CN100338305C - Method for preparing amphiprotic intensifier for paper - Google Patents
Method for preparing amphiprotic intensifier for paper Download PDFInfo
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- CN100338305C CN100338305C CNB2004100213837A CN200410021383A CN100338305C CN 100338305 C CN100338305 C CN 100338305C CN B2004100213837 A CNB2004100213837 A CN B2004100213837A CN 200410021383 A CN200410021383 A CN 200410021383A CN 100338305 C CN100338305 C CN 100338305C
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Abstract
The present invention relates to a preparation method for amphoteric paper reinforcing agents. Five-unit or six-unit copolymer type paper reinforcing agents with the molecular weight of 20 to 40 ten thousand are prepared by acrylamide and derivatives thereof, cation monomers, anion monomers, hydrophobic monomers, crosslinking agents and chain transfer agents through water solution copolymerization in an oxidation-reduction initiation system. The method of the present invention has the advantages of simplicity, practicality, short production cycle, easy control of the molecular weight, and obvious reinforcing effect.
Description
Technical field: the present invention relates to a kind of amphoteric polyacrylamide, is the preparation method who belongs to multiple copolymer type amphoteric polyacrylamide intensifier for paper.
Background technology: at present, preparation amphoteric polyacrylamide intensifier for paper is mainly with acrylamide both at home and abroad, acrylic acid and cationic monomer are the terpolymer or the quadripolymer of raw material, disclose a kind of as Japanese kokai publication hei 8-226092 patent documentation with acrylamide, fumaric acid (or acrylic acid), acrylamido oxypropyl trimethyl ammonium chloride is that main raw material prepares amphoteric intensifier for paper, Japanese kokai publication hei 3-227483,227484,227489,227490 patent documentations disclose a kind of with acrylamide, acrylic acid (or itaconic acid), dimethylamino methyl ethyl acrylate (or methylacryoyloxyethyl trimethyl ammonium chloride, the methylacryoyloxyethyl dimethyl benzyl ammonium chloride) prepares intensifier for paper for main raw material.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of multiple copolymer type amphoteric polyacrylamide intensifier for paper.
The preparation method of multi-component copolymer type amphoteric polyacrylamide intensifier for paper of the present invention, raw material comprises acrylamide monomers, anionic monomer, cationic monomer, it is characterized in that: also add hydrophobic type monomer, crosslinking agent formation mix monomer, and adding chain-transferring agent, aqueous solution copolymerization closes in oxidation-reduction trigger system, obtains multiple copolymer type amphoteric polyacrylamide intensifier for paper.The addition of described hydrophobic type monomer is 1～20% of a mix monomer weight, and the addition of crosslinking agent is 0～5% of a mix monomer weight, and the addition of chain-transferring agent is 2～30% of a mix monomer weight.Other compositions of mix monomer can add according to conventional ratio.Raw materials used is dimethyl diallyl ammonium chloride, acrylamide and derivatives class monomer thereof, as acrylamide, Methacrylamide, N, N-DMAA, methylacryoyloxyethyl trimethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, 2-acrylamido-2-methyl propane sulfonic acid etc., the unsaturated carboxylic acid class, as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid etc., hydrophobic type such as acrylonitrile, vinylacetate monomer, crosslinking agents such as epoxychloropropane, glycerine, methene base bisacrylamide, methyl propenoic acid glycidyl ether.
The present invention adopts aqueous solution polymerization method, uses oxidation-reduction trigger system, and the oxidation-reduction trigger system of use can use according to routine.In order better to realize this method, the oxidant in the oxidation-reduction trigger system is preferably persulfate, and addition is 1～10% of a mix monomer weight, and reductant is preferably sulphite or organic amine salt, and addition is 0.3～5% of a mix monomer weight.
Oxidant is preferably persulfates such as potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, peroxide such as hydrogen peroxide, addition is 1～10% of a mix monomer weight, reductant is sulphite such as sodium sulfite, sodium hydrogensulfite, organic compounds such as ethylenediamine, monoethanolamine, diethanol amine, triethanolamine, ascorbic acid, addition is 0.3～5% of a mix monomer weight.
The present invention preferably adds chain-transferring agents such as methyl alcohol, ethanol, acetone, isopropyl alcohol, sodium formate, urea, regulates molecular weight, and addition is 2～30% of a mix monomer weight.If do not add chain-transferring agent, be difficult to obtain the intensifier for paper of suitable molecular weight.The pH value of copolymerization system reaction preferably is controlled between 2.5～5.5.If pH value is too low or too high, all influence the reinforcing agent performance.The mix monomer concentration of aqueous solution preferably is controlled at 15～30%, and the combined polymerization initiation temperature is preferably 10～80 ℃, and polymerization time is 1～5 hour.
