CN1566166A - Process for preparing poly-diallyldimethyl ammonium chloride - Google Patents
Process for preparing poly-diallyldimethyl ammonium chloride Download PDFInfo
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- CN1566166A CN1566166A CN 03135199 CN03135199A CN1566166A CN 1566166 A CN1566166 A CN 1566166A CN 03135199 CN03135199 CN 03135199 CN 03135199 A CN03135199 A CN 03135199A CN 1566166 A CN1566166 A CN 1566166A
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Abstract
The invention relates to a process for preparing poly-diallyldimethyl ammonium chloride which comprises the steps of, (1) using alkali carbonate and complexing agent mixed solution as decontaminating agent for one time or multiple scouring to the allyl chloride, (2) dropping dimethylamine solution and alkali metal hydride solution into the allyl chloride solution, charging catalyst, (3) controlling the temperature between 40-70 deg. C, the reacting time being 2-4 hours, pumping water and low-boiling-point substance through decompression, obtaining DADMAC, (4) charging initiating agent into DADMAC solution, adjusting the pH value to 6, performing auto-polymerization at atmospheric temperature.
Description
Technical field
The present invention relates to the preparation method of Poly Dimethyl Diallyl Ammonium Chloride.
Background technology
Poly Dimethyl Diallyl Ammonium Chloride is a kind of very useful organic polyelectrolyte.It is unique synthetic polyelectrolyte that is allowed to do the tap water scavenging agent by U.S. F.H.S (Public Health Service), is also allowed to do the flocculation agent of preparation Food Contact with paper by U.S. F.D.A (FDA Food and Drug Administration).As seen it is a kind of eco-friendly chemical assistant.It can be used as water conditioner, paper making additive, dyeing and printing auxiliary, hair cosmetic composition auxiliary agent etc.Different Application Areass has different requirements to polymericular weight, and this just requires us can prepare high molecular weight polymers, and a cover molecular weight control technology is arranged, and the product that can produce various molecular weight is to satisfy different needs.
Poly Dimethyl Diallyl Ammonium Chloride (PDADMAC) is polymerized by cationic monomer diallyldimethylammonChloride Chloride.As everyone knows, some very micro-impurity will make monomeric polymerizing power be greatly affected, and prepare satisfied PDADMAC, and fine dimethyl diallyl ammonium chloride (DADMAC) must be arranged.Many scholars study this, Zheng Yan (a kind of preparation method of monomer of cathionic polymer, Chinese invention patent ZL99114784.7) propenyl chloride, dimethylamine and the sodium hydroxide of mole proportioning such as employing are raw material, press the single stage method synthesization of dimethyl diallyl ammonium chloride that alternately adds alkali and propenyl chloride with airtight low pressure, high temperature, band; Hou Shifa (the synthetic and polymerization studies of dimethyl diallyl ammonium chloride, Chengde Petroleum Higher Junior College's journal, 2002,4 (1), 4-6) with toluene be the organic phase solvent, dimethylamine and chlorallylene are raw material, adopt biliquid phase two step method to synthesize the solid dimethyl diallyl ammonium chloride, use the organic solvent isolation of intermediate products; Feng Yongcheng (organic polymer coargulator, Lanzhou Railway College's journal, 1996,15 (3), 59-63) in the monomer preparation and polymerization technique of Poly Dimethyl Diallyl Ammonium Chloride, adopt washing distillatory method to purify; Quan Yanmei (survey and polymerization studies by the synthetic mirror of dimethyl diallyl ammonium chloride, Xi'an shiyou University's journal, 1992,7 (1), 58-62) pH value, the filtration under diminished pressure by underpressure distillation, hierarchy of control temperature, pressure and solution, the method filtration dimethyl diallyl ammonium chloride of activated carbon decolorizing are proposed then.These methods all exist problems such as purification of raw materials is not enough, and loss is big, and temperature of reaction is too high, and side reaction control is ineffective, make quality product not good, and polymerizing power is relatively poor.
