CN100373004C - Preparation method of cationic colophony sizing agent macromolecule emulsifier system - Google Patents
Preparation method of cationic colophony sizing agent macromolecule emulsifier system Download PDFInfo
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- CN100373004C CN100373004C CNB2006100418253A CN200610041825A CN100373004C CN 100373004 C CN100373004 C CN 100373004C CN B2006100418253 A CNB2006100418253 A CN B2006100418253A CN 200610041825 A CN200610041825 A CN 200610041825A CN 100373004 C CN100373004 C CN 100373004C
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Abstract
The present invention discloses a preparation method of a cationic colophony sizing agent macromolecule emulsifier system, which comprises the following steps: firstly, styrene, propenoate, cationic monomers and oil-soluble evocating agents are uniformly mixed and added to isopropanol or acetone or N, N-dimethylformamide to be polymerized; reduced pressure distillation is carried out to remove organic solvent to obtain water-soluble copolymers; then, the styrene, the propenoate, the cationic monomers, the N, N-dimethyl formamide and the water-soluble copolymers are mixed, pre-emulsified and initiated by ammonium persulfate to be polymerized. The adoption of the present invention can greatly reduce the addition level of aluminium sulfate and increase the retention rate of colophony sizing agents and the application effects of the colophony sizing agents.
Description
Technical field
The invention belongs to the papermaking chemical product field, particularly a kind of preparation method of cationic colophony sizing agent macromolecule emulsifier system.
Background technology
Along with (alkali) propertyization in the paper making system, cation colophony size has obtained using widely because of having from advantages such as keeping, near neutral add, equipment corrosion is little.At present, the emulsifier system of cation colophony size mainly contains following several: cationic emulsifier/nonionic emulsifier, cationic emulsifier/resin cation, nonionic emulsifier, nonionic emulsifier/resin cation.But no matter adopt which kind of emulsification system, all contain small-molecular emulsifier, this is all unfavorable to handling papermaking wastewater and effect, especially the sizing efficiency of sizing agent.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of and can improve the preparation method that rosin sizing agent is kept with effect certainly, do not contained the cationic colophony sizing agent macromolecule emulsifier system of small-molecular emulsifier.
The technical solution used in the present invention is in order to achieve the above object: the cationic monomer of the acrylate of the styrene of 20%-40%, 20%-50% and 20%-40% is mixed make mix monomer at first by mass percentage; After then mix monomer and azodiisobutyronitrile or benzoyl peroxide being mixed by 100: 1～100: 3 weight ratio, be added to isopropyl alcohol or acetone or N, in the dinethylformamide after 60 ℃ of-90 ℃ of following polymerization 1-2 hours, add deionized water and decompression distillation and remove organic solvent, obtain water solubility copolymer; By mass percentage the methylacryoyloxyethyl trimethyl ammonium chloride of the acrylate of the styrene of 20%-40%, 20%-50% and 20%-40% or dimethylaminoethyl methacrylate are mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.4: 0.2～1: 0.8: 0.5 weight ratio mixing and stirring, make mixture; The potassium peroxydisulfate or the ammonium persulfate that add mass percent and be 0.5%-2.0% in mixture are initator, hour get final product at 70-90 ℃ of following polyase 13-5.
Acrylate of the present invention is ethyl acrylate, butyl acrylate or Hexyl 2-propenoate; Cationic monomer is methylacryoyloxyethyl trimethyl ammonium chloride or dimethylaminoethyl methacrylate.
The cationic colophony sizing agent macromolecule emulsifier system that the present invention is prepared, not only can be in order to emulsification rosin and modifier (comprising esterified rosin, self fixing cationic rosin) thereof, can also be directly as the paper neutral sizing agent, preparation method of the present invention can reduce addition, the raising rosin sizing agent retention of aluminum sulfate significantly.
