CN100373004C - Preparation method of cationic rosin sizing agent polymer emulsifier system - Google Patents

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

Preparation method of cationic rosin sizing agent polymer emulsifier system

technical field

The invention belongs to the field of papermaking chemicals, in particular to a preparation method of a cationic rosin sizing agent polymer emulsifier system.

Background technique

With the neutralization (alkaline) of the papermaking system, cationic rosin sizing agents have been widely used because of their advantages such as self-retention, near-neutral addition, and low equipment corrosion. At present, the emulsifier system of cationic rosin sizing agent mainly includes the following types: cationic emulsifier/nonionic emulsifier, cationic emulsifier/cation resin, nonionic emulsifier, nonionic emulsifier/cation resin. However, no matter what kind of emulsification system is used, it contains small molecular emulsifiers, which is not good for the treatment of papermaking wastewater and the application effect, especially the sizing effect of the sizing agent.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned shortcoming of prior art, provide a kind of preparation method of cationic rosin sizing agent macromolecule emulsifier system that can improve rosin sizing agent retention and application effect, does not contain small molecule emulsifier .

In order to achieve the above-mentioned purpose, the technical scheme adopted by the present invention is as follows: firstly, mix 20%-40% styrene, 20%-50% acrylate and 20%-40% cationic monomer according to mass percentage to prepare a mixed single body; then mix the mixed monomers with azobisisobutyronitrile or benzoyl peroxide in a weight ratio of 100:1 to 100:3, and then add isopropanol or acetone or N,N-dimethyl After polymerizing in formamide at 60°C-90°C for 1-2 hours, add deionized water and distill off the organic solvent under reduced pressure to obtain a water-soluble copolymer; 20%-40% styrene, 20% -50% acrylate and 20%-40% methacryloyloxyethyltrimethylammonium chloride or dimethylaminoethyl methacrylate are evenly mixed to obtain mixed monomers; mix the mixed monomers with N, N-dimethylformamide and water-soluble copolymer are mixed and stirred evenly in a weight ratio of 1:0.4:0.2 to 1:0.8:0.5 to prepare a mixture; add 0.5%-2.0% persulfuric acid to the mixture Potassium or ammonium persulfate is used as the initiator, and the polymerization can be carried out at 70-90°C for 3-5 hours.

The acrylate in the present invention is ethyl acrylate, butyl acrylate or hexyl acrylate; the cationic monomer is methacryloyloxyethyltrimethylammonium chloride or dimethylaminoethyl methacrylate.

The cationic rosin sizing agent macromolecular emulsifier system prepared by the present invention can not only be used to emulsify rosin and its modified products (including esterified rosin, cationic rosin itself), but also can be directly used as a neutral sizing agent for paper, The preparation method of the invention can greatly reduce the added amount of aluminum sulfate and improve the retention rate of the rosin sizing agent.

Detailed ways

Example 1, firstly mix 20% styrene, 50% ethyl acrylate and 30% methacryloyloxyethyltrimethylammonium chloride uniformly by mass percentage to prepare mixed monomer; then mix the monomer After the body and azobisisobutyronitrile are mixed uniformly at a weight ratio of 100:1, they are added to isopropanol and polymerized at 60°C for 2 hours, then deionized water is added and the organic solvent is distilled off under reduced pressure to obtain a water-soluble copolymer 20% styrene, 50% ethyl acrylate and 30% methacryloyloxyethyltrimethylammonium chloride are uniformly mixed to obtain a mixed monomer by mass percentage; the mixed monomer is mixed with N, N -Dimethylformamide and water-soluble copolymer are mixed and stirred uniformly in a weight ratio of 1:0.4:0.5 to prepare a mixture; adding 0.5% potassium persulfate as an initiator in the mixture, and polymerizing at 70°C A polymer emulsifier with a solid content of 20% and a zeta potential of 42mV can be obtained in 5 hours.

Embodiment 2, at first 30% styrene, 40% butyl acrylate and 30% dimethylaminoethyl methacrylate are mixed uniformly by mass percentage to make mixed monomers; then mixed monomers and peroxidized Benzoyl was mixed evenly in a weight ratio of 100:1.5, added to acetone and polymerized at 70°C for 1.5 hours, then deionized water was added and the organic solvent was distilled off under reduced pressure to obtain a water-soluble copolymer; % styrene, 40% butyl acrylate and 30% dimethylaminoethyl methacrylate are mixed uniformly to obtain a mixed monomer; the mixed monomer is mixed with N, N-dimethylformamide, water-soluble copolymer According to the weight ratio of 1: 0.5: 0.4, mix and stir evenly to prepare the mixture; add 0.8% potassium persulfate as the initiator in the mixture, and polymerize at 80° C. for 4 hours to obtain a solid content of 25%. A polymer emulsifier with a zeta potential of 44mV.

Example 3, firstly mix 30% styrene, 30% hexyl acrylate and 40% methacryloyloxyethyltrimethylammonium chloride by mass percentage to make mixed monomer; then mix the monomer After mixing homogeneously with benzoyl peroxide in a weight ratio of 100:2, add it to N,N-dimethylformamide and polymerize at 80°C for 1 hour, add deionized water and distill off the organic solvent under reduced pressure , to obtain a water-soluble copolymer; 30% styrene, 30% hexyl acrylate and 40% methacryloyloxyethyltrimethylammonium chloride are uniformly mixed to obtain a mixed monomer by mass percentage; the mixed monomer Body and N, N-dimethylformamide, water-soluble copolymer are mixed and stirred evenly by the weight ratio of 1: 0.6: 0.3, make mixture; Add the ammonium persulfate that mass percentage is 1.2% in the mixture as initiator, The polymer emulsifier with a solid content of 30% and a zeta potential of 45mV can be obtained by polymerizing for 3 hours at 75°C.

Embodiment 4, at first 40% styrene, 40% butyl acrylate and 20% dimethylaminoethyl methacrylate are mixed uniformly by mass percentage to make mixed monomers; then mixed monomers and peroxidized After benzoyl is mixed evenly in a weight ratio of 100:2.5, it is added to N,N-dimethylformamide and polymerized at 85°C for 1 hour, then deionized water is added and the organic solvent is distilled off under reduced pressure to obtain a water-soluble Copolymer; mix 40% styrene, 40% butyl acrylate and 20% dimethylaminoethyl methacrylate uniformly by mass percentage to obtain a mixed monomer; mix the mixed monomer with N, N-dimethyl 1.5% ammonium persulfate is added as an initiator in the mixture, and it is polymerized at 90°C for 3 hours. A polymer emulsifier with a solid content of 35% and a zeta potential of 38mV can be obtained.

Example 5, firstly mix 40% styrene, 20% butyl acrylate and 40% methacryloxyethyltrimethylammonium chloride by mass percentage to make mixed monomer; then mix the monomer After mixing homogeneously with benzoyl peroxide in a weight ratio of 100:3, add it to isopropanol and polymerize at 90°C for 1 hour, add deionized water and distill off the organic solvent under reduced pressure to obtain a water-soluble copolymer ; Mix 40% styrene, 20% butyl acrylate and 40% methacryloyloxyethyltrimethylammonium chloride uniformly by mass percentage to obtain a mixed monomer; mix the mixed monomer with N, N- Dimethylformamide and water-soluble copolymer were mixed and stirred evenly in a weight ratio of 1:0.8:0.5 to prepare a mixture; adding 2.0% ammonium persulfate as an initiator in the mixture was polymerized at 85°C for 5 The polymer emulsifier with a solid content of 40% and a zeta potential of 46mV can be obtained within hours.

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.