CN102225982A - Miniemulsion polymerization method of high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent - Google Patents
Miniemulsion polymerization method of high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent Download PDFInfo
- Publication number
- CN102225982A CN102225982A CN2011101165597A CN201110116559A CN102225982A CN 102225982 A CN102225982 A CN 102225982A CN 2011101165597 A CN2011101165597 A CN 2011101165597A CN 201110116559 A CN201110116559 A CN 201110116559A CN 102225982 A CN102225982 A CN 102225982A
- Authority
- CN
- China
- Prior art keywords
- miniemulsion
- monomer
- parts
- reactor
- initiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a miniemulsion polymerization method of a high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent. The method comprises the following steps: mixing a composite emulsifier with a mixed monomer and then pre-emulsifying so as to obtain pre-emulsion, and carrying out ultrasonic processing so as to obtain a monomer miniemulsion; mixing an composite emulsifier, a buffer and an initiator and deionized water and then stirring, adding the monomer miniemulsion in the presence of noble gas for polymerization so as to obtain seed miniemulsion; dissolving an initiator in deionized water so as to obtain an initiator aqueous solution; simultaneously dropwise adding the seed miniemulsion and 80% of the initiator aqueous solution in a reactor, and adding a molecular weight regulator at the middle and later periods of dropwise addition; after dropwise addition is finished, replenishing residual 20% of the initiator aqueous solution and insulating heat; and filtrating reactant after the reaction is finished, so as to obtain the self-crosslinking surface sizing agent with the solid content of 48%-68%. The styrene-acrylate emulsion surface sizing agent obtained by the method has the characteristics of high solid content, proper viscosity, good stability and the like. In addition, the method has a simple process and low cost.
Description
Technical field
The present invention relates to the preparation technology of styrene-acrylic emulsion surface sizing agent, particularly relate to the fine emulsion polymerization of a kind of high solids content, self-cross linking type styrene-acrylic emulsion surface sizing agent.
Background technology
Along with the continuous development of paper industry, people reinforcement to environmental consciousness, and the increase of paper machine speed, printing industry raising, the use of the papermaking water seal recycle system and the increase of waste paper recycling amount that paper performance is required, the retention of internal sizing agents such as AKD is lower, increase the ionic concn of plain boiled water reuse and handle the difficulty of plain boiled water, easily cause the highlighting of stability problem of phenomenon, the long-time running that is unfavorable for the paper machine and paper such as roll banding, and Surface Size seems more and more important to paper industry.
Polymer Surface Sizing Agent is developed rapidly in paper industry with its particular performances as the product innovation that occurs in recent years, it can give paper numerous excellent properties, satisfy the production demand of various sheet paper products, for the exploitation of high-grade paper and speciality paper provides powerful guarantee.
The benzene emulsion synthesis technique is simple, environmental protection.Have water resisting property preferably, good absorbency and extremely strong film forming properties with its surface treatment paper.Contain multiple functionally active group in its molecular structure, high more a lot of with the avidity of fiber than the avidity of polyvinyl alcohol and fiber, thereby it is poor to fiber affinity to solve the conventional surface sizing agent preferably, causes covering paper page frame table film forming easy disruptive phenomenon in drying process.
In emulsion polymerization process, introduce crosslinkable group as amino, diacetone base, N-methylol or N-butoxymethyl etc., thus the polymeric film that in the emulsion film forming process, relies on the reaction between group to obtain having appropriately crosslinked structure.In film process, the mutual diffusion of latex particle phase, gathering, for the interaction of reactive functional groups provides condition, cross-linking process is accompanied by film process to carry out simultaneously.Mechanical property, water tolerance, solvent resistance, stain resistance that can make film like this etc. is improved.
