CN102153685B - Method for preparing polyvinylamine - Google Patents
Method for preparing polyvinylamine Download PDFInfo
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- CN102153685B CN102153685B CN2011100034076A CN201110003407A CN102153685B CN 102153685 B CN102153685 B CN 102153685B CN 2011100034076 A CN2011100034076 A CN 2011100034076A CN 201110003407 A CN201110003407 A CN 201110003407A CN 102153685 B CN102153685 B CN 102153685B
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- polyvinylamine
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- nucleophilic substitution
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Abstract
The invention discloses a method for preparing polyvinylamine. The method is a direct catalytic ammoniation method in which polyvinyl chloride is taken as a raw material. The method comprises the steps of dissolution, nucleophilic substitution reaction, separation and purification. The method is characterized in that: the nucleophilic substitution reaction of the polyvinyl chloride and ammonia is performed in organic solution in the presence of a transition metal catalyst, a phase transfer catalyst and alkali at room temperature to form the polyvinylamine. By the method, the polyvinylamine is directly synthesized in one step, only the raw material exists besides a product, the principle is simple, the side reaction is greatly reduced, a purification process of the product is simple, and the product has high quality.
Description
One, technical field
The present invention relates to a kind of preparation method of polyvinylamine.
Two, background technology
Polyvinylamine (PVAm) is the water-soluble novel high polymer material of a kind of chain, polyamino, because side functional group amino is very active, so PVAm can carry out amino most of characteristic reactions, thereby obtains many special new functions.PVAm and verivate thereof in the industries such as exploitation processing and building of weaving, medicine, oil as the toughener of flocculation agent, water-holding agent, cementing agent and paper-making industry etc.At present, the compound method of polyvinylamine mainly contains Hofmann edman degradation Edman, poly N-vinyl formylation poly-mer hyrolysis process, SE digestion method.
The synthetic PVAm of Hofmann degradation method is in Youxiaolin and aqueous sodium hydroxide solution, and SEPIGEL 305 carries out the rearrangement reaction of Hofmann degradation, can obtain polyvinylamine.But there are some problems that can form that by product urine bridge is plain with amino, carboxamido-group, need to consume a large amount of alkali in the reaction like carboxamido-group hydrolysis in the polyacrylamide amine molecule, reaction intermediate isocyanic ester in this method, thereby produces problems such as production cost is high, quality product is relatively poor, the amination degree is low.
It is earlier synthetic N-vinyl formamide monomer that poly N-vinyl acetamide hydrolysis legal system is equipped with polyvinylamine, and this monomer obtains the poly N-vinyl methane amide through radical polymerization, and hydrolysis prepares polyvinylamine again.In this method, committed step is convenient, the economic and safe preparation of raw material N-vinyl formamide (NEF).Its compound method has following several kinds: acetaldehyde and methane amide are carried out condensation under the catalysis of acid, generate the ethidine diformamide, thermo-cracking promptly gets NEF again, and NEF is hydrolysis again after polymerization, get final product PVAm; The problem for preparing the polyvinylamine existence in this way is that boiling point and the solvability of the NEF that generates after ethidine diformamide and the cracking is all very close, therefore is difficult to the two separation.Use ethanamide, formaldehyde and methyl alcohol to be raw material; Single stage method is synthesized N-(alkoxyl oxygen alkyl ethyl) methane amide, and thermo-cracking gets the N-vinyl formamide then, the repolymerization posthydrolysis; Though the method for PVAm has solved the midbody separation problem, have reaction conditions problems such as comparatively harshness and yield be lower.The cyaniding of acetaldehyde elder generation, and then with methane amide or liquefied ammonia, formic acid reaction, product is sloughed HCN, obtains polymerization single polymerization monomer NEF, NEF is again through the polymerization posthydrolysis, get final product PVAm, the main drawback of this kind method is to have a large amount of toxic gas prussic acid to emit.
The SE digestion method of existing report is in THF/DMSO or DMF/DMSO solution, NaNO
2With PVC substituted in reaction chlorine atom, obtain nitrated midbody, make catalyzer hydrogenation or hydrazine hydrate reduction midbody with Pd/C again, obtain the mixture of polyvinylamine.This method will be used a large amount of organic solvent THF and DMSO and Pd catalyzer, expensive contaminate environment also not only, and be a mixture with this method synthetic polyvinylamine.
