CN103333352B - A kind of preparation method of cross-linked graft modified polyvinyl alcohol surface reinforcing agent - Google Patents
A kind of preparation method of cross-linked graft modified polyvinyl alcohol surface reinforcing agent Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of cross-linked graft modified polyvinyl alcohol surface reinforcing agent, the method comprises: mixed with water by polyvinyl alcohol and obtain polyvinyl alcohol water solution; This aqueous solution is heated up, adds the vinyl monomer of the vinyl monomer of ketocarbonyl-containing, cationic monomer, vinyl monomer, self-cross linking monomer and other types containing long side-chain radical, obtain vinyl monomer/polyvinyl alcohol mixing liquid; Water is mixed with water soluble starter and obtains initiator solution; In mixed solution, drip initiator solution, system is heated up, reacts to acrylate-free class monomer smell; System is cooled to room temperature, uses alkali adjust ph, add hydrazine or derivatives thereof and stir, cross-linked graft modified polyvinyl alcohol surface reinforcing agent can be obtained.Adopt the present invention, the stability of system can not be affected; Use it for paper surface reinforcing agent, significantly can improve the surface strength of paper, water tolerance, tensile strength and folding endurance etc., improve its film forming properties.
Description
Technical field
The present invention relates to a kind of preparation method of cross-linked graft modified polyvinyl alcohol surface reinforcing agent.
Background technology
Polyvinyl alcohol has superior cohesive strength and film-forming properties, by the long-term top sizing for paper, can improve the tensile strength and folding endurance etc. of paper to a certain extent.But polyvinyl alcohol is used for top sizing still to come with some shortcomings part.Though polyvinyl alcohol surface is containing a large amount of hydroxyl, can not completely and processbearing astrocyte hydrogen bonded, in addition its in damp atmosphere, easily water suction change is damp, paper water resisting property and surface strength poor, in printing process, easily there is hair and powder dropping phenomenon.Therefore, modification need be carried out to expand polyvinyl alcohol Application Areas to it.At present, the method for modifying of polyvinyl alcohol is mainly contained following several: (1) utilizes silicic acid, boric acid or phosphoric acid that the hydroxyl on polyvinyl alcohol is carried out esterification, when polyvinyl alcohol drying and dehydrating, can crosslinking structure be formed, improve its water tolerance.(2) graft copolymerization carried out to polyvinyl alcohol and be cross-linked.As polyvinyl alcohol and methacrylic chloride ethyl-trimethyl salmiac and glycidyl methacrylate carried out graft copolymerization and crosslinked, graft crosslinking modified polyvinyl alcohol is used for paper plasm-glue-blending dry strength agent, have paper and significantly increase dry potent fruit, but this report graft crosslinking modified polyvinyl alcohol being used for paper for surface sizing is little.
Summary of the invention
The object of this invention is to provide and there is good stability, snappiness is strong, film forming properties is high, and for the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent that significantly can improve surface strength of paper, water tolerance, tensile strength, folding endurance and bonding force after paper surface reinforcing agent.
