CN1323064C - Refining method of high-purity cationic monomer dimethyl diallyl ammonium chloride - Google Patents
Refining method of high-purity cationic monomer dimethyl diallyl ammonium chloride Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 54
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 42
- 238000007670 refining Methods 0.000 title abstract description 18
- 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 title abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000012535 impurity Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011780 sodium chloride Substances 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 27
- 238000004821 distillation Methods 0.000 claims description 23
- -1 amine hydrochloride Chemical class 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 19
- 238000000746 purification Methods 0.000 claims description 18
- 230000006837 decompression Effects 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000011552 falling film Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 26
- 239000003513 alkali Substances 0.000 abstract description 6
- 238000004587 chromatography analysis Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000004042 decolorization Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 20
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 14
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 13
- 150000003512 tertiary amines Chemical class 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- BNARKQIAPXUTGS-UHFFFAOYSA-N [Cl-].Cl[NH+](C)C.[Na] Chemical compound [Cl-].Cl[NH+](C)C.[Na] BNARKQIAPXUTGS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- OWXJKYNZGFSVRC-UHFFFAOYSA-N 1-chloroprop-1-ene Chemical group CC=CCl OWXJKYNZGFSVRC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- BXFZQOORJWHJHA-UHFFFAOYSA-N ClC=CC.CNC Chemical compound ClC=CC.CNC BXFZQOORJWHJHA-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
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- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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Abstract
The present invention relates to a method for refining cationic monomer dimethyl diallyl ammonium chloride with high purity. A chromatographic analysis method is adopted to analyze and measure the compositions and the content of various highly volatile and non-volatile impurities in cationic monomer solution to be prepared, the cationic monomer solution is added into a container, and solution of sodium hydroxide as industrial alkali is added under the cooling and stirring condition to free and release amine substances. Water is added to make monomer content in the solution between 35% and 55%, and the solution is distilled by pressure reduction under negative pressure within two temperature ranges. Steam distilled by pressure reduction is absorbed by water to be recycled, and reaction liquid is decompressed or centrifugally filtered to remove precipitated NaCl crystals. Water is added into filtered liquid to regulate the monomer content in the monomer solution, a small amount of activated carbon is added for decolorization, and the activated carbon is removed through filtration to obtain solution of cationic monomer products with small impurity content and high purity. The method of the present invention has the advantages that impurities and the content thereof are specific, so that the phenomena of using various indicators, leading in new impurities and adding excess alkali are avoided; the product purity is high.
Description
One technical field
The present invention relates to the synthetic process for purification of a kind of polymkeric substance with cation quaternary ammonium salt monomeric process for purification, particularly a kind of high purity cationic monomer diallyldimethylammonChloride Chloride.
Two background technologies
Dimethyl diallyl ammonium chloride (Dimethyldiallylammonium Chloride is called for short DMDAAC) is a kind of cationic quaternary ammonium salt monomer that can be used for polyreaction, and its structural formula is as follows:
DMDAAC is a kind of water-soluble fabulous, contains the quaternary ammonium salt of two unsaturated double-bonds, is white needle-like crystals, and fusing point is 146～147 ℃, and easily the moisture absorption is the aqueous solution in air.Therefore, this compound is many preserves with aqueous solution form.Because its electric density height, good water solubility, acid and alkali-resistance, characteristics such as nontoxic, itself and homopolymerization thereof and multipolymer are widely used in oil production, paper industry, textile printing and dyeing, sewage disposal, sludge dewatering and household chemicals field.Yet, no matter directly used as cation quaternary ammonium salt, still be applied as polymerization reaction monomer, the height of its purity or impurities content is most important, influences the important indicator of its range of application and application cost.