Three, summary of the invention
The present invention is directed to existing polyvinylamine preparing method's defective; Aiming to provide a kind of is that the new method of raw material prepares polyvinylamine (PVAm) with PVC; Technical problem to be solved is that the direct amination of PVC generates PVAm, and under the prerequisite that improves product amination degree, reduces the generation of side reaction and by product.
The basic theory of foundation of the present invention is halogenated organic alkane and ammonia prepare aminocompound under the katalysis of transition-metal catalyst a nucleophilic substitution reaction.With copper (Cu) is example, and its mechanism is:
Technical scheme of the present invention is to be the direct catalytic ammoniation method of raw material with SE (PVC); Comprise dissolving, nucleophilic substitution reaction, separation and purifying; Described dissolving is meant selects appropriate solvent dissolving PVC; Nucleophilic substitution reaction is carried out in solution, and described separation is meant separating of title product polyvinylamine (PVAm) and solvent, catalyzer and by product ammonium salt etc., and difference with the prior art is PVC and ammonia (NH
3) in organic solution under the room temperature and transition-metal catalyst, phase-transfer catalyst and alkali existence condition nucleophilic substitution reaction down, the amino chlorine atom that replaces generates PVAm, separation at last obtaining title product.Reaction formula is following:
Described ammonia is selected from liquefied ammonia (containing gaseous ammonia).
The organic solvent that can dissolve PVC is a lot, and commonly used have toluene, chloroform, acetone, THF, MTBE, N, N ' N (DMF), a methyl-sulphoxide (DMSO) etc.
Transition-metal catalyst is selected from Cu salt or Pd saline catalyst; Preferred Pd salt catalyst or nano level Cu salt catalyst; Pd salt catalyst such as palladium, Palladous chloride etc.; Cu salt catalyst such as cuprous iodide, cuprous bromide, cuprous chloride, Red copper oxide, neutralized verdigris, copper sulfate etc., the usage quantity of catalyzer generally is the 5%-10% of the amount of feed molar.
Phase-transfer catalyst is selected from polyethers such as polyoxyethylene glycol, cyclic crown ether class such as beta-cyclodextrin or quaternary ammonium salt such as Tetrabutyl amonium bromide etc., and usage quantity is the 0.5%-1% of the amount of feed molar.
Described alkali is selected from salt of wormwood, yellow soda ash, cesium carbonate etc. or various sodium alkoxide, potassium alcoholate or basic metal and alkaline earth metal hydroxides or solid super base such as Al
2O
3Load KF solid alkali etc.The usage quantity of alkali be feed molar amount 1-3 doubly.
Specific operation process is: at first select the dissolving of appropriate solvent dissolving SE, after treating to dissolve fully, drop into catalyzer, alkali and phase-transfer catalyst; Feed ammonia and carry out nucleophilic substitution reaction, after reaction is accomplished, filter; Solid-liquid separation reclaims solvent and unreacted PVC certainly in the filtrating.Polyvinylamine is insoluble to organic solvent, is present in the filter cake, and filter cake is dissolved in an amount of water.Fully after the dissolving, transfer PH with hydrochloric acid, filter, with the hydrochloride form of separating out polyvinylamine in the filtrating impouring methyl alcohol, the catalyst recovery in the filter cake reuses.The product polyvinylamine hydrochloride of separating out is washed through alkaline purification, separation and alcohol after the methanol wash again and is obtained product.
Adopt the ammonification degree of Conductometric Titration Method product, the ammonification degree of the polyvinylamine of the present invention's preparation can surpass 80%.
The present invention compares with the method for existing preparation polyvinylamine has significant advantage:
1, this scheme is raw material with the SE, and through direct synthesizing polyethylene amine of one step of transition metal catalytic nucleophilic substitution reaction, low in raw material cost is easy to get.
2, utilize the transition metal-catalyzed nucleophilic substitution reaction research of modern organic chemistry newest fruits, adopt transition-metal catalyst among the present invention program, particularly adopt catalyzer such as nano level Cu, Pd, catalytic efficiency (is high, and amino substitution reaction yield is high.And, owing to have only single step reaction, except raw material, be exactly the product that generates, principle is simple, significantly reduces side reaction and takes place, and the product purifying technique is simple, and quality product is high.
3, the organic solvent that adopts in the scheme, but recirculation utilization after reclaiming does not have discharging of waste liquid basically.Simultaneously, also can reuse through handling after the nanocatalyst reaction.
