本文選題：水性聚氨酯 + 聚丙烯酸酯��； 參考：《太原理工大學》2017年碩士論文

【摘要】：水性聚氨酯丙烯酸酯(WPUA)兼具聚氨酯(PU)與聚丙烯酸酯(PA)的優(yōu)點,安全環(huán)保,價格低廉,成膜性能好,物理機械性能優(yōu)異,被廣泛地應用于涂料、膠黏劑、紡織印染等領域。然而,合成WPUA時,常以含羧基的WPU為自乳化劑,PA的含量很難超過40%,制備成本較高;分子鏈上含親水的羧基,其膜的耐水性能較差。為解決這些問題,本文采用異佛爾酮二異氰酸酯(IPDI)、聚氧化丙烯二醇(PPG)、2,2-二羥甲基丙酸(DMPA)、1,4丁二醇(BDO)合成異氰酸基封端的聚氨酯預聚物,進一步用含羥基的乙烯基化合物封端,經中和、乳化,合成可聚合的WPU預聚體乳液。將其和丙烯酸酯聚合,分別合成化學鍵連接的高PA/PU比例、有機硅改性、有機硅氟共改性的WPUA復合乳液,并研究了其物理與化學性能。主要內容如下:1.使用烯丙基聚氧乙烯醚(APEE)作為PU和PA之間的偶聯劑,合成了穩(wěn)定的水性聚氨酯丙烯酸(WPUA)復合乳液,其AC/PU質量比范圍為45/55至70/30。通過該方法可以制備具有低成本且性能優(yōu)異的WPUA復合乳液,并研究了PA用量對其性能的影響。結果表明:制備的WPUA復合乳液呈現出明顯的核殼結構,PU與PA之間通過化學鍵結合,且WPUA分子為線性結構。復合乳液在剪切過程的初始階段表現為剪切變稀,符合牛頓流體特征。隨著PA用量的增加,乳液的粒徑逐漸增加并且分布變寬,乳液黏度逐漸減少,膠膜的拉伸應力、邵氏A硬度、儲能模量、玻璃轉化溫度、耐水性和水接觸角增加。2.使用聚二甲基硅氧烷(PDMS)作為混合軟段引入PU分子鏈段當中,然后與甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)通過原位乳液共聚法制備一系列有機硅改性WPUA復合乳液,并研究PDMS用量對復合乳液及膠膜性能的影響。結果表明:乳液均顯示出剪切變稀行為,隨著PDMS含量的增加,乳液平均粒徑增加,粘度逐漸降低。索氏提取的結果表明,WPUA共聚物為交聯結構,但隨著PDMS含量的增加,交聯度降低。FT-IR分峰研究表明,引入PDMS降低WPUA體系的氫鍵含量,并增加相分離程度。PDMS含量的增加導致膜的拉伸強度,硬度,儲能模量和玻璃化轉變溫度降低,但是斷裂伸長率增加。增加PDMS含量使復合膜的水接觸角顯著增加,極大地改善了復合膜的表面疏水性。3.使用甲基丙烯酸十二氟庚酯(DFMA)作為丙烯酸酯單體與含硅PU預聚體進行乳液共聚,制備一系列有機氟硅改性WPUA復合乳液,研究其對復合乳液及膠膜性能的影響。所有合成乳液均顯示出剪切變稀行為,隨著FDMA含量的增加,乳液平均粒徑而增加,乳液的粘度逐漸降低。FT-IR分峰研究表明,引入FDMA降低WPUA體系的氫鍵含量,并增加相分離程度。FDMA含量的增加導致膜的拉伸強度,硬度,儲能模量和玻璃化轉變溫度降低,但是斷裂伸長率增加。FDMA的引入使得復合膜的水接觸角顯著增加,極大地改善了膜的表面疏水性。
[Abstract]:Waterborne polyurethane acrylate (WPUA) has the advantages of polyurethane (PUU) and polyacrylate (PAA). It has the advantages of safety, environmental protection, low price, good film forming performance, excellent physical and mechanical properties, and has been widely used in the fields of paint, adhesive, textile printing and dyeing and so on. However, in the synthesis of WPUA, the content of WPU with carboxyl group as self-emulsifier is difficult to exceed 40%, and the preparation cost is high, and the hydrophilic carboxyl group on the molecular chain has poor water resistance. In order to solve these problems, isophorone diisocyanate (IPDIN) was used to synthesize isocyanate terminated polyurethane prepolymer, which was further sealed by hydroxyl vinyl compound. A polymerizable WPU prepolymer emulsion was synthesized by neutralization and emulsification. The WPUA composite emulsion with high PA/PU ratio, organic silicon modification and organosilicon fluorine co-modification was synthesized by polymerization with acrylic ester. The physical and chemical properties of the emulsion were studied. The main content is as follows: 1. Using allyl polyoxyethylene ether (APEE) as the coupling agent between pu and PA, a stable waterborne polyurethane acrylic acid (WPA) composite emulsion was synthesized. The AC/PU mass ratio of the emulsion was 45 / 55 to 70 / 30. The WPUA composite emulsion with low cost and excellent performance can be prepared by this method, and the effect of PA content on its properties is studied. The results show that the prepared WPUA composite emulsion exhibits obvious core-shell structure and chemical bonding between pu and PA, and the WPUA molecule is linear. The composite emulsion shows shearing thinning in the initial stage of shear process, which accords with the characteristics of Newtonian fluid. With the increase of PA content, the particle size of emulsion increased and the distribution became wider, the viscosity of emulsion gradually decreased, the tensile stress of the film, Shao's A hardness, storage modulus, glass conversion temperature, water resistance and water contact angle increased by 0.2. Polydimethylsiloxane (PDMS) was used as the mixed soft segment to introduce pu molecular chain into the chain, and then a series of silicone modified WPUA composite emulsions were prepared by in situ emulsion copolymerization with methyl methacrylate (MMA) and butyl acrylate (BA). The effect of PDMS content on the properties of composite emulsion and film was studied. The results showed that all the emulsions showed shear thinning behavior. With the increase of PDMS content, the average particle size increased and the viscosity decreased gradually. The results of Soxhlet extraction showed that the copolymers were crosslinked, but with the increase of PDMS content, the crosslinking degree decreased. FT-IR showed that the introduction of PDMS reduced the hydrogen bond content of WPUA system. The tensile strength, hardness, storage modulus and glass transition temperature decreased, but elongation at break increased with the increase of phase separation degree and PDMS content. The water contact angle of the composite membrane increased significantly with the increase of PDMS content, which greatly improved the hydrophobicity of the composite membrane. A series of organofluorosilicon modified WPUA composite emulsions were prepared by emulsion copolymerization of dodecyl heptyl methacrylate (DFMA) as acrylate monomer and pu prepolymer containing silicon. The effects of these emulsions on the properties of composite emulsion and film were studied. All the synthesized emulsions showed shear thinning behavior. With the increase of FDMA content, the average particle size of the emulsion increased, and the viscosity of the emulsion gradually decreased. The peak value of FT-IR showed that the introduction of FDMA reduced the hydrogen bond content of WPUA system. The tensile strength, hardness, storage modulus and glass transition temperature decreased with the increase of phase separation degree. However, the water contact angle increased with the increase of elongation at break. The surface hydrophobicity of the film is greatly improved.
【學位授予單位】：太原理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ316.334

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