摘要
本文以制备耐低温性能更优的耐寒级丙烯酸酯橡胶为目的。首先通过醇酸酯化法制备了二乙二醇单甲醚丙烯酸酯(MOEOEA),然后以MOEOEA为耐油耐低温单体,与丙烯酸乙酯(EA)、丙烯酸丁酯(BA)及硫化点单体氯乙酸乙烯酯(VCA)进行乳液共聚,制得脆性温度可达-30℃以下的丙烯酸酯橡胶。所得主要结论性成果如下:
1.在丙烯酸和二乙二醇单甲醚进行酯化制备MOEOEA的过程中,考察了共沸剂种类及用量、酸醇摩尔比、酯化时间对转化率、产物收率及纯度的影响。当以为苯共沸剂,用量为原料醇质量的120%,酸醇摩尔比1.2:1,酯化时间在7-8h时,酯化率可达到94%以上。用气质联用色谱仪确定产物的准确结构,用气相色谱测定了产物的纯度大于91%,且在此纯度下,收率可保证80%。
2.采用溶液聚合制得了MOEOEA的均聚物及MOEOEA与EA共聚物,对均聚物和共聚物玻璃化温度测定,结果表明均聚物的玻璃化转变温度(Tg)为-86℃,按FOX方程推算的共聚物的玻璃化转变温度(Tg)与实测值相符。
3.采用氧化还原引发体系,研究了MOEOEA/EA/BA/VCA四元乳液共聚行为。当二乙二醇单甲醚丙烯酸酯的用量为总单体用量的20%时,单体转化率为97%,丙烯酸酯共聚物的凝胶含量可控制在2%以下。采用硫/皂化体系,以HAF N300型炭黑作补强剂,采用二段硫化,硫化胶的拉伸强度可达12MPa以上,扯断伸长率为317%,压缩永久变形小于20%,邵氏A硬度为70,脆性温度-32℃以下,达到了预期目的。
The main purpose in this paper is improving in cold tolerance of acrylic rubber gained by emulsion copolymerization of methoxy ethoxy ethoxy acrylate(MOEOEA) with butyl acrylate(BA), ethyl acrylate(EA) and vinyl chloroacetate(VCA).
Firstly, the monomer of MOEOEA was synthesized through esterifying acrylic acid with diethylene glycol monomethyl ether. The effects of the kind and dosage of dehydrating agent, the mole ratio of acid to alcohol, reaction time on conversion, yield and purity were studied. When benzene was used as dehydrating agent the dosage of benzene is 120% to alcohol, the mole ratio of alcohol to acid is 1.2:1, the reaction time is between 7~8h, the conversion of di-ethylene glycol monomethyl ether can reach to 97% and purity is no less than 97%. The objective monomer's structure was characterized by GC-MS and the purity of monomer can reached above 97% determined Gas Chromatogram.
Secondly, the acrylic homopolymers of MOEOEA and copolymers of EA, BA, MOEOEA, VCA were synthesized by emulsion polymerization. The results of DSC showed that the glass-transition temperature (Tg) of homopolymer is-86℃. The glass-transition temperature (Tg) of copolymer is accord with the calculation value through FOX equation.
Thirdly, the behaviors of emulsion polymerization and properties were studied in the presence of redox initiator system and compound emulsifier. When the dosage of MOEOEA is 20wt% to total monomer, the conversion rate was no less than 97% and gel content of ACM(acrylester butadience rubber) can be controlled among 2-15%.
Fourthly, the vulcanizing behaviors and properties were also investigated in detail with sulfur/soap as vulcanizing agent system and with carbon black (HAF N330) as reinforcing agent. After two steps vulcanized, the strength can reach 12MPa above, the elongation at break is 317%, the rate of permanent deformation is less than 20%, the Shore A hardness is from 70 to 75, the brittle temperature which is far lower than that of current ACM is lower than-32℃.
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