CN103923259B - A kind of polyethylene amine amphoteric polyelectrolyte and preparation method thereof - Google Patents
A kind of polyethylene amine amphoteric polyelectrolyte and preparation method thereof Download PDFInfo
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- CN103923259B CN103923259B CN201410175855.8A CN201410175855A CN103923259B CN 103923259 B CN103923259 B CN 103923259B CN 201410175855 A CN201410175855 A CN 201410175855A CN 103923259 B CN103923259 B CN 103923259B
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Abstract
The invention provides a kind of polyethylene amine amphoteric polyelectrolyte, its preparation method is as follows: 1) join in organic solvent by N-vinyl formamide and vinylformic acid, carries out stirring and refluxing under a nitrogen atmosphere and makes reaction soln; 2) add initiator to react, the product of reaction is carried out drying; 3) by step 2) the polyvinylformamide vinylformic acid prepared, after tying by filter paper packet, put into apparatus,Soxhlet's, inject cleaning solution, carry out heating and extract, extract by paper bag taking-up after terminating, vacuum-drying; 4) by after desciccate and solvent, under nitrogen existent condition, carry out stirring and refluxing, then add sodium hydroxide solution and react, dryly obtain polyethylene amine amphoteric polyelectrolyte.Polyethylene amine amphoteric polyelectrolyte of the present invention role in paper industry is many-sided, can improve the operating performance of paper machine, increase intensity, the set anionic trash material of paper, also may be used for the process of paper waste.
Description
Technical field
The invention belongs to paper making raw material preparing technical field, be specifically related to a kind of polyethylene amine amphoteric polyelectrolyte and preparation method thereof.
Background technology
Along with the development of science and technology and the increase day by day of human wants, the requirement of people to paper strength is more and more higher.And polyvinylamine (PVAm) the straight chain salt ion high molecular weight water soluble polymer that to be a kind of amino be connected directly between on hydrocarbon backbone, because of it, to contain a large amount of polymers amino, so there is very important investigation and application to be worth in polymer science field.As new type of paper toughener and process assistant, the molecular chain length of PVAm and electric density can design according to the needs of practical application.
At present, the preparation method of PVAm mainly contains 4 kinds: 1. utilize the Hofmann DeR of polyacrylamide (PAM) to prepare; 2. prepared by poly N-vinyl carbamate hydrolysis method; 3. the hydrolysis reaction of poly-(N-vinyl) acid amides [mainly poly-(N-vinyl) methane amide (po-1y (N-viny1)-foramide) or poly-(N-vinyl) ethanamide (poly (N-viny1)-acetamide)] is utilized; 4. polyvinyl chloride (PVC) nitrofication process.The method wherein utilizing the Hofmann DeR of PAM to synthesize PVAm has the advantage that reaction process is uncomplicated, reaction conditions is easy to control, and raw material is easy to get.But have that molecular weight is wayward, low conversion rate and a shortcoming such as product concentration is low, this have impact on its using and promoting as paper making intensifier.
Summary of the invention
The object of this invention is to provide a kind of polyethylene amine amphoteric polyelectrolyte and preparation method thereof, effectively can improve transformation efficiency and the product purity of the polyvinylamine polymers of preparation, thus make up the deficiencies in the prior art.
The preparation method of polyethylene amine amphoteric polyelectrolyte of the present invention, comprises following step:
1) N-vinyl formamide (NVF) and vinylformic acid are joined in organic solvent, carry out stirring and refluxing under a nitrogen atmosphere and make reaction soln;
2) to step 1) reaction soln in add initiator and react, the product polyvinylformamide vinylformic acid of reaction is carried out drying;
3) by step 2) the polyvinylformamide vinylformic acid prepared, after tying by filter paper packet, put into apparatus,Soxhlet's, in apparatus,Soxhlet's, inject cleaning solution, carry out heating and extract, extract by paper bag taking-up after terminating, vacuum-drying;
4) by step 3) after desciccate and solvent after process, under nitrogen existent condition, carry out stirring and refluxing, then add sodium hydroxide solution and react, reaction solution dry acquisition polyethylene amine amphoteric polyelectrolyte.