The technical scheme that the present invention takes is: a kind of preparation method of cross-linked graft modified polyvinyl alcohol surface reinforcing agent, it is characterized in that it comprises the following steps: (1) by the polyvinyl alcohol of different polymerization degree, alcoholysis degree and water and mix by the mass ratio of 1 ︰ 5 ~ 15 obtaining polyvinyl alcohol water solution; (2) polyvinyl alcohol water solution containing solid polyethylene alcohol 100 parts is warming up to 70 ~ 75 DEG C, add the vinyl monomer of the vinyl monomer of 5 ~ 15 parts of ketocarbonyl-containings, 2 ~ 10 parts of cationic monomers, 1 ~ 5 part of vinyl monomer containing long side-chain radical, 5 ~ 15 parts of self-cross linking monomers and 1 ~ 45 part of other types, obtain vinyl monomer/polyvinyl alcohol mixing liquid; (3) water and water soluble starter are mixed by the mass ratio of 1 ︰ 0.002 ~ 1 obtain initiator solution; (4) in vinyl monomer/polyvinyl alcohol mixing liquid, initiator solution is dripped, wherein initiator solution accounts for the mass percent of polyvinyl alcohol and monomer total mass is 1% ~ 6%, time for adding is 30 ~ 100 minutes, after dropwising, system is warming up to 70 ~ 85 DEG C, continues reaction 2 ~ 4 little of acrylate-free class monomer smell; (5) system is cooled to room temperature, be 7 ~ 9 by alkali adjust ph, add hydrazine or derivatives thereof, wherein the mol ratio of the vinyl monomer of hydrazine or derivatives thereof and ketocarbonyl-containing is between 3 ︰ 1 ~ 1 ︰ 3, after stirring, cross-linked graft modified polyvinyl alcohol surface reinforcing agent can be obtained.
The preparation method of described a kind of cross-linked graft modified polyvinyl alcohol, it is characterized in that the polyvinyl alcohol trade mark of different polymerization degree, alcoholysis degree is respectively 0588,1099,1750,1788,1799,1899,2099,2488,2497, and can be a kind of, two or more the mixture of any proportioning wherein.
The preparation method of described a kind of cross-linked graft modified polyvinyl alcohol, is characterized in that the vinyl monomer of ketocarbonyl-containing is a kind of, two or more the mixture of any proportioning in diacetone-acryloamide(DAA), methyl vinyl ketone, (methyl) vinylformic acid acetoacetoxyethyl ester, (methyl) vinylformic acid acetoacetyl amido ethyl ester.
The preparation method of described a kind of cross-linked graft modified polyvinyl alcohol, is characterized in that cationic monomer is a kind of, two or more the mixture of any proportioning in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl benzyl ammonium chloride, p-vinylbenzyltrimethyl ammonium chloride, Dimethylaminoethyl Methacrylate Benzyl Chloride quaternary ammonium, diallyldimethylammonium chloride.
The preparation method of described a kind of cross-linked graft modified polyvinyl alcohol, it is characterized in that the vinyl monomer containing long side-chain radical is (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, a kind of, two or more the mixture of any proportioning in Isooctyl acrylate monomer.
The preparation method of described a kind of cross-linked graft modified polyvinyl alcohol, is characterized in that self-cross linking monomer is a kind of, two or more the mixture of any proportioning in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methylol) acrylamide, n-methylolacrylamide, diacetone-acryloamide(DAA), glycidyl methacrylate.
The preparation method of described a kind of cross-linked graft modified polyvinyl alcohol, the vinyl monomer that it is characterized in that other types is (methyl) methyl acrylate, a kind of, two or more the mixture of any proportioning in (methyl) ethyl propenoate, vinylbenzene, alpha-methyl styrene.
The preparation method of described a kind of cross-linked graft modified polyvinyl alcohol, is characterized in that water soluble starter is the one of ammonium cerous sulfate, ceric ammonium nitrate, ammonium persulphate, iron trichloride-potassium metabisulfite, cupric chloride-S-WAT, copper sulfate-S-WAT, Potassium Persulphate, ammonium persulphate-sulfurous acid (hydrogen) sodium, Potassium Persulphate-sulfurous acid (hydrogen) sodium, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine.
The preparation method of described a kind of cross-linked graft modified polyvinyl alcohol, is characterized in that hydrazine or derivatives thereof is the mixture of a kind of, two or more any proportioning in adipic dihydrazide, carbon acid dihydrazide, careless acid dihydrazide, succinic acid hydrazide ii, adipic dihydrazide.
The preparation method of described a kind of cross-linked graft modified polyvinyl alcohol, is characterized in that alkali is the one in ammoniacal liquor, sodium hydroxide, triethylamine.
