无皂微乳液聚合制备加脂型复鞣剂的研究

采用甲基丙烯酸甲酯、丙烯酸丁酯、二乙烯基苯、丙烯酸、反应型乳化剂马来酸酐十二醇单酯钾盐和助乳化剂正戊醇制备得到无皂微乳液。在前期微乳液皮革增强复鞣剂研究的基础上,通过正交试验优化出了反应型乳化剂的最佳合成条件,制备出反应型乳化剂——马来酸酐十二醇单酯钾盐,代替外乳化剂十二烷基硫酸钠,进行无皂微乳液聚合制备具有增强作用的加脂型复鞣剂。将制得的加脂型复鞣剂用于猪二层革的复鞣试验,结果表明：反应型乳化剂与混合单体(丙烯酸丁酯、甲基丙烯酸甲酯和二乙烯基苯)的质量分别为120g和180g,活性单体丙烯酸质量为10g时对皮革的复鞣效果最好。成革的物理机械性能得到了提高,其横向撕裂强度提高58.8%,纵向撕裂强度提高37.4%,崩破强度提高54.1%。     

碱溶性聚(丙烯酸丁酯/丙烯酸)的合成及性能

合成了碱溶性聚(丙烯酸丁酯/丙烯酸)〔P(BA/AA)〕,探讨了丙烯酸用量及不同引发体系对其表面张力、离心稳定性和乳化性的影响,对其结构进行了表征。傅里叶红外光谱(FTIR)分析表明,P(BA/AA)中无C C存在,聚合完全;差示扫描量热(DSC)分析表明,共聚物的玻璃化转变温度(Tg)为21.3℃;透射电镜(TEM)测定了P(BA/AA)的平均粒径小于100 nm,粒径分布均匀。以该共聚物为表面活性剂与丙烯酸酯类进行乳液聚合制备了皮革涂饰剂,应用于皮革涂饰后,革样的物理机械性能较采用常规乳化剂制备的丙烯酸树脂涂饰革样抗水性提高了28.08%,透气性提高了18.5%,耐湿擦性提高了半级,耐折牢度无明显变化。     

无皂微乳液聚合制备加脂型复鞣剂

采用甲基丙烯酸甲酯、丙烯酸丁酯、二乙烯基苯、丙烯酸、反应型乳化剂马来酸酐十二醇单酯钾盐和助乳化剂正戊醇制备得到无皂微乳液。通过正交实验优化出了反应型乳化剂的最佳合成条件:n(马来酸酐):n(十二醇)=1.15:1,反应温度80℃,反应时间3 h,制备出反应型乳化剂———马来酸酐十二醇单酯钾盐,代替外乳化剂十二烷基硫酸钠,进行无皂微乳液聚合制备具有增强作用的加脂型复鞣剂。将制得的加脂型复鞣剂用于猪二层革的复鞣实验,结果表明,反应型乳化剂与混合单体(丙烯酸丁酯、甲基丙烯酸甲酯和二乙烯基苯)的质量分别为120 g和180 g,活性单体丙烯酸质量为10 g时对皮革的复鞣效果最好。成革的物理机械性能得到了提高,其横向撕裂强度提高58.8%,纵向撕裂强度提高37.4%,崩破强度提高54.1%。     

水溶性单体共聚法制备无皂苯丙乳液的研究

以苯乙烯(St)、丙烯酸(AA)、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为共聚单体,制备了无皂苯丙乳液;然后以AA含量、中和度、引发剂含量和软/硬单体配比等为试验因素,以乳液稳定性和粒径为考核指标,采用单因素试验法优选出制备无皂苯丙乳液的最佳工艺条件。结果表明:当w(引发剂)=1.2%和w(AA)=4.5%(均相对于单体总质量而言)、中和度为0.8、m(BA)∶m(St+MMA)=4∶6和反应温度为78℃时,可制得粒径为纳米级的高固含量稳定乳液。     

微交联丙烯酸酯纳米乳液的制备及应用

用半连续种子乳液聚合工艺,合成了微交联丙烯酸酯纳米乳液。讨论了乳化剂、官能性单体、聚合温度及交联改性剂等因素对丙烯酸类聚合物乳液性能的影响。研究结果表明,用本工艺当乳化剂质量分数为2%,N 羟甲基丙烯酰胺质量分数低于0 4%,聚合温度为75～85℃时,可得到平均粒径为49 6nm,多分散性指数为0 149的单峰宽分布丙烯酸酯共聚乳液,将其用于皮革的填充,可显著改善皮革的柔软性、弹性以及革面的手感。     

