CN100344654C - Method for preparing water soluble polymer material - Google Patents
Method for preparing water soluble polymer material Download PDFInfo
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- CN100344654C CN100344654C CNB2005100169716A CN200510016971A CN100344654C CN 100344654 C CN100344654 C CN 100344654C CN B2005100169716 A CNB2005100169716 A CN B2005100169716A CN 200510016971 A CN200510016971 A CN 200510016971A CN 100344654 C CN100344654 C CN 100344654C
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Abstract
The present invention belongs to the technical field of preparing cationic water-soluble macromolecule material. The water-soluble macromolecular material of the present invention is a cationic macromolecule polymer with high molecular weight, which is formed by synthesizing a cationic macromolecule crosslinking agent and nonionic and/or cationic monomers in a reaction mode; the water-soluble macromolecular material mainly comprises the steps: (1) the preparation of the cation polymer crosslinking agent and (2) the preparation of the water-soluble macromolecular material. The prepared products can be used in the fields of paper making, printing, etc.
Description
Technical field
The present invention is the preparing technical field that belongs to water-soluble polymer.
Background technology
The acrylic amide water-soluble polymer is widely used in paper industry, and as paper strengthening agent, the high molecular molecular weight of acrylic amide has very big influence to paper strength, and general big more its enhanced effect of molecular weight is good more.As the molecular weight of the polyacrylamide base polymer of paper pulp pretreating reagent than condensed type cationoid polymerisation object height.But the polyacrylamide that the interpolation molecular weight surpasses certain value can make the paper pulp flocculation again, destroys the evenness of paper, reduces strength of paper.
The preparation method of the paper strengthening agent that high molecular and flocculence are little generally adopts the method for adding linking agent.Linking agent commonly used is methylene radical N, N-diacrylamine, triallylamine or allylation Mierocrystalline cellulose.But because methylene radical N, the distance in the N-diacrylamine structure between two two keys is shorter, and empty inhibition effect is bigger, has influenced the homogeneity of cross-linking set.Proposed in the Japanese Patent (spy opens flat 10-218797) a kind ofly to improve crosslinked all once methods, but fundamentally solved because the cross-linker molecules amount snapshot of oneself rings the problem of polymericular weight by the ratio of adjusting polymer monomer.In addition, the cellulosic reactive behavior of triallylamine or allylation is lower, has influenced the level of response of copolymerization.
In order to address the above problem, the present invention has designed and synthesized a kind of cation type polymer linking agent that has the vinyl latter end, has solved well that traditional linking agent reactive behavior is low, the uneven problem of cross-linking density.
Summary of the invention
Purpose of the present invention is exactly that the monomer mixture copolymerization that constitutes of the water-soluble monomer of the cation type polymer linking agent represented with chemical formula 1 and Methacrylamide or acrylamide and chemical general formula 2 expressions prepares water-soluble high-molecular material, preparation contains the cross-linking type cation water-soluble macromolecular material of cationic components, has solved above-mentioned technical problem.
It is as follows to implement technical scheme of the present invention:
1.. the preparation of cation type polymer linking agent.
The cation type polymer linking agent that the chemical formula 1 that the present invention uses is represented is to be made of alkylamines such as epoxyhalopropane and ammonia, organic primary amine, organic secondary amine and trimethylamines.Epoxyhalopropane is meant epoxy chloropropane, epoxy bromopropane and epoxy iodopropane, can use wherein a kind of also can be used in combination; Organic primary amine is meant methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine; Organic secondary amine refer to dimethylamine, diethylamine, dipropyl amine, thyl methyl amine, first propylamine, pentanoic with and mutual combination; The acyl group monomer that contains organic tertiary amine is N, N dimethylamine base propyl methyl acid amides, N; N dimethylamine base propyl group acrylamide, N, N dimethylamine base propyl methyl acid amides; N; N dimethylamine base propyl group acrylamide, N, N dimethylamine base butyl methyl acrylamide; N; N dimethylamine ylmethyl acrylamide, N, the N-first and second aminocarbonyl propyl acrylamides; N; N dimethylamine ylmethyl vinylformic acid propylamine ester, N, N dimethylamine base vinylformic acid propylamine ester; N; N dimethylamine ylmethyl vinylformic acid methylamine ester, N, N dimethylamine ylmethyl vinylformic acid methylamine ester is applicable to the present invention.N in the acrylic amide, N dimethylamine base propyl group acrylamide, since better than the alkali resistance that in structure, contains ester group, so ad hoc proposal is used.
The end of the cationic polymers linking agent that chemical formula 1 is represented contains two vinyl groups.