Adopt the present invention, introduce in polyvinyl alcohol system by crosslinked for ketone hydrazine, its crosslinking reaction is at room temperature carried out, and only has in use, namely just can occur when drying and dehydrating, and therefore the introducing of this cross-linking system can not affect the stability of system; On polyvinyl alcohol molecule chain, a large amount of reactive groups is introduced by chemical graft copolymerization, use it for paper surface reinforcing agent, effectively can improve polyvinyl alcohol and the interfibrous interaction of paper, form the three-dimensional crosslinked network structure of very high strength, significantly improve the surface strength of paper, water tolerance, tensile strength and folding endurance etc.; Meanwhile, paper fiber surface is mostly electronegative, and the cationization of polyvinyl alcohol also can increase polyvinyl alcohol and the interfibrous bonding force of paper; Containing the introducing of the vinyl monomer of long side-chain radical, the snappiness of polyvinyl alcohol glued membrane can be improved, improve its film forming properties.
Embodiment
Below in conjunction with enforcement, the present invention is described in further detail.
One, embodiment one.It comprises the following steps:
1) by the trade mark be 1799 polyvinyl alcohol and water mix by the mass ratio of 1 ︰ 9 and obtain polyvinyl alcohol water solution;
2) polyvinyl alcohol water solution (wherein solid polyethylene alcohol 100 parts) is warming up to 70 ~ 75 DEG C, add the vinyl monomer of the vinyl monomer of 10 parts of ketocarbonyl-containings, 3 parts of cationic monomers, 2 parts of vinyl monomers containing long side-chain radical, 7 parts of self-cross linking monomers and 20 parts of other types, obtain vinyl monomer/polyvinyl alcohol mixing liquid;
3) water and water soluble starter are mixed by the mass ratio of 1 ︰ 0.01 obtain initiator solution;
4) in vinyl monomer/polyvinyl alcohol mixing liquid, initiator solution is dripped, wherein initiator account for that the mass percent of polyvinyl alcohol and monomer total mass is 3%, time for adding is 60 minutes, after dropwising, system is warming up to 80 DEG C, continues reaction 3 little of acrylate-free class monomer smell;
5) system being cooled to room temperature, is 7 by alkali adjust ph, adds hydrazine or derivatives thereof, and wherein the mol ratio of the vinyl monomer of hydrazine or derivatives thereof and ketocarbonyl-containing is between 1 ︰ 1, after stirring, can obtain cross-linked graft modified polyvinyl alcohol surface reinforcing agent.
The vinyl monomer of described ketocarbonyl-containing is diacetone-acryloamide(DAA); Described cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride; The described vinyl monomer containing long side-chain radical is butyl methacrylate; Described self-cross linking monomer is Rocryl 410; The vinyl monomer of described other types is β-dimethyl-aminoethylmethacrylate; Described water soluble starter is ceric ammonium nitrate; Described hydrazine or derivatives thereof is carbon acid dihydrazide; Described alkali is ammoniacal liquor.
Two, embodiment two.It comprises the following steps:
1) by the trade mark be 1099 polyvinyl alcohol and water mix by the mass ratio of 1 ︰ 10 and obtain polyvinyl alcohol solution;
2) polyvinyl alcohol water solution (wherein solid polyethylene alcohol 100 parts) is warming up to 70 DEG C, add the vinyl monomer of the vinyl monomer of 10 parts of ketocarbonyl-containings, 3 parts of cationic monomers, 3 parts of vinyl monomers containing long side-chain radical, 6 parts of self-cross linking monomers and 12 parts of other types, obtain vinyl monomer/polyvinyl alcohol mixing liquid;
3) water and water soluble starter are mixed by the mass ratio of 1 ︰ 0.05 obtain initiator solution;
4) in vinyl monomer/polyvinyl alcohol mixing liquid, initiator solution is dripped, wherein initiator accounts for the mass percent of polyvinyl alcohol and monomer total mass is 3.5%, time for adding is 80 minutes, after dropwising, system is warming up to 85 DEG C, continues reaction 2.5 little of acrylate-free class monomer smell;
5) system is cooled to room temperature, be 8 by alkali adjust ph, add hydrazine or derivatives thereof, wherein the mol ratio of the vinyl monomer of hydrazine or derivatives thereof and ketocarbonyl-containing is between 1.5 ︰ 1, after stirring, cross-linked graft modified polyvinyl alcohol surface reinforcing agent can be obtained.
