CN101824116A - Cationic core-shell copolymerized styrene-acrylic surface sizing agent and preparation method thereof - Google Patents
Cationic core-shell copolymerized styrene-acrylic surface sizing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cationic core-shell copolymerized styrene-acrylic surface sizing agent and a preparation method thereof. The cationic core-shell copolymerized styrene-acrylic surface sizing agent has a molecular structure shown in the specification. The preparation method for the cationic core-shell copolymerized styrene-acrylic surface sizing agent is characterized by taking polyvinyl alcohol 1788 as a dispersant, ammonium persulfate as an initiator, and styrene, methyl methacrylate, propenol and [2-(methacryloyloxy)ethyl] trimethyl-ammonium chloride as mixed monomers, and performing core-shell emulsion polymerization reaction to form the cationic core-shell copolymerized styrene-acrylic surface sizing agent. The obtained cationic core-shell copolymerized styrene-acrylic surface sizing agent has structures of a hard core and a soft shell; during pulling, the fiber can transfer the pull to latex particles; and during pressing, the hard core positioned in the fiber network bears the pressure; therefore, the cationic core-shell copolymerized styrene-acrylic surface sizing agent can improve the ring pressing strength and stiffness of raw corrugated paper, and can improve the waterproof performance of the raw corrugated paper.
Description
Technical field
The present invention relates to the preparation field of Corrugating Base Paper Surface Size, particularly cationic core-shell copolymerized styrene-acrylic surface sizing agent and preparation method thereof.
Background technology
Raising day by day along with fast growth of national economy and living standards of the people, the corresponding development that obtains advancing by leaps and bounds of packing business, at present, China has begun to take shape the Delta of the Pearl River, Yangtze River Delta and three big main wrapping paper production base and consumption areas, North China, Corrugating Base Paper is the most widely used wrapping material of packaging industry, variation along with Corrugated Box packing use range, specification of quality for the Corrugating Base Paper of making carton is especially more and more high for the requirement of Corrugating Base Paper intensity, be embodied in the following aspects: one, the high speed of the corrugated case making machine of Corrugated Box factory is had higher requirement to the high speed applying of boxboard and Corrugating Base Paper; Its two, the fresh fruit that Corrugated Box is extensively packed and transported, food, vegetables, fresh flower and other agricultural-food, need stand the sea-freight sell, the relative humidity on sea (RH%) is up to more than 90%, and the strength characteristics of watt spinulose tree fern body paper and boxboard to moisture sensitivity very, promptly reduces paper board strength; They are three years old; adopt container technology in the modernization transportation; it requires shipping and warehouse-in to utilize the space as far as possible; the palletizing height is brought up to maximum with load; so need Corrugated Box to have great ability to bear; on the other hand, make full use of regenerated papermaking for saving fiber, the protection environment has great importance.Along with the increase gradually of secondary stock ratio in the pulping and paper-making fibrous material, domestic paper mill is that the trend of raw material production Corrugating Base Paper also increases gradually with waste paper.Because the domestic waste paper source is wide, add and be repeated to utilize, its impurity is many, fiber is short, therefore the Corrugating Base Paper outward appearance that with the domestic waste paper is raw material production is coarse, of low grade, body paper ring crush intensity and deflection are poor, product marketing is not smooth, the market competitiveness is poor, increasing Corrugating Base Paper enterprise begins to adopt the mode of top sizing to reach the purpose of giving paper water resisting property and improving the ring pressure, the Surface Size that present Corrugating Base Paper is using is a Sumstar 190, alkyl ketene dimer (AKD) and common benzene emulsion, Sumstar 190 can improve the ring crush intensity and the deflection of Corrugating Base Paper, but thereby the easy moisture absorption influences water resisting property and ring crush intensity after the film forming, alkyl ketene dimer (AKD) class Surface Size has good water repelling property, but it is poor to there is with the avidity of fiber, contribution to ring pressure and deflection is little, emulsion facile hydrolysis in staging life influences sizing efficiency, and the problem that has the maturation period, be to want certain hour under the paper behind the machine just can reach maximum degree of sizing, in the maturation period, ring crush intensity is declined by a big margin owing to absorb moisture, water resisting property is also descended to some extent, common benzene emulsion passes through emulsion polymerization prepared by vinylbenzene and acrylate monomer, its preparation process is used small-molecular emulsifier more, not only influences the water resistance of Corrugating Base Paper but also have environmental pollution.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide cationic core-shell copolymerized styrene-acrylic surface sizing agent and preparation method thereof, the cationic core-shell copolymerized styrene-acrylic surface sizing agent of gained can improve the ring crush intensity and the deflection of Corrugating Base Paper, and can improve the water repelling property of Corrugating Base Paper.