Chemical formula 1 is:
R wherein
1, R
2, R
3, R
4, R
5The alkyl of=hydrogen, carbon number 1-3 or benzyl,, R
6=hydrogen or methyl, n=0-50, B=O or NH, X=halogen;
Preparation cationic polymers linking agent, its order of addition(of ingredients) is: epoxyhalopropane is added in the reactor, drip ammonia, primary amine or secondary amine, the two reaction back adds the vinyl monomer that contains tertiary amine group and reacts; The vinyl monomer that also can drip ammonia, primary amine or secondary amine in the reactor that is added with epoxyhalopropane and contain tertiary amine group reacts, but will avoid using opposite addition step.Because Michael reaction takes place in ammonia, primary amine, secondary amine and vinyl monomer easily, can obtain the cationic product that end contains halogen so earlier ammonia, primary amine, secondary amine are splashed into the method for epoxyhalopropane, react than the vinyl monomer that is easier to containing tertiary amine group like this.
In the cationic polymers linking agent that chemical formula 1 is represented, ammonia, primary amine, secondary amine carry out suitable adjustment with the mol ratio of epoxyhalopropane by character, structure, the molecular weight of desired linking agent respectively, in the 0.15-1.20 molar range.Mol ratio makes epoxyhalopropane residual easily below 0.15, mol ratio is difficult for when above generating having the end of halogen 1.20, thereby can not react with the vinyl monomer that contains tertiary amine group.
Containing the vinyl monomer of tertiary amine group and the mol ratio of epoxyhalopropane requires to have the unreacted vinyl monomer that contains tertiary amine group at 0.15-0.24 above in this value product.
In the cationic polymers linking agent preparation that chemical formula 1 is represented, ammonia, primary amine, secondary amine are easy to reaction with epoxyhalopropane respectively and obtain resin cation (R.C.).But add basic catalyst accelerated reactions such as sodium hydroxide respectively during at 0.15-1.0 with the ratio of epoxyhalopropane when ammonia, primary amine, secondary amine.Can suitably adjust temperature of reaction according to required character, structure, molecular weight etc. is 10-90 ℃, recommends 20-60 ℃.It is slow to be lower than 20 ℃ of speed of response, is higher than the halogen generation hydrolysis of 60 ℃ of resulting resin ends, can not react with the vinyl monomer that contains tertiary amine group.Reaction times is in 1-24 hour.
2. the preparation of water-soluble high-molecular material.The monomer mixture copolymerization that constitutes of the water-soluble monomer of cation type polymer linking agent of representing with chemical formula 1 and Methacrylamide or acrylamide and chemical general formula 2 expressions has exactly prepared a kind of water-soluble high-molecular material of the cross-linking type that contains cationic components.
Chemical general formula 2 is:
R wherein
7=H, CH
3, R
8, R
9The alkyl of=carbon number 1-3 or alkoxyl group, R
10The alkyl of=H or carbon number 1-3, alkoxyl group or benzyl, E=O or NH, alkyl or the alkoxyl group of F=carbon number 1-3, Y=bears counter ion.
The method for preparing water-soluble high-molecular material of the present invention, the employed preparation method of general radical polymerization is applicable to the present invention: the weight percent concentration that monomer is occupied in reaction soln is used water solution polymerization process when 5-30%; Concentration can be with the method for dispersion polymerization or inverse emulsion polymerization when 20-70%.
The initiator that uses is that the initiator that the water-soluble polymer polymerization is suitable for is azo class, redox class.The usage quantity of azo-initiator is the 0.001-1% of monomer total amount, and the initiator of redox class is the 0.001-1% of monomer total amount.
Polymerization is carried out under protection of inert gas, temperature of reaction 15-95 ℃, recommends 20-75 ℃.It is slow to be lower than 20 ℃ of speed of response, and it is wayward to be higher than 90 ℃ of reactions.
The water-soluble high-molecular material of the present invention's preparation is the graft copolymer that has cation group on the side chain, and molecular weight generally is 10,000-15,000,000.
Water-soluble high-molecular material of the present invention is applicable to various additive for paper making, is 100 when being converted into linear macromolecule when using as paper strengthening agent, and 000-8 is in 000,000 the scope.Using method is identical with existent method, copies paper as the positively charged ion preparation that adds paper pulp solid content 0.01-2% in the intrinsic content paper pulp of 0.5-3%.To the kind of slurrying without limits, machinery pulping, mixed pulp, waste paper pulp all are suitable for.Particularly when B in the chemical formula 1 be-during the NH-group, the scope that the pH when copying paper is can be between neutrality and weakly alkaline higher.
