CN1243822A - A kind of preparation method of cationic polymer monomer - Google Patents
A kind of preparation method of cationic polymer monomer Download PDFInfo
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- CN1243822A CN1243822A CN 99114784 CN99114784A CN1243822A CN 1243822 A CN1243822 A CN 1243822A CN 99114784 CN99114784 CN 99114784 CN 99114784 A CN99114784 A CN 99114784A CN 1243822 A CN1243822 A CN 1243822A
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- 239000000178 monomer Substances 0.000 title claims abstract description 10
- 229920006317 cationic polymer Polymers 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title claims description 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 20
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 14
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 12
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 238000005553 drilling Methods 0.000 abstract description 2
- 150000002892 organic cations Chemical class 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 229920003169 water-soluble polymer Polymers 0.000 abstract description 2
- OWXJKYNZGFSVRC-UHFFFAOYSA-N 1-chloroprop-1-ene Chemical group CC=CCl OWXJKYNZGFSVRC-UHFFFAOYSA-N 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000645 desinfectant Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- -1 oil-displacing agent Chemical class 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本发明涉及一种阳离子单体二甲基二烯丙基氯化铵的合成，它是采有“一步法”将合成二甲基二烯丙基氯化铵的多步反应在一个反应器里实现，属于阳离子聚合物单体的制备方法。The present invention relates to the synthesis of a kind of cationic monomer dimethyl diallyl ammonium chloride, which adopts "one-step method" to synthesize the multi-step reaction of dimethyl diallyl ammonium chloride in a reactor The invention belongs to the preparation method of cationic polymer monomer.
阳离子聚合物单体二甲基二烯丙基氯化铵(Dimethyl DiallylAmmonium Chloride)，简称DMDAAC。分子量161.6，CAS登记号[7398-69-8]，纯品为无色固体，易溶于水，极易吸潮。其结构式为：(CH3)2N+(CH2CH＝CH2)2Cl-。它的合成反应通常有如下三步：Cationic polymer monomer dimethyl diallyl ammonium chloride (Dimethyl Diallyl Ammonium Chloride), referred to as DMDAAC. Molecular weight 161.6, CAS registration number [7398-69-8], the pure product is a colorless solid, easily soluble in water, and easy to absorb moisture. Its structural formula is: (CH 3 ) 2 N + (CH 2 CH=CH 2 ) 2 Cl - . Its synthesis reaction usually has the following three steps:
(1)叔胺化反应(1) Tertiary amination reaction
(2)中和反应
(3)季铵化反应
主要副反应为二甲胺和中间物叔胺与氯化氢形成盐酸盐，以及中和过程的氯丙烯的碱水解反应：The main side reaction is the hydrochloride formation of dimethylamine and intermediate tertiary amine with hydrogen chloride, and the alkali hydrolysis reaction of allyl chloride in the neutralization process:
DMDAAC主要用于合成含有机阳离子的水溶性聚合物，可以改善聚合物的水溶性、溶液流变性，增加吸附能力和杀菌能力等。DMDAAC用于合成新型聚合物驱油剂和钻井液处理剂、水处理剂和杀菌剂，也广泛地用于日化工业和造纸工业上，市场用量越来越大。DMDAAC is mainly used to synthesize water-soluble polymers containing organic cations, which can improve the water solubility and solution rheology of polymers, increase adsorption capacity and bactericidal ability, etc. DMDAAC is used to synthesize new polymer oil displacement agents, drilling fluid treatment agents, water treatment agents and fungicides, and is also widely used in the daily chemical industry and paper industry, and the market usage is increasing.