For achieving the above object, the technical solution used in the present invention is:
The molecular structure of cationic core-shell copolymerized styrene-acrylic surface sizing agent is:
Cationic core-shell copolymerized styrene-acrylic surface sizing agent
Wherein x, y
1, y
2, z
1, z
2, m is the integer greater than zero.
The preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent, with polyvinyl alcohol 1788 is dispersion agent, with the ammonium persulphate is initiator, with vinylbenzene, methyl methacrylate, vinylcarbinol and methylacryoyloxyethyl trimethyl ammonium chloride is that mix monomer carries out core-shell emulsion polymerization prepared in reaction cationic core-shell copolymerized styrene-acrylic surface sizing agent, and its reaction process is as follows:
Styrene methyl methacrylate
The methyl methacrylate vinylcarbinol
Vinylcarbinol methylacryoyloxyethyl trimethyl ammonium chloride
Cationic core-shell copolymerized styrene-acrylic surface sizing agent
Wherein x, y
1, y
2, z
1, z
2, m is the integer greater than zero.
The preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with ammonium persulphate and deionized water with mass ratio at 1: 20,
Second step, polyvinyl alcohol 1788 and deionized water are pressed mass ratio adding in 1: 20 reactor, in the time of 85-95 ℃, stirred 0.5-1.5 hour, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add deionized water formation polyvinyl alcohol water solution in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 60-70 ℃,
The 4th step, give and to add ammonium persulfate aqueous solution respectively in the polyvinyl alcohol water solution and be first mix monomer of making at 15: 6 with mass ratio by vinylbenzene and methyl methacrylate, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.5-1 hour
The 5th step, reactant is warming up to 70-80 ℃, adds ammonium persulfate aqueous solution respectively and be second mix monomer of making at 3: 5 by methyl methacrylate and vinylcarbinol with mass ratio, the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.5-1 hour
The 6th step, reactant is warming up to 80-90 ℃, add ammonium persulfate aqueous solution respectively and be the 3rd mix monomer of making at 6: 8 with mass ratio by vinylcarbinol and methylacryoyloxyethyl trimethyl ammonium chloride, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.5-1 hour
The 7th step, behind reinforced the finishing with reactant in 90-95 ℃ of insulation reaction 1-2 hour,
The 8th step was cooled to 20-30 ℃ with reactant, and with 100-200 order net filtration, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
Because cationic core-shell copolymerized styrene-acrylic surface sizing agent forms stone with rigid monomer polymerization earlier when polymerization, form soft shell with soft monomer polymerization again, and paper fibre is rich in hydroxyl, polar group on the soft shell and cellulosic hydroxy form hydrogen bond, also can form hydrogen bond between the polar group on the soft shell, such structure forms interpenetrating(polymer)networks, when being subjected to pulling force, fiber can be transferred to pulling force on the emulsion particle by hydrogen bond action, when being under pressure, the stone that is arranged in fibre network will bear pressure, so cationic core-shell copolymerized styrene-acrylic surface sizing agent can improve the ring crush intensity and the deflection of Corrugating Base Paper, and can improve the water repelling property of Corrugating Base Paper.
Embodiment
To be described in further detail method of the present invention with specific embodiment below.
