CN101831026B - Cation styrene-acrylic surface sizing agent and preparation method thereof - Google Patents
Cation styrene-acrylic surface sizing agent and preparation method thereof Download PDFInfo
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- CN101831026B CN101831026B CN2010101687840A CN201010168784A CN101831026B CN 101831026 B CN101831026 B CN 101831026B CN 2010101687840 A CN2010101687840 A CN 2010101687840A CN 201010168784 A CN201010168784 A CN 201010168784A CN 101831026 B CN101831026 B CN 101831026B
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- polyvinyl alcohol
- sizing agent
- surface sizing
- acrylic surface
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Abstract
The invention discloses a cation styrene-acrylic surface sizing agent and a preparation method thereof. The molecular structure of the cation styrene-acrylic surface sizing agent is shown in the specification. The preparation method of the cation styrene-acrylic surface sizing agent comprises the following step of carrying out polymerization by using polyvinyl alcohol 1799 as a dispersing agent, using ammonium persulfate as an initiator and using phenylethylene, methyl methacrylate, ethyl acrylate, allyl alcohol and methacrylatoethyl trimethyl ammonium chloride as mixing monomers to prepare the cation styrene-acrylic surface sizing agent. The obtained cation styrene-acrylic surface sizing agent has the characteristics of good combination with fibers, reduction of hair and powder slip, improvement of sizing degree, high surface strength, good ink adsorption, adaptation to high-speed printing and the like.
Description
Technical field
The present invention relates to the preparation field of light paper Surface Size, particularly a kind of cation styrene-acrylic surface sizing agent and preparation method thereof.
Background technology
In the modern paper-making technique, top sizing has become the principal mode that the page top sizing is handled, the Surface Size of excellent performance can alleviate the hair and powder dropping phenomenon of page and improve the surface strength of paper, folding endurance, water resisting property, tensile strength, deflection and the smoothness of paper have been improved simultaneously effectively, reduce Gas permeability, improve printing performance etc., improved the quality scale and the use value of paper significantly.Light paper is a kind of light offset paper, and it has unique production and processing technology, does not contain white dyes, paper fibre light specific gravity, quality bulky, smooth surface, the soft favor that enjoys people of color and luster.Because the light paper quality is lighter, the books and periodicals that print with its approximately can alleviate 20%-30% than the books and periodicals weight with plain paper, have both made things convenient for reader's reading, have also played the effect that reduces logistics cost preferably, are subjected to the welcome of publishing circle.In economically developed countries such as America and Europe and Japan, the books more than 95% are all used this paper printing, and some medium-to-high grade books of China, high-grade books, periodical, ancient books and records, picture album, biography and student textbook etc. also adopt the light paper printing now.Light paper used aborning a large amount of chemimechanical pulps, low add fill out, light technology such as squeezing and light press polish, therefore the light paper surface is relatively coarse, fiber is more stiff, fiber combining power is relatively poor, because the fibrous tissue of light paper is more lax, thickness is relatively large, but its tensile property is relatively also more a little bit poorer, and very easily makes moist and produce the distortion situation, these factors have caused page surface strength and smoothness to descend, so that occur dry linting in the printing process and fall a mao phenomenon.On the other hand along with the continuous introduction of a large amount of import printing machinery is gone into operation, printing technology is improved, the application of high speed printing and high viscosity inks has proposed requirements at the higher level to surface strength of paper, and these requirements that specifically are reflected in indexs such as the surface strength of paper and ink absorptions improve.The traditional Surface Size of light paper has starch, Sumstar 190, phosphate ester starch, polyacrylamide treated starch and polyvinyl alcohol etc., they in use exist with the avidity of fiber relatively poor, the hair that falls in the printing process appears in film forming easy fracture easily, the dry linting phenomenon, water resisting property is relatively poor, shortcomings such as surface strength is not enough, its applicable scope is restricted, bringing into use benzene emulsion at present is by vinylbenzene and the acrylate monomer multipolymer by emulsion polymerization prepared, its preparation process is used small-molecular emulsifier more, not only influence the water resistance of light paper and film forming properties but also had environmental pollution, and mostly be the anionic polymer of water-soluble fluidity, in use owing to contain Al in the water
3+, Ca
2+Deng, can cause the emulsion precipitation has disadvantageous effect to applying glue.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of cation styrene-acrylic surface sizing agent and preparation method thereof, a kind of cation styrene-acrylic surface sizing agent of gained have with fiber in conjunction with good, alleviate hair and powder dropping, improve degree of sizing, ink absorption is good, surface strength height and the advantage that can adapt to high speed printing.