Characteristics of the present invention are to have added chain-transferring agent in copolymerization process, can obtain the intensifier for paper of suitable molecular weight, have also added hydrophobic type monomer and crosslinking agent, can improve paper strength and water resistance.
Specific embodiment:
Embodiment 1, the 216.57kg deionized water is put into still, under agitation add acrylamide 46.23kg, dimethyl diallyl ammonium chloride 13.8kg, fumaric acid 4.83kg, methacrylic acid 4.14kg, vinylacetate 5.52kg, methyl propenoic acid glycidyl ether 0.03kg, isopropyl alcohol 6.9kg, triethanolamine 0.6kg successively, adjusting pH value is 2.8, feed nitrogen flooding except that the dissolved oxygen in the mixed liquor, simultaneously heat temperature raising to 50 ℃ adds 10% persulfate aqueous solution 20.7kg.Thin up behind the polyase 13 hour, obtaining molecular weight is 330,000, and solid content is 15.3%, and pH value is 3.4 intensifier for paper.
Embodiment 2, the 216.57kg deionized water is put into still, under agitation add acrylamide 46.23kg, dimethyl diallyl ammonium chloride 13.8kg, methacrylic acid 4.83kg, crotonic acid 4.14kg, vinylacetate 5.52kg, epoxychloropropane 0.03kg, isopropyl alcohol 6.9kg, diethanol amine 0.6kg successively, adjusting pH value is 3.0, feed nitrogen flooding except that the dissolved oxygen in the reactant liquor, simultaneously heat temperature raising to 60 ℃ adds 10% ammonium persulfate aqueous solution 20.7kg.Polymerization is thin up after 4 hours, and obtaining molecular weight is 270,000, and solid content is 15.2%, and pH value is 3.6 intensifier for paper.
Embodiment 3, the 216.57kg deionized water is put into still, under agitation add acrylamide 41.4kg successively, N, N-DMAA 4.83kg, acrylyl oxy-ethyl-trimethyl salmiac 13.8kg, 2-acrylamido-2-methyl propane sulfonic acid 4.14kg, acrylic acid 4.83kg, acrylonitrile 5.52kg, glycerine 0.05kg, sodium formate 0.9kg, sodium sulfite 0.6kg, adjusting pH value is 2.7, feed nitrogen flooding and remove oxygen, heat temperature raising to 50 ℃ simultaneously, add 10% sodium persulfate aqueous solution 20.7kg, thin up behind the polyase 13 hour, obtaining molecular weight is 220,000, and solid content is 15.4%, and pH value is 3.4 intensifier for paper.
Embodiment 4, the 216.57kg deionized water is put into still, under stirring condition, add Methacrylamide 4.3kg successively, acrylamide 37.1kg, dimethyl diallyl ammonium chloride 11.4kg, itaconic acid 5.3kg, fumaric acid 1.5kg, acrylonitrile 13kg, methene base bisacrylamide 0.001kg, isopropyl alcohol 20kg, triethanol ammonium 0.6kg, regulating pH value is 4.2, feed the nitrogen deoxygenation, heat temperature raising to 73 ℃ simultaneously, add 10% persulfate aqueous solution 17.6kg, polymerization is thin up after 5 hours, and obtaining molecular weight is 120,000, solid content is 15.3%, pH value is 5.2 intensifier for paper.
Embodiment 5, the 216.57kg deionized water is put into still, under stirring condition, add acrylamide 46.23kg successively, methylacryoyloxyethyl trimethyl ammonium chloride 3kg, acrylyl oxy-ethyl-trimethyl salmiac 9.3kg, 2-acrylamido-2-methyl propane sulfonic acid 2.14kg, itaconic acid 6.3kg, acrylonitrile 5.52kg, epoxychloropropane 0.06kg, sodium formate 0.5kg, sodium hydrogensulfite 0.6kg, regulating pH value is 4.8, feed the nitrogen deoxygenation, heat temperature raising to 60 ℃ simultaneously, add 10% persulfate aqueous solution 20.7kg, polymerization is thin up after 5 hours, and obtaining molecular weight is 340,000, solid content is 15.3%, pH value is 5.9 intensifier for paper.