Dimethyl diallyl ammonium chloride (DADMAC) is to be prepared from the presence of sodium hydroxide by dimethylamine and propenyl chloride, and its reaction formula is as follows:
The purity of raw material propenyl chloride is very big to the influence of quality product, prepare high-quality DADMAC, and the reply propenyl chloride carries out purifying treatment.Propenyl chloride easily generates vinyl carbinol, allyl ether, hydrogenchloride and metal ion in producing, store, transporting, all unfavorable to the preparation of DADMAC.The boiling point of propenyl chloride is 44 ℃, and it is effective with the distillatory method propenyl chloride being purified.The shortcoming that rectification method purifies propenyl chloride is that energy consumption is big, workload is big, equipment is many, danger is big, loss big (about 10%), big for environment pollution.There was the human WATER-WASHING METHOD to purify propenyl chloride afterwards, better than distillation method, but general water is more, just can obtain satisfied result more than often will giving a baby a bath on the third day after its birth time, water resource waste is very big.
Summary of the invention
The object of the present invention is to provide the preparation method of Poly Dimethyl Diallyl Ammonium Chloride, this method raw material good washing effect, the reaction conditions gentleness is easy to control, finally can obtain high molecular weight polymers.
The preparation method of Poly Dimethyl Diallyl Ammonium Chloride may further comprise the steps successively:
(1) with alkaline carbonate, complexing agent mol ratio be 1～20: 1 mixing solutions as scavenging agent, the scavenging agent aqueous solution with 0.1～0.2% carries out the one or many washing to the raw material propenyl chloride;
(2) in propenyl chloride solution, drip dimethylamine solution and alkali hydroxide soln, raw material propenyl chloride: dimethylamine: the mol ratio of alkali metal hydroxide is 2.1: 1: 1, and the adding proper catalyst, catalyzer is that alkaline metal fluoride cpd and efficient complexing agent mol ratio are 50: 1～1: 20 mixing solutions;
(3) controlled temperature is at 40～70 ℃, and in 2～4 hours reaction times, a certain amount of water and low boilers are extracted in decompression out then, obtain DADMAC;
(4) in the DADMAC solution that makes, add an amount of initiator, transferring PH is about 6, and normal temperature is placed down, promptly can autopolymerization becomes the high-molecular weight homopolymer of dimethyl diallyl ammonium chloride.
Among the present invention, the propenyl chloride scavenging agent is with the alkaline carbonate and the formulated aqueous solution of complexing agent, alkaline carbonate can be used yellow soda ash, mainly be hydrogenchloride and the metal ion of removing in the raw material propenyl chloride, complexing agent can be used EDTA, remove the metal ion in the raw material propenyl chloride, all can reach decontamination effect improving on arbitrary proportionality principle of alkaline carbonate and complexing agent, but the molar ratio range of using alkaline carbonate and complexing agent is that the decontaminant solutions effect of 1～20: 1 configuration is preferable, and wherein 1～10: 1 effect reaches best.Clean in the water at propenyl chloride, the dosage of scavenging agent is 0.1～0.2%.
The raw materials used dimethylamine of preparation DADMAC is generally 40% and can directly uses.Used alkali metal hydroxide generally uses sodium hydroxide, can buy ion film caustic soda, is mixed with 40% solution use.The mol ratio propenyl chloride of raw material: dimethylamine: sodium hydroxide=2.1: 1: 1, propenyl chloride are excessive slightly, can prevent the generation of many side reactions, and because its wetting ability is little, is easy to by heating, vacuumizes, and remove from the finished product, can guarantee quality product.
Be reflected in the conventional closed reaction kettle and carry out.In the propenyl chloride behind water washing cleaning, under agitation splash into dimethylamine and sodium hydroxide solution, but the pH value of guarantee system is near neutral, big variation can't take place, add proper catalyst simultaneously, controlled temperature is at 40～70 ℃, 2～4 hours reaction times, can progressively heat up, a certain amount of water and low-boiling by-products are extracted in decompression out, and the DADMAC concentration that obtains reaches about 60%.
Reaction is that alkaline metal fluoride cpd and efficient complexing agent molar ratio range are 50: 1～1: 20 mixing solutions with catalyzer, and wherein alkaline metal fluoride cpd is that 5～15: 1 o'clock effect is preferable with efficient complexing agent mol ratio, is 9: 1 o'clock best results.What alkaline metal fluoride cpd was commonly used is Sodium Fluoride or Potassium monofluoride, the most handy diethylene triamine pentacetic acid (DTPA) salt of complexing agent, and the also available EDTA of complexing agent, but effect is less better.
Reaction is if can carry out under nitrogen protection, and then quality product can be more better.