Wherein step 1) organic solvent can be wherein one or more such as ethanol, acetone, sherwood oil, methylene dichloride, ether, methyl-phenoxide, trichloromethane, tetracol phenixin, tetrahydrofuran (THF), zellon, Virahol, benzylalcohol, glycol dimethyl ether, vinyl acetic monomer.
Step 1) in monomer NVF and acrylic acid molar ratio be preferably 3:1;
Step 2) initiator is Potassium Persulphate, Sodium Persulfate, ammonium persulphate, benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile (AIBN), cross two carbonic acid dicyclohexyl esters, cross octanoic acid ter-butyl ester, cross sad tert-pentyl ester, cross in nonane diacid di tert butyl carbonate, t-butyl peroxy-acetate one or more.
Step 2) in the transformation efficiency of consumption on product of initiator have larger impact, when initiator amount is 1% of the total consumption mole number of N-vinyl formamide (NVF) and vinylformic acid (AA), the transformation efficiency of product can reach about 80%.
Step 3) in the cleaning solution used be one or more in acetone, ether, sherwood oil, ethanol, trichloromethane, normal hexane,
Be preferably the cleaning solution that acetone and ether are made in 3:1 ratio; Can the unreacted monomer of more effective removing, improve product purity.
Step 4) in solvent can be in glycol dimethyl ether, tetrahydrofuran (THF), ethanol, isopropylcarbinol one or more.
Step 4) in the preferred vacuum-drying of drying, condition is at 60 DEG C, drying under reduced pressure 12h.
First the present invention uses (N-vinyl) methane amide and acroleic acid polymerization obtain polymkeric substance, and then polymkeric substance is hydrolyzed in the basic conditions and obtains polyethylene amine amphoteric polyelectrolyte.In preparation process, under alkaline condition, polymkeric substance absolutely can be hydrolyzed obtained polyvinylamine-sodium acrylate, and production concentration is high.Polyvinylamine-sodium acrylate has both sexes, molecular weight about 800,000, even molecular weight distribution.Polyethylene amine amphoteric polyelectrolyte of the present invention role in paper industry is many-sided, can improve the operating performance of paper machine, increase intensity, the set anionic trash material of paper, also may be used for the process of paper waste.In addition, it has very wide application prospect in the industry such as medicine, isolation technique, makeup, and due to the physicochemical property of self uniqueness, can be applied in more field.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described further, but the present invention is not limited to these embodiments, still can modifies to the technical scheme of following each embodiment.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Method of the present invention, includes following step:
1) N-vinyl formamide (NVF) and vinylformic acid are joined in organic solvent, carry out stirring and refluxing under a nitrogen atmosphere and make reaction soln;
2) to step 1) reaction soln in add initiator and react, the product polyvinylformamide vinylformic acid of reaction is carried out drying;
3) by step 2) the polyvinylformamide vinylformic acid prepared, after tying by filter paper packet, put into apparatus,Soxhlet's, in apparatus,Soxhlet's, inject cleaning solution, carry out heating and extract, extract by paper bag taking-up after terminating, vacuum-drying;
Step 3) in the polyvinylformamide vinylformic acid synthesized is immersed in cleaning solution, in order to except unreacted NVF in dereaction, and by product polyvinylamine and polyacrylic acid, also have unreacted vinylformic acid, treated, the purity of target product improves a lot.
4) by step 3) after desciccate and solvent after process, under nitrogen existent condition, carry out stirring and refluxing, then add sodium hydroxide solution and react, reaction solution dry acquisition polyethylene amine amphoteric polyelectrolyte.
Below in conjunction with embodiment, method of the present invention is described in detail.
Embodiment 1
1) N-vinyl formamide (NVF) and vinylformic acid are joined in organic solvent, carry out stirring and refluxing under a nitrogen atmosphere and make reaction soln;
10gNVF solution, 2.03g vinylformic acid and 61ml tetrahydrofuran (THF) is added, stirring and refluxing at 55 DEG C, logical nitrogen deoxygenation in the there-necked flask of 250ml,
2) to step 1) reaction soln in add initiator and react, the product polyvinylformamide vinylformic acid of reaction is carried out drying;
To step 1) slowly drip the mixed solution (dropping funnel dripped off in 1 hour) of 0.2772g Diisopropyl azodicarboxylate (AIBN) and 20ml tetrahydrofuran (THF) in the reaction soln prepared, namely reaction 7h obtains product polyvinylformamide vinylformic acid.