The expression formula of DMDAAC building-up reactions is as follows:
Reactive tertiary amine:
Dimethylamine propenyl chloride (DMAA) tertiary amine dimethylamine hydrochloride
Neutralization reaction, tertiary amine reaction: (formula 2)
(formula 3)
Quaterisation:
(formula 4)
DMDAAC
Its main side reaction has:
Salt-forming reaction:
(formula 5)
Amine from Tertiary Amine Hydrochloride
Hydrolysis reaction:
(formula 6)
Vinyl carbinol
Oxidizing reaction:
(formula 7)
Allyl aldehyde
Single stage method is in the aqueous solution of dimethylamine, propenyl chloride and sodium hydroxide, and the collection polystep reaction is an one, directly prepares the method for making of DMDAAC.Reaction solution is removed the sodium chloride of separating out after filtration, and purifying through distillation to obtain the DMDAAC aqueous solution or its crystal product again.It is simple and safe that one-step technology has technology, and the productive rate height is produced and purification process does not need usefulness organic solvent, characteristics that " three wastes " are few.But because polystep reaction is carried out simultaneously, cause side reaction increase (formula 2, formula 5～formula 7) in the process, impurity level is many in the product, and the reactive behavior when making it as polymer monomer is low.Major ingredient that it is generally acknowledged its impurity is unreacted raw material, intermediate and a by product completely.For example, dimethylamine (or its salt), tertiary amine (or its salt), propenyl chloride, vinyl carbinol, allyl aldehyde, sodium-chlor etc.
Usually adopt dual mode to solve this problem in the prior art: the one, the control by synthetic technological condition, make reaction process more reasonable, reduce the formation amount of impurity such as by product in the preparation process: the 2nd, the synthetic crude product that obtains is purified, as underpressure distillation, remove volatile impurity, activated carbon decolorizing is removed difficult evaporable impurity.For example: document 1 (Jeery E.Boothe, Synthesis of Dimethyldiallylammonium Chloride, US 3 461 163,1969), prepare in the DMDAAC process, by reducing temperature of reaction to 10 ℃ in single stage method, and notice if will obtain the highly purified DMDAAC aqueous solution, should make reaction process keep neutral, need control sodium hydroxide and dimethylamine, reduce the generation of impurity such as by product vinyl carbinol the propenyl chloride competing reaction.For this reason, adopted at low temperatures earlier by waiting amount of substance, again with the method that alternately adds 50% sodium hydroxide and propenyl chloride than adding the reaction of propenyl chloride and dimethylamine.In the end add after the remaining propenyl chloride, be warmed up to 45 ℃ again, reaction 6.5h makes system be in nearly neutrality, and finishes quaterisation under the lesser temps, has prevented that high temperature is down because the too high product decomposition that may cause of pH value.Products therefrom obtains the finished product DMDAAC aqueous solution through underpressure distillation and adding activated carbon decolorizing.Document 2 (Jeery E.Boothe, Process for Parifying Dialkyl Diallylammonium Chloride and DiallylDimethallylammonium Chloride, US 3 472 740,1969) then further propose to through the cationic monomer DMDAAC of underpressure distillation and activated carbon decolorizing solution after adding accounts for the total scale of construction 0.04% phenolphthalein indicator, the NaOH aqueous solution with 5% is regulated pH=10.5～11.5, under 110 ℃, carry and heat up in a steamer (distillation) with water vapor under pressurization or the normal pressure to remove impurity, up to distillate liquation penetrate index constant till, obtain peach liquid, after after cooling off, being filled with the gac pillar of 300g excessively, remove gac with filter method again.It is high purity that the monomer DMDAAC aqueous solution of handling by above-mentioned document 2 methods has obviously more original document 1 method get DMDAAC.With the monomer polymerization reactions performance is example: the solution of content 60%, 231g (about 0.5mol) monomer DMDAAC, regulate pH value to 6.5, and be warming up to 80 ℃.Under nitrogen protection, with a certain amount of (NH
4)
2S
2O
8Initiator initiation reaction 100min, again 80 ℃ the reaction 0.5h obtain its homopolymer.This homopolymer 5% and 10% viscosity in aqueous solution are respectively 6.0cps (centipoise) and 390cps, and the viscosity of the homopolymerization product that obtains by the cationic monomer DMDAAC polymerization under the same conditions that document 1 method obtains only is 3.2cps and 20cps.Chromatography analysis shows have the kurtosis of a unknown material obviously to remove by refining the making in original cationic monomer DMDAAC solution of document 2 methods.Document 3 (Nippon Kayaku Co., Ltd., Japan, Diallyldimethylammonium Chloride and its Polymer.JP 5,601 6448,1981), adopt and add propenyl chloride 820g among the 50% dimethylamine agueous solution 900g (wherein methylamine content is less than 240mg/kg), 0 ℃ down reinforced, and propenyl chloride is about 1/3 adding, behind the time 1h, begin the parallel adding 50%NaOH aqueous solution (10.7mol), add with 2h again.React 16h down at 36～45 ℃, products therefrom water steam stripping 1h, obtaining cationic monomer DMDAAC content through decolorizing with activated carbon is 70%, the aqueous solution of 2188g.This monomeric products can get its homopolymerization product with the tert-butyl peroxide initiation under 40 ℃.During 20 ℃ of this homopolymerization products, 0.5% content viscosity in aqueous solution promptly reaches 180cps, and its intrinsic viscosity is 2.8dL/g (30 ℃ are measured in the 5%NaCl aqueous solution, calculates).
