可开发作高效有机缩膨剂的化合物探讨

An Investigation into Effective Swelled Clay Shrinkage Organic Chemicals

在选定条件下由二甲基二烯丙基氯化铵(DMDAAC)、环氧氯丙烷与二甲胺、三甲胺或二乙烯三胺合成了链结构不同的6种聚季铵盐及一种单季铵盐;按石油天然气行业标准方法,以KC l和商品缩膨剂RUN为对比剂,测定了这7种季铵盐及DMDAAC单体在10、20、50 g/L溶液中对钙基膨润土的防膨率和对已水化膨胀钙基膨润土的缩膨率。除DMDAAC聚合物PDMD(50 g/L溶液)和DMDAAC(20和50 g/L)外,这8种季铵盐均无缩膨性,认为具缩膨性的季铵盐分子中不应含非离子极性基因如羟基和醚基,阳离子应在支链或杂环上,且相对分子质量适当。KC l和RUN缩膨处理的持久性均不如DMDAAC单体。以亚硫酸钠/过硫酸铵引发体系合成较低相对分子质量PDMD的正交设计实验结果表明:合成的所有PDMD在溶液浓度为10 g/L时均无缩膨性,溶液浓度20和50 g/L时缩膨率最大值分别为16.06%和22.86%;以防膨率或缩膨率为目的指标合成PDMD的条件不同;在最佳条件下合成的PDMD的缩膨率,溶液浓度20和50 g/L时分别为13.12%和22.20%,接近或略低于RUN和KC l的水平;将该样品与KC l复配不能提高缩膨率。考察了用PDMD缩膨和防膨处理后的钙基膨润土的红外光谱特征。

Six organic polymeric quarternary ammonium salts（QASs） and one monomeric QAS were prepared from dimethyldiallyl ammonium chloride（DMDAAC） and from epichlorohydrin and dimethylamine,trimethylamine or diethylenetriamine under specially designed conditions;these 7 QASs together with DMDAAC were investigated by determining antiswelling rate（AWR） of Ca-bentonite and shrinking rate（SR） of swelled Ca-bentonite by these QASs in 10,20,and 50 g/L solution in comparison with a commercial swelled clay shrinkage agent RUN and KCl.It was shown that besides of PDMD in 50 g/L solution and DMDAAC in 20 and 50 g/L solution these QASs had no shrinking ability and concluded that a shrinkage chemicl should contain no nonionic polar functionality（es） such as hydroxyl and ether linkage,be of medium molar mass,and have cationic functionality（es） in side group（s） or in heterocycle（s） in chain.Through orthogonally designed experiments of synthesizing relatively low molar mass DMDAAC polymers using sodium sulfile/ammonium persulfate initiating system,it was shown that all the PDMD samples synthesized had no shrinking ability in 10 g/L solution;the highest SR value in 20 and 50 g/L solution of PDMD was of 16.06% and 22.86%,respectively;the parameters of sythesis of PDMD as antiswelling or shrinkage agent were different;for a PDMD sample synthesized under a set of optimal conditions,the SR value in 20 and 50 g/L solution was of 13.12% and 22.20%,a value similar to or slightly lower than that of RUN and KCl;the shrinking ability of the PDMD could not be improved by compounding with KCl.The IR-spectra of ca-bentonite treated by PDMD for swelling prevention and shrinkage were presented and discussed.