3) 1g step 2 is taken) the polyvinylformamide vinylformic acid prepared, after bandaging with filter paper (0.3136g), put into apparatus,Soxhlet's, the cleaning solution that acetone and ether are made in 3:1 ratio is injected in there-necked flask, amount can not exceed 2/3 of there-necked flask capacity, heating in water bath (temperature reaches the boiling point of acetone and ether mixing solutions) at 90 DEG C, after extracting 10h, paper bag is taken out, be placed in ventilation opening to dry, claim its weight (0.5277g) again, the acrylic acid quality of polyvinylformamide (0.2141g) after extracting can be obtained through converting.In surname extraction, cleaning solution used, compared with other solvent (as methyl alcohol, zellon, tetracol phenixin etc.) better effects if, can remove unreacted monomer and most of by product, and target product is insoluble in this extraction agent, waste very few, purity improves a lot.
4) by step 3) after desciccate and solvent after process, under nitrogen existent condition, carry out stirring and refluxing, then add sodium hydroxide solution and react, reaction solution dry acquisition polyethylene amine amphoteric polyelectrolyte.
Join in the there-necked flask of 250ml by 0.2141g polyvinylformamide vinylformic acid and 30ml ether, 50 DEG C of stirring and refluxing, slowly drip the NaOH solution 5ml of 2.5mol/L in bottle, reaction 11h, product polyvinylamine-sodium acrylate.
Analyzed by ir data, characteristic group's amide group of feed N-vinyl methane amide is at 1668cm
-1there is strong absorption peak at place, and product is at 3430cm
-1there is peak value in place, has occurred the stretching vibration of C-H, at 1605cm
-1place and 1385cm
-1near there is absorption peak, show containing-NH
2group and-COO
-1, and at 2097cm
-1absorption peak is very weak, determines to obtain polyethylene amine amphoteric polyelectrolyte.
Embodiment 2
15gNVF solution, 7.5ml vinylformic acid and 130ml ethanol is added in the there-necked flask of 250ml, stirring and refluxing at 85 DEG C, logical nitrogen deoxygenation, slowly drip the mixed solution (dropping funnel dripped off in 1 hour) of 3.5g lauroyl peroxide and 35ml ethanol again, namely reaction 8h obtains product (polyvinylformamide vinylformic acid).Take 1.6g polyvinylformamide vinylformic acid, after bandaging with filter paper (0.4555g), put into apparatus,Soxhlet's, the cleaning solution (amount can not exceed 2/3 of there-necked flask capacity) that acetone and ether are made in 3:1 ratio is injected in there-necked flask, heating in water bath (temperature reaches the boiling point of normal hexane and trichloromethane mixing solutions) at 60 DEG C, after extracting 9.5h, paper bag is taken out, be placed in ventilation opening to dry, claim its weight (1.1277g) again, the acrylic acid quality of polyvinylformamide (0.6722g) after extracting can be obtained through converting.Join in the there-necked flask of 250ml by 0.6722g polyvinylformamide vinylformic acid and 41ml Virahol, 83 DEG C of stirring and refluxing, slowly drip the NaOH solution 10ml of 2.0mol/L in bottle, reaction 12h, obtained product polyethylene amine amphoteric polyelectrolyte.
Analyzed by ir data, characteristic group's amide group of feed N-vinyl methane amide is at 1669cm
-1there is strong absorption peak at place, and product is at 3432cm
-1there is peak value in place, has occurred the stretching vibration of C-H, at 1609cm
-1place and 1390cm
-1near there is absorption peak, show containing-NH
2group and-COO
-1, and at 2113cm
-1absorption peak is very weak, determines to obtain polyethylene amine amphoteric polyelectrolyte.