Document 4 (Quan Yanmei etc.; the synthetic discriminating and the research of dimethyl diallyl ammonium chloride; the Xi'an petroleum journal; 1992; 7 (1): 58～60) developed a kind of disposable reinforced single stage method; under sealing, protection of inert gas and pressurized conditions, less than 60 ℃, the method for reaction 30h prepares DMDAAC.Reaction finishes to remove by filter NaCl, adds less water, underpressure distillation to distillate water be in the pure water analyse the light rate or pH reaches 7, remove by filter the NaCl that separates out, obtain cationic monomer product D MDAAC solution with decolorizing with activated carbon.Document 5 (Zheng Yan, the monomeric preparation method of a kind of cationoid polymerisation, CN 1243 88A, 1999), developed a kind of in reactor after amount propenyl chloride such as adding earlier and the dimethylamine, in 65～85 ℃, 0.2MPa under the pressure, alternately add propenyl chloride and sodium hydroxide, 4～5h finishes reaction.NaCl is removed in the underpressure distillation of products therefrom warp-0.08MPa pressure under 55～65 ℃, and obtains the product D MDAAC aqueous solution.Document 6 (Zhao Huazhang etc., synthetic and the analysis of cationic polymer flocculent PDMDAAC and P (DMDAAC-AM), fine chemistry industry, 2001,18 (11): 645) adopt less than under 20 ℃ of conditions, control pH value is 9.5～10.5, drip chloro propylene and sodium hydroxide in dimethylamine agueous solution, and back flow reaction is to finishing reaction then.After the reaction solution that obtains separates NaCl, remove NaCl that impurity and leaching separates out etc. by decompression (vacuum) distillation again, gained DMDAAC product monomer solution in 40 ℃ with the initiator initiated polymerization inclusive NAND ion monomer acrylamide copolymerization 8h that accounts for monomer mass 1%, obtain homopolymer PDMDAAC and cationic degree respectively and be 10% copolymer p (DMDAAC-AM), its intrinsic viscosity value is respectively 1.96dL/g (having used hexanol and acetone recrystallization flush away small molecules) and 9.26dL/g (under 30 ℃, measuring in the 1MNaCl aqueous solution).
Among the cationic monomer DMDAAC for preparing by single stage method, have the formation of impurity such as by product.Thereby, not only in preparation technology, adopt the parameters such as pH value of feed ratio, feed way, temperature of reaction and medium are controlled and reduce the by product generation, but also rough cation mono liquid solution is carried out underpressure distillation, activated carbon decolorizing, perhaps add and make with extra care monomer with the method for high-temperature water vapor profit reduction and reserving after alkali is regulated the pH value, by removing the purity that impurity improves cationic monomer DMDAAC solution.Yet the various all process for purification that propose to reduce impurity in the monomer DMDAAC product up to now are empirical data, lack correct theoretical direction and reasonably analytical procedure support, thereby the major defect that these process for purification exist are:
1. for the cationic monomer DMDAAC solution that makes by single stage method, though through the volatile impurity in simple underpressure distillation part that can be removed, remove part NaCl by dewatering and filtering, remove most of coloring matter through activated carbon decolorizing, but most unreacted difficult volatilizations and water-soluble fabulous impurity.As: salts substances, the tertiary amine that the aqueous solution is good, vinyl carbinol can't effectively be removed, as document 1, document 4, document 5 and document 6; Retain a percentage of the total profits for the enterprise's own use some unknown impuritie that to remove in the ion monomer DMDAAC solution that makes by single stage method though 2. notice the pressurization back with the high-temperature water vapor of normal pressure and pressurization, improved the polyreaction performance of cationic monomer DMDAAC, but, the pH value is that peralkaline ambient condition of 10.5～11.5 and 110 ℃ of high-temperature water vapors are carried heating up in a steamer and may be caused new side reaction: the decomposition of monomeric quaternary ammonium salt or the generation of autohemagglutination, as document 2, document 3; 3. except by removing by filter a certain amount of NaCl that separates out and reducing the colourity by activated carbon decolorizing, existing various process for refining and purifying can not provide explanation and and guide process for refining to improve to the changing conditions of the various impurity in the cationic monomer DMDAAC product water solution before and after refining, as document 1～6 etc., and only be by monomer DMDAAC before and after refining being participated in the relative molecular mass or the polymerization degree that reaction obtains homopolymer and multipolymer, characterize size, the effect of coming the comparison process for purification with viscosity under the certain temperature and intrinsic viscosity.For example document 2, document 3, document 6.Above-mentioned many disadvantages has caused by existing various one-step preparation process and has been difficult to obtain high purity and stay-in-grade cationic monomer DMDAAC product.
