新型小分子阻垢分散剂的合成与构效关系研究
摘要
随着世界水资源短缺加剧、水污染日益严重和工业生产装置运行周期的延长，对工业水处理技术的要求不断提高，促进了水处理剂的迅速发展，新型、高效、多功能的缓蚀阻垢剂已成为人们竞向开发的热点。
以重要的中间体膦基丁二酸酯(简称中间体Ⅰ)为主要原料，经烷基化、磺化和水解等步骤，合成了如下6种具有新型结构的阻垢分散剂：
(1)：2-膦基-4-磺酸-1，2二羧酸丁烷(PSBD)
(2)：2-膦基-5-磺酸-1，2-二羧酸-戊烷(PSPD)
(3)：2-膦基-6-磺酸-1，2-二羧酸-己烷(PSHD)
(4)：2-膦基-7-磺酸-1，2-二羧酸-庚烷(PSHPD)
(5)：2-膦基-8-磺酸-1，2-二羧酸-辛烷(PSOD)
(6)：2-膦基-12-磺酸-1，2-二羧酸-十二烷(PSDD)
考察了它们的合成条件。第一步，用中间体Ⅰ和卤代烃进行烷基化反应，主要影响因素是催化剂和溶剂。当选用强碱NaH作催化剂，且在非质子的无水溶剂(如苯、DMF等)中，反应可以顺利进行，反应产物经减压蒸馏，得到2-二甲氧基膦基-X-溴-1，2-二羧酸乙酯-x烷(简称烃化产物)。
第二步，将烃化产物与亚硫酸钠在水溶液中进行磺化反应，产物经离子交换树脂分离提纯，得到2-二甲氧基膦基-X-磺酸-1，2-二羧酸乙酯-x烷(简称磺化产物)。
第三步，将磺化产物在HC1水溶液中进行水解，经蒸馏除去其它杂质，得到目标化合物。
对各中间体和目标化合物分别用核磁共振进行结构分析。P~(31)，C~(13)NMR结果表明，得到的化合物与所设计的结构相符。
用静态阻垢试验方法对合成的化合物的主要性能进行评定。结果表明，阻磷酸钙垢和阻碳酸钙垢性能较常用的有机瞵羧酸阻垢剂2-膦基-1，2，4-三羧酸-丁烷(PBTC)都有明显提高。
钙容忍度试验结果表明，合成的化合物PSHD与钙容忍度较好的PBTC相当，钙容忍度都大于100mg／L，而一般有机膦酸如HEDP的钙容忍度小于10mg／L。
耐氯试验结果表明，合成的化合物PSHD，PSHPD与耐氯分解性能较好的PBTC相当。在质量浓度为10mg／L的强氯精的作用下，72h的分解率，三者分别为17.2％、19.1％、14.9％，而HEDP的分解率超过80％。
旋转挂片腐蚀实验结果表明，预膜加锌条件下，合成的化合物
PSHD和 PBTC的缓蚀性能相当，预膜不加锌条件下，较PBTC缓蚀
性略好，缓蚀率达95二％。
对合成的化合物的构效关系研究结果表明，当化合物中所含官能
团种类和个数相同时，影响化合物阻磷酸钙垢效果的主要因素是烷基
碳链的长短，当碳链中碳原子个数分别为3～6时，化合物阻磷酸钙
垢效果好，如碳原子个数为 6，质量浓度 10mg几时，阻磷酸钙垢的
阻垢率达到68．3％。但碳链长度对阻碳酸钙垢影响不大，证明阻碳酸
钙垢的机理与阻磷酸钙垢的机理不同。
当化合物结构相似、碳原子数相同、官能团不同时，含磺酸基的
化合物阻磷酸钙垢的效果明显优于不含磺酸基团的化合物，说明磺酸
基团对阻磷酸钙垢的能力较强。化合物中含磺酸基团与否，对阻碳酸
钙垢的效果影响不大。
In view of excessive exploration of world wide water resource,
serious water pollution and extension of industrial apparatus'operating
period, cooling water treatment technology is facing a challenge to
develop chemicals having high effect against scale and corrosion for
cooling water treatment. Accordingly, the goal of this thesis is to
synthesize multiple-functional water treatment chemicals and investigate
the relationship between structure and effect.
Used dimethyl dietheyl phosphono succinate (I) as
scale inhibitors containing novel
three-stepped reaction: alkylation,
following six
synthesized by
dehydration.