Present invention will be further described for some following examples, but it is not construed as limiting right of the present invention.
Embodiment (one). the embodiment of the preparation of the cationic polymers linking agent that chemical formula 1 is represented:
Add epoxy chloropropane 150g in being furnished with thermometer, agitator arm, dropping funnel four-hole boiling flask, dripping concentration in following 2 hours at 40-50 ℃ is 33% dimethyl amine aqueous solution 145g, drips the back 45 ℃ of reactions 1 hour; (at this moment, show that with gel volumetry measurement result the reaction conversion ratio of dimethyl amine is 100%; Show with amine neutralization titration measurement result in addition, generate 0.67% tertiary amine; Result with liquid chromatography for measuring shows that the transformation efficiency of epoxy chloropropane is 100%);
After the reaction, in system, add 21.0g dimethylamino-propyl acrylamide,, add the 36.5g deionized water, obtain 70% faint yellow water-soluble cationic polymer linking agent 327.9g in 25 ℃ of reactions 15 hours.(result who measures with the amine neutralization titration shows, generates 8.5% tertiary amine, is 1,460 by Molecular Weight for Polyacrylamide conversion weight-average molecular weight, and cationic degree is 6.52meq/g.)
Embodiment
Below be the embodiment of the preparation of water-soluble high-molecular material:
Embodiment 1
In the there-necked flask that is equipped with thermometer, stirrer, add linking agent 17.8g, the acrylamide 95.0g of 50% concentration of 50% concentration of the foregoing description () preparation and the acrylic acid aqueous solution 6.0g of 60% concentration, adjusting the pH value with ammoniacal liquor and deionized water is 3.5, and to make total amount be 270g.Under nitrogen protection, add the ammonium persulphate 1.5g of 10% concentration and the sodium bisulfite 4.8g of 10% concentration, 25 ℃ of arrest reactions of room temperature 12 hours.It is 20% that polymer concentration is adjusted with deionized water 23.7g in the reaction back.It the results are shown in Table 1.
Embodiment 2
The linking agent 16.8g, the acrylamide 84.0g of 50% concentration, the vinylformic acid 5.7g and the dimethylamino methyl ethyl propenoate 6.2g of 60% concentration that in the there-necked flask that is equipped with thermometer, stirrer, add 50% concentration of the foregoing description () preparation; adjust pH value to 3.5 with hydrochloric acid; under nitrogen protection, add the ammonium persulphate 1.5g of 10% concentration and the sodium bisulfite 4.5g of 10% concentration; 25 ℃ of arrest reactions of room temperature 12 hours, it is 20% that polymer concentration is adjusted with deionized water 24g in the reaction back.The results are shown in Table 1.
Embodiment 3
In the there-necked flask that is equipped with thermometer, stirrer, add linking agent 0.96g, the methacryloxyethyl trimethyl ammonium chloride 30g of 80% concentration of 50% concentration of the foregoing description () preparation, the 2-methyl-sodium allyl sulfonate 0.48g and the 88.56g deionized water of concentration 1% concentration; be warming up to 60 ℃; the V50 initiator 0.6g that under nitrogen protection, adds 10% concentration; react termination reaction after 4 hours; adding deionized water 1.8g adjustment polymer concentration is 20%, and it the results are shown in Table 1.
Embodiment 4
In the there-necked flask of being furnished with thermometer and whipping appts, add linking agent 5g, the dimethylamino-propyl acrylamide 25g of 50% concentration of the foregoing description () preparation, the 2-methyl-sodium allyl sulfonate 8g and the 82g deionized water of 1% concentration; be warming up to 60 ℃; the V50 initiator 0.6g that under nitrogen protection, adds 10% concentration; react termination reaction after 4 hours; adding deionized water 6.25g adjustment polymer concentration is 20%, the results are shown in Table 1.
Embodiment 5
Linking agent 1.32g, the acryloxy ethyl-trimethyl salmiac 30g of 80% concentration, 1% concentration 2-methyl-sodium allyl sulfonate 0.72g and the 87.96g deionized water that in the there-necked flask of being furnished with thermometer and whipping appts, add 50% concentration of the foregoing description () preparation; be warming up to 60 ℃; the V50 initiator 0.6g that under nitrogen protection, adds 10% concentration; react termination reaction after 4 hours; adding deionized water 2.7g adjustment polymer concentration is 20%, the results are shown in Table 1.