The specific embodiment
Embodiment 1, the methylacryoyloxyethyl trimethyl ammonium chloride of 20% styrene, 50% ethyl acrylate and 30% mixed make mix monomer at first by mass percentage; After then mix monomer and azodiisobutyronitrile being mixed by 100: 1 weight ratio, be added in the isopropyl alcohol and after 2 hours, add deionized water and decompression distillation and remove organic solvent, obtain water solubility copolymer 60 ℃ of following polymerizations; By mass percentage the methylacryoyloxyethyl trimethyl ammonium chloride of 20% styrene, 50% ethyl acrylate and 30% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.4: 0.5 weight ratio mixing and stirring, make mixture; The adding mass percent is that 0.5% potassium peroxydisulfate is an initator in mixture, and can obtain solid content in 5 hours 70 ℃ of following polymerizations is 20%, and zeta potential is the macromolecule emulsifier of 42mV.
Embodiment 2, the dimethylaminoethyl methacrylate of 30% styrene, 40% butyl acrylate and 30% is mixed make mix monomer at first by mass percentage; After then mix monomer and benzoyl peroxide being mixed by 100: 1.5 weight ratio, be added in the acetone and after 1.5 hours, add deionized water and decompression distillation and remove organic solvent, obtain water solubility copolymer 70 ℃ of following polymerizations; By mass percentage the dimethylaminoethyl methacrylate of 30% styrene, 40% butyl acrylate and 30% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.5: 0.4 weight ratio mixing and stirring, make mixture; The adding mass percent is that 0.8% potassium peroxydisulfate is an initator in mixture, and can obtain solid content in 4 hours 80 ℃ of following polymerizations is 25%, and zeta potential is the macromolecule emulsifier of 44mV.
Embodiment 3, the methylacryoyloxyethyl trimethyl ammonium chloride of 30% styrene, 30% Hexyl 2-propenoate and 40% is mixed make mix monomer at first by mass percentage; After then mix monomer and benzoyl peroxide being mixed by 100: 2 weight ratio, be added to N,, add deionized water and decompression distillation and remove organic solvent after 1 hour 80 ℃ of following polymerizations in the dinethylformamide, obtain water solubility copolymer; By mass percentage the methylacryoyloxyethyl trimethyl ammonium chloride of 30% styrene, 30% Hexyl 2-propenoate and 40% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.6: 0.3 weight ratio mixing and stirring, make mixture; Adding mass percent and be 1.2% ammonium persulfate in mixture is initator, and hour can obtain solid content at 75 ℃ of following polyase 13s is 30%, and zeta potential is the macromolecule emulsifier of 45mV.
Embodiment 4, the dimethylaminoethyl methacrylate of 40% styrene, 40% butyl acrylate and 20% is mixed make mix monomer at first by mass percentage; After then mix monomer and benzoyl peroxide being mixed by 100: 2.5 weight ratio, be added to N,, add deionized water and decompression distillation and remove organic solvent after 1 hour 85 ℃ of following polymerizations in the dinethylformamide, obtain water solubility copolymer; By mass percentage the dimethylaminoethyl methacrylate of 40% styrene, 40% butyl acrylate and 20% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.7: 0.2 weight ratio mixing and stirring, make mixture; Adding mass percent and be 1.5% ammonium persulfate in mixture is initator, and hour can obtain solid content at 90 ℃ of following polyase 13s is 35%, and zeta potential is the macromolecule emulsifier of 38mV.
Embodiment 5, the methylacryoyloxyethyl trimethyl ammonium chloride of 40% styrene, 20% butyl acrylate and 40% is mixed make mix monomer at first by mass percentage; After then mix monomer and benzoyl peroxide being mixed by 100: 3 weight ratio, be added in the isopropyl alcohol and after 1 hour, add deionized water and decompression distillation and remove organic solvent, obtain water solubility copolymer 90 ℃ of following polymerizations; By mass percentage the methylacryoyloxyethyl trimethyl ammonium chloride of 40% styrene, 20% butyl acrylate and 40% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.8: 0.5 weight ratio mixing and stirring, make mixture; The adding mass percent is that 2.0% ammonium persulfate is an initator in mixture, and can obtain solid content in 5 hours 85 ℃ of following polymerizations is 40%, and zeta potential is the macromolecule emulsifier of 46mV.
