水相悬浮法制备氯化聚氯乙烯新工艺.pdf

塑料工业
第40卷第9期
CHINA PLASTICS INDUSTRY
2012年9月
水相悬浮法制备氯化聚氯乙烯新工艺
陈国文,何丽蓉,张未星
(浙江大学化学工程与生物工程学系,浙江杭州310027)
摘要:采用水相悬浮法氯化的一种新工艺以大摩尔质量的SC3型国产聚氯乙烯(PVC)树脂为原料,制备高摩尔
质量和高氯含量的氯化聚氯乙烯(CPVC)树脂,考察了工艺条件对CPVC摩尔质量和氯含量的影响。结果表明,氯
化后产品CPVC的数均摩尔质量M。和重均摩尔质量M值分别为93174g/mol和196153g/mol,分别大于PVC的
88487g/mol和186607g/mol;在PVC与盐酸溶液固液比25%,反应温度60℃,1,2-二氯乙烷与PVC质量比0.5,
偶氮二异丁腈和紫外光双引发,氯气流量0.4L/min条件下,产品CPVC氯含量最高可达70.86%。该工艺下SC3型
PVC树脂可成功氯化,氯化过程分子链没有发生断裂,氯化效率好,达到国外专用PVC树脂的氯化水平。
关键词:水相悬浮法;氯化聚氯乙烯;摩尔质量;氯化工艺
中图分类号:TQ325.3
文献标识码:B
文章编号:1005-5770(2012)09-0026-0
A New Process for Preparation of Chlorinated P C by Aqueous Suspension Method
CHEN Guo-wen, HE Li-rong, ZHANG Wei-xing
( Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China)
Abstract: A kind of high moleeular weight and high chlorine content of chlorinated polyvinyl chloride
(CPVC)resin was prepared by a new aqueous suspension method that SG3 type domestic PVC was used as
reactant, and the effects of process conditions on molecular weight and chlorine content of CPVC were studied
in this paper. The results showed that: the M and M values of the product CPVC were 93 174 g/mol an
196 153 g/mol, both of which were greater than PVC'S88487 g/mol and 186 607 g/mol respectively. When
PVC was chlorinated under the conditions of PVC and hydrochloric acid solution solid-liquid ratio 25%
reaction temperature 60 C, 1, 2-dichloroethane and PVC feed ratio 0.5, initiations of UV and
azobisisobutyronitrile, 0. 4 L/min chlorine flow, the largest chlorine content of CP C could reach 70. 86%
Therefore, $G3 type P C resin could be chlorinated successfully and the chain scission of PVC did not occur
in this chlorination process, the efficiency of chloride was good, which reached foreign chlorination levels o
special PVC resin
Keywords: Aqueous Suspension Method; CPVC; Molecular Weight; Chlorination Process
氯化聚氯乙烯(CPVC)是聚氯乙烯(PVC)氯艺简单,操作流程短,制得的产品有良好的耐热性、
化改性的一种新型材料,理论氯含量为73.2%,热稳定性和机械强度,生产过程“三废”污染少,
商品级CPVC氯含量一般为61%~68%?,氯化后易于处理,不会造成环境污染,是目前国内外CPVC
分子链极性增加,产品CPVC除具有PVC的优良性主要生产方法。
能外,还具有耐热性好,阻燃性高,机强度大等特
硬质管材是CPVC的应用范围最广的领域,但日
点31,在化工、建材和电器等领域有广泛应用,前国内厂家还没有能生产出符合优质管材要求的
特别是PVC氯化后维卡软化点在90~120℃,被广CPVC产品,究其原因主要是没有符合要求的PVC原
泛用作热水管。目前,产品CPVC的制备方法有料树脂和成熟的氯化工艺技术,国外采用无皮膜、孔
溶剂法?、水相悬浮法?和气固相法的三种。溶剂隙率高的专用PVC树脂氯化制备CPVC,而国产的
法需要使用大量有毒有机溶剂,污染大,正逐渐被淘PVC皮膜厚,孔隙率小,氯化时分子链易发生断裂,
汰;气固相法氯化不均匀,产品CPVC加工后期易脱表面氯含量高,数均摩尔质量普遍小于硬质管材要求
HCl变色,目前正处于试验研究阶段;水相悬浮法工的75000gy/mol?,CPVC产品质量不高。 Tadashi
作者简介:陈国文,男,1988年生,硕土研究生,主要从事高分子材料改性方面研究。jiayouchenguowent@163.com