For achieving the above object, the technical solution used in the present invention is:
A kind of molecular structure of cation styrene-acrylic surface sizing agent is:
Cation styrene-acrylic surface sizing agent
Wherein x, y, z, m, n are the integer greater than zero.
A kind of preparation method of cation styrene-acrylic surface sizing agent is: with polyvinyl alcohol 1799 is dispersion agent, with the ammonium persulphate is initiator, with vinylbenzene, methyl methacrylate, ethyl propenoate, vinylcarbinol and methylacryoyloxyethyl trimethyl ammonium chloride is that mix monomer carries out emulsifier-free emulsion polymerization prepared in reaction cation styrene-acrylic surface sizing agent, and its reaction process is as follows:
Styrene methyl methacrylate ethyl propenoate vinylcarbinol methylacryoyloxyethyl trimethyl ammonium chloride
Cation styrene-acrylic surface sizing agent
Wherein x, y, z, m, n are the integer greater than zero.
A kind of preparation method of cation styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step, with vinylbenzene, methyl methacrylate, ethyl propenoate and vinylcarbinol by 12: 3: 15: 5 mass ratio is mixed and made into mix monomer,
Second step, ammonium persulphate and deionized water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 3rd step, polyvinyl alcohol 1799 and deionized water press mass ratio add reactor at 1: 20 and stirred 0.5-1.5 hour 85-95 ℃ the time, polyvinyl alcohol 1799 is dissolved,
The 4th step, to give to add deionized water formation polyvinyl alcohol water solution in the dissolved polyvinyl alcohol 1799, the mass ratio of polyvinyl alcohol 1799 and deionized water is 1: 127, is cooled to 60-70 ℃,
The 5th step, give and add ammonium persulfate aqueous solution and mix monomer in the polyvinyl alcohol water solution, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and mix monomer is 148: 21: 35, continue to drip the methylacryoyloxyethyl trimethyl ammonium chloride after dripping mix monomer, the mass ratio of mix monomer and methylacryoyloxyethyl trimethyl ammonium chloride is 35: 8, the whole reinforced time is 1-2 hour
The 6th step, behind reinforced the finishing with reactor in 80-90 ℃ of insulation reaction 2.0-3.0 hour,
The 7th step cooled to 20-30 ℃ with reactor, and with 100-200 order net filtration, discharging obtains a kind of cation styrene-acrylic surface sizing agent.
Because not residual small-molecular emulsifier in a kind of cation styrene-acrylic surface sizing agent, have advantages such as excellent water tolerance, weathering resistance, film-forming properties, shortcoming and pollution that small-molecular emulsifier causes have been eliminated, thereby a kind of cation styrene-acrylic surface sizing agent can form the sticking power that strong ionic linkage can improve latex film and paper with electronegative paper fibre, improved surface strength of paper, alleviate the hair and powder dropping phenomenon of page, improved the performances such as folding endurance, water resisting property, tensile strength, deflection and smoothness of paper.Cation group on the cation styrene-acrylic surface sizing agent has good adsorption to anionic inks, can improve the sharpness and the plumpness of printing, has not only improved the speed of printing but also can scumming in the offset printing, and ink jet printing performance is also fine.
Embodiment
To be described in further detail method of the present invention with specific embodiment below.
Embodiment one
A kind of preparation method of cation styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step, 12 gram vinylbenzene, 3 gram methyl methacrylates, 15 gram ethyl propenoates and 5 are restrained vinylcarbinols by 12: 3: 15: 5 mass ratio is mixed and made into mix monomer,
Second step, 1 gram ammonium persulphate and 20 gram deionized waters are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 3rd step, 1 gram polyvinyl alcohol 1799 and 20 gram deionized waters press mass ratio 1: 20 add reactor and stirred 0.5 hour 85 ℃ the time, polyvinyl alcohol 1799 is dissolved,
The 4th step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1799, the mass ratio of polyvinyl alcohol 1799 and deionized water is 1: 127, is cooled to 60 ℃,
The 5th step, give and add 21 gram ammonium persulfate aqueous solutions and 35 gram mix monomers in the polyvinyl alcohol water solution, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and mix monomer is 148: 21: 35, continue to drip 8 gram methylacryoyloxyethyl trimethyl ammonium chlorides after dripping mix monomer, the mass ratio of mix monomer and methylacryoyloxyethyl trimethyl ammonium chloride is 35: 8, the whole reinforced time is 1 hour
The 6th step, behind reinforced the finishing with reactor in 80 ℃ of insulations, reacted 2.0 hours,
The 7th step cooled to 20 ℃ with reactor, and with 100 order net filtrations, discharging obtains a kind of cation styrene-acrylic surface sizing agent.