Claims (7)
1. the preparation method of cationic colophony sizing agent macromolecule emulsifier system is characterized in that:
1) the cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride of the acrylate of the styrene of 20%-40%, 20%-50% and 20%-40% or dimethylaminoethyl methacrylate are mixed make mix monomer at first by mass percentage;
2) then mix monomer and azodiisobutyronitrile or benzoyl peroxide are mixed by 100: 1～100: 3 weight ratio after, be added to isopropyl alcohol or acetone or N, in the dinethylformamide after 60 ℃ of-90 ℃ of following polymerization 1-2 hours, add deionized water and decompression distillation and remove organic solvent, obtain water solubility copolymer;
3) the methylacryoyloxyethyl trimethyl ammonium chloride of the acrylate of the styrene of 20%-40%, 20%-50% and 20%-40% or dimethylaminoethyl methacrylate are mixed obtain mix monomer by mass percentage;
4) with mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.4～0.8: 0.2～0.5 weight ratio mixing and stirring, make mixture;
5) adding mass percent in mixture is that potassium peroxydisulfate or the ammonium persulfate of 0.5%-2.0% is initator, hour gets final product at 70-90 ℃ of following polyase 13-5.
2. the preparation method of cationic colophony sizing agent macromolecule emulsifier system according to claim 1, it is characterized in that: said acrylate is ethyl acrylate, butyl acrylate or Hexyl 2-propenoate.
3. the preparation method of cationic colophony sizing agent macromolecule emulsifier system according to claim 1 is characterized in that: the methylacryoyloxyethyl trimethyl ammonium chloride of 20% styrene, 50% ethyl acrylate and 30% is mixed make mix monomer at first by mass percentage; After then mix monomer and azodiisobutyronitrile being mixed by 100: 1 weight ratio, be added in the isopropyl alcohol and after 2 hours, add deionized water and decompression distillation and remove organic solvent, obtain water solubility copolymer 60 ℃ of following polymerizations; By mass percentage the methylacryoyloxyethyl trimethyl ammonium chloride of 20% styrene, 50% ethyl acrylate and 30% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.4: 0.5 weight ratio mixing and stirring, make mixture; The adding mass percent is that 0.5% potassium peroxydisulfate is an initator in mixture, and obtaining solid content in 5 hours 70 ℃ of following polymerizations is 20%, and zeta potential is the macromolecule emulsifier of 42mV.
4. the preparation method of cationic colophony sizing agent macromolecule emulsifier system according to claim 1 is characterized in that: the dimethylaminoethyl methacrylate of 30% styrene, 40% butyl acrylate and 30% is mixed make mix monomer at first by mass percentage; After then mix monomer and benzoyl peroxide being mixed by 100: 1.5 weight ratio, be added in the acetone and after 1.5 hours, add deionized water and decompression distillation and remove organic solvent, obtain water solubility copolymer 70 ℃ of following polymerizations; By mass percentage the dimethylaminoethyl methacrylate of 30% styrene, 40% butyl acrylate and 30% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.5: 0.4 weight ratio mixing and stirring, make mixture; The adding mass percent is that 0.8% potassium peroxydisulfate is an initator in mixture, and obtaining solid content in 4 hours 80 ℃ of following polymerizations is 25%, and zeta potential is the macromolecule emulsifier of 44mV.