Embodiment 3
16.5gNVF solution, 8.5ml vinylformic acid and 140ml methylene dichloride is added in the there-necked flask of 250ml, stirring and refluxing at 75 DEG C, logical nitrogen deoxygenation, slowly drip the mixed solution (dropping funnel dripped off in 1 hour) that 4g crosses t-butyl peroxy-acetate and 40ml methylene dichloride again, namely reaction 8.5h obtains product (polyvinylformamide vinylformic acid).Take 2g polyvinylformamide vinylformic acid, after bandaging with filter paper (0.4555g), put into apparatus,Soxhlet's, the cleaning solution (amount can not exceed 2/3 of there-necked flask capacity) that acetone and ether are made in 3:1 ratio is injected in there-necked flask, heating in water bath (temperature reaches the boiling point of butanone solution) at 82 DEG C, after extracting 10.5h, paper bag is taken out, be placed in ventilation opening to dry, claiming its weight (1.5277g) again, the acrylic acid quality of polyvinylformamide (1.0722g) after extracting can be obtained through converting.Join in the there-necked flask of 250ml by 1.0722g polyvinylformamide vinylformic acid and 70ml sherwood oil, 80 DEG C of stirring and refluxing, slowly drip the NaOH solution 15ml of 2.7mol/l in bottle, reaction 15h, product.
Analyzed by ir data, characteristic group's amide group of feed N-vinyl methane amide is at 1670cm
-1there is strong absorption peak at place, and product is at 3428cm
-1there is peak value in place, has occurred the stretching vibration of C-H, at 1606cm
-1place and 1398cm
-1near there is absorption peak, show containing-NH
2group and-COO
-1, and at 2095cm
-1absorption peak is very weak, determines to obtain polyethylene amine amphoteric polyelectrolyte.
In embodiment 1, monomer NVF is 3:1 with the ratio of acrylic acid molar weight, and massfraction is 10%, and when initiator amount is 1% of whole monomer molar consumption, the productivity ratio embodiment 2,3 of polyethylene amine amphoteric polyelectrolyte all wants high a lot.
In example 2, when naoh concentration is 2N, when polymer concentration is 2wt%, polymkeric substance (polyvinylformamide vinylformic acid) can complete hydrolysis, and embodiment 1,3 does not reach complete hydrolysis.Find through test, when sodium hydroxide is less than 1 with the ratio of the molar weight of acid amides, the sodium hydroxide of 1 molecule can cause the hydrolysis of the amide group of unnecessary 1 molecule.
Polyethylene amine amphoteric polyelectrolyte embodiment 1 synthesized is used in as toughener in papermaking, and folding, the anti-tensile of its paper are all improved largely.Specific embodiment is as follows:
Enhancement test: according to calculating, get the slurry (needlebush of 700ml1% concentration, solid content is 24.835%), low speed 500rpm adds under stirring that a certain amount of (0.2%, 0.4%, 0.6% relative to bone dry fiber, form specific as follows) embodiment 1 prepare polyethylene amine amphoteric polyelectrolyte, after stirring 5min, add a certain amount of water dilution mixing (0.5%) again, therefrom get 400ml (2g bone dry fiber), constant volume is to 1000ml again, carries out beating degree mensuration.Remaining point slurry 3 times, each 320ml (1.6g fiber often opens paper), copying to get on device at pattern and carry out handsheet, is quantitatively 80g/m
2, label, squeezes 1min by l Water Paper page at 4MPa pressure, then dry in pattern moisture eliminator.The paper more than copied carries out anti-tensile (folder spacing 60.0mm; Quantitative 80g/m
2; Length 60mm; Width 15mm) and folding mensuration, specific as follows, the tensile index Ls of blank sample is 3.043Km, and folding is 20 times.
The polyethylene amine amphoteric polyelectrolyte adopting embodiment 2 and embodiment 3 to prepare also has the effect similar with the product of embodiment 1; Show that method of the present invention stable can prepare polyethylene amine amphoteric polyelectrolyte.