目前国内外已经实现DMDAAC的工业化生产，由于它的常规生产过程较为复杂，副反应多，反应和操作步骤多，转化率转低，造成价格昂贵。目前从国内外相关资料来看，制备DMDAAC的方法多采用常压低温工艺，原料和中间物需纯化，如Hunter，Wood E.Sieder，Theodore P.(US 4151202A，1979)采用过滤后水洗涤工艺来纯化氯丙烯，然后在常压低温(＜47℃)与二甲胺反应合成DMDAAC；或者反应物投料不等量，如Ballschuh，Detlef；Jaeger，Werner；et al.(GB 1573239A，1980)采用100mol二甲胺在15℃下加入25mol氯丙烯中，然后迅速加入185mol氯丙烯，并保持温度为15℃下缓慢而均匀地加入100mol 50％NaOH溶液，充入氮气后再加热至100℃保持2小时，此工艺中氯丙烯过量5％；国内权艳梅、胡旭光等人采用改进的DMDAAC合成与分析方法(油田化学，1997，Vol 14，No 2：159-161)，常压合成、减压蒸馏和过滤提纯，产物收率可以达到85％左右；徐燕莉(石油化工，1998，Vol 27，No.7：517-520)采用交替加料、分步加热，氯丙烯过量5.0～7.5％，在45℃反应6～7小时，最后给出DMDAAC的收率最高可以达到92％。由于主要原料二甲胺(CH3)2NH和氯丙烯CH2＝CHCH2Cl的沸点低于45℃，使得常压反应温度低，反应时间长，室温下氯丙烯和二甲胺很难完全冷凝，极易挥发损失，因此反应物投料比总是不等量，致使收率低、环境污染大、生产成本高。这些主要缺陷导致DMDAAC生产量太小，市场紧缺，极大地限制了其工业生产应用。At present, the industrialized production of DMDAAC has been realized at home and abroad. Because of its complicated conventional production process, many side reactions, many reaction and operation steps, and low conversion rate, it is expensive. At present, from relevant information at home and abroad, the method for preparing DMDAAC mostly adopts normal pressure and low temperature process, and raw materials and intermediates need to be purified, such as Hunter, Wood E.Sieder, Theodore P. (US 4151202A, 1979) adopts the water washing process after filtration to purify chloropropene, and then react with dimethylamine at normal pressure and low temperature (<47°C) to synthesize DMDAAC; or the reactants are charged in different amounts, such as Ballschuh, Detlef; Jaeger, Werner; et al. (GB 1573239A, 1980) adopts Add 100mol of dimethylamine to 25mol of chloropropene at 15°C, then quickly add 185mol of chloropropene, and keep the temperature at 15°C, slowly and evenly add 100mol of 50% NaOH solution, fill with nitrogen and then heat to 100°C for 2 Hours, 5% excess of chloropropene in this process; domestic Quan Yanmei, Hu Xuguang and others adopt improved DMDAAC synthesis and analysis method (Oilfield Chemistry, 1997, Vol 14, No 2: 159-161), normal pressure synthesis, reduction pressure distillation and filtration purification, the product yield can reach about 85%; After reacting at 45°C for 6-7 hours, the yield of DMDAAC can reach up to 92%. Since the boiling points of the main raw materials dimethylamine (CH 3 ) 2 NH and chloropropene CH 2 =CHCH 2 Cl are lower than 45°C, the reaction temperature under normal pressure is low and the reaction time is long, and it is difficult for chloropropene and dimethylamine to completely Condensation is very easy to volatilize and lose, so the feed ratio of reactants is always unequal, resulting in low yield, large environmental pollution, and high production costs. These main defects lead to too small production volume of DMDAAC, and the market is in short supply, which greatly limits its industrial production application.
本发明的目的在于克服现有常压低温制备工艺的缺陷，提出一种具有高反应速度、高收率、高质量和低成本、低污染的阳离子单体二甲基二烯丙基氯化铵的制备新方法。The purpose of the present invention is to overcome the defects of the existing normal pressure and low temperature preparation process, and propose a cationic monomer dimethyl diallyl ammonium chloride with high reaction speed, high yield, high quality, low cost and low pollution new method of preparation.