1: 2-phosphono-4-sulfonic-1 ,2-dicarboxylic acid butane (PSBD)
2: 2-phosphono-5-sulfonic- 1 ,2-dicarboxylic acid pentane (PSPD)
3: 2-phosphono-6-sulfonic- 1 ,2-dicarboxylic acid hexane (PSHD)
4: 2-phosphono-7-sulfonic- 1 ,2-dicarboxylic acid heptane (PSHPD)
5: 2-phosphono-8-sulfonic-1,2-dicarboxylic acid octane (PSOD)
6: 2-phosphono- 1 2-sulfonic- 1 ,2-dicarboxylic acid dodecane
(PSDD)
In step 1, when catalyst sodium hydride and non-proton solvent
such as benzene or DMIF used, (I) reacted successfully with
halohydracarbon. Product 2-dimethyl phosphono-x-bromo- 1,2-
dicarboxylic acid -x-alkane[intermediate (II) ] was purified by distilling
' reaction mixture.
In step 2, (II) reacted with sodium sulfite and reaction mixture was
purified by ion exchangers. Finally 2-dimethyl phosphono-x-sulfonic-
1 ,2-dicarboxylic acid -x-alkylane [intermediate (III)] was obtained.
In step 3, (III) was dehydrated by HC1 in aqueous. Target product
was obtained by distillation.
All the intermediates and target products were characterized by
P31NMR and C7NMR.
By static scale inhibition test, most of six new-typed scale inhibitors
showed higher effect against phosphate scale and carbonate scale than 2-
phosphono- 1 ,2,4-tricarboxylic butane (PBTC).
Calcium tolerance test and chlorine tolerance test revealed that
target scale inhibitors had as high effect as PBTC.
Weight-losing corrosion test proved that the new-typed scale
inhibitors showed as high effect against corrosion as PBTC.
Study on relationship between structure and effect revealed that
effect of compounds with all the same other structural factors against
phosphate scale was determined by their carbon chain length and the
preferred number of carbon atom was respectively 3,4,5,6; e.g. a
starting material,
structures were
sulfonation and
compound with 6-carbon chain showed ratio of 70% inhibiting
phosphate scale by using amount of 10 mg/L. However, the change in
carbon chain length exhibited little different effect on carbonate scale
inhibition, which could be explained by the different mechanism between
carbonate scale inhibition and phosphate sle inhibition.
Among compounds having only structural difference in functional
group, one type of which containing sulfonic group had better effect of
inhibiting phosphate scale than that without it; which proved sulfonic
group contributed greatly to the above effect; however sulfonic group
contributed little to the effect of carbon scale inhibition.
以重要的中间体膦基丁二酸酯(简称中间体Ⅰ)为主要原料，经烷基化、磺化和水解等步骤，合成了如下6种具有新型结构的阻垢分散剂：
(1)：2-膦基-4-磺酸-1，2二羧酸丁烷(PSBD)
(2)：2-膦基-5-磺酸-1，2-二羧酸-戊烷(PSPD)
(3)：2-膦基-6-磺酸-1，2-二羧酸-己烷(PSHD)
(4)：2-膦基-7-磺酸-1，2-二羧酸-庚烷(PSHPD)
(5)：2-膦基-8-磺酸-1，2-二羧酸-辛烷(PSOD)
(6)：2-膦基-12-磺酸-1，2-二羧酸-十二烷(PSDD)
考察了它们的合成条件。第一步，用中间体Ⅰ和卤代烃进行烷基化反应，主要影响因素是催化剂和溶剂。当选用强碱NaH作催化剂，且在非质子的无水溶剂(如苯、DMF等)中，反应可以顺利进行，反应产物经减压蒸馏，得到2-二甲氧基膦基-X-溴-1，2-二羧酸乙酯-x烷(简称烃化产物)。
第二步，将烃化产物与亚硫酸钠在水溶液中进行磺化反应，产物经离子交换树脂分离提纯，得到2-二甲氧基膦基-X-磺酸-1，2-二羧酸乙酯-x烷(简称磺化产物)。
第三步，将磺化产物在HC1水溶液中进行水解，经蒸馏除去其它杂质，得到目标化合物。
对各中间体和目标化合物分别用核磁共振进行结构分析。P~(31)，C~(13)NMR结果表明，得到的化合物与所设计的结构相符。
用静态阻垢试验方法对合成的化合物的主要性能进行评定。结果表明，阻磷酸钙垢和阻碳酸钙垢性能较常用的有机瞵羧酸阻垢剂2-膦基-1，2，4-三羧酸-丁烷(PBTC)都有明显提高。
钙容忍度试验结果表明，合成的化合物PSHD与钙容忍度较好的PBTC相当，钙容忍度都大于100mg／L，而一般有机膦酸如HEDP的钙容忍度小于10mg／L。
耐氯试验结果表明，合成的化合物PSHD，PSHPD与耐氯分解性能较好的PBTC相当。在质量浓度为10mg／L的强氯精的作用下，72h的分解率，三者分别为17.2％、19.1％、14.9％，而HEDP的分解率超过80％。
旋转挂片腐蚀实验结果表明，预膜加锌条件下，合成的化合物
PSHD和 PBTC的缓蚀性能相当，预膜不加锌条件下，较PBTC缓蚀
性略好，缓蚀率达95二％。
对合成的化合物的构效关系研究结果表明，当化合物中所含官能
团种类和个数相同时，影响化合物阻磷酸钙垢效果的主要因素是烷基
碳链的长短，当碳链中碳原子个数分别为3～6时，化合物阻磷酸钙
垢效果好，如碳原子个数为 6，质量浓度 10mg几时，阻磷酸钙垢的
阻垢率达到68．3％。但碳链长度对阻碳酸钙垢影响不大，证明阻碳酸
钙垢的机理与阻磷酸钙垢的机理不同。
当化合物结构相似、碳原子数相同、官能团不同时，含磺酸基的
化合物阻磷酸钙垢的效果明显优于不含磺酸基团的化合物，说明磺酸
基团对阻磷酸钙垢的能力较强。化合物中含磺酸基团与否，对阻碳酸
钙垢的效果影响不大。
In view of excessive exploration of world wide water resource,
serious water pollution and extension of industrial apparatus'operating
period, cooling water treatment technology is facing a challenge to
develop chemicals having high effect against scale and corrosion for
cooling water treatment. Accordingly, the goal of this thesis is to
synthesize multiple-functional water treatment chemicals and investigate
the relationship between structure and effect.
