CN101544717A - Styrene-acrylic microemulsion surface sizing agent with high solid content and core shell structure and preparation method and application thereof - Google Patents
Styrene-acrylic microemulsion surface sizing agent with high solid content and core shell structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a styrene-acrylic microemulsion surface sizing agent with high solid content and core shell structure and a preparation method and an application thereof. The preparation method comprises the following steps: adopting a seed emulsion method to synthesize core emulsion, dropping core pre-emulsified monomer solution and redox initiator into core the emulsion, controlling the dropping time, filtering the product of reaction by using a 250 mesh or 300 mesh sieve, discharging, and obtaining the microemulsion with hard core and soft core shell structure, wherein the microemulsion has a grain diameter of 20-100nm and the solid content of 40-48 percent. The surface sizing agent has the base characteristics of styrene-acrylic emulsion, good stability, core shell structure, small grain diameter, high solid content, and better gluing effect and can endow paper with better water resisting property and improve the surface property of the paper.
Description
Technical field
The present invention relates to a kind of styrene-acrylic emulsion surface sizing agent and preparation method thereof and application, particularly a kind of high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent and preparation method thereof and application.
Background technology
Improving paper water resisting property can realize by plasm-glue-blending technology, also can realize by surface sizing technique.
Plasm-glue-blending technology can improve paper water resisting property preferably, but used internal sizing agent has shortcomings such as retention is low, water resisting property is limited, not environmental protection.
Surface sizing technique can make page have surface property and physical property preferably, can overcome some shortcoming of plasm-glue-blending, raising as the waste paper recycling rate, the application of high yield pulp, straw pulp and the use of high amount of filler etc., thereby for enterprise brings big benefit, therefore, surface sizing technique replaces plasm-glue-blending becomes inevitable.Add the water repelling property that water repellent agent not only can obviously improve paper in surface size, can also obtain following function: (1) obviously improves surface propertys such as surface strength of paper, smoothness and printability; (2) improve physical index such as strength of paper, improve paper surface structure and performance; (3) the applying glue cost is low, has in limited time at internal sizing, can further improve sizing efficiency, and alleviates the caused paper machine of internal sizing agent and stain and problem such as plain boiled water load increase; (4) the sizing agent retention is near 100%, service efficiency height, environmental protection; (5) alleviate the obstruction of paper machine woollen blanket, increase work-ing life.
At present, the top sizing water repellent agent of use is generally the mixed solution of polymkeric substance and surface sizing starch.Polymkeric substance can strengthen the avidity of starch surface sizing agent and fiber, overcomes covering starch film on paper and shrinks consequently disruptive shortcoming along with the evaporation of moisture.Simultaneously, polymkeric substance also can replenish the function that starch does not have owing to containing great amount of hydroxy group, as water resisting property, resistance to acids and bases, thermotolerance, printing printability etc.Polymkeric substance is generally synthetic base polymer, is mainly styrene-acrylic polymer (adopt solution method synthetic styrene acrylic polymers SAA and adopt emulsion method synthetic styrene-acrylate class emulsion SAE), fluorocarbon polymer and modified product thereof.The anti-water effect of fluorine carbon polymkeric substance excellence, but price is higher, and the synthesis technique complexity is promoted the big difficulty of existence on a large scale; SAA is a dispersion medium with the organism, is unfavorable for the requirement of environmental protection and green product development.Therefore, the development trend of water resistant type Surface Size is SAE.Lyophobic performance, impact resistance that vinylbenzene has excellence are stronger; Esters of acrylic acid has good film-forming properties and cohesiveness; The film-forming properties and the snappiness of the emulsion that both copolymerization obtain are stronger, has stronger sticking power at paper surface, have stronger bonding force and simultaneously can give paper good water resisting property with fiber, and such emulsion is to be medium with water, meet the requirement and the developing direction of present green product.
U.S. Pat 6734232B2 discloses the benzene emulsion that vinylbenzene according to a certain percentage, butyl acrylate, maleic anhydride and stablizer polyvinyl alcohol etc. have synthesized solid content 15～50%, particle diameter 0.01～2 μ m, this product and treated starch are shared, obtain top sizing effect preferably, but the emulsifying agent consumption is 7.5% of a monomer consumption, also added a large amount of assistant for emulsifying agent (monomer consumption 50%) simultaneously, this influences the anti-water effect of emulsion to a great extent.Chinese patent CN101205696A discloses esters of acrylic acid soft monomer, hard monomer and ion monomer and synthesized soap-free surface sizing agent under the initiator effect, but median size is about 300nm.It is dispersion agent that Chinese patent CN1944792A discloses with the gelatin, vinylbenzene, emulsifying agent, cationic monomer and methacrylic acid (ester) class monomer is carried out free-radical emulsion polymerization, the composite back of emulsion that obtains and Sumstar 190 is to applying glues such as fluting board, white boards, the Cobb value significantly reduces, but be to use many dispersion agents and emulsifying agent, be unfavorable for environmental protection.In " preparation of hud typed Surface Size and application " literary composition that Li Jianwen etc. were delivered in " Chinese papermaking " 2006 25 3 phases of volume with vinylbenzene, butyl acrylate is a principal monomer, methyl methacrylate, vinylformic acid, methacrylic acid, maleic anhydride is the functional type monomer, sodium vinyl sulfonate and lauryl mercaptan are reaction emulsifier, ammonium persulphate is an initiator, adopt semi-continuous process to synthesize the core/shell type benzene emulsion, the composite applying glue liquid of this product and Sumstar 190 is to the art base paper applying glue, the Cobb value reduces significantly, but the monomer consumption is 1: 10 with the ratio of emulsifying agent consumption, the emulsifying agent consumption is more and solid content is lower, and median size big (being 280nm).