Embodiment two
A kind of preparation method of cation styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step, 12 gram vinylbenzene, 3 gram methyl methacrylates, 15 gram ethyl propenoates and 5 are restrained vinylcarbinols by 12: 3: 15: 5 mass ratio is mixed and made into mix monomer,
Second step, 1 gram ammonium persulphate and 20 gram deionized waters are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 3rd step, 1 gram polyvinyl alcohol 1799 and 20 gram deionized waters press mass ratio 1: 20 add reactor and stirred 0.7 hour 87 ℃ the time, polyvinyl alcohol 1799 is dissolved,
The 4th step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1799, the mass ratio of polyvinyl alcohol 1799 and deionized water is 1: 127, is cooled to 62 ℃,
The 5th step, give and add 21 gram ammonium persulfate aqueous solutions and 35 gram mix monomers in the polyvinyl alcohol water solution, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and mix monomer is 148: 21: 35, continue to drip 8 gram methylacryoyloxyethyl trimethyl ammonium chlorides after dripping mix monomer, the mass ratio of mix monomer and methylacryoyloxyethyl trimethyl ammonium chloride is 35: 8, the whole reinforced time is 1.2 hours
The 6th step, behind reinforced the finishing with reactor in 82 ℃ of insulations, reacted 2.2 hours,
The 7th step cooled to 22 ℃ with reactor, and with 120 order net filtrations, discharging obtains a kind of cation styrene-acrylic surface sizing agent.
Embodiment three
A kind of preparation method of cation styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step, 12 gram vinylbenzene, 3 gram methyl methacrylates, 15 gram ethyl propenoates and 5 are restrained vinylcarbinols by 12: 3: 15: 5 mass ratio is mixed and made into mix monomer,
Second step, 1 gram ammonium persulphate and 20 gram deionized waters are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 3rd step, 1 gram polyvinyl alcohol 1799 and 20 gram deionized waters press mass ratio 1: 20 add reactor and stirred 0.9 hour 89 ℃ the time, polyvinyl alcohol 1799 is dissolved,
The 4th step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1799, the mass ratio of polyvinyl alcohol 1799 and deionized water is 1: 127, is cooled to 64 ℃,
The 5th step, give and add 21 gram ammonium persulfate aqueous solutions and 35 gram mix monomers in the polyvinyl alcohol water solution, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and mix monomer is 148: 21: 35, continue to drip 8 gram methylacryoyloxyethyl trimethyl ammonium chlorides after dripping mix monomer, the mass ratio of mix monomer and methylacryoyloxyethyl trimethyl ammonium chloride is 35: 8, the whole reinforced time is 1.4 hours
The 6th step, behind reinforced the finishing with reactor in 84 ℃ of insulations, reacted 2.4 hours,
The 7th step cooled to 24 ℃ with reactor, and with 140 order net filtrations, discharging obtains a kind of cation styrene-acrylic surface sizing agent.
Embodiment four
A kind of preparation method of cation styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step, 12 gram vinylbenzene, 3 gram methyl methacrylates, 15 gram ethyl propenoates and 5 are restrained vinylcarbinols by 12: 3: 15: 5 mass ratio is mixed and made into mix monomer,
Second step, 1 gram ammonium persulphate and 20 gram deionized waters are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 3rd step, 1 gram polyvinyl alcohol 1799 and 20 gram deionized waters press mass ratio 1: 20 add reactor and stirred 1.1 hours 91 ℃ the time, polyvinyl alcohol 1799 is dissolved,
The 4th step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1799, the mass ratio of polyvinyl alcohol 1799 and deionized water is 1: 127, is cooled to 66 ℃,
The 5th step, give and add 21 gram ammonium persulfate aqueous solutions and 35 gram mix monomers in the polyvinyl alcohol water solution, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and mix monomer is 148: 21: 35, continue to drip 8 gram methylacryoyloxyethyl trimethyl ammonium chlorides after dripping mix monomer, the mass ratio of mix monomer and methylacryoyloxyethyl trimethyl ammonium chloride is 35: 8, the whole reinforced time is 1.6 hours
The 6th step, behind reinforced the finishing with reactor in 86 ℃ of insulations, reacted 2.6 hours,
The 7th step cooled to 26 ℃ with reactor, and with 160 order net filtrations, discharging obtains a kind of cation styrene-acrylic surface sizing agent.