The vinyl monomer of described ketocarbonyl-containing is diacetone-acryloamide(DAA); Described cationic monomer is acrylyl oxy-ethyl-trimethyl salmiac; The described vinyl monomer containing long side-chain radical is N-Hexyl methacrylate; Described self-cross linking monomer is n-methylolacrylamide; The vinyl monomer of described other types is β-dimethyl-aminoethylmethacrylate; Described water soluble starter is ammonium persulphate; Described hydrazine or derivatives thereof is adipic dihydrazide; Described alkali is ammoniacal liquor.
Three, embodiment three.It comprises the following steps:
1) by the trade mark be 2099 polyvinyl alcohol and water mix by the mass ratio of 1 ︰ 15 and obtain polyvinyl alcohol solution;
2) polyvinyl alcohol water solution (wherein solid polyethylene alcohol 100 parts) is warming up to 75 DEG C, add the vinyl monomer of the vinyl monomer of 12 parts of ketocarbonyl-containings, 3 parts of cationic monomers, 5 parts of vinyl monomers containing long side-chain radical, 5 parts of self-cross linking monomers and 9 parts of other types, obtain vinyl monomer/polyvinyl alcohol mixing liquid;
3) water and water soluble starter are mixed by the mass ratio of 1 ︰ 0.01 obtain initiator solution;
4) in vinyl monomer/polyvinyl alcohol mixing liquid, initiator solution is dripped, wherein initiator accounts for the mass percent of polyvinyl alcohol and monomer total mass is 4%, time for adding is 60 minutes, after dropwising, system is warming up to 80 DEG C, continues reaction 3 little of acrylate-free class monomer smell;
5) system is cooled to room temperature, be 7 by alkali adjust ph, add hydrazine or derivatives thereof, wherein the mol ratio of the vinyl monomer of hydrazine or derivatives thereof and ketocarbonyl-containing is between 1.2 ︰ 1, after stirring, cross-linked graft modified polyvinyl alcohol surface reinforcing agent can be obtained.
The vinyl monomer of described ketocarbonyl-containing is acetoacetoxyethyl ethyl ester; Described cationic monomer is acryloxyethyldimethyl benzyl ammonium chloride; The described vinyl monomer containing long side-chain radical is butyl acrylate; Described self-cross linking monomer is diacetone-acryloamide(DAA); The vinyl monomer of described other types is vinylbenzene; Described water soluble starter is cupric chloride-S-WAT; Described hydrazine or derivatives thereof is carbon acid dihydrazide; Described alkali is sodium hydroxide.
Four, embodiment four.It comprises the following steps:
1) to be 1788 polyvinyl alcohol by the trade mark with water mix by the mass ratio of 1 ︰ 12 obtains polyvinyl alcohol solution;
2) polyvinyl alcohol water solution (wherein solid polyethylene alcohol 100 parts) is warming up to 75 DEG C, add the vinyl monomer of the vinyl monomer of 12 parts of ketocarbonyl-containings, 4 parts of cationic monomers, 5 parts of vinyl monomers containing long side-chain radical, 8 parts of self-cross linking monomers and 12 parts of other types, obtain vinyl monomer/polyvinyl alcohol mixing liquid;
3) water and water soluble starter are mixed by the mass ratio of 1 ︰ 0.005 obtain initiator solution;
4) in vinyl monomer/polyvinyl alcohol mixing liquid B, initiator solution is dripped, wherein initiator accounts for the mass percent of polyvinyl alcohol and monomer total mass is 4%, time for adding is 60 minutes, after dropwising, system is warming up to 80 DEG C, continues reaction 4 little of acrylate-free class monomer smell;
5) system being cooled to room temperature, is 8 by alkali adjust ph, adds hydrazine or derivatives thereof, and wherein the mol ratio of the vinyl monomer of hydrazine or derivatives thereof and ketocarbonyl-containing is between 2 ︰ 1, after stirring, can obtain cross-linked graft modified polyvinyl alcohol surface reinforcing agent.