5. the preparation method of cationic colophony sizing agent macromolecule emulsifier system according to claim 1 is characterized in that: the methylacryoyloxyethyl trimethyl ammonium chloride of 30% styrene, 30% Hexyl 2-propenoate and 40% is mixed make mix monomer at first by mass percentage; After then mix monomer and benzoyl peroxide being mixed by 100: 2 weight ratio, be added to N,, add deionized water and decompression distillation and remove organic solvent after 1 hour 80 ℃ of following polymerizations in the dinethylformamide, obtain water solubility copolymer; By mass percentage the methylacryoyloxyethyl trimethyl ammonium chloride of 30% styrene, 30% Hexyl 2-propenoate and 40% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.6: 0.3 weight ratio mixing and stirring, make mixture; Adding mass percent and be 1.2% ammonium persulfate in mixture is initator, and hour obtaining solid content at 75 ℃ of following polyase 13s is 30%, and zeta potential is the macromolecule emulsifier of 45mV.
6. the preparation method of cationic colophony sizing agent macromolecule emulsifier system according to claim 1 is characterized in that: the dimethylaminoethyl methacrylate of 40% styrene, 40% butyl acrylate and 20% is mixed make mix monomer at first by mass percentage; After then mix monomer and benzoyl peroxide being mixed by 100: 2.5 weight ratio, be added to N,, add deionized water and decompression distillation and remove organic solvent after 1 hour 85 ℃ of following polymerizations in the dinethylformamide, obtain water solubility copolymer; By mass percentage the dimethylaminoethyl methacrylate of 40% styrene, 40% butyl acrylate and 20% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.7: 0.2 weight ratio mixing and stirring, make mixture; Adding mass percent and be 1.5% ammonium persulfate in mixture is initator, and hour obtaining solid content at 90 ℃ of following polyase 13s is 35%, and zeta potential is the macromolecule emulsifier of 38mV.
7. the preparation method of cationic colophony sizing agent macromolecule emulsifier system according to claim 1 is characterized in that: the methylacryoyloxyethyl trimethyl ammonium chloride of 40% styrene, 20% butyl acrylate and 40% is mixed make mix monomer at first by mass percentage; After then mix monomer and benzoyl peroxide being mixed by 100: 3 weight ratio, be added in the isopropyl alcohol and after 1 hour, add deionized water and decompression distillation and remove organic solvent, obtain water solubility copolymer 90 ℃ of following polymerizations; By mass percentage the methylacryoyloxyethyl trimethyl ammonium chloride of 40% styrene, 20% butyl acrylate and 40% is mixed and obtain mix monomer; With mix monomer and N, dinethylformamide, water solubility copolymer are pressed 1: 0.8: 0.5 weight ratio mixing and stirring, make mixture; The adding mass percent is that 2.0% ammonium persulfate is an initator in mixture, and obtaining solid content in 5 hours 85 ℃ of following polymerizations is 40%, and zeta potential is the macromolecule emulsifier of 46mV.
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Cited By (1)
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| CN101298029B (en) * | 2008-06-25 | 2010-06-09 | 广州英科新材料有限公司 | Gum rosin base emulsifier and preparation and use thereof |
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| EP1967545A1 (en) * | 2007-03-09 | 2008-09-10 | Rohm and Haas France SAS | Cationic polymer latex |
| CN101148842B (en) * | 2007-06-28 | 2010-04-21 | 上海东升新材料有限公司 | Paper surface sizing agent and preparation method thereof |
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| CN101871184B (en) * | 2010-05-11 | 2012-01-25 | 陕西科技大学 | Cationic styrene-acrylate surface sizing agent and preparation method thereof |
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| CN103866624B (en) * | 2014-02-25 | 2015-11-25 | 苏州恒康新材料有限公司 | A kind of sizing agent for papermaking and preparation method thereof |
| CN107236093A (en) * | 2016-03-29 | 2017-10-10 | 上海东升新材料有限公司 | A kind of preparation method for being used to produce the Shuangzi emulsifying agent of cationic rosin size |
| CN108396589B (en) * | 2018-02-06 | 2020-09-04 | 齐鲁工业大学 | Cationic rosin size emulsifier and preparation method thereof |
| CN110407973B (en) * | 2018-04-27 | 2022-02-08 | 上海东升新材料有限公司 | Preparation method of cationic emulsifier for rosin size |
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