室温自交联CPA-ATPE复合乳液的制备及胶膜性能

发布时间：2018-04-13 19:49

本文选题：阳离子丙烯酸树脂 + 乳液聚合　；参考：《陕西科技大学》2017年硕士论文

【摘要】：在皮革制品涂饰领域,阳离子型的丙烯酸树脂涂饰产品占有极大的比重,其主要用在皮革加工工序的底涂和顶涂中。因其凸显的阳离子性能可以实现“三明治”涂饰,市场前景广阔。但传统的阳离子丙烯酸树脂存在热黏冷脆、机械性能及耐溶剂性较差等缺陷。因此,为了提高阳离子丙烯酸树脂的耐热性、机械性能及耐溶剂性等,本研究主要通过交联改性思路来设计胶膜分子结构,将不同的乙烯基单体进行共聚,制备阳离子丙烯酸树脂乳液(CPA),添加交联剂对其进行改性,形成具有室温自交联功能的复合乳液(CPA-ATPE),并分别对各乳液及其胶膜性能进行测试,具体研究内容如下:首先,固定单体总量及各单体比例,分别采用偶氮二异丁腈(AIBN)和2,2-偶氮二异丙基咪唑啉盐酸盐(AIBI)为引发剂,以单体转化率、凝胶率、预乳化液稳定性、乳液气味、聚合物分子量为指标,考察引发剂的类别、用量及加料方式对聚合工艺过程的影响。研究结果表明:AIBI具有更高的引发效能,最佳质量分数为1.2%。随后,以乳液Zeta电位及乳液的贮存稳定性为指标,考察了DMAEMA的用量对聚合物乳液的影响。研究表明:随着DMAEMA用量的逐渐增加,乳液电位持续增高,当DMAEMA的质量分数达到3%时,聚合物乳液的稳定性良好,Zeta电位为14.5mV,当W(DMAEMA)超过3%时,CPA乳液的稳定性基本不变,因此W(DMAEMA)=3%。在此基础上,固定DMAEMA和AIBI用量,探讨1631/OS-15与1227/OS-15两种复合乳化体系的乳化能力、配比及其用量对CPA乳液粒径及PDI、凝胶率、稳定性及外观的基影响。研究结果表明:复合乳化剂1227/OS-15的综合乳化性能较佳,其最佳应用参数:总用量为W(1227/OS-15)=3%,m(1227):m(OS-15)=1:2。其次,通过控制AAEM功能交联单体用量以及相应ATPE的添加量,制备CPA-ATPE复合乳液。采用FT-IR、XRD、AFM等对CPA及CPA-ATPE胶膜的结构和形貌进行表征;测定乳液粒径及PDI、最低成膜温度、Zeta电位及稳定性和胶膜的亲水性、吸水率、机械强度、耐溶剂性及玻璃化转变温度(Tg),考察AAEM的用量对CPA-ATPE复合乳液及其胶膜性能影响。研究表明:CPA-ATPE复合胶膜中AAEM的活性酮羰基与ATPE的端氨基已成功进行了交联,AFM显示胶膜表面凸起均匀;与CPA乳液相比,CPA-ATPE复合乳液平均粒径减小,分散系数减小且其分布趋于均匀,电位呈现正电性,胶膜耐溶剂性、亲水性、吸水率,抗张能力和断裂伸长率均提高,玻璃化温度(Tg)提高了2.5℃,耐热性能增强;随着AAEM用量的增加,CPA-ATPE复合乳液的最低成膜温度从15.8℃降到13℃,表现为更易成膜,胶膜的机械性能增强,吸水率降低,胶膜吸水率从67.2%降至17.8%,耐溶剂性增强,当W(AAEM)=3%时,CPA-ATPE复合乳液及胶膜的综合性能优异。最后,将不同结构的ATPE添加至CPA乳液中,制得系列CAP-ATPE复合乳液。考察胶膜的亲水性、吸水率、机械强度、耐溶剂性,探讨ATPE的结构对CPA-ATPE复合乳液及胶膜基本性能的影响。采用FT-IR及AFM对系列胶膜的结构及表面构造进行表征。结果发现:系列胶膜中AAEM的酮羰与不同结构的ATPE均已交联;随着ATPE分子链的增长,AFM图中白点增多,交联程度下降,胶膜吸水率增强,断裂伸长率稍微增加,抗张强度减小,接触角减小,耐溶剂性缓慢降低,因此使用ATPE作为交联剂时,其分子链不宜过长。
[Abstract]:In the field of leather finishing, cationic acrylic resin finishing products occupy a great proportion, which is mainly used in leather processing base coating and top coating. Because of its prominent cationic properties can achieve the "sandwich" finishing, the market prospect is broad. But the traditional cationic acrylic resin adhesive of thermal cold brittle the mechanical properties and solvent resistance and other defects. Therefore, in order to improve the heat resistance of cationic acrylic resin, the mechanical properties and solvent resistance, this study mainly through the cross linking modification ideas to the design film molecular structure, different vinyl monomers were copolymerized to prepare cationic acrylic resin emulsion (CPA). Adding a crosslinking agent to modify it, forming a self crosslinkable functional composite emulsion (CPA-ATPE), and were tested on the properties of the emulsion and film. The specific contents are as follows: firstly, fixed The amount of monomer and monomer ratio, respectively using two azo isobutyronitrile (AIBN) and 2,2- azo two isopropyl imidazoline hydrochloride (AIBI) as the initiator, the monomer conversion rate, gel rate, pre emulsion stability, emulsion odor, polymer molecular weight as index, effects of initiator dosage categories, influence and the feeding mode on the polymerization process. The results show that AIBI has led to higher efficiency, the best concentration was 1.2%. then to Zeta potential and storage stability of emulsion emulsion as the index, the effects of DMAEMA content on the properties of polymer emulsion. The results show that: with the gradual increase of the amount of DMAEMA increased continuously