The adding of catalyzer can not only be quickened quaterisation, and can increase the polymerizing power of finished product.Can cause with initiator system commonly used when using the DADMAC polymerization that the present invention makes, as all reaching result preferably with persulfate initiator, redox initiator or azo initiator.
Compared with prior art, the present invention has following beneficial effect:
(1) with the scavenging agent aqueous solution of the present invention propenyl chloride is washed, generally wash secondary, can obtain purified propenyl chloride, improved clean efficient, saved energy consumption and water, protected environment;
(2) be raw material by purified propenyl chloride, prepared high-quality DADMAC, use it in the polymer manufacture, can reach the purpose of effective raising and control molecular weight;
(3) the present invention adopts alkali metal hydroxide and dimethylamine is splashed into method in the propenyl chloride, big variation can't take place near neutral in the pH value that has guaranteed system, and used propenyl chloride surpasses stoichiometry slightly, can prevent the generation of many side reactions, also easily after reaction is finished, remove;
(4) be configured to catalyzer with alkaline metal fluoride cpd solution and efficient enveloping agent solution, the adding of catalyzer can not only be quickened quaterisation, and can increase the polymerizing power of finished product.Can cause with initiator system commonly used when using the DADMAC polymerization that the present invention makes, all can reach effect preferably;
(5) reaction conditions gentleness of the present invention is easy to control, finally can obtain high molecular weight polymers.
Embodiment
Below by embodiment, further specify the present invention.
Embodiment 1
245Kg industry propenyl chloride is put in the reactor, adds the water 50Kg that contains scavenging agent 50g, scavenging agent is 4%Na
2CO
3, 4%EDTA-2Na balanced mix solution (mol ratio is 3.5: 1), the dosage of scavenging agent in water is 0.1%, mixes half an hour, the clarification layering after, put the layer that anhydrates.If the interface is dirtier, then wash once more as stated above.
Fluorinse with 4% and 4% diethylene triamine pentacetic acid (DTPA) sodium solution balanced mix (mol ratio is 9.4: 1) are configured to catalyzer.
With adding catalyzer 100g in the dimethylamine agueous solution of 168.8Kg40%, under the normal temperature, in propenyl chloride, splash into the NaOH aqueous solution 150Kg of dimethylamine and 40%, in whole dropping process, under nitrogen protection, constantly stir, top temperature is no more than 45 ℃.After being added dropwise to complete, be warming up to 50～60 ℃ of reactions 2 hours, 70 ℃ were reacted 1 hour, and decompression is extracted out based on the about 76Kg of the mixture of water, and the about 80Kg of elimination NaCl obtains 60% DADMAC 407.8Kg.
Embodiment 2
Get the above DADMAC 25Kg that makes, add pure water 5Kg and stir evenly, add initiator A PS 5g (be made into 20% the aqueous solution), normal temperature is placed down, and along with the carrying out of polyreaction, system temperature rises gradually, keeping polymerization temperature is 50 ℃ after 10 hours, makes heavy-gravity PDADMAC solution.Recording limiting viscosity with the sodium-chlor of 0.5M as solvent is 1.24, presses η
∞=3.982 * 10
-4M
0.566Calculate M=1.49 * 10
6
Claims (8)
- The preparation method of 1 Poly Dimethyl Diallyl Ammonium Chloride may further comprise the steps successively:(1) with alkaline carbonate, complexing agent mol ratio be 1～20: 1 mixing solutions as scavenging agent, the scavenging agent aqueous solution with 0.1～0.2% carries out the one or many washing to the raw material propenyl chloride;(2) in propenyl chloride solution, drip dimethylamine solution and alkali hydroxide soln, raw material propenyl chloride: dimethylamine: the mol ratio of alkali metal hydroxide is 2.1: 1: 1, and the adding proper catalyst, catalyzer is that alkaline metal fluoride cpd and efficient complexing agent mol ratio are 50: 1～1: 20 mixing solutions;(3) controlled temperature is at 40～70 ℃, and in 2～4 hours reaction times, a certain amount of water and low boilers are extracted in decompression out then, obtain DADMAC;(4) in the DADMAC solution that makes, add an amount of initiator, transferring PH is about 6, and normal temperature is placed down, promptly can autopolymerization becomes the high-molecular weight homopolymer of dimethyl diallyl ammonium chloride.