The vinyl monomer of described ketocarbonyl-containing is diacetone-acryloamide(DAA); Described cationic monomer is Dimethylaminoethyl Methacrylate Benzyl Chloride quaternary ammonium; The described vinyl monomer containing long side-chain radical is butyl methacrylate; Described self-cross linking monomer is hydroxyethyl methylacrylate; The vinyl monomer of described other types is ethyl propenoate; Described water soluble starter is iron trichloride-potassium metabisulfite; Described hydrazine or derivatives thereof is succinic acid hydrazide ii; Described alkali is ammoniacal liquor.
Five, the detected result of embodiment.
The four kinds of cross-linked graft modified polyvinyl alcohol surface reinforcing agents obtained by example 1 ~ 4 are respectively used to paper for surface sizing, and detect the correlated performance of body paper and applying glue pattern, and result is as table 1.
Table 1
| Embodiment | Tensile strength (KN/m) | Surface strength (m/s) | Degree of sizing (s) | Folding endurance (two times) |
| Body paper | 2.1 | 0.4 | 0.0 | 8 |
| Embodiment one | 3.8 | 1.6 | 30 | 138 |
| Embodiment two | 3.5 | 1.5 | 29 | 106 |
| Embodiment three | 4.0 | 1.8 | 32 | 155 |
| Embodiment four | 4.2 | 1.9 | 35 | 129 |
Claims (10)
1. a preparation method for cross-linked graft modified polyvinyl alcohol surface reinforcing agent, is characterized in that it comprises the following steps: (1) by the polyvinyl alcohol of different polymerization degree, alcoholysis degree and water and mixes by the mass ratio of 1 ︰ 5 ~ 15 obtaining polyvinyl alcohol water solution; (2) polyvinyl alcohol water solution containing solid polyethylene alcohol 100 parts is warming up to 70 ~ 75 DEG C, add the vinyl monomer of the vinyl monomer of 5 ~ 15 parts of ketocarbonyl-containings, 2 ~ 10 parts of cationic monomers, 1 ~ 5 part of vinyl monomer containing long side-chain radical, 5 ~ 15 parts of self-cross linking monomers and 1 ~ 45 part of other types, obtain vinyl monomer/polyvinyl alcohol mixing liquid; (3) water and water soluble starter are mixed by the mass ratio of 1 ︰ 0.002 ~ 1 obtain initiator solution; (4) in vinyl monomer/polyvinyl alcohol mixing liquid, initiator solution is dripped, wherein initiator solution accounts for the mass percent of polyvinyl alcohol and monomer total mass is 1% ~ 6%, time for adding is 30 ~ 100 minutes, after dropwising, system is warming up to 70 ~ 85 DEG C, continues reaction 2 ~ 4 little of acrylate-free class monomer smell; (5) system is cooled to room temperature, be 7 ~ 9 by alkali adjust ph, add hydrazine or derivatives thereof, wherein the mol ratio of the vinyl monomer of hydrazine or derivatives thereof and ketocarbonyl-containing is between 3 ︰ 1 ~ 1 ︰ 3, after stirring, cross-linked graft modified polyvinyl alcohol surface reinforcing agent can be obtained.
2. the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent according to claim 1, it is characterized in that the polyvinyl alcohol trade mark of different polymerization degree, alcoholysis degree is respectively 0588,1099,1750,1788,1799,1899,2099,2488,2497, and can be a kind of, two or more the mixture of any proportioning wherein.