本发明提供的制备方法其主要技术特征是：采用密闭低压、高温、等摩尔反应物配比，交替加碱和氯丙烯的“一步法”新工艺合成DMDAAC。以工业级氯丙烯、二甲胺和氢氧化钠为原料，按照等摩尔反应物配比，在密闭反应釜中进行操作。本发明的制备方法是：先在反应釜中，加入一定量的40％二甲胺溶液，密闭反应釜并搅拌，再缓慢加入等摩尔的氯丙烯，在低压(小于0.2MPa)条件下，控制反应温度在65～85℃，再交替加碱(NaOH溶液)和氯丙烯使反应体系的酸碱环境接近中性，合成反应时间约需2小时。本制备方法由于反应温度可以提高到65～85℃而不受氯丙烯的沸点45℃的局限，因而加快了反应速度。由于交替加碱和氯丙烯使反应体系PH为中性，很好地解决了避免氯丙烯水解与保持胺的亲核反应活性之间的矛盾。在叔胺化和中和反应后不必将中间物烯丙基二甲基胺分离出来，而直接与氯丙烯进行下一步季铵化反应，实现一步法合成。生产时采用两个带有回气管的恒压计量罐，分别对氯丙烯和碱溶液进行带压交替加料。在浓缩过程中，采用列管式真空膜蒸发器，实现低温快速浓缩，使副产物氯化钠容易结晶析出，有利于过滤除去。The main technical features of the preparation method provided by the invention are: adopting a "one-step" new process of sealing low pressure, high temperature, equimolar reactant ratio, and adding alkali and allyl chloride alternately to synthesize DMDAAC. Using industrial-grade chloropropene, dimethylamine and sodium hydroxide as raw materials, the operation is carried out in a closed reactor according to the ratio of equimolar reactants. The preparation method of the present invention is as follows: first, add a certain amount of 40% dimethylamine solution into the reaction kettle, seal the reaction kettle and stir, then slowly add equimolar chloropropene, and under the condition of low pressure (less than 0.2MPa), control The reaction temperature is 65-85° C. Alternately adding alkali (NaOH solution) and allyl chloride makes the acid-base environment of the reaction system close to neutral, and the synthesis reaction time is about 2 hours. In the preparation method, since the reaction temperature can be increased to 65-85 DEG C and not limited by the boiling point of chloropropene at 45 DEG C, the reaction speed is accelerated. Since the pH of the reaction system is neutral by alternately adding alkali and allyl chloride, the contradiction between avoiding the hydrolysis of allyl chloride and maintaining the nucleophilic reactivity of the amine is well resolved. After the tertiary amination and neutralization reaction, it is not necessary to separate the intermediate allyl dimethylamine, but directly carry out the next step quaternization reaction with allyl chloride to realize the one-step synthesis. During production, two constant-pressure metering tanks with air return pipes are used to alternately feed allyl chloride and alkali solution under pressure. During the concentration process, a tube-and-tube vacuum film evaporator is used to achieve low-temperature rapid concentration, so that the by-product sodium chloride is easy to crystallize and precipitate, which is beneficial to filtration and removal.
本发明产品的制备方法与现有技术相比，具有如下优点：Compared with the prior art, the preparation method of the product of the present invention has the following advantages:
(1)不分离中间产物，而直接与下一步原料反应，因而可以将三步反应操作减少为一步，提高了产品质量、降低了生产成本。(1) The intermediate product is not separated, but is directly reacted with the raw material of the next step, so the three-step reaction operation can be reduced to one step, which improves the product quality and reduces the production cost.
(2)本工艺具有操作步骤较少，因反应温度提高至65～85℃，而加快了反应速度，缩短了整个生产过程的时间。(2) This process has fewer operation steps, and because the reaction temperature is increased to 65-85° C., the reaction speed is accelerated and the time of the whole production process is shortened.
(3)可以实现等摩尔反应物投料比，反应物摩尔比依据反应方程式为：氯丙烯∶二甲胺∶氢氧化钠＝2.0∶1.0∶1.0，提高了转化率，收率高达95％，成本低，在工艺上不产生三废排放。(3) Equimolar reactant feed ratio can be realized, and the reactant mol ratio is according to the reaction equation: allyl chloride: dimethylamine: sodium hydroxide=2.0: 1.0: 1.0, which improves the conversion rate, and the yield is up to 95%, and the cost Low, no three wastes are produced in the process.