Three summary of the invention
The object of the present invention is to provide that a kind of technology is simple, running cost is low, do not have " three wastes " substantially, the product purity height, quality index is clear and definite, the process for purification of stay-in-grade high purity cationic monomer diallyldimethylammonChloride Chloride.
The technical solution that realizes the object of the invention is: a kind of process for purification of high purity cationic monomer diallyldimethylammonChloride Chloride is characterized in that technical process and operational condition carry out as follows:
1. the chromatographically method is analyzed the composition and the content of various impurity in the cationic monomer diallyldimethylammonChloride Chloride solution that is made by single stage method, records various volatile and difficult volatilization impurity components and content;
2. in still kettle or falling-film evaporator, add cationic monomer diallyldimethylammonChloride Chloride solution, content according to the amine hydrochloride that records, by the amine hydrochloride: the amount of substance ratio of sodium hydroxide is 1.00: 0.90～1.00, adds the industrial soda sodium hydroxide solution with the free amine substance that discharges under cooling and stirring;
3. add the water account for monomer mass 1/6～1/2 and make that monomer content is 35%～55% in the solution, and be lower than under the 0.090MPa pressure, carry out underpressure distillation 0.5～3.5h 40 ± 5 ℃ and 60 ± 5 ℃ of two temperature ranges respectively, each goes on foot equal underpressure distillation and arrives till the no obvious distillate, and the steam that decompression steams absorbs reuse through water;
4. reaction solution is removed the crystal NaCl that separates out through decompression or centrifuging;
5. the content that adds monomer diallyldimethylammonChloride Chloride in the water adjusting monomer solution in the filtrate is 60 ± 5%, and add the small amount of activated processing of decolouring, remove by filter gac, it is few to obtain foreign matter content, the cationic monomer diallyldimethylammonChloride Chloride product solution that purity is high.
The present invention compared with prior art, its remarkable advantage is: 1, use chromatogram analysis method, various volatile impurity dimethylamine possible in the cationic monomer DMDAAC product solution, tertiary amine, vinyl carbinol, propenyl chloride, allyl aldehyde and difficult volatilization impurity NaCl, Amine from Tertiary Amine Hydrochloride, dimethylamine hydrochloride etc. are carried out quantitative analysis, as the foundation of purification, overcome in the prior art impurity object and the inapt defective of its content; 2, the amine hydrochloride content that obtains by analysis, the amount of the industrial soda sodium hydroxide that design adds, make the amine hydrochloride amine that dissociates become volatile impurity, make it to be easy to quantitatively remove, avoided introducing and adding the appearance of base excess situation with adding phenolphthalein indicator and adding new impurity that the alkali terminal point causes with the indication of pH value by underpressure distillation; 3, by adding water, add diluted alkaline, the method of stepwise procedure intensification underpressure distillation and underpressure distillation under relatively lower temp, remove various volatile impurity and add volatile amine substance dimethylamine and the tertiary amine that dissociates out after the alkaline purification, avoided under the alkaline condition, occur partial over-alkali during pyrogenic distillation in monomer solution, the too high side reaction that causes of temperature takes place---decomposition and the autohemagglutination inactivation of cationic quaternary ammonium salt monomer DMDAAC; 4, by adding the NaCl that alkali generates, concentrate by underpressure distillation and separate out, remove by filter.Filtrate is removed the difficulty volatilization impurity that may form in the treating process with the activated carbon decolorizing processing and is further purified; 5, obtain by process for purification of the present invention that dopant species and content can be characterized by the stratographic analysis result in the cationic monomer DMDAAC product solution, and can with refining before the situation ratio of opposing; The polymerization activity of refining back monomer solution can be by (massfraction is 65% monomer solution, by (the NH that accounts for monomer mass 0.5% under the same terms
4)
2S
2O
8Initiator is in 50 ℃ of initiation reaction 9h) the relative molecular mass size (by the intrinsic viscosity value representation) of the polymerisate Poly Dimethyl Diallyl Ammonium Chloride of cationic monomer DMDAAC (Poly-DMDAAC is called for short PDMDAAC) contrasts.Specifically see Table 1.
