两亲性树形-线团大单体的合成及其丙烯酸共聚乳液的流变行为

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将3,4,5-三(十六烷基氧基)苯甲酰氯先后与分子量为1000的聚乙二醇、甲基丙烯酰氯反应合成了一种新的可聚合两亲性树形-线团大单体——3,4,5-三(十六烷氧基)苯甲酰氧基聚氧乙烯甲基丙烯酸酯(6).通过核磁、红外、元素分析等对产物进行了表征.然后将其与甲基丙烯酸、丙烯酸乙酯进行乳液共聚合,制备了一种疏水树形侧链改性的碱溶性乳液(DHASE).采用应力控制型流变仪对不同固含量及pH值的DHASE乳液的流变行为进行了初步的探讨,并与甲基丙烯酸、丙烯酸乙酯的共聚物乳液(MAAEA)的流变行为进行了比较.结果显示,当pH≥6.8,高分子固含量≥1 wt%时,DHASE水溶液有明显的触变性,且零切黏度远远大于MAAEA水溶液的,同时,DHASE水溶液的贮能模量(G’)大于损耗模量(G″),相反,在同一条件下MAAEA水溶液呈现牛顿流体的行为,其G’小于G″,说明在上述条件下DHASE水溶液中存在物理交联的疏水网络结构.研究阐明了这种新的两亲性树形-线团大单体在疏水改性的碱溶性丙烯酸乳液及缔合增稠剂领域中的潜在应用. A new polymerizable amphiphilic tree-line was synthesized by reacting 3,4,5-tris (hexadecyloxy) benzoyl chloride with polyethylene glycol and methacryloyl chloride with molecular weight of 1000 3,4,5 - tris (hexadecyloxy) benzoyloxypolyoxyethylene methacrylate (6). The product was characterized by NMR, IR, elemental analysis and so on. Then, a kind of hydrophobic side-chain-modified alkali-soluble emulsion (DHASE) was prepared by emulsion copolymerization of methacrylic acid and ethyl acrylate.The stress-controlled rheometer was used to measure the content of DHASE emulsion rheological behavior of a preliminary study, and with methacrylic acid, ethyl acrylate copolymer emulsion (MAAEA) rheological behavior were compared.The results show that when the pH ≥ 6.8, the polymer solid content ≥ 1 wt%, DHASE aqueous solution has obvious thixotropy, and the zero-shear viscosity is far greater than the MAAEA aqueous solution. Meanwhile, the storage modulus (G ’) of DHASE aqueous solution is larger than the loss modulus (G “ The MAAEA aqueous solution behaved as a Newtonian fluid with G ’less than G ”, indicating that there was physical crosslinking in the aqueous solution of DHASE under the above conditions Of the hydrophobic network structure.The study illustrates the potential application of this new amphiphilic tree-coil macromonomer in the field of hydrophobically modified alkali-soluble acrylic emulsions and associative thickeners.
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