Existing technology shows, the emulsifying agent consumption very little, when the ordinary emulsion solid content increases, the bad stability of emulsion, easily cohesion; If reduce the ordinary emulsion solid content, then will increase the cost of packing and transportation; The emulsifying agent consumption is many, has influenced the effect of hydrophobic monomer again to a certain extent, so that styrene-acrylic emulsion surface sizing agent water repelling property deficiency.The emulsion particle median size is big, will influence emulsion particle and penetrate into page inside, has weakened interfibrous bonding force, so that emulsion particle can not be poor attached to paper surface and film-forming properties preferably, influences the strength of paper performance.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the deficiencies in the prior art and defective, a kind of solid content height (40～48%) is provided, particle diameter little (20～100nm) and emulsifying agent consumption few (1～4%), the high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent of good stability.This Surface Size has characteristics such as preferable water resisting property and sticking power, is fit to the paper that all needs top sizings such as all cultural papers, package paper are handled.
Another object of the present invention also provides the preparation method of above-mentioned high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent.
A further object of the present invention also provides the application of above-mentioned high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent.
Purpose of the present invention is achieved through the following technical solutions:
A kind of high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent, form by following component in mass fraction:
25～75 parts of soft monomers
25～75 parts of hard monomers
0.5～1 part of functional monomer
0.5～2 part of alkyl methacrylate
0.5～2 part of linking agent
1～4 part of compound emulsifying agent
0.5～1 part of buffer reagent
0.5～0.8 part in oxygenant
0.5～2.4 part of sodium bisulfite
95.1～146 parts of distilled water;
The quality summation of described soft monomer and hard monomer is necessary for 100 parts;
Described hard monomer is an ethylene compounds;
Described ethylene compounds is a vinyl aromatic compounds;
A kind of or at least two kinds of mixtures of described vinyl aromatic compounds optimization styrene, vinyl toluene, chlorostyrene, t-butyl styrene;
Described soft monomer is an acrylic ester compound;
A kind of or at least two kinds of mixtures of the preferred methyl acrylate of described acrylic ester compound, ethyl propenoate, butyl acrylate, Ethyl acrylate or Isooctyl acrylate monomer;
Described functional monomer is a kind of of vinylformic acid, α-Jia Jibingxisuan, maleic anhydride or methylene-succinic acid or at least two kinds of mixtures;
Described alkyl methacrylate is a kind of or at least two kinds of mixtures of methyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester or n octyl methacrylate;
Described linking agent is a kind of or at least two kinds of mixtures of N-methoxymethyl acrylamide, N-carboxylic methoxymethyl propenamide, glycidyl allyl ether or vinylformic acid glycidyl ether;
Described compound emulsifying agent is that anionic emulsifier mixes by mass ratio 1:4～4:1 with the nonionic emulsifying agent mixture;
Described anionic emulsifier is a kind of or at least two kinds of mixtures in alkyloyl Sodium L-aspartate, sulfo-succinic acid mono alkyl ester disodium salt, sodium lauryl sulphate, the Sodium dodecylbenzene sulfonate;
Described nonionic emulsifier is a kind of or at least two kinds of mixtures in undecyl glucose amide, sorbitol monooleate, polyoxyethylene nonylphenol ether, the polyoxyethylene octylphenol ether;
Described buffer reagent is sodium bicarbonate or SODIUM PHOSPHATE, MONOBASIC;
Described oxygenant is Potassium Persulphate or ammonium persulphate.