核/壳型微乳液皮革填充黏合剂的合成及性能研究

以丙烯酸酯类单体为主要原料、以阴离子型乳化剂(F-20)和反应型非离子型乳化剂(X-03)为阴/非离子型复合乳化剂,采用预乳化半连续种子乳液聚合法合成了核/壳型丙烯酸酯微乳液。研究结果表明:当m(F-20)∶m(X-03)=3∶1、m(釜底乳化剂)∶m(预乳化液中乳化剂)=3∶1、m(核层中乳化剂)∶m(壳层中乳化剂)=1∶1、w(复合乳化剂)=9.0%、w(引发剂)=0.20%、固含量为25%和w(AA)=6%～8%时,相应核/壳型微乳液的综合性能良好,其平均粒径为29.1 nm,PDI(粒径分布指数)为0.223;将该乳液作为皮革填充黏合剂时,其填充性能优于单层微乳液,并且接近于国外同类产品。     

高固含量苯丙微乳液的制备与性能研究

以苯乙烯(St)、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为共聚单体,丙烯酸(AA)为功能单体,反应型乳化剂(DNS-86)、十二烷基硫酸钠(SDS)和壬基酚醚磺基琥珀酸酯钠盐(OS)为复合乳化剂,采用种子乳液聚合法制备了粒径小、耐水性好且固含量为50%的苯丙微乳液。研究结果表明:当w(引发剂)=0.7%、m(MMA+St)∶m(BA)∶m(AA)=5.0∶4.7∶0.3、w(St)=15%~25%、m(DNS-86)∶m(SDS+OS)=3∶2且w(复合乳化剂)=5%时,高固含量苯丙微乳液的综合性能良好。     

核壳型苯丙乳液的制备

用种子乳液和预乳化工艺,以苯乙烯(St)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、丙烯酸(AA)为单体,十二烷基硫酸钠(SDS)、烷基酚聚氧乙烯醚(OP-10)为混合乳化剂,过硫酸铵为引发剂,制备了具有核壳结构的苯丙乳液。探讨了乳化剂、引发剂、丙烯酸对乳液性能的影响。合适的反应条件为:MMA∶BA∶St∶AA=14∶25∶16∶2,乳化剂用量为3.2%,引发剂用量0.35%~0.42%,温度80℃。     

中空聚合物乳液的制备及其性能研究

以甲基丙烯酸甲酯(MMA)、丙烯酸(AA)、丙烯酸丁酯(BA)、丙烯腈(AN)和苯乙烯(St)为共聚单体,过硫酸铵(APS)为引发剂,十二烷基硫酸钠(SDS)和非离子型乳化剂(OP-10)为阴/非离子型复合乳化剂,采用种子乳液聚合法和碱溶胀后处理法制备了P(MMA/AA/BA)为核、P(St/AA/AN)为壳的纸张施胶用中空聚合物乳液。研究结果表明:当w(引发剂)=0.80%、m(SDS)∶m(OP-10)=2∶1和w(乳化剂)=1.5%时,中空乳液的综合性能较好,其单体转化率较高、乳液黏度适中、粒径较小且分布较窄。     

VAc共聚乳液对道路浮尘的粘接作用

以APS(过硫酸铵)为引发剂,VAc(醋酸乙烯酯)、BA(丙烯酸丁酯)、AA(丙烯酸)和HEA(丙烯酸羟乙酯)为单体,采用半连续加料法合成了物理性能优良、能促进浮尘粘接作用的VAc共聚乳液。研究结果表明:当w(乳化剂)=2.0%、w(APS)=1.2%、w(AA)=3.0%(相对于单体总质量而言)时,VAc共聚乳液黏度为620 mPa·s,平均粒径为183 nm,乳液储存稳定。单体AA用量为3.0%时,VAc共聚乳液改善了浮尘的润湿与粘接性能,密实度提高,表面邵D硬度高达43。     

Synthesis and application of methyl methacrylate/butyl acrylate copolymer nanoemulsions as efficient retanning and lubricating agents for chrome‐tanned leather

Two different nano‐emulsions based on methyl methacrylate/butyl acrylate copolymers have been synthesized to be used as retanning and lubricating agents for chrome‐tanned leather. The main difference and characteristics of the two prepared copolymers were studied. The nano particle size of the two copolymers was confirmed using transmission electron microscope (TEM). The influence of the prepared copolymers on chrome‐tanned leather as retanning agents was investigated. The properties of the retanned leather, namely, physicomechanical properties as tensile strength, elongation at break and water absorption, were measured. Thermal gravimetric analysis (TGA) technique was used to examine the thermal stability of the retanned leather. Also, the texture of the grain surface and fibers were inspected using scanning electron microscope (SEM). The retanned leather showed an improvement in its physicomechanical properties, as well as enhancement of its thermal stability as compared with the chrome‐tanned leather. Furthermore, the retanned leather has uniform dyestuff, softness, and firmness of grain. All these promising results provide evidence to the applicability of the prepared copolymer emulsions as efficient retanning and lubricating agents for chrome‐tanned leather. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

