有机硅改性聚丙烯酸酯乳液的细乳液合成及应用.doc
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1、浙 江 理 工 大 学材 料 与 纺 织 学 院毕业设计(论文)诚信声明我谨在此保证:本人所写的毕业设计(论文),凡引用他人的研究成果均已在参考文献或注释中列出。设计(论文)主体均由本人独立完成,没有抄袭、剽窃他人已经发表或未发表的研究成果行为。如出现以上违反知识产权的情况,本人愿意承担相应的责任。声明人(签名):年 月 日摘 要 聚丙烯酸酯因成膜性好,粘结性强,耐热等优点而被广泛应用于涂料印花粘合剂,但其存在胶膜硬度大,耐水性差,冷脆热黏等缺点而影响了印花产品的质量。聚硅氧烷疏水性强,链段柔顺,将含有乙烯基的聚硅氧烷对聚丙烯酸进行改性,能有效改善聚丙烯酸酯粘合剂的缺点,提高涂料印花的色牢度与
2、手感。因此本文合成出双端乙烯基聚二甲基硅氧烷(diVi-PDMS),并将其用于改性聚丙烯酸酯,制得一种新型涂料印花粘合剂,使得涂料印花织物兼具良好的耐摩擦牢度和手感。主要研究内容分为两部分: 第一部分:双端乙烯基聚二甲基硅氧烷的合成及表征。采用1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷和八甲基环四硅氧烷为原料,以三氟甲基磺酸为催化剂,通过阳离子开环聚合合成双端乙烯基聚硅氧烷(diVi-PDMS)。研究了催化剂用量,反应温度和反应时间对产物转化率和封端率的影响,优化了合成工艺条件并采用红外光谱(FTIR)和核磁共振(1H-NMR)对产物结构进行表征。结果表明:双端乙烯基聚硅氧烷(diVi-
3、PDMS)的优化工艺条件为催化剂用量0.15%,反应温度70,反应时间6h,产物转化率达到91%,FTIR和1H-NMR谱图分析表明了产物为双端乙烯基聚硅氧烷(diVi-PDMS)。第二部分:diVi-PDMS改性聚丙烯酸酯细乳液的合成及其性能研究。采用自制的双端乙烯基聚硅氧烷(diVi-PDMS)改性聚丙烯酸酯,通过细乳液聚合制得有机硅改性聚丙烯酸酯乳液。研究了传统乳化剂(SDS:O-10)/可聚合乳化剂(V-20S)配比及用量,有机硅单体分子量对聚合稳定性、乳液性能、胶膜性能及涂料印花性能的影响,并用红外光谱仪(FTIR)、热重分析仪(TG)、差示扫描量热仪(DSC)等对聚合物的结构和性能
4、进行测定和表征。结果表明:乳化剂配比为1.5:1:1、用量为6%时,聚合稳定性及乳液稳定性良好,乳液粒径小,分布窄,且相比传统乳化剂,复配可聚合乳化剂明显提升胶膜的力学性能;随着diVi-PDMS分子量的增大,胶膜交联度降低,耐水性降低,力学性能变差,涂料印花织物耐摩擦牢度变差,当diVi-PDMS分子量为约为1600时,胶膜水接触角为94.9,吸水率为7.39%,印花织物干、湿摩擦牢度可达4级,手感柔软。红外分析表明产物为有机硅改性聚丙烯酸酯,DSC和TG分析表明经改性后聚合物的玻璃化温度降低,热分解温度提高,耐热稳定性增强。论文研究表明,以双端乙烯基聚硅氧烷(diVi-PDMS)为改性单体
5、,采用细乳液聚合,制备有机硅改性聚丙烯酸酯乳液粘合剂,应用于印花涂料,其印花织物耐干、湿摩擦牢度均达到4级,手感柔软,印花织物具有良好的耐摩擦牢度,又具有柔软的手感。关键词:聚丙烯酸酯;双端乙烯基聚硅氧烷;细乳液聚合;涂料印花Abstract Polyacrylate has been widely used as pigment printing binder because of its advantages, such as good film-forming ability, strong adhesion, good heat resistance, etc. However, th
6、e polyacrylate generally exists many defects which affect the quality of the printing products, such as high hardness, poor property of waterproof, hot sticky-cool brittle performance of the latex film. There are many advantages in polydimethylsiloxane (PDMS), such as good hydrophobicity and flexibi
7、lity. PDMS which contains vinyl group was applied in the modification of polyacrylate, in order to improve the color fastness and handle of pigment printing fabric. In this paper, a double Vinyl-terminated polydimethylsiloxane (diVi-PDMS) was synthesized and applied in the preparation of silicone-mo
8、dified polyacrylate emulsion for pigment printing binder, so as to be good color fastness and softer handle of pigment printed fabric. There are two parts in this paper.Part 1: Synthesis and characterization of diVi-PDMSIn this part, diVi-PDMS was synthesized by ring-opening polymerization reaction
9、of cationic with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and Octamethyl cyclotetrasiloxane, using trifluoromethanesulfonic acid as a catalyst. The influences of reaction factors such as amount of catalyst, reaction temperature and time on the conversion rate and yield of termination were investiga