Conventional semi-continuous emulsion polymerizing and micro-emulsion polymerization prepare relatively difficulty of high solid content emulsion, and the emulsion solid content of preparation does not generally reach 50%, and the emulsifying agent consumption of use is also more, has had a strong impact on the water resisting property of emulsion.Chinese patent CN101092470A discloses a kind of high solids content room-temperature self crosslinking polystyrene-vinylformic acid (ester) preparation of microemulsion method, and the emulsifying agent consumption is about 3% ~ 8%, and emulsion solid content is about 45%.Chinese patent CN101544717A discloses high solid content core-shell structure styrene-acrylic microemulsion surface sizing agent and preparation method thereof and application, and the emulsion solid content of preparation is 40% ~ 48%.Chinese patent CN101768895A discloses a kind of benzene emulsion efficient surface sizing agent and preparation method thereof, the emulsifying agent consumption is about 3% ~ 13% and has added a large amount of dispersion agents simultaneously, be unfavorable for environmental protection and can reduce water resisting property to a certain extent, the solid content of the Surface Size of preparation is about 30%.
Summary of the invention
The object of the present invention is to provide the fine emulsion polymerization of a kind of high solids content, self-cross linking type styrene-acrylic emulsion surface sizing agent, overcome conventional semi-continuous emulsion polymerizing and micro-emulsion polymerization prepare emulsifying agent consumption in the high solid content emulsion too much, the defectives such as high solid content emulsion workability difference prepared.
Miniemulsion is a thermodynamics meta system, can not spontaneously form, and must rely on mechanical work to overcome the surface energy of oil phase internal cohesive energy and formation drop, makes it to be dispersed in the water.Because mechanical dispersion efficient is low, must use the high strength homogenizer when disperseing preparation submicron miniemulsion.Homogenization installation commonly used has rotational shear type homogenizer, ultrasonic homogenizer and high pressure spraying homogenizer.
Destroy polymer particle for fear of homogenizing, mini-emulsion polymerization often divides thin emulsification and two stages of polymerization.The preparation of miniemulsion generally includes 3 steps.(1) pre-emulsification: emulsifying agent is soluble in the aqueous phase, and co-stabilizer is dissolved in monomer; (2) emulsification: above-mentioned solution is mixed, mix by mechanical stirring; (3) thin emulsification: with the homogenizing of said mixture by efficient homogenizer, monomer is dispersed into the submicron monomer droplet, only needs lower mixing to get final product in the polymerization stage system.
Mini-emulsion polymerization provides effective means for production high solids content, low viscous emulsion.Its principal character is to have introduced co-stabilizer in reaction system, the monomer droplet nucleation.But most applications or in essence, the osmotic pressure that is produced by co-stabilizer has been resisted the Laplace pressure difference between big small droplets, reduced the monomer diffusion between the different size drop, suppressed the Ostwald ageing of emulsion, thereby improved the stability of small droplets greatly, made miniemulsion obtain enough kinetic stabilities.Under suitable emulsifying agent and co-stabilizer acting in conjunction, miniemulsion can reach the thermodynamics metastable condition, and monomer droplet is dispersed into the fine drop about 50～500nm, and monomer directly carries out polymerization therein.Mini-emulsion polymerization has been expanded the range of application of letex polymerization, and the multipolymer composition of having avoided generating differs big, the difficult problem of hydrophobicity copolymer emulsion preparation with the initial mol ratio of monomer.And the consumption of emulsifying agent generally accounts for the monomer consumption below 5% in the mini-emulsion polymerization, has greatly weakened the disadvantageous effect of emulsifying agent to the polymer latex performance.