Described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent may further comprise the steps:
(1) preparation of shell portion pre-emulsion:
Getting 25～75 mass fraction soft monomers, 0.5～2 mass fraction alkyl methacrylate, 0.5～1 mass fraction functional monomer, the buffer reagent that is equivalent to soft monomer quality 0.5～1%, the compound emulsifying agent that is equivalent to soft monomer quality 0.5～1% and distilled water A mixes, under 30～40 ℃, rotating speed with 500～700rpm stirred 20～40 minutes, the fully pre-emulsification of soft monomer, obtain shell portion pre-emulsion;
(2) preparation of nuclear portion emulsion:
I, 25～75 mass fraction hard monomers, 0.5～2 mass fraction linking agent are mixed, obtain nuclear portion mixed monomer solution;
II, then, getting 3/20～2/5 of nuclear portion mixed monomer solution total amount mixes with the compound emulsifying agent that is equivalent to hard monomer quality 0.5～1%, the buffer reagent that is equivalent to hard monomer quality 0.5～1% and distilled water B, under 30～40 ℃, speed with rotating speed 500～700rpm stirred 20～40 minutes, formed the pre-emulsified monomer solution of nuclear portion;
III, usefulness distilled water C dissolving 0.5～0.8 mass fraction oxygenant, the oxygenant mass concentration is 1%; Toward wherein adding the sodium bisulfite that is equivalent to 1/3～1 times of oxygenant quality, mix again, obtain redox initiator solution;
IV, under protection of inert gas, add thermonuclear portion pre-emulsified monomer solution to 75～80 ℃, stirring velocity is transferred to 150～300rpm, add 4～32% redox initiator solution of the redox initiator solution quality number that accounts for step (2) III preparation; Under 75～80 ℃, be incubated to emulsion and blue light (being that polyreaction begins) occurs, and then be incubated 10～20 minutes, obtain seed emulsion;
V, then, drip remaining nuclear portion mixed monomer solution (promptly 3/5～17/20 of nuclear portion mixed monomer solution total amount) in the seed emulsion simultaneously and account for 43～64% redox initiator solution of the redox initiator solution quality number of step (2) III preparation, the dropping time is 2～3.5 hours; After dropwising, be warming up to 90～95 ℃ and be incubated 1～1.5 hour down, obtain nuclear portion emulsion;
(3) preparation high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent:
75～80 ℃ and stirring velocity is under 150～300rpm condition, drip shell portion pre-emulsion simultaneously in the nuclear portion emulsion and account for redox initiator solution quality several 25～32% that step (2) III prepares redox initiator solution; Shell portion pre-emulsion and redox initiator drips of solution add the time and were respectively 2～3.5 hours; Dropwise back insulation 1.5～2 hours, be cooled to then below 40 ℃, regulate pH value to 7～8 with ammoniacal liquor, with the strainer filtering of 250 orders or 300 orders (aperture is 65 μ m or 50 μ m), discharging obtains the high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent;
The quality summation of described soft monomer and hard monomer is necessary for 100 parts;
The quality summation of described distilled water A, distilled water B and distilled water C is 95.1～146 parts, and wherein, the ratio of distilled water A and distilled water B is 1:4～1:6.5;
Described rare gas element is nitrogen, helium or argon gas;
Described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent is to be stone with the ethylene compounds, polyacrylic ester is the compound of soft shell, its solid content is 40～48%, and particle diameter is 20～100nm, and the emulsifying agent consumption is equivalent to 1～4% of soft monomer and hard monomer total mass number sum.
Described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent is applied to field of papermaking.
Described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent is used for all needs top sizing/coating to wait the surface-treated paper surface to handle.
Compared with prior art, the present invention has following advantage:
1, compares with existing phenylpropyl alcohol series emulsion Surface Size, the product solid content that prescription that the present invention adopts and preparation method obtain is 40～48%, particle diameter is 20～100nm, emulsifying agent consumption (accounting for soft monomer and hard monomer total mass number sum) is 1～4%, and the water resisting property of product strengthens and sticking power improves.
2, adopt the emulsion particle particle diameter of core/shell structure emulsion and micro-emulsion polymerization process preparation thinner, good stability, sizability and effect are remarkable.
3, product of the present invention can reduce traffic capacity and trucking costs, at least 7 months storage periods because the solid content height is convenient to transportation.
4, product of the present invention and preparation method thereof environmental protection, product do not have generation of waste materials, environmentally safe when using.
5, product of the present invention not only can replace internal sizing agent fully, possesses the water resisting property effect that plasm-glue-blending reaches, but also can improve the physical index such as printing adaptability, tensile strength of paper.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation solid content is 40% core-shell structure styrene-acrylic microemulsion surface sizing agent, may further comprise the steps:
(1) preparation of shell portion pre-emulsion:
Getting 25g butyl acrylate, 0.5g n octyl methacrylate, 0.5g α-Jia Jibingxisuan, 0.25g sodium bicarbonate, 0.25g compound emulsifying agent (sodium lauryl sulphate is mixed by mass ratio with the undecyl glucose amide at 1: 1) and 8.86g distilled water mixes, under 30 ℃, rotating speed with 500rpm stirred 20 minutes, the fully pre-emulsification of soft monomer, obtain shell portion pre-emulsion;
(2) preparation of nuclear portion emulsion:
A, 75g vinyl toluene, 1g glycidyl allyl ether are mixed, obtain nuclear portion mixed monomer solution;
B, then, getting 11.4g nuclear portion mixed monomer solution, 0.75g compound emulsifying agent (sodium lauryl sulphate is mixed by mass ratio 1:1 with the undecyl glucose amide), 0.75g sodium bicarbonate and 56.73g distilled water mixes, under 40 ℃, speed with rotating speed 700rpm stirred 40 minutes, formed the pre-emulsified monomer solution of nuclear portion;
C, 79.2g dissolved in distilled water 0.8g Potassium Persulphate; Toward wherein adding the 0.4g sodium bisulfite, mix again, obtain redox initiator solution;
D, under nitrogen protection, add thermonuclear portion pre-emulsified monomer solution to 80 ℃, stirring velocity is transferred to 300rpm, add 25.73g redox initiator solution; Under 80 ℃, be incubated to emulsion and blue light (being that polyreaction begins) occurs, and then be incubated 15 minutes, obtain seed emulsion;
E, then drips remaining nuclear portion's mixed monomer solution (being 64.6g nuclear portion mixed monomer solution) and 34.57g redox initiator solution simultaneously in seed emulsion, the dropping time is 3.5 hours; After dropwising, be warming up to 95 ℃ and be incubated 1.5 hours down, obtain nuclear portion emulsion;
(3) preparation high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent:
Is under the 300rpm condition at 80 ℃ with stirring velocity, drips shell portion pre-emulsion and 20.1g redox initiator solution simultaneously in nuclear portion emulsion; Pre-emulsion and redox initiator drips of solution add the time and were respectively 2 hours; Dropwise back insulation 1.5 hours, be cooled to then below 40 ℃, regulate pH value to 7 with ammoniacal liquor, with 300 purpose strainer filterings, discharging, promptly making with the polyvinyltoluene is stone, butyl polyacrylate is the nano level styrene-acrylic microemulsion of the high solid content core-shell structure of soft shell.
