硅改性丙烯酸酯类核壳乳液的制备

研究了以种子乳夜聚合法制得聚丙烯酸酯——三甲基氯硅烷胶乳粒子,以P(BA—MMA)为核,P(ST—BA—MMA—TMC)为壳的核壳乳液的成膜性能较丙烯酸树脂的成膜性能有明显的提高。     

氟化丙烯酸树脂涂饰剂的合成、表征及应用

以十二烷基磺酸钠和壬基酚聚氧乙烯醚为混合乳化剂,采用两步乳液聚合方法合成了壳层富含氟的具有核壳结构的氟化聚丙烯酸酯共聚物乳液。研究表明:该乳液具有良好的稳定性,乳液粒子平均粒径约为90nm,并且乳液粒子的核壳结构清晰。在成膜过程中,氟碳链能够迁移至膜表面富集。因此,即使引入少量的氟单体,也能够显著降低成膜的表面能,从而显著提高膜的防水、防油性能。初步皮革涂饰应用试验表明,所合成的氟化丙烯酸树脂,能显著提高皮革的防水性能。     

新型涂料印花粘合剂的合成与表征

合成了一种新型涂料印花粘合剂.它是具有最低成膜温度（MFT）的核壳型VAc/St/BA聚合物乳液,与无规共聚乳液相比,MFT低,成本低廉,性能相当;经乳液性能的测试和电镜观察,证明了乳液粒子为核壳结构.     

食品包装水性油墨连接料的研究

采用核壳乳液聚合的方法合成一种内交联型聚丙烯酸酯乳液,并探讨其乳液在室温和热固化下的成膜物对常用食品包装材料(塑料、玻璃及金属等基材)的附着性、耐水性、耐溶剂性、硬度等性能的影响.结果表明,不同合成工艺的核壳设计、软硬单体配比及功能单体的选择与用量等因素对水性油墨连接料的性能有很大的影响.     

低温无甲醛涂料印花粘合剂的合成与应用

采用核壳乳液聚合的方法制备低温自交联的无甲醛涂料印花粘合剂：通过对主单体配比、功能型单体用量及聚合工艺的研究，确定了最佳合成工艺条件该粘合剂的乳液、成膜、印花性能及牢度和手感均为良好。     

玉米醇溶蛋白核壳结构微粒的制备及应用研究进展

玉米醇溶蛋白是一种来自玉米的储存蛋白,因其良好的成膜性、独特的溶解性和自组装性能在食品、制药和生物技术等领域具有广泛的应用。基于玉米醇溶蛋白在不同溶剂体系的溶解特性和自组装特性,可采用多种方法制备具有核壳结构特征的玉米醇溶蛋白微粒,该微粒可作为生物活性物质的递送载体、乳液稳定剂和纳米纤维材料等。本文综述了玉米醇溶蛋白核壳结构微粒的不同制备方法及其功能特性,旨在为玉米醇溶蛋白核壳结构微粒的制备及其在食品领域的应用提供理论依据和实际指导。     

环保型高性能自交联涂料印花粘合剂FL的制备

采用无甲醛交联剂经核-壳聚合，制备了丙烯酸酯类高性能自交联涂料印花粘合剂．该粘合剂储存稳定，成膜无色透明，弹性强，适合纯棉与合成纤维织物进行涂料印花．应用试验表明，其各项性能均达到国家标准．     

聚丙烯酸酯筛基硅核壳结构皮革涂饰剂的制备和性能研究

采用种子乳液聚合法并以十二烷基硫酸钠（SDS）和脂肪醇聚氧乙烯醚（AEO-9）复配作为乳化剂制备了壳层含烯基硅的核壳型聚丙烯酸酯皮革涂饰剂。重点考察了有机硅乙烯基三乙氧基硅烷（A-151）用量对乳液性能及成膜后性能的影响。并分别通过傅里叶红外光谱（FT—IR）和激光粒度Zeta电位仪对乳液的结构、粒径大小和粒径分布进行表征。结果表明A-151用量为10％时,烯基硅改性聚丙烯酸酯乳液的稳定性最佳。与纯的聚丙烯酸酯相比较,有机硅A-151改性后的聚丙烯酸酯成膜后的耐水性提高。FT—IR谱图表明,有机硅A-151与聚丙烯酸酯之间有Si-O-C键形成,激光粒度电位Zeta杖焘明核亭乳液的平均粒径122.4nm,并且粒径分布均匀。     