Embodiment one
The preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 85 ℃, stirred 0.5 hour, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 60 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.5 hour
The 5th step, reactant is warming up to 70 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.5 hour
The 6th step, reactant is warming up to 80 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.5 hour
The 7th step, behind reinforced the finishing with reactant in 90 ℃ of insulation reaction 1 hour,
The 8th step was cooled to 20 ℃ with reactant, and with 100 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
Embodiment two
The preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 87 ℃, stirred 0.7 hour, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 62 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.6 hour
The 5th step, reactant is warming up to 72 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.6 hour
The 6th step, reactant is warming up to 82 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.6 hour
The 7th step, behind reinforced the finishing with reactant in 91 ℃ of insulation reaction 1.2 hours,
The 8th step was cooled to 22 ℃ with reactant, and with 120 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
Embodiment three
The preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 89 ℃, stirred 0.9 hour, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 64 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.7 hour
The 5th step, reactant is warming up to 74 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.7 hour
The 6th step, reactant is warming up to 84 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.7 hour
The 7th step, behind reinforced the finishing with reactant in 92 ℃ of insulation reaction 1.4 hours,
The 8th step was cooled to 24 ℃ with reactant, and with 140 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
Embodiment four
The preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 91 ℃, stirred 1.1 hours, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 66 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.8 hour
The 5th step, reactant is warming up to 76 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.8 hour
The 6th step, reactant is warming up to 86 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.8 hour
The 7th step, behind reinforced the finishing with reactant in 93 ℃ of insulation reaction 1.6 hours,
The 8th step was cooled to 26 ℃ with reactant, and with 160 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
Embodiment five
The preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 93 ℃, stirred 1.3 hours, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 68 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.9 hour
The 5th step, reactant is warming up to 78 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.9 hour
The 6th step, reactant is warming up to 88 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.9 hour
The 7th step, behind reinforced the finishing with reactant in 94 ℃ of insulation reaction 1.8 hours,
The 8th step was cooled to 28 ℃ with reactant, and with 180 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
Embodiment six
The preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 95 ℃, stirred 1.5 hours, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 70 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 1 hour
The 5th step, reactant is warming up to 80 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 1 hour
The 6th step, reactant is warming up to 90 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 1 hour
The 7th step, behind reinforced the finishing with reactant in 95 ℃ of insulation reaction 2 hours,
The 8th step was cooled to 30 ℃ with reactant, and with 200 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
Claims (9)
1. cationic core-shell copolymerized styrene-acrylic surface sizing agent, it is characterized in that: the molecular structure of cationic core-shell copolymerized styrene-acrylic surface sizing agent is:
Cationic core-shell copolymerized styrene-acrylic surface sizing agent
Wherein x, y
1, y
2, z
1, z
2, m is the integer greater than zero.
2. the preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent, it is characterized in that: with polyvinyl alcohol 1788 is dispersion agent, with the ammonium persulphate is initiator, is that mix monomer carries out core-shell emulsion polymerization prepared in reaction cationic core-shell copolymerized styrene-acrylic surface sizing agent with vinylbenzene, methyl methacrylate, vinylcarbinol and methylacryoyloxyethyl trimethyl ammonium chloride.
3. the preparation method of cationic core-shell copolymerized styrene-acrylic surface sizing agent according to claim 2 is characterized in that: specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with ammonium persulphate and deionized water with mass ratio at 1: 20,
Second step, polyvinyl alcohol 1788 and deionized water are pressed mass ratio adding in 1: 20 reactor, in the time of 85-95 ℃, stirred 0.5-1.5 hour, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add deionized water formation polyvinyl alcohol water solution in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 60-70 ℃,
The 4th step, give and to add ammonium persulfate aqueous solution respectively in the polyvinyl alcohol water solution and be first mix monomer of making at 15: 6 with mass ratio by vinylbenzene and methyl methacrylate, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.5-1 hour
The 5th step, reactant is warming up to 70-80 ℃, adds ammonium persulfate aqueous solution respectively and be second mix monomer of making at 3: 5 by methyl methacrylate and vinylcarbinol with mass ratio, the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.5-1 hour
The 6th step, reactant is warming up to 80-90 ℃, add ammonium persulfate aqueous solution respectively and be the 3rd mix monomer of making at 6: 8 with mass ratio by vinylcarbinol and methylacryoyloxyethyl trimethyl ammonium chloride, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.5-1 hour
The 7th step, behind reinforced the finishing with reactant in 90-95 ℃ of insulation reaction 1-2 hour,