The nano level styrene-acrylic microemulsion solid content of the high solid content core-shell structure that obtains is 40%, the emulsifying agent consumption is equivalent to 1% of soft monomer and hard monomer quality summation, median size is a 58nm (Mastersizer2000 laser diffraction granularity analyser, Malvern Instruments Ltd., England).
Embodiment 2
The preparation solid content is 43% core-shell structure styrene-acrylic microemulsion surface sizing agent, may further comprise the steps:
(1) preparation of shell portion pre-emulsion:
Getting 75g Isooctyl acrylate monomer, 1g methyl methacrylate, 0.8g methylene-succinic acid, 0.38g SODIUM PHOSPHATE, MONOBASIC, 1.13g compound emulsifying agent (sodium lauryl sulphate is mixed by mass ratio 3:1 with the undecyl glucose amide) and 11.07g distilled water mixes, under 40 ℃, rotating speed with 700rpm stirred 40 minutes, the fully pre-emulsification of soft monomer, obtain shell portion pre-emulsion;
(2) preparation of nuclear portion emulsion:
A, 25g hard monomer (vinylbenzene mixes by mass ratio 1:1 with chlorostyrene), 1.5g N-carboxylic methoxymethyl propenamide are mixed, obtain nuclear portion mixed monomer solution;
B, then, getting 9.28g nuclear portion mixed monomer solution, 1g compound emulsifying agent (Sodium dodecylbenzene sulfonate mixes by mass ratio 1:3 with polyoxyethylene octylphenol ether), 0.12g SODIUM PHOSPHATE, MONOBASIC and 55.36g distilled water mixes, under 30 ℃, speed with rotating speed 500rpm stirred 20 minutes, formed the pre-emulsified monomer solution of nuclear portion;
C, 59.4g dissolved in distilled water 0.6g ammonium persulphate; Mix toward wherein adding the 0.2g sodium bisulfite again, obtain redox initiator solution;
D, under nitrogen protection, add thermonuclear portion pre-emulsified monomer solution to 75 ℃, stirring velocity is transferred to 150rpm, add 3.61g redox initiator solution; Under 75 ℃, be incubated to emulsion and blue light (being that polyreaction begins) occurs, and then be incubated 10 minutes, obtain seed emulsion;
E, then drips remaining nuclear portion's mixed monomer solution (being 17.22g nuclear portion mixed monomer solution) and 38.53g redox initiator solution simultaneously in seed emulsion, the dropping time is 2 hours; After dropwising, be warming up to 90 ℃ and be incubated 1.4 hours down, obtain nuclear portion emulsion;
(3) preparation high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent:
Is under the 200rpm condition at 75 ℃ with stirring velocity, drips shell portion pre-emulsion and 18.06g redox initiator solution simultaneously in nuclear portion emulsion; Shell portion pre-emulsion and redox initiator drips of solution add the time and were respectively 2.5 hours; Dropwise back insulation 2 hours, be cooled to then below 40 ℃, regulate pH value to 8 with ammoniacal liquor, with 300 purpose strainer filterings, discharging, promptly making with vinylbenzene and chlorostyrene multipolymer is stone, the nano level styrene-acrylic microemulsion of the high solid content core-shell structure that the different monooctyl ester homopolymer of polyacrylic acid is a soft shell.
The nano level styrene-acrylic microemulsion solid content of the high solid content core-shell structure that obtains is 43%, the emulsifying agent consumption is equivalent to 2.12% of soft monomer and hard monomer quality summation, median size is a 55nm (Mastersizer2000 laser diffraction granularity analyser, Malvern Instruments Ltd., England).