Claims (6)
1. a polyethylene amine amphoteric polyelectrolyte, is characterized in that, described polyethylene amine amphoteric polyelectrolyte is prepared by following method:
1) N-vinyl formamide NVF and vinylformic acid are joined in organic solvent, carry out stirring and refluxing under a nitrogen atmosphere and make reaction soln; Described organic solvent is one or more in ethanol, acetone, sherwood oil, methylene dichloride, ether, methyl-phenoxide, trichloromethane, tetracol phenixin, tetrahydrofuran (THF), zellon, Virahol, benzylalcohol, glycol dimethyl ether, vinyl acetic monomer;
2) to step 1) reaction soln in add initiator and react, the product polyvinylformamide vinylformic acid of reaction is carried out drying; Described initiator is Potassium Persulphate, Sodium Persulfate, ammonium persulphate, benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, cross two carbonic acid dicyclohexyl esters, cross octanoic acid ter-butyl ester, cross sad tert-pentyl ester, cross in nonane diacid di tert butyl carbonate, t-butyl peroxy-acetate one or more;
3) by step 2) the polyvinylformamide vinylformic acid prepared, after tying by filter paper packet, put into apparatus,Soxhlet's, in apparatus,Soxhlet's, inject cleaning solution, carry out heating and extract, extract by paper bag taking-up after terminating, vacuum-drying; Described cleaning solution is one or more in acetone, ether, sherwood oil, ethanol, trichloromethane, normal hexane;
4) by step 3) after desciccate and solvent after process, under nitrogen existent condition, carry out stirring and refluxing, then add sodium hydroxide solution and react, reaction solution dry acquisition polyethylene amine amphoteric polyelectrolyte; Described solvent is one or more in glycol dimethyl ether, tetrahydrofuran (THF), ethanol, isopropylcarbinol.
2. polyethylene amine amphoteric polyelectrolyte as claimed in claim 1, is characterized in that described step 1) in monomer NVF and acrylic acid molar ratio be 3:1.
3. polyethylene amine amphoteric polyelectrolyte as claimed in claim 1, is characterized in that described step 2) in initiator amount be 1% of the total consumption mole number of N-vinyl formamide and vinylformic acid.
4. polyethylene amine amphoteric polyelectrolyte as claimed in claim 1, is characterized in that described step 3) in cleaning solution be that acetone and ether are made in 3:1 ratio.
5. polyethylene amine amphoteric polyelectrolyte as claimed in claim 1, is characterized in that described step 4) in drying be vacuum-drying, condition is at 60 DEG C, drying under reduced pressure 12h.
6. the application of polyethylene amine amphoteric polyelectrolyte according to claim 1 in paper industry.
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| CN105859961B (en) * | 2016-04-22 | 2018-03-13 | 大连理工大学 | A kind of polyvinylamine co acrylic type dyestuffs and its preparation method and application |
| CN109280126A (en) * | 2018-09-27 | 2019-01-29 | 青岛科技大学 | A kind of preparation method of polyvinylamine-diene acrylic alkyl dimethyl ammonium chloride |
| CN109904471A (en) * | 2019-01-30 | 2019-06-18 | 天津大学 | A kind of preparation method of all-solid-state flexible metal-air battery |
| CN115073662B (en) * | 2022-02-19 | 2023-09-26 | 郑州大学 | Synthesis method of perfluorinated-substituent polyvinylamine copolymer and application of perfluorinated-substituent polyvinylamine copolymer in perovskite resistive random access memory |
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| EP0438744A1 (en) * | 1990-01-23 | 1991-07-31 | BASF Aktiengesellschaft | Use as water-treating agents of hydrosoluble copolymers based on monoethylenic and N-vinylamides |
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| EP0438744A1 (en) * | 1990-01-23 | 1991-07-31 | BASF Aktiengesellschaft | Use as water-treating agents of hydrosoluble copolymers based on monoethylenic and N-vinylamides |
| US5630907A (en) * | 1992-12-07 | 1997-05-20 | Basf Aktiengesellschaft | Use of hydrolyzed copolymers of N-vinylcarboxamides and monoethylenically unsaturated carboxylic acids in papermaking |
| CN1678649A (en) * | 2002-09-04 | 2005-10-05 | 巴斯福股份公司 | The production of aqueous dispersions of cationic homo- and copolymers using amphoteric protective colloids |
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