The 8th step was cooled to 20-30 ℃ with reactant, and with 100-200 order net filtration, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
4. according to the preparation method of claim 2 or 3 described cationic core-shell copolymerized styrene-acrylic surface sizing agents, it is characterized in that: specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 85 ℃, stirred 0.5 hour, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 60 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.5 hour
The 5th step, reactant is warming up to 70 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.5 hour
The 6th step, reactant is warming up to 80 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.5 hour
The 7th step, behind reinforced the finishing with reactant in 90 ℃ of insulation reaction 1 hour,
The 8th step was cooled to 20 ℃ with reactant, and with 100 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
5. according to the preparation method of claim 2 or 3 described cationic core-shell copolymerized styrene-acrylic surface sizing agents, it is characterized in that: specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 87 ℃, stirred 0.7 hour, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 62 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.6 hour
The 5th step, reactant is warming up to 72 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.6 hour
The 6th step, reactant is warming up to 82 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.6 hour
The 7th step, behind reinforced the finishing with reactant in 91 ℃ of insulation reaction 1.2 hours,
The 8th step was cooled to 22 ℃ with reactant, and with 120 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
6. according to the preparation method of claim 2 or 3 described cationic core-shell copolymerized styrene-acrylic surface sizing agents, it is characterized in that: specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 89 ℃, stirred 0.9 hour, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 64 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.7 hour
The 5th step, reactant is warming up to 74 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.7 hour
The 6th step, reactant is warming up to 84 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.7 hour
The 7th step, behind reinforced the finishing with reactant in 92 ℃ of insulation reaction 1.4 hours,
The 8th step was cooled to 24 ℃ with reactant, and with 140 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
7. according to the preparation method of claim 2 or 3 described cationic core-shell copolymerized styrene-acrylic surface sizing agents, it is characterized in that: specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 91 ℃, stirred 1.1 hours, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 66 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.8 hour
The 5th step, reactant is warming up to 76 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.8 hour
The 6th step, reactant is warming up to 86 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.8 hour
The 7th step, behind reinforced the finishing with reactant in 93 ℃ of insulation reaction 1.6 hours,
The 8th step was cooled to 26 ℃ with reactant, and with 160 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
8. according to the preparation method of claim 2 or 3 described cationic core-shell copolymerized styrene-acrylic surface sizing agents, it is characterized in that: specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 93 ℃, stirred 1.3 hours, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 68 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 0.9 hour
The 5th step, reactant is warming up to 78 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 0.9 hour
The 6th step, reactant is warming up to 88 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 0.9 hour
The 7th step, behind reinforced the finishing with reactant in 94 ℃ of insulation reaction 1.8 hours,
The 8th step was cooled to 28 ℃ with reactant, and with 180 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
9. according to the preparation method of claim 2 or 3 described cationic core-shell copolymerized styrene-acrylic surface sizing agents, it is characterized in that: specifically may further comprise the steps:
The first step is made ammonium persulfate aqueous solution with 1 gram ammonium persulphate and 20 gram deionized waters with mass ratio at 1: 20,
Second step, 1 gram polyvinyl alcohol 1788 and 20 gram deionized waters are pressed mass ratio adding in 1: 20 reactor, in the time of 95 ℃, stirred 1.5 hours, make polyvinyl alcohol 1788 dissolvings,
The 3rd step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1788, the mass ratio of polyvinyl alcohol 1788 and deionized water is 1: 127, is cooled to 70 ℃,
The 4th step, to adding 7 gram ammonium persulfate aqueous solutions in the polyvinyl alcohol water solution respectively and restraining methyl methacrylates by 15 gram vinylbenzene and 6 is first mix monomer of making at 15: 6 with mass ratio, the mass ratio of polyvinyl alcohol solution, ammonium persulfate aqueous solution and first mix monomer is 148: 7: 21, the reinforced time is 1 hour
The 5th step, reactant is warming up to 80 ℃, and adding 7 gram ammonium persulfate aqueous solutions respectively and restraining vinylcarbinols by 3 gram methyl methacrylates and 5 is second mix monomer of making at 3: 5 with mass ratio, and the mass ratio of the ammonium persulfate aqueous solution and second mix monomer is 7: 8, the reinforced time is 1 hour
The 6th step, reactant is warming up to 90 ℃, adding 7 gram ammonium persulfate aqueous solutions respectively and restraining the methylacryoyloxyethyl trimethyl ammonium chlorides by 6 gram vinylcarbinols and 8 is the 3rd mix monomer of making at 6: 8 with mass ratio, the mass ratio of ammonium persulfate aqueous solution and the 3rd mix monomer is 7: 14, the reinforced time is 1 hour
The 7th step, behind reinforced the finishing with reactant in 95 ℃ of insulation reaction 2 hours,
The 8th step was cooled to 30 ℃ with reactant, and with 200 order net filtrations, discharging obtains cationic core-shell copolymerized styrene-acrylic surface sizing agent.
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