耐电解质增稠剂的合成与测试
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摘要
本文以研制开发耐电解质增稠剂为目标,首先在实验室合成了丙烯酸十八酯和丙烯类单体ZXDW,利用正交实验研究了丙烯酸和这两种单体共聚的工艺条件,通过单因素分析得到比较理想的配方和工艺,并做了其性能测试,具体研究内容和结论如下:
丙烯酸和丙烯酸十八酯进行反相乳液共聚。共聚前,须把丙烯酸用氢氧化钠中和到一定程度,所以丙烯酸大部分以盐的形式参加共聚,而丙烯酸十八酯是疏水性的则溶解在油相,致使在聚合反应中聚合不能平稳进行,得到的产品增稠能力和耐电解质能力不理想。
丙烯酸和丙烯酸十八酯进行溶液聚合。丙烯酸、丙烯酸十八酯和N,N-亚甲基双丙烯酰胺溶解在苯中,以偶氮二异丁氰为引发剂,保持80℃聚合3h,过滤,干燥,得到白色粉末。把粉末加入到溶有Span-80的溶剂油中高速搅拌,滴加氨水中和,加入壬基苯基聚氧乙烯醚(Tx-10)转相得到白色的增稠剂。得到的产品颗粒不均匀,增稠能力差,耐电解质能力较好。
丙烯酸和丙烯类单体ZXDW进行反相乳液聚合。实验室自制单体ZXDW的端基为磺酸基团,磺酸根离子为强酸根离子,有较强的水溶性,使单体能溶于水。以过硫酸铵-亚硫酸氢钠为引发剂,以N,N-亚甲基双丙烯酰胺(NMBA)为交联剂,反相聚合丙烯酸和单体ZXDW,聚合完毕后减压蒸馏脱水,加入壬基苯基聚氧乙烯醚(Tx-10)转相得到淡黄色粘稠的增稠剂,其增稠能力和粘度系数与增稠剂PTF相当,耐电解质能力是普通增稠剂的3-5倍。
Aiming to research and develop electrolyte-resistant thickener, this paper synthesized stearyl acrylate and ZXDW monomers. Then the conditions to prepare thickener have been studied particularly by orthogonal design. We have got ideal conditions to produce the thickening by single factor analyzing. And we have made performance tests as follows:
First, the copolymer was prepared in inverse emulsion solution using AA and octadecyl acrylate as monomers. The acrylic acid was neutralized by sodium hydroxide before the preparation, so the acrylic acid was changed into sodium acrylic by some degree. Therefore when there was water and oil, most of it could stay in water. But the stearyl acrylate is a hydrophobe, so it is in oil when the reaction takes place. So the reaction could not go on favorably. And the product had bad performance.
Second, the copolymer was prepared in benzene solution using AA and octadecyl acrylate as monomers, AIBN as initiator, and N,N-methylenebisacrylamide(MBA) as crosslinker. When it took place, we must make sure that the temperature was at 80℃and it must be like this for more than 3 hours. Then filtrated it and dried it to get white powders. Next, pour the powders into the solution which was got by blending Span-80 and gasoline and stirred it strongly. After that, dripped ammonium into it to neutralize acid. Finally, we added Tx-10 into it to change the solution from W/O to O/W. It was unexpected that it had high eletrolyte-resistance ability but low thicken ability.
Third, we made ZXDW monomer first, and The electrolyte-resistant thickener was prepared by inverse emulsion polymerization using acrylic acid and ZXDW as monomers, Span-80 as emulsifier, ammonium persulfate-sodium bisulfate as initiator, and N,N—methylenebisacrylamide(NMBA) as crosslinker. Because there was a hydrophile group, it could dissolved in water easily. After the reaction was over, we distilled it at low pressure to make sure that it had little water at last. When water was as little as we supposed, we added Tx-10 into it and stirred it thoroughly. So we could get light yellow paste with good performance. And its thicken ability and PVI is as well as imported products, for exemple PTE But the electrolyte-resistance ability is from twice to four times more than that of PTF.
丙烯酸和丙烯酸十八酯进行反相乳液共聚。共聚前,须把丙烯酸用氢氧化钠中和到一定程度,所以丙烯酸大部分以盐的形式参加共聚,而丙烯酸十八酯是疏水性的则溶解在油相,致使在聚合反应中聚合不能平稳进行,得到的产品增稠能力和耐电解质能力不理想。
丙烯酸和丙烯酸十八酯进行溶液聚合。丙烯酸、丙烯酸十八酯和N,N-亚甲基双丙烯酰胺溶解在苯中,以偶氮二异丁氰为引发剂,保持80℃聚合3h,过滤,干燥,得到白色粉末。把粉末加入到溶有Span-80的溶剂油中高速搅拌,滴加氨水中和,加入壬基苯基聚氧乙烯醚(Tx-10)转相得到白色的增稠剂。得到的产品颗粒不均匀,增稠能力差,耐电解质能力较好。
丙烯酸和丙烯类单体ZXDW进行反相乳液聚合。实验室自制单体ZXDW的端基为磺酸基团,磺酸根离子为强酸根离子,有较强的水溶性,使单体能溶于水。以过硫酸铵-亚硫酸氢钠为引发剂,以N,N-亚甲基双丙烯酰胺(NMBA)为交联剂,反相聚合丙烯酸和单体ZXDW,聚合完毕后减压蒸馏脱水,加入壬基苯基聚氧乙烯醚(Tx-10)转相得到淡黄色粘稠的增稠剂,其增稠能力和粘度系数与增稠剂PTF相当,耐电解质能力是普通增稠剂的3-5倍。
Aiming to research and develop electrolyte-resistant thickener, this paper synthesized stearyl acrylate and ZXDW monomers. Then the conditions to prepare thickener have been studied particularly by orthogonal design. We have got ideal conditions to produce the thickening by single factor analyzing. And we have made performance tests as follows:
First, the copolymer was prepared in inverse emulsion solution using AA and octadecyl acrylate as monomers. The acrylic acid was neutralized by sodium hydroxide before the preparation, so the acrylic acid was changed into sodium acrylic by some degree. Therefore when there was water and oil, most of it could stay in water. But the stearyl acrylate is a hydrophobe, so it is in oil when the reaction takes place. So the reaction could not go on favorably. And the product had bad performance.