Embodiment 3
The preparation solid content is 43% core-shell structure styrene-acrylic microemulsion surface sizing agent, may further comprise the steps:
(1) preparation of shell portion pre-emulsion:
Getting 70g soft monomer (ethyl propenoate and butyl acrylate are pressed mass ratio 1:2 and mixed), 1g n octyl methacrylate, 1g maleic anhydride, 0.7g sodium bicarbonate, 1.05g compound emulsifying agent (sodium lauryl sulphate is mixed by mass ratio 1:4 with the undecyl glucose amide) and 11.01g distilled water mixes, under 38 ℃, rotating speed with 650rpm stirred 35 minutes, the fully pre-emulsification of soft monomer, obtain shell portion pre-emulsion;
(2) preparation of nuclear portion emulsion:
A, 30g vinyl toluene, 1.5g glycidyl allyl ether are mixed, obtain nuclear portion mixed monomer solution;
B, then, getting 12.6g nuclear portion mixed monomer solution, 0.9g compound emulsifying agent (sodium lauryl sulphate sodium mixes by mass ratio 2:1 with polyoxyethylene octylphenol ether), 0.15g sodium bicarbonate and 55.05g distilled water mixes, under 30 ℃, speed with rotating speed 550rpm stirred 30 minutes, formed the pre-emulsified monomer solution of nuclear portion;
C, 59.4g dissolved in distilled water 0.6g ammonium persulphate; Mix toward wherein adding the 0.2g sodium bisulfite again, obtain redox initiator solution;
D, under nitrogen protection, add thermonuclear portion pre-emulsified monomer solution to 78 ℃, stirring velocity is transferred to 200rpm, add 3.01g redox initiator solution; Under 78 ℃, be incubated to emulsion and blue light (being that polyreaction begins) occurs, and then be incubated 10 minutes, obtain seed emulsion;
E, then drips remaining nuclear portion's mixed monomer solution (18.9g nuclear portion is a mixed monomer solution) and 37.93g redox initiator solution simultaneously in seed emulsion, the dropping time is 2.5 hours; After dropwising, be warming up to 90 ℃ and be incubated 1 hour down, obtain nuclear portion emulsion;
(3) preparation high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent:
Is under the 150rpm condition at 78 ℃ with stirring velocity, drips shell portion pre-emulsion and 19.26g redox initiator solution simultaneously in nuclear portion emulsion; Shell portion pre-emulsion and redox initiator drips of solution add the time and were respectively 3.5 hours; Dropwise back insulation 2 hours, be cooled to then below 40 ℃, regulate pH value to 7.6 with ammoniacal liquor, with 250 purpose strainer filterings, discharging, promptly making with the vinyl toluene homopolymer is stone, and butyl acrylate and ethyl acrylate copolymer are the nano level styrene-acrylic microemulsion of the high solid content core-shell structure of soft shell.
The nano level styrene-acrylic microemulsion solid content of the high solid content core-shell structure that obtains is 43%, the emulsifying agent consumption is equivalent to 1.95% of soft monomer and hard monomer quality summation, median size is a 70nm (Mastersizer2000 laser diffraction granularity analyser, Malvern Instruments Ltd., England).Embodiment 4
The preparation solid content is 45% core-shell structure styrene-acrylic microemulsion surface sizing agent, may further comprise the steps:
(1) preparation of shell portion pre-emulsion:
Getting 60g Ethyl acrylate, 2g alkyl methacrylate (methyl methacrylate mixes by mass ratio 1:1 with n octyl methacrylate), 1g methylene-succinic acid, 0.42g SODIUM PHOSPHATE, MONOBASIC, 1.2g compound emulsifying agent (the alkyloyl Sodium L-aspartate mixes by mass ratio 1:1 with sorbitol monooleate) and 12.74g distilled water mixes, under 35 ℃, rotating speed with 550rpm stirred 30 minutes, the fully pre-emulsification of soft monomer, obtain shell portion pre-emulsion;
(2) preparation of nuclear portion emulsion:
A, 40g hard monomer (vinylbenzene mixes by mass ratio 1:1 with t-butyl styrene), 2g vinylformic acid glycidyl ether are mixed, obtain nuclear portion mixed monomer solution;
B, then, getting 12.6g nuclear portion mixed monomer solution, 1.2g compound emulsifying agent (Sodium dodecylbenzene sulfonate mixes by mass ratio 1:1 with polyoxyethylene octylphenol ether), 0.2g SODIUM PHOSPHATE, MONOBASIC and 50.96g distilled water mixes, under 35 ℃, speed with rotating speed 600rpm stirred 25 minutes, formed the pre-emulsified monomer solution of nuclear portion;
C, 49.5g dissolved in distilled water 0.5g Potassium Persulphate; Mix toward wherein adding the 0.5g sodium bisulfite again, obtain redox initiator solution;
D, under helium protection, add thermonuclear portion pre-emulsified monomer solution to 75 ℃, stirring velocity is transferred to 250rpm, add 5.05g redox initiator solution; Under 75 ℃, be incubated to emulsion and blue light (being that polyreaction begins) occurs, and then be incubated 20 minutes, obtain seed emulsion;
E, then drips remaining nuclear portion's mixed monomer solution (being 29.4g nuclear portion mixed monomer solution) and 31.31g redox initiator solution simultaneously in seed emulsion, the dropping time is 2.5 hours; After dropwising, be warming up to 93 ℃ and be incubated 1 hour down, obtain nuclear portion emulsion;
(3) preparation high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent:
Is under the 220rprm condition at 75 ℃ with stirring velocity, drips shell portion pre-emulsion and 14.14g redox initiator solution simultaneously in nuclear portion emulsion; Shell portion pre-emulsion and redox initiator drips of solution add the time and were respectively 2.8 hours; Dropwise back insulation 2 hours, be cooled to then below 40 ℃, regulate pH value to 7.5 with ammoniacal liquor, with 250 purpose strainer filterings, discharging, promptly making with vinylbenzene and t-butyl styrene multipolymer is stone, the own ester of polyacrylic acid is the nano level styrene-acrylic microemulsion of the high solid content core-shell structure of soft shell.