Foreign matter content and polymerization activity before and after table 1 cationic monomer is refining
| Sequence number | Impurity/(mgkg -1) | Product intrinsic viscosity/(dlg -1) | |||||||
| Propenyl chloride | Dimethylamine | Vinyl carbinol | Allyl aldehyde | Tertiary amine | NaCl | Tertiary ammonium salt | Dimethylamine salt | PDMDAAC | |
| 1 refining before | 10～50 | 10～100 | 100～ 500 | 0～10 | 3000 ～10000 | 80000 ～100000 | 10000 ～35000 | 1000 ～4000 | 1.0 |
| 2 refining after | - | - | - | - | - | 400～ 3000 | 10～100 | 10～ 1500 | ＞2.9 |
Annotate: 1. "-" expression does not detect, and detects to be limited to 1mg/kg (down together);
2. the product intrinsic viscosity is in 30 ± 0.1 ℃, and one-point method is measured and calculated (down together) among the 1MNaCl.
Four description of drawings
Accompanying drawing is the process flow diagram of high purity cationic monomer diallyldimethylammonChloride Chloride process for purification of the present invention.
Five embodiments
Below in conjunction with accompanying drawing the present invention is described in further detail.
Embodiment 1.
In conjunction with the accompanying drawings, the process for purification of high purity cationic monomer diallyldimethylammonChloride Chloride of the present invention is concrete
Embodiment is:
The first step, composition and the content for the treatment of various impurity in the purified cationic monomer DMDAAC aqueous solution that the systems analysis of chromatographically method is made by one-step technology, its contained volatile and difficult fugitive constituent impurity are respectively dimethylamine, propenyl chloride, vinyl carbinol, allyl aldehyde and sodium-chlor, dimethylamine hydrochloride, the corresponding content of Amine from Tertiary Amine Hydrochloride sees Table 2.
Second step, in 120L still kettle or 200L falling-film evaporator, add and treat that purified content is 60% single stage method monomer DMDAAC solution A 50kg, the total amount of the amine hydrochloride (dimethylamine hydrochloride, Amine from Tertiary Amine Hydrochloride) that obtains according to chromatography analysis is 0.87 (7.66mol), by the amine hydrochloride: the ratio of the amount of substance of sodium hydroxide is 1.00: 1.00～0.99, adds content and be 8.0% NaOH aqueous solution 3.79kg (7.58mol) under cooling and stirring.
The 3rd step added entry 15.0kg, and under-0.098MPa pressure, at 40 ± 5 ℃ and 60 ± 5 ℃ of each underpressure distillation 1.5～2.5h, per step all is distilled to till the no obvious distillate respectively.The tail gas that underpressure distillation goes out absorbs through water and reclaims.
The 4th step: monomer solution is removed the crystal NaCl that separates out through decompress filter or centrifuging.
The 5th step: solution adds water, and to be adjusted to monomer content be (60 ± 5) %, and add the activated carbon decolorizing processing less than monomer mass 1%.Treatment temp is 45～65 ℃, and the time is 0.5～1.5h.Decompress filter removes by filter gac, obtains high purity cationic monomer DMDAAC product solution, and its impurities sees Table 2.