三元两亲共聚物作乳化剂制备核壳型改性酪素皮革涂饰剂

采用无皂乳液聚合法同时引入三元两亲共聚物作乳化剂,合成具有核壳结构的聚丙烯酸酯改性酪素皮革涂饰剂,考察了乳化剂的加入方式及其用量对乳液性能(稀释稳定性、耐酸性、耐碱性等)及成膜性能(耐水性、机械力学性能)的影响,并分别通过红外光谱(FT-IR)、透射电镜(TEM)和动态激光光散射(DLS),对乳液结构、形貌和粒径大小进行表征。结果表明:当三元两亲性共聚物在单体后加入,用量为4%时,制备的皮革涂饰剂性能最优。与未采用三元两亲共聚物做乳化剂制备的乳液相比,采用本方法所制备的乳液成膜耐水性、抗张强度和断裂伸长率均有所提高。FT-IR谱图显示三元两亲共聚物成功接枝到聚合物中,TEM和DLS结果显示所制备的乳胶粒具有明显的核壳结构,粒径约为40～50nm,且分布均匀。     

核壳结构骨仿生纳米纤维的制备及生物性能研究

利用自制的同轴静电纺丝装置,以HA水溶液为核,TSF水溶液为壳,成功制备了不同比例的HA/TSF核壳结构纳米纤维。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)及拉伸测试对核壳结构纳米纤维的形貌和力学性能进行了研究。此外,还通过将不同核壳比HA/TSF的核壳结构纳米纤维在体外与人成骨肉瘤细胞(MG-63)进行复合培养,对其生物性能进行了研究,并通过荧光显微镜测试和四甲基偶氮噻唑蓝比色(MTT)法对核壳结构纳米纤维的生物学性能进行了表征。结果表明,核壳结构纳米纤维均具有良好的生物相容性,都能促进细胞的增殖,尤以HA/TSF为2∶1时效果最为明显。     

一种热敏胶膜的制备及其性质

通过三步法制备一种具有疏水内核、亲水外壳的聚合物微胶粒。首先,通过乳液聚合制备得到甲基丙烯酸丁酯与异丁烯酸甲酯共聚物（P（BMA—MMA））乳液。然后,在适当控制的条件下,利用一种氧化还原引发体系将P（BMA—MMA）微胶粒的表面引入一层聚甲基丙烯酸缩水甘油酯（p-GMA）外壳。最后,将外壳层的部分环氧基团转化为季铵盐,从而形成一种亲水性的外壳。这种核一壳型固体粒子能在水中再分散并形成稳定的乳状液,无须借助分散剂、乳化剂或其他添加剂的帮助。利用这种核一壳乳液制备的乳液薄膜与水的接触角为16°（25℃）,而经150℃短时间处理后的接触角超过90°,表明完全由亲水性转变成疏水性。此外,乳液薄膜在加热处理前很容易被中性水从基板上冲洗掉,但在加热处理后不能被洗掉。当在乳液薄膜中加入一种在830nm有最大吸收的红外染料后,薄膜对830nm激光敏感,并经曝光、中性水显影后可形成阴图型图像。     

纳米材料在皮革涂饰剂中的应用

以苯乙烯、甲基丙烯酸甲酯、丙烯腈为核单体，丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸、交联剂为壳单体，采用种子聚合技术，制备丙烯酸树脂乳液，并在壳层引入新型纳米级TiO2。重点在其制备方法、产品性能及结构表征方面进行了探索。     