What introduce below is comparative example:
Comparative example 1
The acrylamide 96.2g, the vinylformic acid 5.6g and the dimethylin ethyl propenoate 8.6g of 60% concentration that in the there-necked flask of being furnished with thermometer and whipping appts, add 50% concentration, adjust pH value to 3.5 with aqueous hydrochloric acid, adding the total system weight of deionized water adjustment is 270g.Be warming up to 60 ℃, add ammonium persulphate and the sodium bisulfite 1.35g and the 1.35g of 10% concentration respectively, reaction stopped in 12 hours under nitrogen protection, adjusted polymer concentration to 20% with deionized water, the results are shown in Table 1.
Comparative example 2
The acrylamide 96.2g, vinylformic acid 5.6g, the dimethylin ethyl propenoate 8.6g of 60% concentration, the 1% concentration methylene radical N that in the there-necked flask of being furnished with thermometer and whipping appts, add 50% concentration, N-diacrylamine 3.0g and 1% concentration 2-methyl-sodium allyl sulfonate 1.8g, adjust pH value to 3.5 with aqueous hydrochloric acid, adding the total system weight of deionized water adjustment is 270g.Be warming up to 60 ℃, add ammonium persulphate and the sodium bisulfite 1.74g and the 1.74g of 10% concentration respectively, reaction stopped in 12 hours under nitrogen protection, adjusted polymer concentration to 20% with deionized water, the results are shown in Table 1.
Table 1
| 20% solution viscosity (mpa.s) | Weight-average molecular weight/Mw | Molecular weight distribution/Mn/Mw | |
| Embodiment 1 | 4220 | 594,000 | 13.6 |
| Embodiment 2 | 1530 | 369,000 | 13.5 |
| Embodiment 3 | 1600 | 195,000 | 12.8 |
| Embodiment 4 | 1784 | 195,000 | 15.4 |
| Embodiment 5 | 2340 | 107,000 | 10.9 |
| Comparative example 1 | 16700 | 326,000 | 2.21 |
| Comparative example 2 | 13000 | 428,000 | 2.67 |
20% solution viscosity is sticking as seen with rotation, and embodiment compares the molecular weight distribution of prepared product with comparative example very wide, illustrates that the action effect of novel crosslinker is fairly obvious.
Claims (6)
1, a kind of preparation method of water-soluble high-molecular material, its preparation process and condition comprise:
2. the preparation of water-soluble high-molecular material: be exactly the monomer system copolymerization of the cation type polymer linking agent of representing with chemical formula 1 that 1. prepares with step and the water-soluble monomer formation of Methacrylamide or acrylamide and chemical general formula 2 expressions, prepare a kind of water-soluble high-molecular material;
Said chemical general formula 2 is:
R wherein
7=H, CH
3, R
8, R
9The alkyl of=carbon number 1-3 or alkoxyl group, R
10The alkyl of=H or carbon number 1-3, alkoxyl group or benzyl, E=O or NH, alkyl or the alkoxyl group of F=carbon number 1-3, Y=bears counter ion;
The preparation method that general radical polymerization is used is applicable to the present invention: the weight percent concentration that monomer is occupied in reaction soln is used water solution polymerization process when 5-30%; Concentration can be with the method for dispersion polymerization or inverse emulsion polymerization when 20-70%;
The initiator that uses is that the initiator that the water-soluble polymer polymerization is suitable for is azo class, redox class, and the usage quantity of azo-initiator is the 0.001-1% of monomer total amount, and the initiator usage quantity of redox class is the 0.001-1% of monomer total amount; Polymerization is carried out under protection of inert gas, temperature of reaction 15-95 ℃;
It is characterized in that the present invention also comprises the preparation of step cation type polymer linking agent 1.:
The cation type polymer linking agent of representing with chemical formula 1 is to be made of epoxyhalopropane and ammonia, organic primary amine, organic secondary amine and trimethylamine; Epoxyhalopropane is meant epoxy chloropropane, epoxy bromopropane and epoxy iodopropane, can use wherein a kind of also can be used in combination; Organic primary amine is meant methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine; Organic secondary amine refer to dimethylamine, diethylamine, dipropyl amine, thyl methyl amine, first propylamine, pentanoic with and mutual combination; The acyl group monomer that contains organic tertiary amine is N, N dimethylamine base propyl methyl acid amides, N, N dimethylamine base propyl group acrylamide, N, N dimethylamine base propyl methyl acid amides, N, N dimethylamine base propyl group acrylamide, N, N dimethylamine base butyl methyl acrylamide, N, N dimethylamine ylmethyl Methacrylamide, N, the N-first and second aminocarbonyl propyl acrylamides, N, N dimethylamine ylmethyl vinylformic acid propylamine ester, N, N dimethylamine base vinylformic acid propylamine ester, N, N dimethylamine ylmethyl vinylformic acid methylamine ester;