Purpose of the present invention specifically is achieved through the following technical solutions:
(1) preparation monomer pre-emulsion: in mass fraction, in reactor, add 20 parts～60 parts deionized waters, 0.5 part～4 parts compound emulsifying agents, obtain water behind dispersed with stirring 10min～30min; 0.5 part～3 parts cross-linking monomers are dissolved in above-mentioned water, obtain the aqueous solution; 25 parts～50 parts soft monomers, 25 parts～50 parts hard monomers, 0.5 part～3 parts function monomers, 0.5 part～3 parts cross-linking monomers are mixed with 0.5 part～4 parts co-stabilizers, obtain oil phase; Again with oil phase and aqueous solution, stir pre-emulsification 20min～30min after, obtain pre-emulsion;
(2) preparation monomer miniemulsion: behind above-mentioned pre-emulsion supersound process 5min～25min, obtain the monomer miniemulsion;
(3) preparation seed miniemulsion: 0.25 part～2 parts compound emulsifying agents, 0.1 part～0.4 part buffer reagent, 0.05 part～0.2 part initiator, 10 parts～30 parts deionized waters are added in the reactor, rotating speed with 120 rpm～280 rpm stirs 5 min～15min, forms water; With water heating in water bath to 75 ℃～85 ℃, feed rare gas element then again, get 5%～10% of the prepared monomer miniemulsion of step (2) again and join aqueous phase; Reduce stirring velocity to 5 rpm～50rpm, polyreaction 1 min～10min obtains the seed miniemulsion;
(4) preparation initiator solution: 0.15 part～0.6 part initiator with 3.4 parts～10 parts deionized water dissolvings, is obtained initiator solution;
(5) semicontinuous dropping polyreaction: the prepared seed miniemulsion of 80% and step (3) of the initiator solution that step (4) is prepared drops in the reactor simultaneously, and the dropping time is 3.5h～4.5h; When the dropping time is 3h, in reactor, add 0.1 part～0.4 part molecular weight regulator; Continue to drip seed miniemulsion and initiator solution, the dropping time is 0.5h～1.5h again, and the temperature of controlling reactor is 75 ℃～85 ℃ in the dropping process;
(6) slaking: after the semicontinuous dropping polyreaction of completing steps (5), again reactor is warming up to 85 ℃～90 ℃, and adds remaining 20% initiator solution, be incubated 1.5 h～2.5h, obtain the slaking reaction thing;
(7) cooling discharge: after completing steps (6) slaking, temperature of reactor is reduced to 40 ℃～50 ℃, with the filter cloth filtration slaking reaction thing of 100 orders～300, the filtrate of gained is the self-cross linking type styrene-acrylic emulsion surface sizing agent.
Described hard monomer is more than one in vinylbenzene, methyl methacrylate or the vinyl acetate; Described soft monomer is an alkyl acrylate; Described function monomer is the mixture of vinylformic acid, methacrylic acid or vinylformic acid and methacrylic acid; Described cross-linking monomer is a kind of in N hydroxymethyl acrylamide, acrylamide or the Methacrylamide.
Described alkyl acrylate is butyl acrylate or ethyl propenoate.
Described co-stabilizer is hexadecanol or n-Hexadecane.
Described compound emulsifying agent comprises anionic emulsifier and nonionic emulsifying agent; Described anionic emulsifier is a kind of in sodium lauryl sulphate, Sodium palmityl sulfate, the Sodium dodecylbenzene sulfonate; Described nonionic emulsifying agent is a kind of in polyoxyethylene nonylphenol ether (NP-10), the alkylphenol polyoxyethylene (OP-10); The mass ratio of described anionic emulsifier and nonionic emulsifying agent is 1:3～3:1.
Described initiator is Potassium Persulphate or ammonium persulphate.
Described molecular weight regulator is lauryl mercaptan or Stearyl mercaptan.
Described buffer reagent is a sodium bicarbonate.
Described rare gas element is a kind of in helium, argon gas or the nitrogen.
Prepared its solid content of self-cross linking type styrene-acrylic emulsion surface sizing agent of the present invention is 48%～68%.
The soft monomer that the present invention is used is given emulsion snappiness, film-forming properties etc.; Used hard monomer is given emulsion water tolerance, resistance to oily stain, hardness, sticking power etc.; Used function monomer is given emulsion water tolerance, wear resistance, adhesion strength, resistance to oily stain, film-forming properties, heat-resisting, ageing resistance etc.The present invention adopts mini-emulsion polymerization technology, is the effective way of preparation high solids content, low viscosity emulsion, is particularly suitable for the monomeric polymerization of high hydrophobicity.Regulate the solid content and the viscosity of polymerization system by regulating polymerization process condition, the Surface Size that prepare the ideal high solids content, have good workability, water resisting property is good, and can with the starch complex applying glue in electro-photographic paper, fluting board body paper etc., improve the water resisting property, surface strength of paper etc.