Second, the copolymer was prepared in benzene solution using AA and octadecyl acrylate as monomers, AIBN as initiator, and N,N-methylenebisacrylamide(MBA) as crosslinker. When it took place, we must make sure that the temperature was at 80℃and it must be like this for more than 3 hours. Then filtrated it and dried it to get white powders. Next, pour the powders into the solution which was got by blending Span-80 and gasoline and stirred it strongly. After that, dripped ammonium into it to neutralize acid. Finally, we added Tx-10 into it to change the solution from W/O to O/W. It was unexpected that it had high eletrolyte-resistance ability but low thicken ability.
Third, we made ZXDW monomer first, and The electrolyte-resistant thickener was prepared by inverse emulsion polymerization using acrylic acid and ZXDW as monomers, Span-80 as emulsifier, ammonium persulfate-sodium bisulfate as initiator, and N,N—methylenebisacrylamide(NMBA) as crosslinker. Because there was a hydrophile group, it could dissolved in water easily. After the reaction was over, we distilled it at low pressure to make sure that it had little water at last. When water was as little as we supposed, we added Tx-10 into it and stirred it thoroughly. So we could get light yellow paste with good performance. And its thicken ability and PVI is as well as imported products, for exemple PTE But the electrolyte-resistance ability is from twice to four times more than that of PTF.
引文
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3 娄光伟.聚醚型聚氨酯增稠剂的合成与性能测试:[学位论文]兰州:兰州大学,2006.4.
4 赵军子.活性染料印花用合成增稠剂的研究:[学位论文]杭州:浙江大学,2002.8.
5 陈溥,王志刚.纺织印染助剂实用手册[M].北京:化学工业出版社,2003.313-314.
6 陈胜慧.染整助剂新品种应用及开发[M].北京:中国纺织出版社,2002.284.
7 张高奇,梁伯润,赵振河.丙烯酸系反相乳液聚合及增稠性能的研究[J].精细石油化工进展,2002,3(4):1-4.
8 周明,倪成淘,姜武.环保柔软型印花增稠剂的合成与应用[J].染整技术,2005,27(10):35-37.
9 刘玉勇,于善普.反相乳液聚合制备增稠剂[J].精细石油化工进展,2003,4(8):25-29.
10 赵军子,牛俊峰.疏水缔合型聚丙烯酸盐增稠剂的研究[J].印染助剂,2004,21(1):9-12.
11 姜英涛.涂料用丙烯酸树脂的溶液聚合及分子量影响因素[J].涂料工业.1989(2).39-41
12 张洋,马榴强.聚合物制备工程[M].北京:中国轻工业出版社,2001.22-26.
13 赵振河,张高奇.增稠剂的反相乳液聚合及增稠性能研究[J].化学研究与应用.2002.14(5):545-548.
14 李聚源,戚朝荣等.丙烯酸十八酯-顺丁烯二酸酐共聚物的合成及其降凝性能的研究[J],西安石油学院学报,2003.9(18)5:65-67.
15 于善普.丙烯酸系增稠剂的合成、聚合动力学及性能的研究[D].上海:上海大学,2000.12.
16 Willmer K,Fischer T.Thickener for textile printing whichis a polymer dispersion and hasimproved biodegradability[P].美国专利:US 6 696508,2004-02-24.
17 陈振斌.丙烯酸系耐盐性高吸水树脂研究:[学位论文]兰州:兰州大学,2007.26.
18 叶高勇,张宝华.水性丙烯酸增稠剂的合成及性能研究[J].印染助剂,2004,21(6):9-11.
19 刘淑玲,张宝华,陵琴芳,等.耐盐聚丙烯酸阴离子增稠剂的研制[J].上海化工,2005,30(1):21-23.
20 邱光鸿.种子聚合在乳液聚合中的应用[J].涂料工业.
21 马松梅.聚丙烯酸系耐盐性高吸水性树脂制备及性能:[学位论文]兰州:兰州大学,2004.34-39.
22 I.Ogawa,H.Yamano,K.Miyagama,J.Apply.Polym.Sci,1993,47;217.
23 P.J.Flory.Principles of Polymer Chemistry,Comell University Press,1954.
24 大森英三.功能性丙烯酸树脂[M].北京:化学工业出版社,1994.30.
25 田玲,王九思等.AA/AMPS二元共聚物的合成及阻垢性能研究[J].兰州交通大学学报,2005,24(1):81-83.
26 李旭东,史显宗,王进等.影响涂料印花增稠剂增稠及抗渗化性能的因素[J].青岛化工学院学报,1998,19(4):352-356.
27 余一鹗.涂料印染技术[M].北京:中国纺织出版社,2003.37.
28 潘祖仁.高分子化学[M].北京:化学工业出版社,2004.50.
29 W.F.Lee,et al.J.Appl.Polym.Sci,1997.64;2371
30 姬兰琴,涂玉碧,董仲生等.合成增稠剂QY-1在涂料印花中的性能[J].印染助剂,1999,16(5):17-19.
31 冯世宏.乳液型丙烯酸酯增稠剂的研究[J].辽宁工学院学报,2001,21(1):17-18.
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