Embodiment 6, the 216.57kg deionized water is put into still, under stirring condition, add acrylamide 56.23kg successively, methylacryoyloxyethyl trimethyl ammonium chloride 2kg, acrylyl oxy-ethyl-trimethyl salmiac 5.3kg, acrylic acid 2.14kg, itaconic acid 3.3kg, acrylonitrile 3.52kg, methene base bisacrylamide 0.03kg, sodium formate 0.6kg, sodium hydrogensulfite 0.6kg, regulating pH value is 3.6, feed the nitrogen deoxygenation, heat temperature raising to 40 ℃ simultaneously, add 10% persulfate aqueous solution 20.7kg, polymerization is thin up after 4.5 hours, obtains molecular weight 460,000, solid content is 15.4%, pH value is 4.8 intensifier for paper.
Claims (4)
1. amphoteric intensifier for paper preparation method, comprise acrylamide monomers, the anionic monomer, cationic monomer, the hydrophobic type monomer, crosslinking agent carries out aqueous solution copolymerization at interior mix monomer and chain-transferring agent and closes in oxidation-reduction initiating system, obtain multiple copolymer type amphoteric polyacrylamide intensifier for paper, the addition of described hydrophobic type monomer is 1～20% of a mix monomer weight, the addition of crosslinking agent is 0～5% of a mix monomer weight, the addition of chain-transferring agent is 2～30% of a mix monomer weight, oxidant in the described oxidation-reduction initiating system is a persulfate, addition is 1～10% of a mix monomer weight, reductant is sulphite or organic amine salt, addition is 0.3～5% of a mix monomer weight, the pH value that aqueous solution copolymerization closes is 2.5～5.5, co-polymerization temperature is 10～80 ℃, and the combined polymerization time is 1～5 hour.
2. intensifier for paper preparation method according to claim 1 is characterized in that the hydrophobic type monomer is acrylonitrile or vinylacetate.
3. the intensifier for paper preparation method who states according to claim 2 is characterized in that crosslinking agent is epoxychloropropane, glycerine, methene base bisacrylamide or methyl propenoic acid glycidyl ether.
The 4 intensifier for paper preparation methods that state according to claim 1 or 2 or 3 is characterized in that chain-transferring agent is methyl alcohol, ethanol, acetone, isopropyl alcohol, sodium formate or urea.
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| CNB2004100213837A CN100338305C (en) | 2004-03-11 | 2004-03-11 | Method for preparing amphiprotic intensifier for paper |
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| CNB2004100213837A CN100338305C (en) | 2004-03-11 | 2004-03-11 | Method for preparing amphiprotic intensifier for paper |
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| CN100338305C true CN100338305C (en) | 2007-09-19 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062963B (en) * | 2006-04-24 | 2011-09-21 | 播磨化成株式会社 | Preparation method for water-soluble polymers and paper-making additive |
| CN101666059B (en) * | 2009-09-15 | 2013-03-06 | 浙江传化华洋化工有限公司 | Reinforcing agent of amphoteric polyacrylamide cardboard paper |
| CN102050915B (en) * | 2010-11-30 | 2014-05-07 | 广州星业科技股份有限公司 | Method for preparing polymer for improving paper strength |
| CN102776802B (en) * | 2011-05-10 | 2014-08-06 | 永港伟方（北京）科技股份有限公司 | Reinforcing agent for papermaking and preparation method thereof |
| CN102720094B (en) * | 2012-06-29 | 2014-08-06 | 上海东升新材料有限公司 | Branch type dry strength agent and preparation method thereof |
| CN103981759B (en) * | 2014-04-21 | 2015-11-25 | 苏州恒康新材料有限公司 | Emulsion-type wet strength agent and preparation method thereof |
| CN106188402B (en) * | 2016-06-30 | 2018-08-14 | 浙江弘利新材料有限公司 | A kind of waterborne epoxy modified acrylic lotion and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02139494A (en) * | 1988-11-17 | 1990-05-29 | Harima Chem Inc | Additive for paper making |
| JPH05272092A (en) * | 1992-03-17 | 1993-10-19 | Arakawa Chem Ind Co Ltd | Production of additive for paper production |
| CN1226567A (en) * | 1997-11-28 | 1999-08-25 | 三井化学株式会社 | Novel polymer and application thereof |
| CN1388288A (en) * | 2002-02-20 | 2003-01-01 | 杭州市化工研究所 | Dry paper reinforcer |
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- 2004-03-11 CN CNB2004100213837A patent/CN100338305C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02139494A (en) * | 1988-11-17 | 1990-05-29 | Harima Chem Inc | Additive for paper making |
| JPH05272092A (en) * | 1992-03-17 | 1993-10-19 | Arakawa Chem Ind Co Ltd | Production of additive for paper production |
| CN1226567A (en) * | 1997-11-28 | 1999-08-25 | 三井化学株式会社 | Novel polymer and application thereof |
| CN1388288A (en) * | 2002-02-20 | 2003-01-01 | 杭州市化工研究所 | Dry paper reinforcer |
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