emulsion potential, when the mass fraction of DMAEMA reached 3%, the stability of polymer emulsion is good, Zeta potential is 14.5mV, when the W (DMAEMA) more than 3%, the stability of CPA emulsion is basically unchanged, so W (DMAEMA) =3%. on the basis of solid DMAEMA and AIBI investigate the dosage, emulsifying capacity of 1631/OS-15 and 1227/OS-15 two composite emulsion system, gel ratio and dosage of rate on the particle size of CPA emulsion and PDI, influence the appearance and stability of the base. The results show that the comprehensive performance of emulsion compound emulsifier 1227/OS-15 were the best, the best application parameters: the total amount of W (1227/OS-15) =3%, m (1227): m (OS-15) =1:2. second, by controlling the AAEM function of the amount of crosslinking monomer and the amount of the corresponding ATPE CPA-ATPE composite emulsion prepared by FT-IR, XRD, AFM etc. the structure and morphology of CPA and CPA-ATPE film were characterized; determination of particle size and PDI. The minimum film forming temperature, hydrophilicity, Zeta potential and stability and film water absorption, mechanical strength, solvent resistance and glass transition temperature (Tg), to investigate the effect of AAEM dosage on CPA-ATPE composite emulsion and film performance. The study shows that CPA-ATPE compound The activity of amino ketone carbonyl and ATPE membrane in AAEM has been successfully carried out crosslinking, AFM display surface projection film evenly; compared with CPA emulsion, CPA-ATPE emulsion mean particle size decreases, the dispersion coefficient decreases and the distribution becomes uniform, showing the potential positive film, solvent resistant, hydrophilic, water absorption rate, tensile strength and elongation were increased, the glass transition temperature (Tg) increased by 2.5 DEG C, heat resistance increased; with the increase of AAEM content, the minimum film forming temperature from 15.8 degrees down to 13 degrees of CPA-ATPE composite emulsion, performance is more likely to film, enhance the mechanical properties of the film, water absorption rate reduced film water absorption rate decreased from 67.2% to 17.8%, solvent resistance increased, when W (AAEM) =3%, the comprehensive performance of CPA-ATPE composite emulsion and film excellent. Finally, the different structure of ATPE added to CPA emulsion, CAP-ATPE emulsion prepared series of hydrophilic film on, Water absorption, mechanical strength, solvent resistance, to investigate the effect of ATPE structure on the basic properties of CPA-ATPE composite emulsion and film. The FT-IR and AFM structure and surface structure of the series of glue film were characterized. The results showed that the AAEM film in the series with different structure ATPE ketone carbonyl was crosslinked with ATPE; the molecular chain growth, increase the white AFM diagram, the crosslinking degree decreased, film absorption rate increased slightly increase the elongation, tensile strength decreases, the contact angle decreased, solvent resistance decreased slowly, so the use of ATPE as a crosslinking agent, its molecular chain should not be too long.

【学位授予单位】：陕西科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ325.7;TS529.5

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