Embodiment five
A kind of preparation method of cation styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step, 12 gram vinylbenzene, 3 gram methyl methacrylates, 15 gram ethyl propenoates and 5 are restrained vinylcarbinols by 12: 3: 15: 5 mass ratio is mixed and made into mix monomer,
Second step, 1 gram ammonium persulphate and 20 gram deionized waters are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 3rd step, 1 gram polyvinyl alcohol 1799 and 20 gram deionized waters press mass ratio 1: 20 add reactor and stirred 1.3 hours 93 ℃ the time, polyvinyl alcohol 1799 is dissolved,
The 4th step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1799, the mass ratio of polyvinyl alcohol 1799 and deionized water is 1: 127, is cooled to 68 ℃,
The 5th step, give and add 21 gram ammonium persulfate aqueous solutions and 35 gram mix monomers in the polyvinyl alcohol water solution, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and mix monomer is 148: 21: 35, continue to drip 8 gram methylacryoyloxyethyl trimethyl ammonium chlorides after dripping mix monomer, the mass ratio of mix monomer and methylacryoyloxyethyl trimethyl ammonium chloride is 35: 8, the whole reinforced time is 1.8 hours
The 6th step, behind reinforced the finishing with reactor in 88 ℃ of insulations, reacted 2.8 hours,
The 7th step cooled to 28 ℃ with reactor, and with 180 order net filtrations, discharging obtains a kind of cation styrene-acrylic surface sizing agent.
Embodiment six
A kind of preparation method of cation styrene-acrylic surface sizing agent specifically may further comprise the steps:
The first step, 12 gram vinylbenzene, 3 gram methyl methacrylates, 15 gram ethyl propenoates and 5 are restrained vinylcarbinols by 12: 3: 15: 5 mass ratio is mixed and made into mix monomer,
Second step, 1 gram ammonium persulphate and 20 gram deionized waters are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 3rd step, 1 gram polyvinyl alcohol 1799 and 20 gram deionized waters press mass ratio 1: 20 add reactor and stirred 1.5 hours 95 ℃ the time, polyvinyl alcohol 1799 is dissolved,
The 4th step, to give to add 127 gram deionized waters formation polyvinyl alcohol water solutions in the dissolved polyvinyl alcohol 1799, the mass ratio of polyvinyl alcohol 1799 and deionized water is 1: 127, is cooled to 70 ℃,
The 5th step, give and add 21 gram ammonium persulfate aqueous solutions and 35 gram mix monomers in the polyvinyl alcohol water solution, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and mix monomer is 148: 21: 35, continue to drip 8 gram methylacryoyloxyethyl trimethyl ammonium chlorides after dripping mix monomer, the mass ratio of mix monomer and methylacryoyloxyethyl trimethyl ammonium chloride is 35: 8, the whole reinforced time is 2 hours
The 6th step, behind reinforced the finishing with reactor in 90 ℃ of insulations, reacted 3.0 hours,
The 7th step cooled to 30 ℃ with reactor, and with 200 order net filtrations, discharging obtains a kind of cation styrene-acrylic surface sizing agent.
Claims (3)
2. the preparation method of a cation styrene-acrylic surface sizing agent, it is characterized in that: with polyvinyl alcohol 1799 is dispersion agent, with the ammonium persulphate is initiator, is that mix monomer carries out polyreaction and prepares cation styrene-acrylic surface sizing agent with vinylbenzene, methyl methacrylate, ethyl propenoate, vinylcarbinol and methylacryoyloxyethyl trimethyl ammonium chloride.
3. the preparation method of a kind of cation styrene-acrylic surface sizing agent according to claim 2 is characterized in that: specifically may further comprise the steps:
The first step, with vinylbenzene, methyl methacrylate, ethyl propenoate and vinylcarbinol by 12: 3: 15: 5 mass ratio is mixed and made into mix monomer,
Second step, ammonium persulphate and deionized water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 3rd step, polyvinyl alcohol 1799 and deionized water press mass ratio add reactor at 1: 20 and stirred 0.5-1.5 hour 85-95 ℃ the time, polyvinyl alcohol 1799 is dissolved,
The 4th step, to give to add deionized water formation polyvinyl alcohol water solution in the dissolved polyvinyl alcohol 1799, the mass ratio of polyvinyl alcohol 1799 and deionized water is 1: 127, is cooled to 60-70 ℃,
The 5th step, give and add ammonium persulfate aqueous solution and mix monomer in the polyvinyl alcohol water solution, the mass ratio of polyvinyl alcohol water solution, ammonium persulfate aqueous solution and mix monomer is 148: 21: 35, continue to drip the methylacryoyloxyethyl trimethyl ammonium chloride after dripping mix monomer, the mass ratio of mix monomer and methylacryoyloxyethyl trimethyl ammonium chloride is 35: 8, the whole reinforced time is 1-2 hour
The 6th step, behind reinforced the finishing with reactor in 80-90 ℃ of insulation, reacted 2.0-3.0 hour,
The 7th step cooled to 20-30 ℃ with reactor, and with 100-200 order net filtration, discharging obtains a kind of cation styrene-acrylic surface sizing agent.
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