下面结合本发明提供的技术方案进一步说明该发明的生产实施办法：Further illustrate the production implementation method of this invention below in conjunction with the technical scheme that the present invention provides:
在0.25m3搪玻反应釜中，泵入40％二甲胺溶液620mol，密闭反应釜并搅拌，通过恒压计量罐缓慢加入氯丙烯620mol，约40～60分钟加完。控制温度低于65℃，压力低于0.2MPa(表压)。将620mol NaOH溶于60Kg水中，与另外620mol氯丙烯一起通过恒压计量罐平均分5～10次交替加入，约1～2小时加完。控制反应温度在65～85℃，保持釜内压力低于0.2MPa。每隔30分钟取样检测至PH为中性(6.5-8.5)，且折光率为恒定，结束反应。此过程约需2小时。将反应混合物用离心机过滤除去固体物氯化钠。母液为约50％的DMDAAC，用真空膜蒸发器进行真空浓缩(温度55～65℃，压力小于-0.08MPa)，约40分钟后浓缩至DMDAAC的浓度(折光率法)达75～85℃时，再过滤出结晶氯化钠，将母液继续浓缩，最后得到含量达98％以上的晶体状阳离子单体DMDAAC。Into a 0.25m3 glass-lined reactor, pump 620mol of 40% dimethylamine solution, seal the reactor and stir, slowly add 620mol of allyl chloride through a constant pressure metering tank, and finish adding in about 40 to 60 minutes. Control the temperature below 65°C and the pressure below 0.2MPa (gauge pressure). Dissolve 620mol of NaOH in 60Kg of water, and add 620mol of chloropropene together with another 620mol of chloropropene through a constant pressure metering tank for 5 to 10 times and alternately add in about 1 to 2 hours. Control the reaction temperature at 65-85°C, and keep the pressure in the kettle lower than 0.2MPa. Samples were taken every 30 minutes until the pH was neutral (6.5-8.5) and the refractive index was constant, then the reaction was terminated. This process takes about 2 hours. The reaction mixture was centrifuged to remove solid sodium chloride. The mother liquor is about 50% DMDAAC, which is concentrated in vacuum with a vacuum film evaporator (temperature 55-65°C, pressure less than -0.08MPa), and concentrated after about 40 minutes until the concentration of DMDAAC (refractive index method) reaches 75-85°C , and then filter out the crystalline sodium chloride, continue to concentrate the mother liquor, and finally obtain the crystalline cationic monomer DMDAAC with a content of more than 98%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006069504A1 (en) * | 2004-12-31 | 2006-07-06 | Nanjing University Of Science & Technology | A purification method for the cationic monomer of dimethyldiallylammonium chloride with high purity |
| CN101906050A (en) * | 2010-06-07 | 2010-12-08 | 浙江华晟化学制品有限公司 | Preparation method of dimethyldiallylammonium chloride monomer |
| CN109438250A (en) * | 2018-12-20 | 2019-03-08 | 山东天成化工有限公司 | A kind of preparation method of high purity dimethyl diallyl ammonium chloride monomer high yield |
| CN114212869A (en) * | 2021-12-09 | 2022-03-22 | 苏州业华环境科技有限公司 | Preparation method of polycation polymer, compound oil removal agent and oil removal process |
-
1999
- 1999-04-09 CN CN99114784A patent/CN1089087C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006069504A1 (en) * | 2004-12-31 | 2006-07-06 | Nanjing University Of Science & Technology | A purification method for the cationic monomer of dimethyldiallylammonium chloride with high purity |
| CN1323064C (en) * | 2004-12-31 | 2007-06-27 | 南京理工大学 | Refining method of high-purity cationic monomer dimethyl diallyl ammonium chloride |
| CN101906050A (en) * | 2010-06-07 | 2010-12-08 | 浙江华晟化学制品有限公司 | Preparation method of dimethyldiallylammonium chloride monomer |
| CN109438250A (en) * | 2018-12-20 | 2019-03-08 | 山东天成化工有限公司 | A kind of preparation method of high purity dimethyl diallyl ammonium chloride monomer high yield |
| WO2020140187A1 (en) * | 2018-12-20 | 2020-07-09 | 山东天成化工有限公司 | Method for preparing high purity dimethyl diallyl ammonium chloride monomer in high yield |
| CN114212869A (en) * | 2021-12-09 | 2022-03-22 | 苏州业华环境科技有限公司 | Preparation method of polycation polymer, compound oil removal agent and oil removal process |
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