3. the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent according to claim 1, is characterized in that the vinyl monomer of ketocarbonyl-containing is a kind of, two or more the mixture of any proportioning in methyl vinyl ketone, (methyl) vinylformic acid acetoacetoxyethyl ester, (methyl) vinylformic acid acetoacetyl amido ethyl ester.
4. the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent according to claim 1, is characterized in that cationic monomer is a kind of, two or more the mixture of any proportioning in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryloxyethyldimethyl benzyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl benzyl ammonium chloride, p-vinylbenzyltrimethyl ammonium chloride, Dimethylaminoethyl Methacrylate Benzyl Chloride quaternary ammonium, diallyldimethylammonium chloride.
5. the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent according to claim 1, is characterized in that the vinyl monomer containing long side-chain radical is (methyl) butyl acrylate, a kind of, two or more the mixture of any proportioning in (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, Isooctyl acrylate monomer.
6. the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent according to claim 1, is characterized in that self-cross linking monomer is a kind of, two or more the mixture of any proportioning in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, n-methylolacrylamide, glycidyl methacrylate.
7. the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent according to claim 1, is characterized in that the vinyl monomer of other types is (methyl) methyl acrylate, a kind of, two or more the mixture of any proportioning in (methyl) ethyl propenoate, vinylbenzene, alpha-methyl styrene.
8. the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent according to claim 1, is characterized in that water soluble starter is the one of ammonium cerous sulfate, ceric ammonium nitrate, ammonium persulphate, iron trichloride-potassium metabisulfite, cupric chloride-S-WAT, copper sulfate-S-WAT, Potassium Persulphate, ammonium persulfate-sodium bisulfite, Potassium Persulphate-sodium bisulfite, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine.
9. the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent according to claim 1, is characterized in that hydrazine or derivatives thereof is the mixture of a kind of, two or more any proportioning in adipic dihydrazide, carbon acid dihydrazide, careless acid dihydrazide, succinic acid hydrazide ii, adipic dihydrazide.
10. the preparation method of a kind of cross-linked graft modified polyvinyl alcohol surface reinforcing agent according to claim 1, is characterized in that alkali is the one in ammoniacal liquor, sodium hydroxide, triethylamine.
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| CN104119480B (en) * | 2014-07-10 | 2017-05-24 | 九洲生物技术（苏州）有限公司 | High-branch type polyvinyl alcohol-acrylamide graft copolymer, preparing method thereof and applications of the copolymer |
| CN104452426B (en) * | 2014-11-20 | 2016-08-24 | 浙江恒达新材料股份有限公司 | A kind of preparation method of speciality paper reinforcing fiber |
| CN105062389A (en) * | 2015-08-26 | 2015-11-18 | 界首市天鸿新材料股份有限公司 | Adhesive for package paper |
| CN106283867A (en) * | 2016-06-03 | 2017-01-04 | 山东源根化学技术研发有限公司 | A kind of table glue reinforcing agent and preparation method thereof |
| CN106866886A (en) * | 2016-12-30 | 2017-06-20 | 浙江可思克高新材料股份有限公司 | A kind of paper both sexes drying strengthening agent |
| CN108554391A (en) * | 2017-12-08 | 2018-09-21 | 孝感市锐思新材科技有限公司 | One kind three（Trimethyl silane）The preparation method of borate polymeric material |
| CN114072436B (en) * | 2019-06-24 | 2023-12-08 | 凯米拉公司 | Polymeric structure and use thereof |
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| CN114686015B (en) * | 2022-04-25 | 2023-03-14 | 杭州美盾医用材料有限公司 | Environment-friendly biomass-based degradable material and preparation method thereof |
| CN115531215B (en) * | 2022-09-27 | 2023-08-22 | 上海昉科瑆材料科技有限公司 | Solid mask and preparation method thereof |
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