- 2 the method for claim 1 is characterized in that, alkaline carbonate is a yellow soda ash in the scavenging agent of step (1), and complexing agent is EDTA.
- 3 the method for claim 1 is characterized in that, the mol ratio of alkaline carbonate and complexing agent is 1～10: 1 in the scavenging agent of step (1).
- 4 the method for claim 1 is characterized in that, the alkali metal hydroxide of step (2) is a sodium hydroxide.
- 5 the method for claim 1 is characterized in that, in the catalyzer of step (2), alkaline metal fluoride cpd is Sodium Fluoride or Potassium monofluoride, and complexing agent is diethylene triamine pentacetic acid (DTPA) salt or EDTA.
- 6 the method for claim 1 is characterized in that, in the catalyzer of step (2), alkaline metal fluoride cpd is 5～15: 1 with efficient complexing agent mol ratio.
- 7 methods as claimed in claim 6 is characterized in that, in the catalyzer of step (2), alkaline metal fluoride cpd is 9: 1 with efficient complexing agent mol ratio.
- 8 the method for claim 1 is characterized in that, the initiator of step (4) is persulfate initiator, redox initiator or azo initiator.
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| CN 03135199 CN1243775C (en) | 2003-06-16 | 2003-06-16 | Process for preparing poly-diallyldimethyl ammonium chloride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357501C (en) * | 2006-04-21 | 2007-12-26 | 北京科技大学 | Poly-diallyldimethyl ammonium chloride single-chain single crystal and method for preparing same |
| CN101891854A (en) * | 2010-07-05 | 2010-11-24 | 南京理工大学 | Relative molecular mass controlled polyquaternium color fixing agent and synthesizing method thereof |
| CN102628237A (en) * | 2012-04-06 | 2012-08-08 | 无锡德冠生物科技有限公司 | Reactive dye color fixing agent and production method thereof |
| CN102924285A (en) * | 2012-11-01 | 2013-02-13 | 江苏富淼科技股份有限公司 | Preparation method of dimethyldiallylammonium chloride |
| CN106190077A (en) * | 2016-07-11 | 2016-12-07 | 工合聚能(天津)石油精化科技发展有限公司 | Heavy oil component deposit solution dirt agent and preparation method thereof |
| CN109535295A (en) * | 2018-11-13 | 2019-03-29 | 深圳市点石源水处理技术有限公司 | A kind of line style polydimethyl diallyl ammonium chloride and preparation method thereof |
-
2003
- 2003-06-16 CN CN 03135199 patent/CN1243775C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357501C (en) * | 2006-04-21 | 2007-12-26 | 北京科技大学 | Poly-diallyldimethyl ammonium chloride single-chain single crystal and method for preparing same |
| CN101891854A (en) * | 2010-07-05 | 2010-11-24 | 南京理工大学 | Relative molecular mass controlled polyquaternium color fixing agent and synthesizing method thereof |
| CN101891854B (en) * | 2010-07-05 | 2011-12-21 | 南京理工大学 | Relative molecular mass controlled polyquaternium color fixing agent and synthesizing method thereof |
| CN102628237A (en) * | 2012-04-06 | 2012-08-08 | 无锡德冠生物科技有限公司 | Reactive dye color fixing agent and production method thereof |
| CN102924285A (en) * | 2012-11-01 | 2013-02-13 | 江苏富淼科技股份有限公司 | Preparation method of dimethyldiallylammonium chloride |
| CN102924285B (en) * | 2012-11-01 | 2013-11-20 | 江苏富淼科技股份有限公司 | Preparation method of dimethyldiallylammonium chloride |
| CN106190077A (en) * | 2016-07-11 | 2016-12-07 | 工合聚能(天津)石油精化科技发展有限公司 | Heavy oil component deposit solution dirt agent and preparation method thereof |
| CN106190077B (en) * | 2016-07-11 | 2019-01-15 | 工合聚能(天津)石油精化科技发展有限公司 | Heavy oil component deposit solution dirt agent and preparation method thereof |
| CN109535295A (en) * | 2018-11-13 | 2019-03-29 | 深圳市点石源水处理技术有限公司 | A kind of line style polydimethyl diallyl ammonium chloride and preparation method thereof |
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| CN1243775C (en) | 2006-03-01 |
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