Foreign matter content variation in the monomer DMDAAC solution before and after table 2 is refining
| Sequence number | Impurity/(mgkg -1) | |||||||
| Propenyl chloride | Dimethylamine | Vinyl carbinol | Allyl aldehyde | Tertiary amine | NaCl | Tertiary ammonium salt | Dimethylamine salt | |
| 1 refining before | 50 | 80 | 100 | 10 | 300 | 80000 | 14900 | 2500 |
| 2 refining after | - | - | - | - | - | 2000 | 280 | - |
Embodiment 2.
In conjunction with the accompanying drawings, the embodiment of the process for purification of high-purity cationic monomer dimethyl diallyl ammonium chloride of the present invention is:
The first step, the systems analysis of chromatographically method is treated various impurity components and content among the purified cationic monomer DMDAAC aqueous solution B by what one-step technology made, its contained volatile and difficult fugitive constituent impurity is respectively: dimethylamine, propenyl chloride, vinyl carbinol, allyl aldehyde and sodium-chlor, dimethylamine hydrochloride, Amine from Tertiary Amine Hydrochloride, its content sees the following form 3.
Second step, in 120L still kettle or 200L falling-film evaporator, add and treat that purified content is 65% single stage method monomer DMDAAC solution B 50kg, the total amount of the hydrochloride (dimethylamine hydrochloride, Amine from Tertiary Amine Hydrochloride) of the amine that obtains according to chromatography analysis is 1.35kg (11.81mol), hydrochloride by amine: the ratio of the amount of sodium hydroxide is 1.00: 1.00, under cooling conditions, adding content is 6.0% NaOH aqueous solution 7.87kg (11.81mol).
The 3rd step added entry 12.0kg, and under-0.099MPa pressure in two steps respectively at 45 ± 5 ℃ and 60 ± 5 ℃ of each underpressure distillation 2.5～3.5h, each step all is distilled to till the no obvious distillate, the tail gas of underpressure distillation is through the reuse of water absorption confession building-up reactions.
In the 4th step, monomer solution is removed the crystal NaCl that separates out through decompress filter or centrifuging.
The 5th step, filtrate adds water, and to be adjusted to monomer content be (60 ± 5) %, and adding is handled less than the activated carbon decolorizing of monomer mass 1%, treatment temp is 60 ± 5 ℃, time is 0.5～1.5h, gac is removed in decompress filter or centrifugation, obtains high purity cationic monomer DMDAAC product solution, and its impurities amount sees Table 3.
Foreign matter content variation in the monomer DMDAAC solution before and after table 3 is refining
| Sequence number | Foreign matter content/(mgkg -1) | |||||||
| Propenyl chloride | Dimethylamine | Vinyl carbinol | Allyl aldehyde | Tertiary amine | NaCl | Tertiary ammonium salt | Dimethylamine salt | |
| 1 refining before | - | - | - | - | 600 | 2000 | 23500 | 3500 |
| 2 refining after | - | - | - | - | - | 2000 | 20 | - |
Claims (3)
1, a kind of process for purification of high purity cationic monomer diallyldimethylammonChloride Chloride is characterized in that technical process and operational condition carry out as follows:
1.1 the chromatographically method is analyzed the composition and the content of various impurity in the cationic monomer diallyldimethylammonChloride Chloride solution that is made by single stage method, records various volatile and difficult volatilization impurity components and content;
1.2 in still kettle or falling-film evaporator, add cationic monomer diallyldimethylammonChloride Chloride solution, content according to the amine hydrochloride that records, by the amine hydrochloride: the amount of substance ratio of sodium hydroxide is 1.00: 0.90～1.00, adds the industrial soda sodium hydroxide solution with the free amine substance that discharges under cooling and stirring;
Make that monomer content is 35%～55% in the solution 1.3 add the water account for monomer mass 1/6～1/2, and be lower than-0.090MPa pressure under, carry out underpressure distillation 0.5～3.5h 40 ± 5 ℃ and 60 ± 5 ℃ of two temperature ranges respectively, each goes on foot equal underpressure distillation and arrives till the no obvious distillate, and the steam that decompression steams absorbs reuse through water;
1.4 reaction solution is removed the crystal NaCl that separates out through decompression or centrifuging;
1.5 adding the content of monomer diallyldimethylammonChloride Chloride in the water adjusting monomer solution in the filtrate is 60 ± 5%, and add the small amount of activated processing of decolouring, remove by filter gac, it is few to obtain foreign matter content, the cationic monomer diallyldimethylammonChloride Chloride product solution that purity is high.