4, the mild condition of reaction, easy and simple to handle, product cost is low, and industrializing implementation is convenient.
Four, description of drawings
Fig. 1 is the PVAm infrared spectrum of present method preparation, with stdn spectrogram basically identical.
Five, embodiment
Through specific embodiment, technical scheme of the present invention is done further explanation, but the present invention is not limited to these instances below.
Embodiment 1
The acetone that in there-necked flask, adds 125mL successively, molecular-weight average are 4.3 * 10
4SE 6.25g (molar weight of PVC is calculated as 0.1mol with the molecular weight of monomer vinylchlorid, down with), stir, treat that material pvc dissolves fully; Add 21.2g yellow soda ash again, diameter is nanometer cuprous iodide 0.95g and phase-transfer catalyst Tetrabutyl amonium bromide 0.33g about 50nm, continue to stir, and in reaction mixture, slowly feeds ammonia, carries out nucleophilic substitution reaction.After question response carried out 10 hours, the sampling analysis reactor product reached and stops logical ammonia behind the target amination degree, finishes reaction.Filter out solvent, filter cake is dissolved in an amount of water fully dissolves.Transfer PH=2 with 22% hydrochloric acid, filter, the methyl alcohol of 4 times of volumes of filtrating impouring is separated out the hydrochloride form of polyvinylamine, washed with methanol filters out product; Catalyst recovery reuses in the filter cake.The solid of this hydrochloride form is soluble in water, use 5%NaOH solution save to pH as 10-11 after, separate out solid in the impouring methyl alcohol, suction filtration, vacuum-drying obtains product 4.6g, yield 73.8%.Use conductometric titration method check and analysis product ammonification degree 82.11%.Filter back methanol aqueous solution distillation and reclaim the methanol loop use.
Through the ir data analysis, characteristic group's carboxamido-group of raw material SEPIGEL 305 is at 1668cm
-1There is strong absorption peak at the place, and product is at 3430cm
-1Peak value appears in the place, the stretching vibration of C-H occurred, at 1605cm
-1Place and 1500cm
-1Near absorption peak appears, show to contain-NH
2Group reaches-NH
3 +, and at 1666cm
-1Absorption peak very a little less than, confirm to obtain polyvinylamine.
Embodiment 2
The THF that in there-necked flask, adds 125mL successively, molecular-weight average are 4.3 * 104 SE 6.25g, stir, and treat that material pvc dissolves fully; Add 20.7g salt of wormwood again, diameter is nanometer cuprous bromide 1.43g and phase-transfer catalyst TBAH 0.26g about 50nm, continue to stir, slowly logical ammonia carries out nucleophilic substitution reaction in reaction mixture.After question response carried out 10 hours, sampling analysis reactor product amination degree reached and stops logical ammonia behind the target amination degree, finishes reaction.Filter out solvent, filter cake is dissolved in an amount of water fully dissolves.Transfer PH=2 with 22% hydrochloric acid, filter, the methyl alcohol of 4 times of volumes of filtrating impouring is separated out the hydrochloride form of polyvinylamine, washed with methanol filters out product; Catalyst recovery reuses in the filter cake.The solid of this hydrochloride form is soluble in water, use 5%NaOH solution save to pH as 10-11 after, separate out solid in the impouring methyl alcohol, suction filtration, vacuum-drying obtains product 4.2g, yield 67.4%.Use conductometric titration method check and analysis product ammonification degree 80.64%.Filter the back methanol aqueous solution and reclaim the methanol loop use.
Through the ir data analysis, characteristic group's carboxamido-group of raw material SEPIGEL 305 has strong absorption peak at the 1668cm-1 place, and product peak value occurs at the 3430cm-1 place, the stretching vibration of C-H occurred, at 1591cm
-1Place and 1500cm
-1Near absorption peak appears, show to contain-NH
2Group reaches-NH
3 +, and at 1666cm
-1Absorption peak very a little less than, confirm to obtain polyvinylamine.