10、ted, then the synthesis conditions were optimized and the structure of product was characterized by FTIR and 1H-NMR. The results showed that the optimal condition for the preparation of diVi-PDMS was that the amounts of catalyst were 0.2%, reaction temperature was 70 and reaction time was 6h. In the
11、 optimal condition, the conversion rate can reach 91%. The results of FTIR and 1H-NMR analysis indicated that the structure of product was diVi-PDMS. Part 2: Synthesis and characterization of diVi-PDMS modified polyacrylate miniemulsion In this part, the diVi-PDMS modified polyacrylate miniemulsion
12、was prepared with diVi-PDMS and polyacrylate via miniemulsion polymerization. The ratio and dosage of traditional emulsifier(SDS:O-10)/polymeric emulsifier(V-20S), the molecular weight of organic silicon monomer on the polymerization stability and the properties of silicone-modified polyacrylate emu
13、lsion, latex film and pigment printing were studied. The polymer structure and properties were characterized by FTIR, TGA and DSC. The results showed that when the mass ratio of polymerizable emulsifier was 1.5:1:1 and the amount of compound emulsifier was 6%, the polymerization and latex had good s
14、tability, the latex had small particle size and narrow distribution. Compared to conventional emulsifier, complex polymeric emulsifier can significantly improve the mechanical properties of the film. With the increase of molecular weight of diVi-PDMS, the crosslinking degree of the film, the water r
15、esistance, the mechanical properties and the rubbing fastness of pigment printing fabric became worse. It was found that the molecular weight of diVi-PDMS was about 1600, the water contact angle of the film was 94.9 , the water absorption was 7.39%, the dry and wet rubbing fastness of pigment printi
16、ng fabric reached 4 grade, and the printed fabrics handle became softer. The results of FTIR analysis indicated that the product was silicone-modified polyacrylate miniemulsion, DSC and TG analysis displayed that the glass transition temperatures of silicone-modified polymer was reduced, thermal dec
17、omposition temperature and heat-resistant stability was increased. The results of project showed that the diVi-PDMS modified polyacrylate adhesive lates prepared by miniemylsion polymerization can be used as pigment printing ,the colour fastness to dry and wet rubbing of the printed fabric could rea
18、ch grade 4,and its handle was softer,basically achieved the objective unification of handle and fastness.key words:Polyacrylate; diVi-PDMS; Miniemulsion polymerization; Pigment printing iii目 录摘 要Abstract第1章 绪论11.1引言11.2聚丙烯酸酯粘合剂的发展11.3有机硅改性聚丙烯酸酯的研究现状21.3.1有机硅改性单体21.3.2有机硅单体聚合机理31.3.3有机硅改性聚丙烯酸的聚合方法51.