AIM增韧剂的合成及其增韧PVC的研究

采用种子乳液聚合法合成了核-壳结构丙烯酸酯类冲击改性剂(AIM),并用其增韧聚氯乙烯(PVC)树脂。采用动态激光粒度分析仪、DMA测试了AIM的乳胶粒子尺寸和玻璃化转变温度。对PVC/AIM共混物力学性能的分析表明:当PVC/AIM=100/8时,通过调节AIM交联剂含量和粒子尺寸,可以使PVC/AIM共混物冲击强度达到1443J/m。     

常温酮肼自交联纳米环氧树脂乳液的制备与表征

以环氧树脂E-20合成了环氧月桂酸酯, 以丙烯酸单体与双丙酮丙烯酰胺(DAAM)对其进行接枝改性, 添加己二酸二酰肼(ADH)制备了常温酮肼自交联纳米环氧树脂乳液。以红外光谱仪表征了合成过程中各步产物及乳液固化后的结构, 结果表明得到了设计结构的树脂, 干燥后涂膜的FTIR谱图表明酮羰基与酰肼基发生交联反应生成了腙;DSC分析表明合成的树脂具有两个玻璃化温度(T_g), 分别为丙烯酸接枝环氧树脂和纯丙烯酸树脂的T_g, 前者低于常温, 表明可以实现常温自交联。在改性环氧树脂乳液的合成过程中, 以粒径分析和综合性能分析对功能性单体配比进行了研究, 结果发现当MAA与E-20质量比为11.0%~14.7%、DAAM的用量为2%~3%、m(ADH)/m(DAAM)为0.8~1.0时, 制得的乳液具有良好的储存稳定性和涂膜性能。透射电镜及粒径测试表明乳液粒径为纳米级, 约88 nm, 且粒径分布均匀, 基本呈稳定的球形结构。将所制备的纳米乳液配制成防腐涂料, 性能测试表明该涂料具有良好的综合性能。     

Synthesis and characterization of urethane/acrylate composite latex

Polyurethane dispersion and urethane/acrylate composite latex were synthesized and characterized by using a particle size analyzer, gel permeation chromatograph (GPC), Fourier transform infrared spectroscopy coupled with attenuated total reflectance (FTIR‐ATR), dynamic mechanical analysis (DMA), and instron test machine. The amount of solvent and dimethylolpropionic acid (DMPA) used during synthesis of polyurethane resin straightway affected the average particle size and stability of aqueous polyurethane dispersion. The particle size of polyurethane dispersion had nothing to do with that of composite latex. FTIR‐ATR analyses displayed both air‐facing and substrate‐facing surfaces, containing more polyurethane component than the average composition. Some crosslinking reactions occurred in preparing urethane/acrylic composite latex, as indicated by FTIR analyses and solvent extraction. DMA demonstrated three glass transitions for the film from composite latex. Instron tests exhibited better film performance properties for the composite latex than for the corresponding blend latex. A possible particle growth mechanism for preparing urethane/acrylate composite latex was proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1620–1628, 2002; DOI 10.1002/app.10526     

Poly(MAA-AN-DM)两性聚合物复鞣剂的制备及性能

以甲基丙烯酸(MAA)、丙烯腈(AN)和甲基丙烯酸二甲基氨基乙酯(DM)为原料,过硫酸铵(APS)为引发剂,水为反应介质,经自由基共聚合制备了Poly(MAA-AN-DM)两性聚合物复鞣剂,并将其用于皮革的复鞣。用红外光谱、核磁共振氢谱、凝胶渗透色谱、胶体电荷滴定等对聚合产物的结构和性能进行了表征。用多功能材料实验机和色度计考察了聚合物组成对复鞣革性能的影响。较佳合成条件为:聚合温度80℃,单体量比n(MAA)∶n(AN)∶n(DM)=0.9∶0.3∶0.3,引发剂w(APS)=1.5%,w(单体)=30%,反应时间5.0 h。胶体电荷滴定测出共聚物的等电点为4.36,凝胶渗透色谱分析出共聚物的数均相对分子质量为84 688,分散系数为2.07。用w〔Poly(MAA-AN-DM)〕=2%的聚合物对猪蓝湿革进行复鞣,可使蓝湿革收缩温度提高5.5℃,抗张强度增加76.5%,增厚13.2%,革身饱满、无败色现象。     

