液-固本体法氯磺化聚乙烯的制备及与溶液法产品的比较
|
摘要
以高密度聚乙烯为原料,用磺酰氯代替二氧化硫气体以提高其利用率,采用液-固本体法制备了氯磺化聚乙烯(CSM),探讨了磺酰氯的用量;采用邻苯二甲酸二辛酯(DOP)包覆磺酰氯的工艺来提高其热分解温度,以改善氯磺酰基在分子链上的分布均匀性,并研究了其与分散剂白炭黑的用量配比;采用两段升温方式考察了低温下预氯化程度对CSM性能的影响。结果表明,采用液-固本体法制备CSM时,高密度聚乙烯与磺酰氯的最佳用量配比为50 g/0.2 mol;经DOP包覆后的氯磺酰基在分子链中的分布更加均匀,磺酰氯、DOP及分散剂白炭黑三者的最佳配比为0.2 mol/0.03 mol/7.5 g;采用两段氯化工艺时,在温度达到110℃前进行初步氯化至含氯质量分数达到10%的产物性能最佳。液-固本体法制备的CSM比用溶液法工业生产的CSM 40的氯分布更加均匀,硫含量基本一致,力学性能则更为优异,远优于GB/T 30920—2014的要求。
The chlorosulfonated polyethylene(CSM) was prepared by liquid-solid bulk polymerization using high density polyethylene(HDPE) and sulfonyl chloride as reagents. The amount of sulfonyl chloride was discussed; the thermal decomposition temperature of sulfonyl chloride coated with dioctyl phthalate(DOP) was increased to improve the uniformity of the distribution of chlorosulfonyl group in the molecular chain. The ratio of DOP to silica was also studied, and the effect of pre-chlorination degree on CSM performance at low temperature was investigated by two-stage heating method. The results showed that the optimum ratio of HDPE to sulfonyl chloride was 50 g/0.2 mol when CSM was prepared by liquid-solid bulk method. The distribution of chlorosulfonyl groups in the molecular chain was more uniform after DOP coating. The optimum ratio of sulfonyl chloride, DOP and dispersant silica was 0.2 mol/0.03 mol/7.5 g. Two-stage chlorination process was used to obtain the best performance of the product when initial chlorination was carried out before the temperature reached 110 ℃ and the mass fraction of chlorine reached 10%. CSM prepared by liquid-solid method has more uniform chlorine distribution, similar sulfur content and better mechanical properties than CSM 40 manufactured by solution method. Its mechanical properties were far better than the requirements of GB/T 30920—2014.
The chlorosulfonated polyethylene(CSM) was prepared by liquid-solid bulk polymerization using high density polyethylene(HDPE) and sulfonyl chloride as reagents. The amount of sulfonyl chloride was discussed; the thermal decomposition temperature of sulfonyl chloride coated with dioctyl phthalate(DOP) was increased to improve the uniformity of the distribution of chlorosulfonyl group in the molecular chain. The ratio of DOP to silica was also studied, and the effect of pre-chlorination degree on CSM performance at low temperature was investigated by two-stage heating method. The results showed that the optimum ratio of HDPE to sulfonyl chloride was 50 g/0.2 mol when CSM was prepared by liquid-solid bulk method. The distribution of chlorosulfonyl groups in the molecular chain was more uniform after DOP coating. The optimum ratio of sulfonyl chloride, DOP and dispersant silica was 0.2 mol/0.03 mol/7.5 g. Two-stage chlorination process was used to obtain the best performance of the product when initial chlorination was carried out before the temperature reached 110 ℃ and the mass fraction of chlorine reached 10%. CSM prepared by liquid-solid method has more uniform chlorine distribution, similar sulfur content and better mechanical properties than CSM 40 manufactured by solution method. Its mechanical properties were far better than the requirements of GB/T 30920—2014.
引文
[1] Wang Zhe,Ni Hongzhe.The preparation and thermodynamic behaviors of chlorosulfonated polyethylene [J].Journal of Applied Polymer Science,2010,116(4):2095-2100.
[2] 赵若飞,孙岩,黄拥军,等.气固法合成氯磺化聚乙烯(Ⅰ):气-固相反应机理[J].华东理工大学学报,2001,27(1):68-52.
[3] 宋结东.基于气固相法的高粘度高填充性氯磺化聚乙烯的制备方法:中国,CN 101735350 A[P].2010-06-16.
[4] 白杰.一种气固液三相反应制备氯磺化聚乙烯的方法:中国,CN 102153683 A[P].2011-08-17.
[5] 赵季若,冯莺,曹桂芳,等.固相法合成氯磺化聚乙烯[J].石油化工,1996,25(3):172-175.
[6] Zhao Ruofei,Cheng Shujun,Shun Yan,et al.Preparation of chlorosulfonated polyethylene by the gas-solid method[J].Journal of Applied Polymer Science,2001,81(14):3582-3588.
[7] 轩卫华,蒋琨,熊新阳,气固相法氯磺化聚乙烯合成技术进展及发展建议[J].中国氯碱,2017(4):22-24.
[8] Li Qibiao,Li Mingyi.The main-chain structure and chlorine distribution of chlorosulfonated polyethylene via gas-solid phase method[J].Advanced Materials Research,2013,821/822(10):965-970.
[2] 赵若飞,孙岩,黄拥军,等.气固法合成氯磺化聚乙烯(Ⅰ):气-固相反应机理[J].华东理工大学学报,2001,27(1):68-52.
[3] 宋结东.基于气固相法的高粘度高填充性氯磺化聚乙烯的制备方法:中国,CN 101735350 A[P].2010-06-16.
[4] 白杰.一种气固液三相反应制备氯磺化聚乙烯的方法:中国,CN 102153683 A[P].2011-08-17.
[5] 赵季若,冯莺,曹桂芳,等.固相法合成氯磺化聚乙烯[J].石油化工,1996,25(3):172-175.
[6] Zhao Ruofei,Cheng Shujun,Shun Yan,et al.Preparation of chlorosulfonated polyethylene by the gas-solid method[J].Journal of Applied Polymer Science,2001,81(14):3582-3588.
[7] 轩卫华,蒋琨,熊新阳,气固相法氯磺化聚乙烯合成技术进展及发展建议[J].中国氯碱,2017(4):22-24.
[8] Li Qibiao,Li Mingyi.The main-chain structure and chlorine distribution of chlorosulfonated polyethylene via gas-solid phase method[J].Advanced Materials Research,2013,821/822(10):965-970.