The nano level styrene-acrylic microemulsion solid content of the high solid content core-shell structure that obtains is 45%, the emulsifying agent consumption is equivalent to 2.4% of soft monomer and hard monomer quality summation, median size is a 65nm (Mastersizer2000 laser diffraction granularity analyser, Malvern Instruments Ltd., England).
Embodiment 5
The preparation solid content is 45% core-shell structure styrene-acrylic microemulsion surface sizing agent, may further comprise the steps:
(1) preparation of shell portion pre-emulsion:
Getting 50g soft monomer (Ethyl acrylate is mixed by mass ratio 1:2 with butyl acrylate), 1g methacrylic acid pentyl ester, 0.8g α-Jia Jibingxisuan, 0.25g SODIUM PHOSPHATE, MONOBASIC, 2g compound emulsifying agent (the alkyloyl Sodium L-aspartate mixes by mass ratio 1:1 with polyoxyethylene nonylphenol ether) and 6.25g distilled water mixes, under 30 ℃, rotating speed with 700rpm stirred 40 minutes, the fully pre-emulsification of soft monomer, obtain shell portion pre-emulsion;
(2) preparation of nuclear portion emulsion:
A, 50g t-butyl styrene, 1.5g vinylformic acid glycidyl ether are mixed, obtain nuclear portion mixed monomer solution;
B, then, getting 20.6g nuclear portion mixed monomer solution, 2g compound emulsifying agent (sodium lauryl sulphate is mixed by mass ratio 2:1 with polyoxyethylene octylphenol ether), 0.4g SODIUM PHOSPHATE, MONOBASIC and 37.52g distilled water mixes, under 40 ℃, speed with rotating speed 600rpm stirred 30 minutes, formed the pre-emulsified monomer solution of nuclear portion;
C, 69.3g dissolved in distilled water 0.7g ammonium persulphate; Mix toward wherein adding the 0.5g sodium bisulfite again, obtain redox initiator solution;
D, under helium protection, add thermonuclear portion pre-emulsified monomer solution to 75 ℃, stirring velocity is transferred to 250rpm, add 12.69g redox initiator solution; Under 75 ℃, be incubated to emulsion and blue light (being that polyreaction begins) occurs, and then be incubated 20 minutes, obtain seed emulsion;
E, then drips remaining nuclear portion's mixed monomer solution (being 30.9g nuclear portion mixed monomer solution) and 39.48g redox initiator solution simultaneously in seed emulsion, the dropping time is 2.5 hours; After dropwising, be warming up to 95 ℃ and be incubated 1.5 hours down, obtain nuclear portion emulsion;
(3) preparation high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent:
Is under the 300rpm condition at 75 ℃ with stirring velocity, drips shell portion pre-emulsion and 18.33g redox initiator solution shell portion simultaneously in nuclear portion emulsion; Pre-emulsion and redox initiator drips of solution add the time and were respectively 3.5 hours; Dropwise back insulation 2 hours, be cooled to then below 40 ℃, regulate pH value to 8 with ammoniacal liquor, with 300 purpose strainer filterings, discharging, promptly making with poly-t-butyl styrene is stone, and Ethyl acrylate and butyl acrylate copolymer are the nano level styrene-acrylic microemulsion of the high solid content core-shell structure of soft shell.
The nano level styrene-acrylic microemulsion solid content of the high solid content core-shell structure that obtains is 45%, the emulsifying agent consumption is equivalent to 4% of soft monomer and hard monomer quality summation, median size is a 25nm (Mastersizer2000 laser diffraction granularity analyser, Malvern Instruments Ltd., England).
