.15 and 0.2 wt % during the core stage and shell stage, respectively, DVB contents are 1% during the preparation of shell copolymers, and the monomer ratio of the core particle to shell layer is 1 : 8. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1505–1510, 2005     

Preparation and structure control of hollow polymer particles: Influence of seeded emulsion polymerization and alkalization treatment process

Hollow polymer latex particles containing a hydrophilic core were prepared by seeded emulsion polymerization with MAA/BA/MMA/St as comonomers, followed by stepwise alkalization treatment with ammonia. The size and morphology of composite latex particles was determined by TEM. The effects of the seeded emulsion polymerization conditions and alkalization treatment on the size and hollow structure of latex were investigated. The results showed that the optimum content of crosslinking agent in the shell polymers was about 0.5–1.0 wt %, emulsifier was about 0.8–1.1 wt %, and the core/shell weight ratio was 1/7. To obtain uniform hollow latex particles with large size, the starved feeding technique should be adopted in seeded emulsion polymerization, and the neutralization temperature should equal to the T_g of the shell polymer. Then, the obtained polymer particles under this condition had an excellent hollow structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Stability and copolymerization of concentrated emulsion of styrene and butyl acrylate in the presence of polyurethane macromonomer

A study has been made of the stability and copolymerization of concentrated emulsion of styrene (St) and butyl acrylate (BA) in the presence of polyurethane macromonomer (DPUA), which contains C?C at one end. First, the DPUA macromonomer was synthesized from the appropriate amount of 2,4‐diisocyanate (TDI), polypropylene glycol (PPG), 2‐hydroxyethyl methylacrylate (HEMA), dimethylolpropionic acid (DMPA), and triethylamine (TEA) by four steps. Then, the DPUA was dissolved in St‐BA monomer mixtures. The DPUA/St‐BA concentrated emulsion copolymerization using sodium dodecyl sulfate/cetyl alcohol (SDS/CA) as composite surfactant and polyvinyl alcohol (PVA) as liquid film reinforcer, and ammonium persulfate/sodium hydrogen sulfate (APS/SHS) as redox initiator system was carried out at 30°C. The effect of NCO/OH molar ratio, surfactants' concentration, mass ratio of DPUA/St‐BA, initiators' concentration, volume fraction of the monomer phase (Φ), and temperature on the stability or the copolymerization of the concentrated emulsion of DPUA/St‐BA were investigated. The average size and distribution of the latex particles obtained under different conditions were also analyzed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1992–1999, 2007     

Preparation and characterization of imidazole‐functionalized microspheres

The preparation of imidazole‐functionalized latex microspheres by a two‐stage emulsion copolymerization process and their characterization are reported on. Emulsifier‐free emulsion copolymerization of styrene (St) and 1‐vinyl imidazole (VIMZ) exhibited bimodal particle size distributions caused by secondary homogeneous nucleation process. However, secondary nucleation can be avoided by using cetyltrimethylammonium bromide (CTAB) as a stabilizer at a concentration below its cmc (critical micelle concentration). This would result in the formation of monodisperse latex particles. The final particle size diameter depended on the concentration of CTAB as well as the amount of VIMZ. To control the amount of the functional imidazole groups on the latex particle surfaces, independent of the latex diameters, without secondary nucleation of particles, the seeded emulsion copolymerization of styrene and VIMZ was explored as a second‐stage polymerization at different concentrations and ratios of monomers in the presence of the previously prepared monodisperse poly(styrene‐co‐1‐vinyl imidazole) seed latex particles. The concentration of imidazole functional groups on the surface of the latex particles could also be varied through the rearrangement of hydrophilic imidazole groups by varying the second‐stage monomer addition process such as the utilization of monomer‐swollen seed particles or a shot addition of monomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 120:5753–5762, 2006     

油气田固井专用羧基丁苯胶乳的合成

以丁二烯、苯乙烯(St)为主要单体,引入不饱和羧酸、磺酸盐等作为功能性单体,采用复合乳化体系,以乳液聚合方式合成出油气田固井专用羧基丁苯胶乳。试验结果表明:最适宜的合成条件是w(复合乳化剂)=1.5%～2.0%、m(丁二烯)∶m(St)=(45～65)∶(55～35)、w(不饱和功能单体)=2.5%～3.5%(相对于总单体而言)、w(不饱和磺酸盐功能单体)=0.20%～1.00%、w(调节剂)=0.45%、m(烃)∶m(水)=100∶(120～130)、在(75±3)℃条件下聚合且w(过硫酸盐)=0.5%～0.6%;在最佳合成条件下制取的羧基丁苯胶乳,完全满足固井施工的要求。     

核/壳型聚硅氧烷丙烯酸酯复合乳液的制备

采用种子乳液聚合的方法制备了具有核/壳结构的聚硅氧烷丙烯酸酯复合乳液,研究了乳化剂、单体的投料方式及配比对乳液性质的影响。结果表明:通过种子乳液聚合,得到了含氢聚硅氧烷/丙烯酸丁酯/苯乙烯/甲基丙烯酸甲酯/甲基丙烯酸（PHMS/BA/St/MMA/MAA）共聚物复合乳液,乳液性能稳定,该乳液所制得的胶膜具有优良的性能。     

自交联型改性苯丙乳液的制备及其用于防水涂料的性能研究

以丙烯酸（AA）、丙烯酸丁酯（ BA）和苯乙烯（St）为基础单体,通过调控功能单体甲基丙烯酸缩水甘油酯（ GMA）的用量制备了一种自交联型改性苯丙乳液（ PGSA）对乳液粒径大小与分布、形态与形貌以及乳液涂膜吸水性能进行了表征。以 PGSA乳液为液料辅以无,机水泥等填料制备了双组分聚合物水泥防水涂料,对其抗渗及力学性能进行了研究。结果表明：当 GMA用量为 7%时（以单体 AA、BA和 St的总质量计）,PGSA乳液的粒径为 210 nm、粒径分布（PDI）为 0. 17~0. 21,且放置 6个月后乳液的粒径及分布基本保持不变。此外,随着 GMA用量的增加, PGSA乳液涂膜的吸水率呈下降趋势。 PGSA基防水涂料的抗渗性、抗拉强度及断裂伸长率都符合 GB/T 23445—2009《聚合物水泥防水涂料》标准的要求,应用前景广阔。