核壳型含氟丙烯酸酯乳液的合成及其在棉织物整理中的应用

以聚丙烯酸丁酯(BA)-甲基丙烯酸甲酯(MMA)为核,丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、双(丙烯酰氧丙基)四甲基二硅氧烷和丙烯酸十三氟辛酯(TEAC-6)共聚物为壳,采用饥饿态半连续种子乳液聚合法,制备出具有核壳结构的含氟丙烯酸酯乳液。通过红外光谱(FT-IR)、X射线光电子能谱(XPS)、透射电镜(TEM)、热重分析(TG)及接触角(CA)研究了核壳粒子的形貌结构和热稳定性,以及不同含氟量与交联剂用量对整理织物拒水拒油性和织物表面特性的影响。结果表明,含氟单体与有机硅交联剂参与了共聚合,所合成乳液具有明显的核壳结构,粒径为76 nm左右。当核壳结构共聚物乳液的氟含量为6.7%,交联剂用量为3%时,用于织物整理效果最佳,整理棉织物的拒水评分达到80,拒油达5级,水接触角为138.2°。共聚时有机硅交联剂的加入使整理织物拒水拒油和耐热性有较大改善。     

Characterization of associated proteins and phospholipids in natural rubber latex

Non-rubber components present in natural rubber (NR) latex, such as proteins and phospholipids, are presumed to be distributed in the serum fraction as well as surrounding the rubber particle surface. The phospholipid-protein layers covering the rubber particle surface are especially interesting due to their ability to enhance the colloidal stability of NR latex. In this study, we have characterized the components surrounding the NR particle surface and investigated their role in the colloidal stability of NR particles. Proteins from the cream fraction were proteolytically removed from the NR latex and compare to those from the serum fractions using SDS-polyacrylamide gel electrophoresis revealing that both fractions contained similar proteins in certain molecular weights such as 14.5, 25 and 27 kDa. Phospholipids removed from latex by treatment with NaOH were analyzed using (1)H-NMR spectroscopy and several major signals were assignable to -(CH(2))(n)-, -CH(2)OP, -CH(2)OC═O and -OCH(2)CH(2)NH-. These signals are important evidence that indicates phospholipids associate with the rubber chain. The colloidal behavior of rubber lattices before and after removal of protein-lipid membrane was evaluated by zeta potential analysis and scanning electron microscope (SEM). The lowest zeta potential value of NR particles was observed at pH 10, consequently leading to the highest stability of rubber particles. Additionally, SEM micrographs clearly displayed a gray ring near the particle surface corresponding to the protein-lipid membrane layer.     

基于核-壳型乳液粒子的亲和性变化型热敏材料体系的制备及性能评价

为了研制可中性水显影的亲和性变化型热敏成像体系,设计合成了一种反应型加成裂解链转移剂（DT-PA）,在它存在的条件下进行丙烯酸的聚合,得到平均聚合度为5的反应性大分子乳化剂（DTPA AA 5）。利用该乳化剂的钠盐作为表面活性剂,制备了具有亲油内核和表面含有高密度羧酸盐基团的核壳型乳液,该乳液固含量高、稳定性好。将该乳液与水溶性成膜树脂聚乙烯醇（PVA1788）配合使用并制备了乳液薄膜。该乳液薄膜能被中性水洗掉,但经160℃烤版后失去水溶性。当在该体系中引入一种红外增感染料（最大吸收为830nm）后,所制备的薄膜可用830nm的红外激光曝光成像,中性水显影后可得到阴图型图像。为实现更好的成膜性,该体系的配方仍需调整。     

离子型聚氨酯聚丙烯酸酯胶乳互穿聚合物网络

本文介绍了离子型聚氨酯（ＩＰＵ）与聚丙烯酸酯（ＰＡ）胶乳互穿聚合物网络（ＬＩＰＮ）合成的原理和穿梭聚合工艺。研究了影响胶乳稳定性的因素;通过透射电镜的观察,证明胶乳粒子为核壳结构;用示差扫描量仪对其相容性进行研究,互穿聚合增进了聚氨酯和聚丙烯酸酯两种聚合物间的相容性;对ＬＩＰＮ成膜物物理机械性能的测试表明：穿梭共聚物获得了两种聚合物的折衷性能。     