Embodiment 6
The preparation solid content is 48% core-shell structure styrene-acrylic microemulsion surface sizing agent, may further comprise the steps:
(1) preparation of shell portion pre-emulsion:
Getting 67g Ethyl acrylate, 1.5g methacrylic acid pentyl ester, 1g vinylformic acid, 0.4g sodium bicarbonate, 2.01g compound emulsifying agent (Sodium dodecylbenzene sulfonate mixes by mass ratio 2:1 with polyoxyethylene nonylphenol ether) and 9.99g distilled water mixes, under 40 ℃, rotating speed with 680rpm stirred 40 minutes, the fully pre-emulsification of soft monomer, obtain shell portion pre-emulsion;
(2) preparation of nuclear portion emulsion:
A, 33g vinyl toluene, 2g N-methoxymethyl acrylamide are mixed, obtain nuclear portion mixed monomer solution;
B, then, getting 8.75g nuclear portion mixed monomer solution, 0.66g compound emulsifying agent (Sodium dodecylbenzene sulfonate mixes by mass ratio 2:1 with polyoxyethylene nonylphenol ether), 0.33g sodium bicarbonate and 39.95g distilled water mixes, under 40 ℃, speed with rotating speed 700rpm stirred 30 minutes, formed the pre-emulsified monomer solution of nuclear portion;
C, 49.5g dissolved in distilled water 0.5g ammonium persulphate; Mix toward wherein adding the 0.5g sodium bisulfite again, obtain redox initiator solution;
D, under helium protection, add thermonuclear portion pre-emulsified monomer solution to 80 ℃, stirring velocity is transferred to 300rpm, add 7.58g redox initiator solution; Under 80 ℃, be incubated to emulsion and blue light (being that polyreaction begins) occurs, and then be incubated 20 minutes, obtain seed emulsion;
E, then drips remaining nuclear portion's mixed monomer solution (being 26.25g nuclear portion mixed monomer solution) and 26.76g redox initiator solution simultaneously in seed emulsion, the dropping time is 2.5 hours; After dropwising, be warming up to 95 ℃ and be incubated 1.5 hours down, obtain nuclear portion emulsion;
(3) preparation high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent:
Is under the 300rpm condition at 80 ℃ with stirring velocity, drips shell portion pre-emulsion and 16.16g redox initiator solution simultaneously in nuclear portion emulsion; Pre-emulsion and redox initiator drips of solution add the time and were respectively 3.5 hours; Dropwise back insulation 2 hours, be cooled to then below 40 ℃, regulate pH value to 8 with ammoniacal liquor, with 300 purpose strainer filterings, discharging, promptly making with the polyvinyltoluene is stone, the own ester of polyacrylic acid is the nano level styrene-acrylic microemulsion of the high solid content core-shell structure of soft shell.
The nano level styrene-acrylic microemulsion solid content of the high solid content core-shell structure that obtains is 48%, the emulsifying agent consumption is equivalent to 2.67% of soft monomer and hard monomer quality summation, median size is a 95nm (Mastersizer2000 laser diffraction granularity analyser, Malvern Instruments Ltd., England).
Embodiment 7
Select the computer copy paper body paper (70g/m of the processing of not carrying out plasm-glue-blending and top sizing for use
2).The top sizing water repellent agent emulsion that embodiment 1～6 prepares is mixed by mass ratio 1:30 with Sumstar 190 respectively, and difference is called after sample 1～6 successively.Carry out applying glue under identical applying glue condition respectively, the applying glue temperature is 75 ℃.Dry and test Cobb60 value (promptly 60 seconds cobb values) (ZZ-100 type Cobb pH-value determination pH instrument) after the applying glue immediately.Experimental result sees Table 1:
Each sample of table 1 to 70g/m
2Cobb60 value after the applying glue of computer copy paper body paper
Use 1～6 pair of copy paper body paper of sample to carry out applying glue, the Cobb60 of pros and cons is all less than 30g/m
2, meet quality standard.As seen, high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent of the present invention has more superior water repelling property.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1, a kind of high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent is characterized in that, is made up of following component in mass fraction:
25～75 parts of soft monomers
25～75 parts of hard monomers
0.5～1 part of functional monomer
0.5～2 part of alkyl methacrylate
0.5～2 part of linking agent
1～4 part of compound emulsifying agent
0.5～1 part of buffer reagent
0.5～0.8 part in oxygenant
0.5～2.4 part of sodium bisulfite
95.1～146 parts of distilled water;
The quality summation of described soft monomer and hard monomer is 100 parts;
Described hard monomer is an ethylene compounds;
Described soft monomer is an acrylic ester compound;
Described functional monomer is a kind of of vinylformic acid, α-Jia Jibingxisuan, maleic anhydride or methylene-succinic acid or at least two kinds of mixtures;
Described alkyl methacrylate is a kind of or at least two kinds of mixtures of methyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester or n octyl methacrylate;
Described linking agent is a kind of or at least two kinds of mixtures of N-methoxymethyl acrylamide, N-carboxylic methoxymethyl propenamide, glycidyl allyl ether or vinylformic acid glycidyl ether;
Described compound emulsifying agent is that anionic emulsifier mixes by mass ratio 1:4～4:1 with the nonionic emulsifying agent mixture;
Described buffer reagent is sodium bicarbonate or SODIUM PHOSPHATE, MONOBASIC;
Described oxygenant is Potassium Persulphate or ammonium persulphate.