2, the process for purification of high purity cationic monomer diallyldimethylammonChloride Chloride according to claim 1 is characterized in that: wherein step 1.2 is that to add content under cooling and stirring be that 4%～32% industrial soda sodium hydroxide solution is with the free amine substance that discharges.
3, the process for purification of high purity cationic monomer diallyldimethylammonChloride Chloride according to claim 1 and 2, it is characterized in that: wherein step 1.5 is to add the processing of decolouring of gac less than monomer solution quality 1%, treatment temp is 45 ℃～65 ℃, time is 0.5～1.5h, remove by filter gac, it is few to obtain foreign matter content, the cationic monomer diallyldimethylammonChloride Chloride product solution that purity is high.
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| CNB2004101030782A CN1323064C (en) | 2004-12-31 | 2004-12-31 | Refining method of high-purity cationic monomer dimethyl diallyl ammonium chloride |
| PCT/CN2005/000614 WO2006069504A1 (en) | 2004-12-31 | 2005-04-30 | A purification method for the cationic monomer of dimethyldiallylammonium chloride with high purity |
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| CN101993380B (en) * | 2009-08-11 | 2013-05-01 | 兆联实业股份有限公司 | Recovery equipment and method thereof for tetramethylammonium hydroxide |
| 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 |
| 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 |
| CN102993028B (en) * | 2012-12-26 | 2014-07-30 | 四川康庄生物化工有限责任公司 | Purifying method of dimethyl diallyl ammonium chloride monomer |
| CN103463956B (en) * | 2013-09-16 | 2015-06-17 | 张家港市金源生物化工有限公司 | Recycling method of n-propylamine tail gas |
| CN106526049A (en) * | 2015-09-09 | 2017-03-22 | 南京理工大学 | Accurate detection method of organic impurities in dimethyl diallyl ammonium chloride monomer |
| CN106518689B (en) * | 2015-09-09 | 2019-01-18 | 南京理工大学 | A kind of preparation method of high purity dimethyl diallyl ammonium chloride monomer |
| CN112266083B (en) * | 2020-10-10 | 2022-08-19 | 南京理工大学 | Method for reducing formaldehyde contained in industrial monomer dimethyl diallyl ammonium chloride |
| CN114225864B (en) * | 2021-12-16 | 2024-04-26 | 江苏富淼科技股份有限公司 | Method and device for decoloring green-emitting dimethyl diallyl ammonium chloride |
| CN114456075B (en) * | 2022-02-22 | 2023-05-23 | 山东蓝湾新材料有限公司 | Industrial dimethyl diallyl ammonium chloride synthesis method |
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| US3461163A (en) * | 1967-03-16 | 1969-08-12 | Calgon Corp | Synthesis of dimethyl diallyl ammonium chloride |
| US3472740A (en) * | 1967-03-28 | 1969-10-14 | Calgon Corp | Process for purifying dialkyl diallyl ammonium chloride and dialkyl dimethallyl ammonium chloride |
| CN1243822A (en) * | 1999-04-09 | 2000-02-09 | 西南石油学院 | A kind of preparation method of cationic polymer monomer |
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| JPS541282B1 (en) * | 1969-08-26 | 1979-01-23 | ||
| DE3528985A1 (en) * | 1985-08-13 | 1987-02-19 | Hoechst Ag | CONTINUOUS PROCESS FOR PRODUCING DIMETHYL DIALLYLAMMONIUM CHLORIDE |
| JPH09278721A (en) * | 1996-04-16 | 1997-10-28 | Daiso Co Ltd | Treatment of diallyldialkylammonium compound |
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| US3461163A (en) * | 1967-03-16 | 1969-08-12 | Calgon Corp | Synthesis of dimethyl diallyl ammonium chloride |
| US3472740A (en) * | 1967-03-28 | 1969-10-14 | Calgon Corp | Process for purifying dialkyl diallyl ammonium chloride and dialkyl dimethallyl ammonium chloride |
| CN1243822A (en) * | 1999-04-09 | 2000-02-09 | 西南石油学院 | A kind of preparation method of cationic polymer monomer |
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