Preparation cationic polymers linking agent, its order of addition(of ingredients) is: epoxyhalopropane is added in the reactor, drip ammonia, primary amine or secondary amine, the two reaction back adds the vinyl monomer that contains tertiary amine group and reacts; The vinyl monomer that also can drip ammonia, primary amine or secondary amine in the reactor that is added with epoxyhalopropane and contain tertiary amine group reacts, but avoid using opposite addition step, because Michael reaction takes place in ammonia, primary amine, secondary amine and vinyl monomer easily, can obtain the cationic product that end contains halogen so earlier ammonia, primary amine, secondary amine are splashed into the method for epoxyhalopropane, react than the vinyl monomer that is easier to containing tertiary amine group like this;
The end of the cationic polymers linking agent that said chemical formula 1 is represented contains two vinyl groups;
Chemical formula 1 is:
R wherein
1, R
2, R
3, R
4, R
5The alkyl of=hydrogen, carbon number 1-3 or benzyl,, R
6=hydrogen or methyl, n=0-50, B=0 or NH, X=halogen;
The cationic polymers linking agent represented of preparation chemical formula 1, ammonia, primary amine, secondary amine respectively with the ratio of epoxyhalopropane in the 0.15-1.20 molar range; The proportion requirement that contains the vinyl monomer of tertiary amine group and epoxyhalopropane is in the 0.15-0.24 molar range;
Temperature of reaction is at 10-90 ℃;
Reaction times is in 1-24 hour.
2,, it is characterized in that the B of the chemical formula 1 of said step in 1. be-NH-formation cation type polymer linking agent by the preparation method of the said a kind of water-soluble high-molecular material of claim 1.
3, the preparation method by claim 1 or the said a kind of water-soluble high-molecular material of 2 any one claim is characterized in that, the temperature of reaction of said step in 1. is 20-60 ℃.
4, by the preparation method of the said a kind of water-soluble high-molecular material of claim 1, it is characterized in that, said step 1. in, when ammonia, primary amine, secondary amine respectively when the ratio of epoxyhalopropane is in the 0.15-1.0 molar range, can add sodium hydroxide alkalescence catalyzer.
5, by the preparation method of the said a kind of water-soluble high-molecular material of claim 1, it is characterized in that, said step 1. in, use the N in the acrylic amide, N dimethylamine base propyl group acrylamide.
6,, it is characterized in that the polymeric reaction temperature that said step is carried out in 2. is 20-75 ℃ by the preparation method of the said a kind of water-soluble high-molecular material of claim 1 under protection of inert gas.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101402738B (en) * | 2007-07-23 | 2012-06-06 | 中国科学院成都有机化学有限公司 | Cationic polymer |
| CN102153697B (en) * | 2010-01-20 | 2014-09-03 | 荒川化学工业株式会社 | Water-soluble polymer dispersion liquid, paper strength agent, papermaking filter aid and papermaking retention agent |
| CN101818464B (en) * | 2010-03-16 | 2011-11-09 | 华泰集团有限公司 | Multi-arm branched cationic polymer retention and drainage aid for papermaking, and preparation method and application thereof |
| FR3056217B1 (en) * | 2016-09-21 | 2020-06-19 | S.P.C.M. Sa | PROCESS FOR OBTAINING CATIONIC POLYMERS WITH REDUCED HALIDE CONTENT |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046742A (en) * | 1989-04-26 | 1990-11-07 | 南朝鲜化学研究所 | The macromolecular material of no condensing water droplet and manufacture method thereof |
| EP0763547A1 (en) * | 1988-12-19 | 1997-03-19 | Cytec Technology Corp. | Microemulsified functionalized polymers |
| JPH0977810A (en) * | 1995-09-11 | 1997-03-25 | Mitsubishi Chem Corp | Production of water-absorbing resin |
| EP0736060B2 (en) * | 1993-12-23 | 2001-04-25 | STOCKHAUSEN GmbH & CO. KG | Cross-linked polymers with a porous structure |
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2005
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0763547A1 (en) * | 1988-12-19 | 1997-03-19 | Cytec Technology Corp. | Microemulsified functionalized polymers |
| CN1046742A (en) * | 1989-04-26 | 1990-11-07 | 南朝鲜化学研究所 | The macromolecular material of no condensing water droplet and manufacture method thereof |
| EP0736060B2 (en) * | 1993-12-23 | 2001-04-25 | STOCKHAUSEN GmbH & CO. KG | Cross-linked polymers with a porous structure |
| JPH0977810A (en) * | 1995-09-11 | 1997-03-25 | Mitsubishi Chem Corp | Production of water-absorbing resin |
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