2, high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent according to claim 1 is characterized in that: described acrylic ester compound is a kind of of methyl acrylate, ethyl propenoate, butyl acrylate, Ethyl acrylate or Isooctyl acrylate monomer or at least two kinds of mixtures;
Described ethylene compounds is a vinyl aromatic compounds;
Described anionic emulsifier is a kind of or at least two kinds of mixtures in alkyloyl Sodium L-aspartate, sulfo-succinic acid mono alkyl ester disodium salt, sodium lauryl sulphate, the Sodium dodecylbenzene sulfonate;
Described nonionic emulsifier is a kind of or at least two kinds of mixtures in undecyl glucose amide, sorbitol monooleate, polyoxyethylene nonylphenol ether, the polyoxyethylene octylphenol ether.
3, high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent according to claim 2 is characterized in that: described vinyl aromatic compounds is a kind of or at least two kinds of mixtures of vinylbenzene, vinyl toluene, chlorostyrene, t-butyl styrene.
4, the preparation method of each described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent of claim 1～3 is characterized in that, may further comprise the steps:
(1) preparation of shell portion pre-emulsion:
Getting 25～75 mass fraction soft monomers, 0.5～2 mass fraction alkyl methacrylate, 0.5～1 mass fraction functional monomer, the buffer reagent that is equivalent to soft monomer quality 0.5～1%, the compound emulsifying agent that is equivalent to soft monomer quality 0.5～1% and distilled water A mixes, under 30～40 ℃, rotating speed with 500～700rpm stirred 20～40 minutes, the fully pre-emulsification of soft monomer, obtain shell portion pre-emulsion;
(2) preparation of nuclear portion emulsion:
I, 25～75 mass fraction hard monomers, 0.5～2 mass fraction linking agent are mixed, obtain nuclear portion mixed monomer solution;
II, then, getting 3/20～2/5 of nuclear portion mixed monomer solution total amount mixes with the compound emulsifying agent that is equivalent to hard monomer quality 0.5～1%, the buffer reagent that is equivalent to hard monomer quality 0.5～1% and distilled water B, under 30～40 ℃, speed with rotating speed 500～700rpm stirred 20～40 minutes, formed the pre-emulsified monomer solution of nuclear portion;
III, usefulness distilled water C dissolving 0.5～0.8 mass fraction oxygenant, the oxygenant mass concentration is 1%; Toward wherein adding the sodium bisulfite that is equivalent to 1/3～1 times of oxygenant quality, mix again, obtain redox initiator solution;
IV, under protection of inert gas, add thermonuclear portion pre-emulsified monomer solution to 75～80 ℃, stirring velocity is transferred to 150～300rpm, add 4～32% redox initiator solution of the redox initiator solution quality that accounts for step (2) III preparation; Under 75～80 ℃, be incubated to emulsion and blue light occurs, and then be incubated 10～20 minutes, obtain seed emulsion;
V, then drips remaining nuclear portion's mixed monomer solution simultaneously in the seed emulsion and accounts for 43～64% redox initiator solution of redox initiator solution quality number that step (2) III prepares, and the dropping time is 2～3.5 hours; After dropwising, be warming up to 90～95 ℃ and be incubated 1～1.5 hour down, obtain nuclear portion emulsion;
(3) preparation high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent:
75～80 ℃ and stirring velocity is under 150～300rpm condition, drip shell portion pre-emulsion simultaneously in the nuclear portion emulsion and account for redox initiator solution quality several 25～32% that step (2) III prepares redox initiator solution; Shell portion pre-emulsion and redox initiator drips of solution add the time and were respectively 2～3.5 hours; Dropwising back insulation 1.5～2 hours, be cooled to then below 40 ℃, regulate pH value to 7～8 with ammoniacal liquor, is the strainer filtering of 65 μ m or 50 μ m with the aperture, and discharging obtains the high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent;
The quality summation of described soft monomer and hard monomer is 100 parts;
The quality summation of described distilled water A, distilled water B and distilled water C is 95.1～146 parts, and wherein, the ratio of distilled water A and distilled water B is 1:4～1:6.5.
5, according to the preparation method of the described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent of claim 4, it is characterized in that: described rare gas element is nitrogen, helium or argon gas.
6, according to the preparation method of the described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent of claim 4, it is characterized in that: described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent is to be stone with the ethylene compounds, polyacrylic ester is the compound of soft shell, its solid content is 40～48%, particle diameter is 20～100nm, and the emulsifying agent consumption is equivalent to 1～4% of soft monomer and hard monomer total mass number sum.
7, the application of each described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent of claim 1～3 is characterized in that, described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent is applied to field of papermaking.
8, according to the application of the described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent of claim 7, it is characterized in that: described high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent is applied to the top sizing or the surface coated of paper surface.
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Assignee: Hangzhou Huawang New Materials Technology Co., Ltd. Assignor: South China University of Technology Contract record no.: 2011330001096 Denomination of invention: Styrene-acrylic microemulsion surface sizing agent with high solid content and core shell structure and preparation method and application thereof Granted publication date: 20100929 License type: Exclusive License Open date: 20090930 Record date: 20110822 |
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