19、3.4乳化体系61.4本课题的研究意义、内容和创新点71.4.1本课题的研究意义71.4.2本课题的研究内容71.4.3本课题的创新点8第2章 双端乙烯基聚硅氧烷(diVi-PDMS)的制备与表征82.1引言92.2实验部分92.2.1实验材料与仪器92.2.2实验方法102.2.3性能测试方法102.3结果与讨论112.3.1催化剂用量对产率及封端率的影响112.3.2反应温度对产率及封端率的影响122.3.3反应时间对产率及封端率的影响132.3.4合成产物的结构表征142.4本章小结16第3章 有机硅改性聚丙烯酸酯的制备与表征163.1引言163.2实验部分173.2.1实验材料与仪器1
20、73.2.2有机硅改性聚丙烯酸酯乳液的合成183.2.3印花方法183.2.4性能测试方法193.3结果与讨论213.3.1乳化剂配比优化213.3.2乳化剂用量优化243.3.3有机硅单体分子量的选择283.3.4合成产物的结构与性能表征313.4本章小结34第4章 结论35参考文献35致谢38I浙江理工大学本科毕业论文有机硅改性聚丙烯酸酯乳液的细乳液合成及应用第1章 绪论1.1引言 涂料印花工序简单,印制后无需水洗,生产成本低,环保节能。它是借助粘合剂将颜料固着在纤维表面来获得所需图案的印花工艺1,其涂料印花产品的质量和档次很大程度上取决于涂料印花粘合剂的性能,因此制备高性能的粘合剂是提高
21、涂料印花技术和质量的措施之一。目前,常用的粘合剂主要有聚氨酯和聚丙烯酸酯。其中聚氨酯虽然弹性好、手感柔软,但其耐溶剂性、热稳定性和耐老化性差且价格较高;而丙烯酸酯成膜性好、粘接性能强、透明度高而被广泛使用。但其皮膜冷脆热粘且不耐水,严重影响印花织物的湿摩擦牢度和手感,而有机硅氧烷链段柔顺且疏水性强,应用其进行改性,可提高丙烯酸酯胶膜的拒水性和柔软性,改善印花织物的质量。因而有机硅改性一直是丙烯酸酯粘合剂的研究热点。 本课题采用自制的双端乙烯基聚硅氧烷(diVi-PDMS)对聚丙烯酸酯进行改性,将制得的diVi-PDMS改性聚丙烯酸酯粘合剂应用于涂料印花,使印花织物具有良好的耐摩擦牢度和柔软的手
22、感。1.2聚丙烯酸酯粘合剂的发展国外对于粘合剂的发展迅速,更新换代速度快。其中丙烯酸酯粘合剂主要经过了四个阶段:第一代粘合剂是不能交联的高分子成膜物质,如丙烯酸酯与丙烯腈或苯乙烯单体的共聚物,其印花织物牢度、手感差,很快被新产品所取代;第二代粘合剂是在前代的基础上引进CN、OH、NH2、COOH等活性基团的高聚物,这些活性基团可与纤维中的羟基或氨基等形成共价键,一定程度上提高了印花织物的色牢度;第三代粘合剂是在组分中加入自交联单体,以提高牢度,降低焙烘温度,缩短焙烘时间,常用的自交联单体有羟甲基丙烯酰胺;由于高温焙烘耗能大,第四代印花粘合剂低温交联型粘合剂很快出现2,3,其交联剂分子结构中具有
23、强的活性基团,能在100左右与羟基或氨基反应,既可提高成膜的耐摩牢度,又可大大节省能源。我国粘合剂的生产始于二十世纪六十年代,目前国内涂料印花粘合剂的研究方向主要集中在改性单体、交联体系及环保合成工艺等方面4-8,但与国外同类产品相比,在手感、牢度和稳定性等方面尚有差距。1.3有机硅改性聚丙烯酸酯的研究现状有机硅改性聚丙烯酸酯由聚二甲基硅氧烷(PDMS)与丙烯酸酯单体进行共聚而成。其中聚二甲基硅氧烷因其特殊的分子结构而表现出许多独特的性能,如玻璃化温度、表面张力低,热稳定性、生物相容性好,且其主链柔顺性高,再加上有机基团的屏蔽作用,这赋予有机硅分子优异的柔软性和疏水性,但其强度低,粘附力差,而
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