The effect of nonionic monomer HAM on properties of cationic surfactant‐free acrylic/alkyd hybrid emulsion

A series of cationic acrylic/alkyd resin (CPAAR) hybrid emulsions was successfully prepared through surfactant‐free emulsion polymerization, using methacryloxyethyltrimethyl ammonium chloride, methyl methacrylate, butyl acrylate and alkyd resin as reaction monomers. And nonionic N‐hydroxymethyl acrylamide (HAM) of different content was simultaneously incorporated into the CPAAR backbone. The structure of CPAAR copolymer was characterized by Fourier transform infared spectrometer, and then the effect of HAM content on properties of CPAAR emulsions was studied by particle size analyzer, transmission electron microscopy and rheometer. In addition, thermal properties, water absorption and contact angle of CPAAR latex films were also investigated. The results showed that the CPAAR emulsions prepared with 4.9 wt % HAM displayed smallest average particle size of 92.2 nm. As HAM content increased from 0 to 19.6 wt %, the initial viscosity of the emulsions increased from 22.48 to 53 mPa.s. At the same time, the emulsions transferred from Newtonian fluid to pseudoplastic fluid, and a transition from viscous liquid to elastic liquid was also detected. Meanwhile, the degradation temperature at 5% weight loss increased by 30.59°C. In addition, with increasing HAM content from 0 to 4.9 wt %, the water absorption and surface free energy of films increased by 4.42% and 5.02 mJ m^?2, respectively. However, the water absorption and surface free energy kept almost invariable with further increase in HAM content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41406.     

胶原蛋白改性丙烯酸类复鞣剂的制备

该文以过硫酸铵为引发剂,以马来酸酐和丙烯酸为主要原料,通过水溶液共聚合成共聚产物,用胶原蛋白对共聚物进行接枝改性,合成了胶原蛋白改性聚丙烯酸类复鞣剂。讨论了单体质量比、反应温度、时间等条件对产品性能的影响,最佳反应条件为:m(过硫酸铵)∶m(马来酸酐)∶m(丙烯酸)∶m(胶原蛋白)=0.25∶2∶3∶0.5,共聚反应温度80℃,共聚反应时间1 h,加入胶原蛋白后在60℃继续反应3 h。对该复鞣剂进行了复鞣应用实验,讨论了该复鞣剂对皮革湿热稳定性和透水气性能的影响。结果表明,经该复鞣剂复鞣过的皮革与经商业化复鞣剂TGR复鞣过的皮革相比,表现出更好的粒面性能、丰满度、弹性及填充性能,可使皮革的收缩温度提高6℃,使皮革的透水气性能提高20%以上。     

Effect of acrylic monomer content on the properties of waterborne poly(urethane‐urea)/acrylic hybrid materials

Stable waterborne poly(urethane‐urea) (WBPU; soft segment content: 57%; dimethylol propionic acid: 19 mol %/5.8 wt %)–polyacrylate(methyl methacrylate/n‐butyl acrylate) (weight ratio: 4/1) hybrid latex (emulsions) with different acrylic contents [0, 10, 20, 30, and 40 wt % based on poly(urethane‐urea)] and without external surfactant were successfully prepared by in situ polymerization during a prepolymer mixing process. However, the as‐polymerized hybrid latex containing 50 wt % of acrylic monomer content was found to be unstable, indicating that about 50 wt % of acrylic monomer content was beyond the limit value of self‐emulsifying ability of WBPU anionomer prepared in this study. The breadth of particle size distribution of hybrid latex increased markedly from 20–75 to 55–275 nm with increasing acrylic monomer content from 0 to 40 wt %. The pristine WBPU and hybrid latex samples containing 10, 20, and 30 wt % of acrylic monomer showed unimodal distributions, whereas the hybrid sample having 40 wt % acrylic monomer content displayed a bimodal distribution with the broadest breadth. As acrylic monomer content increased, the yield point of stress–strain curve, hardness, glass transition, and water resistance of hybrid film samples increased, whereas their abrasion resistance, elongation at break, and elasticity decreased. The tensile strength of hybrid film samples (10–30 wt % of acrylic monomer content) was almost the same as that of pristine WBPU film sample, indicating the intimate molecular mixing between poly(urethane‐urea) and polyacrylate molecules in hybrids. However, the hybrid sample having 40 wt % acrylic monomer showed significantly diminished performance, which might be due to the deviation from intimate molecular mixing. From these results, the optimum acrylic monomer content was found to be about 30 wt %, which realized reasonably advantages of both poly(urethane‐urea) and acrylic polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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。