Compared with prior art, the present invention has the following advantages:
(1) more traditional letex polymerization and the micro-emulsion polymerization of fine emulsion polymerization of the present invention obtains the high solids content product, greatly reduces the use of emulsifying agent, reduced the influence of emulsifying agent to product performance, thereby improved the water resisting property of Surface Size;
(2) monomer of the present invention is cheap and easy to get, and more more economical than the water resisting property that improves Surface Size with organosilicon, fluorine monomer modification, technology is simple, and cost is low;
(3) fine emulsion polymerization of the present invention is simpler than core-shell emulsion polymerization method, microemulsion polymerization method operation;
(4) prepared high solids content, the self-cross linking type styrene-acrylic emulsion surface sizing agent of the present invention can improve plant factor; Have lower transportation cost, and can reduce the energy consumption of unit product.
Embodiment
The invention will be further described below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Various embodiments of the present invention reaction desired substance is all in mass fraction, and 1 mass parts is 1g.
Embodiment 1
(1) preparation monomer pre-emulsion:
Add 20g deionized water, 1.5g Sodium dodecylbenzene sulfonate and alkylphenol polyoxyethylene compound emulsifying agent (Sodium dodecylbenzene sulfonate wherein: the mass ratio of alkylphenol polyoxyethylene=1.5:1) in the reactor, disperse 10min to dissolve fully to emulsifying agent through agitator, obtain water; The 0.5gN-n-methylolacrylamide is soluble in the aqueous phase; 50g butyl acrylate, 23g methyl methacrylate, 22g vinylbenzene, 1g vinylformic acid are mixed with the 2g hexadecanol, obtain oil phase; Oil phase is joined aqueous phase,, obtain pre-emulsion through the pre-emulsification 30min of agitator;
(2) preparation monomer miniemulsion:
With the pre-emulsion 15min that in processor for ultrasonic wave, homogenizes, obtain about 120ml monomer miniemulsion;
(3) preparation seed miniemulsion:
With 0.75g compound emulsifying agent, 0.15g buffer reagent NaHCO
3, 0.1g initiator potassium persulfate, 10g deionized water be added in the reactor that has condensing works, temperature indicating device, stirs 10min with 160rpm and make it to be uniformly dispersed, and forms water; Heating in water bath feeds nitrogen flooding oxygen; When the question response actuator temperature was raised to 77 ℃, 9.5ml joined aqueous phase with the preparation-obtained monomer miniemulsion of step (2); Again agitator speed is reduced to 10rpm, polyreaction 2min obtains the sufficient seed miniemulsion of blue light;
(4) preparation initiator solution:
With the 0.3g Potassium Persulphate, obtain persulfate aqueous solution with the 3.4g deionized water dissolving; Wherein 80% persulfate aqueous solution is as dripping material, and remaining 20% as the material of adding after the polymerization end;
(5) the seed miniemulsion of 80% and the step (3) of respectively that above-mentioned steps (4) is prepared persulfate aqueous solution preparation evenly drops in the reactor with peristaltic pump simultaneously, and the dropping time is 4h; When the dropping time is 3h, in reactor, splash into the molecular weight regulator lauryl mercaptan of 0.2g; Continue then to drip seed miniemulsion and persulfate aqueous solution, the dropping time is 1h; In the temperature that drips the process control reactor is 77 ℃;
(6) slaking: after the semicontinuous dropping polyreaction of step (5) finishes, reactor is continued to be warming up to 85 ℃, add remaining 20% persulfate aqueous solution, insulation 2h obtains the slaking reaction thing;
(7) cooling discharge: after step (6) slaking is finished, temperature of reactor is reduced to 40 ℃, filter the slaking reaction thing with 200 order filter clothes, discharging, it is 68% self-cross linking type styrene-acrylic emulsion surface sizing agent that the filtrate that obtains is solid content.
The quality of compound emulsifying agent be equivalent to add 1.55% of monomer total mass.