涂层固化过程中胶乳粒子迁移的机理（Ⅱ）

研究了涂布纸涂层固化过程中胶乳粒子向涂层表面发生迁移的现象,对此提出了一种新的基于Einstein经典粒子扩散理论和表面效应的机理来进行解释,澄清了涂料及相关领域对粒子迁移机理的争议。以微米级高岭土、亚微米级羧基丁苯胶乳为主要原料制备涂料进行涂布,用 X射线光电子能谱仪（XPS）检测涂层表面的元素组成和含量,建立了原子数比值与胶乳用量之间的回归方程;通过该方程将不同条件下固化的涂层表面XPS检测结果转化为表面胶乳含量,定量分析了不同因素对胶乳粒子迁移程度的影响。结果表明,干燥温度升高、高温干燥时间延长、涂料初始固含量降低会促进胶乳向涂层表面迁移,而胶乳粒径增大、涂料黏度增加、基质吸收性增强会抑制其迁移,验证了新机理的合理性。     

Structural characterization of natural rubber based on recent evidence from selective enzymatic treatments

A structural characterization of natural rubber (NR) was carried out by a combination of selective enzymatic treatment and high-resolution characterization techniques. The nitrogenous groups in NR from Hevea brasiliensis have been regarded as an important factor governing cured rubber properties, although there is no structural evidence to prove that relationship. The nitrogenous compounds in highly purified NR were characterized to determine the origin of the nitrogenous groups in NR. The rubber particles of fresh latex were purified by washing, i.e., a successive dilution of the cream fraction and concentration by centrifugation in the presence of a surfactant. The nitrogen content of the NR formed from the washed rubber particles decreased from 0.281% to 0.015% after washing 3-5 times; this content was similar to that of NR deproteinized by a proteolytic enzyme. The presence of 1-2 nitrogen atoms per rubber chain was estimated on the basis of nitrogen content and number-average molecular weight (Mn). The nitrogen content of fractionated rubber fractions from rubber particles washed for five times increased with increasing Mn. The nitrogenous groups in rubber chains are postulated to mostly originate from phospholipids associating with branch points and functional groups formed by oxidation and successive reactions in NR latex. An analysis of the structure of the chain end group (alpha-terminal) was carried out by treating the deproteinized NR (DPNR) latex with lipase, phosphatase, and phospholipases A(2), B, C and D. The enzymatic treatment of DPNR latex significantly decreased the long-chain fatty acid ester content in DPNR, and also the Mn and Higgins'k' constant, except for phospholipase D treatment. This indicates the presence of phospholipid molecules in NR, which connect rubber molecules together. (1)H-NMR results of rubber obtained from DPNR latex showed weak signals due to monophosphate, diphosphate and phospholipids at the alpha-terminal. Treating DPNR latex with lipase and phosphatase decreased the relative intensity of the (1)H-NMR signals corresponding to phospholipids; however, with the same treatment, no change in the signals due to mono- and diphosphates was observed. The presence of mono- and diphosphates as well as some phospholipid signals after lipase and phosphatase treatment indicates that mono- and diphosphate groups are directly linked to the modified structure at their alpha-terminals; such connections are considered to be due to the association or linkage of such groups with phospholipid.     

PAE与聚丙烯酸丁酯／甲基丙烯酸甲酯核壳乳液的共混改性及其应用研究

运用粒子设计的方法制备了ＰＡＥ改性的聚丙烯酸丁酯／甲基丙烯酸甲酯核壳乳液。该乳液颗粒具有软核硬壳结构,表面吸附了一层ＰＡＥ大分子,呈阳电性。在纸浆中添加少量该乳液即能明显改善纸张的干、湿强度和柔软度。