Used dimethyl dietheyl phosphono succinate (I) as
scale inhibitors containing novel
three-stepped reaction: alkylation,
following six
synthesized by
dehydration.
1: 2-phosphono-4-sulfonic-1 ,2-dicarboxylic acid butane (PSBD)
2: 2-phosphono-5-sulfonic- 1 ,2-dicarboxylic acid pentane (PSPD)
3: 2-phosphono-6-sulfonic- 1 ,2-dicarboxylic acid hexane (PSHD)
4: 2-phosphono-7-sulfonic- 1 ,2-dicarboxylic acid heptane (PSHPD)
5: 2-phosphono-8-sulfonic-1,2-dicarboxylic acid octane (PSOD)
6: 2-phosphono- 1 2-sulfonic- 1 ,2-dicarboxylic acid dodecane
(PSDD)
In step 1, when catalyst sodium hydride and non-proton solvent
such as benzene or DMIF used, (I) reacted successfully with
halohydracarbon. Product 2-dimethyl phosphono-x-bromo- 1,2-
dicarboxylic acid -x-alkane[intermediate (II) ] was purified by distilling
' reaction mixture.
In step 2, (II) reacted with sodium sulfite and reaction mixture was
purified by ion exchangers. Finally 2-dimethyl phosphono-x-sulfonic-
1 ,2-dicarboxylic acid -x-alkylane [intermediate (III)] was obtained.
In step 3, (III) was dehydrated by HC1 in aqueous. Target product
was obtained by distillation.
All the intermediates and target products were characterized by
P31NMR and C7NMR.
By static scale inhibition test, most of six new-typed scale inhibitors
showed higher effect against phosphate scale and carbonate scale than 2-
phosphono- 1 ,2,4-tricarboxylic butane (PBTC).
Calcium tolerance test and chlorine tolerance test revealed that
target scale inhibitors had as high effect as PBTC.
Weight-losing corrosion test proved that the new-typed scale
inhibitors showed as high effect against corrosion as PBTC.
Study on relationship between structure and effect revealed that
effect of compounds with all the same other structural factors against
phosphate scale was determined by their carbon chain length and the
preferred number of carbon atom was respectively 3,4,5,6; e.g. a
starting material,
structures were
sulfonation and
compound with 6-carbon chain showed ratio of 70% inhibiting
phosphate scale by using amount of 10 mg/L. However, the change in
carbon chain length exhibited little different effect on carbonate scale
inhibition, which could be explained by the different mechanism between
carbonate scale inhibition and phosphate sle inhibition.
Among compounds having only structural difference in functional
group, one type of which containing sulfonic group had better effect of
inhibiting phosphate scale than that without it; which proved sulfonic
group contributed greatly to the above effect; however sulfonic group
contributed little to the effect of carbon scale inhibition.
引文
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2 王京．常用阻垢剂的分析及其阻垢机理研究．石油化工科学研究院博士论文．1998．7
3 杨璋，李寿椿．新型水处理剂—IDPA．《工业水处理》，1987，(4)：25-29
4 李寿椿．膦酸，羧酸化合物与水处理性能的研究．《工业水处理》，1987，(2)：26-29
5 朱传芳，李中华．含磷的金属螯合剂—N，N，N，N—烃基二氨基四亚甲基膦酸的合成研究(Ⅲ)．化学试剂，1995(2)：109-110
6 唐坤明，周君，二乙烯三胺五甲叉膦酸(钠)的合成．化学世界，1993，(3)：111-114
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8 Redmore D. N, N-dimethylene phosphonic acids of alkylene diamines. USP 4330487. 1982
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