Embodiment 3
In there-necked flask, add the N (DMF) of 125mL successively, molecular-weight average is 4.3 * 10
4SE 6.25g, stir, treat that material pvc dissolves fully; Add sodium hydroxide 4g, palladium 1.12g and phase-transfer catalyst Tetrabutyl amonium bromide 0.33g again, continue to stir, in reaction mixture, slowly feed ammonia, carry out nucleophilic substitution reaction.After question response carried out 10 hours, sampling analysis reactor product amination degree reached and stops logical ammonia behind the target amination degree, finishes reaction.Filter out solvent, filter cake is dissolved in an amount of water fully dissolves.Transfer PH=2 with 22% hydrochloric acid, filter, the methyl alcohol of 4 times of volumes of filtrating impouring is separated out the hydrochloride form of polyvinylamine, washed with methanol filters out product; Catalyst recovery reuses in the filter cake.The solid of this hydrochloride form is soluble in water, use 5%NaOH solution save to pH as 10-11 after, separate out solid in the impouring methyl alcohol, suction filtration, vacuum-drying obtains product 4.3g, yield 68.8%.Use conductometric titration method check and analysis product ammonification degree 78.32%.Filter back methanol aqueous solution distillation and reclaim the methanol loop use.
Through the ir data analysis, characteristic group's carboxamido-group of raw material SEPIGEL 305 has strong absorption peak at the 1668cm-1 place, and product peak value occurs at the 3430cm-1 place, the stretching vibration of C-H occurred, at 1608cm
-1Place and 1490cm
-1Near absorption peak appears, show to contain-NH
2Group reaches-NH
3 +, and at 1666cm
-1Absorption peak very a little less than, confirm to obtain polyvinylamine.
Claims (5)
1. the preparation method of a polyvinylamine; Be to be the direct catalytic ammoniation method of raw material with the SE; Comprise dissolving, nucleophilic substitution reaction, separation and purifying, it is characterized in that: SE and ammonia generate polyvinylamine in carrying out nucleophilic substitution reaction under the room temperature and under transition-metal catalyst, phase-transfer catalyst and the alkali existence condition in organic solution; Described transition-metal catalyst is selected from palladium salt catalyst or copper salt catalyst, and its consumption is the 5%-10% of material pvc molar weight; Described phase-transfer catalyst is selected from Tetrabutyl amonium bromide, and its consumption is the 0.5%-1% of material pvc molar weight.
2. preparation method according to claim 1 is characterized in that: described transition-metal catalyst is selected from palladium salt catalyst or nanosized copper salt catalyst.
3. preparation method according to claim 1 and 2 is characterized in that: described copper salt catalyst is selected from cuprous iodide or cupric bromide.
4. preparation method according to claim 1 and 2 is characterized in that: described palladium salt catalyst is selected from palladium.
5. preparation method according to claim 1; It is characterized in that: described alkali is selected from salt of wormwood, yellow soda ash, cesium carbonate, sodium alkoxide, potassium alcoholate, basic metal and alkaline earth metal hydroxides or solid super base, and its consumption is 1-3 a times of material pvc molar weight.
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| CN107118291B (en) * | 2017-06-07 | 2019-06-25 | 中国海洋石油集团有限公司 | A kind of cross-linked gel, its dedicated crosslinking agent and preparation method step by step |
| CN108822903B (en) * | 2018-06-20 | 2021-05-28 | 湖南辰砾新材料有限公司 | Gasoline additive and preparation method thereof |
| CN111205176B (en) * | 2020-01-14 | 2022-06-14 | 大连九信精细化工有限公司 | Synthetic method of 3, 5-dihalogen-2-pentanone |
| CN112918052A (en) * | 2021-01-28 | 2021-06-08 | 江苏厚生新能源科技有限公司 | Ultraviolet radiation-proof polyethylene fabric and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1606574A (en) * | 2001-12-21 | 2005-04-13 | 西巴特殊化学品控股有限公司 | Poly(vinylalcohol)-co-poly(vinylamine)polymers comprising functional moieties |
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|---|---|---|---|---|
| KR100674613B1 (en) * | 2005-05-04 | 2007-01-25 | 해동화학(주) | Modification of Polyvinylchloride or Polyvinylchloride Copolymer and Its Preparation Method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1606574A (en) * | 2001-12-21 | 2005-04-13 | 西巴特殊化学品控股有限公司 | Poly(vinylalcohol)-co-poly(vinylamine)polymers comprising functional moieties |
Non-Patent Citations (2)
| Title |
|---|
| N Bicak et al.Vinylamine polymer via chemical modification of PVC.《European Polymer Journal》.2001,第37卷(第4期),801-805. * |
| 张娟 等.功能性聚乙烯胺及其衍生物合成的研究进展.《高分子材料科学与工程》.2006,第22卷(第1期),6-10. * |
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