Embodiment 2
(1) preparation monomer pre-emulsion:
Add 30g deionized water, 1.5g Sodium palmityl sulfate and alkylphenol polyoxyethylene compound emulsifying agent (Sodium palmityl sulfate wherein: the mass ratio of alkylphenol polyoxyethylene=1:2) in the reactor, disperse 12min to dissolve fully to emulsifying agent through agitator, obtain water; The 1g Methacrylamide is soluble in the aqueous phase; 50g ethyl propenoate, 23g methyl methacrylate, 22g vinylbenzene, 1g methacrylic acid are mixed with the 1.5g hexadecanol, obtain oil phase; Oil phase is joined aqueous phase,, obtain pre-emulsion through the pre-emulsification 25min of agitator;
(2) preparation monomer miniemulsion:
The 20min that again pre-emulsion of gained homogenized in processor for ultrasonic wave obtains about 130ml monomer miniemulsion;
(3) preparation seed miniemulsion:
With 0.75g compound emulsifying agent, 0.25g buffer reagent NaHCO
3, 0.1g initiator ammonium persulfate, 15g deionized water in the reactor that has condensing works, temperature indicating device, stir 20min with 160rpm and make it to be uniformly dispersed, form water; Heating in water bath feeds nitrogen flooding oxygen; Temperature is raised to 78 ℃ in the question response device, and 10.5ml joins aqueous phase with the preparation-obtained monomer miniemulsion of step (2); Again agitator speed is reduced to 10rpm, polyreaction 2min obtains the sufficient seed miniemulsion of blue light;
(4) preparation initiator solution:
With the 0.3g ammonium persulphate, obtain ammonium persulfate aqueous solution with the 5g deionized water dissolving; Wherein 80% ammonium persulfate aqueous solution is as dripping material, and remaining 20% as the material of adding after the polymerization end;
(5) semicontinuous dropping polyreaction:
The seed miniemulsion of 80% and above-mentioned (3) preparation of respectively that step (4) is prepared ammonium persulfate aqueous solution, in the even dropwise reaction device of peristaltic pump, the dropping time is 3.5h; When the dropping time is 3h, in reactor, splash into the molecular weight regulator lauryl mercaptan of 0.1g; Continue then to drip careful emulsion and persulfate aqueous solution, the dropping time is 0.5h; The controlling reactor temperature is 78 ℃ in the dropping process;
(6) slaking: after the semicontinuous dropping polyreaction of step (5) finishes, reactor is warming up to 87 ℃, adds remaining 20% initiator solution, insulation 2h obtains the slaking reaction thing;
(7) cooling discharge: after step (6) slaking is finished, temperature of reactor is reduced to 40 ℃, filter with 200 order filter clothes, discharging, it is 61% self-cross linking type styrene-acrylic emulsion surface sizing agent that the filtrate that obtains is solid content.
The quality of compound emulsifying agent be equivalent to add 1.55% of monomer total mass.
Embodiment 3
(1) preparation monomer pre-emulsion:
Add 40g deionized water, 2.5g sodium lauryl sulphate and alkylphenol polyoxyethylene compound emulsifying agent (sodium lauryl sulphate wherein: the mass ratio of alkylphenol polyoxyethylene=1:1) in the reactor, disperse 13min to dissolve fully to emulsifying agent through agitator, obtain water, the 1.5gN-n-methylolacrylamide is soluble in the aqueous phase; By prescription weighing monomer, 50g butyl acrylate, 47g vinylbenzene, 0.75g vinylformic acid, 0.75g methacrylic acid are mixed with the 2g n-Hexadecane, obtain oil phase; Oil phase is joined aqueous phase,, obtain pre-emulsion through the pre-emulsification 25min of agitator;
(2) preparation monomer miniemulsion:
The 20min that again pre-emulsion of gained homogenized in processor for ultrasonic wave obtains about 145ml monomer miniemulsion;
(3) preparation seed miniemulsion:
With 1.25g compound emulsifying agent, 0.4g buffer reagent NaHCO
3, 0.2g initiator potassium persulfate, 20g deionized water in the reactor that has condensing works, temperature indicating device, stir 20min with 160rpm and make it to be uniformly dispersed, form water; Heating in water bath feeds nitrogen flooding oxygen; Temperature is raised to 78 ℃ in the question response device, and 11.5ml joins aqueous phase with the preparation-obtained monomer miniemulsion of step (2); Again agitator speed is reduced to 10rpm, polyreaction 2min obtains the sufficient seed miniemulsion of blue light;
(4) preparation initiator solution:
With the 0.4g Potassium Persulphate, obtain persulfate aqueous solution with the 6.5g deionized water dissolving; Wherein 80% persulfate aqueous solution is as dripping material, and remaining 20% as the material of adding after the polymerization end;
(5) semicontinuous dropping polyreaction:
The seed miniemulsion of 80% and step (3) preparation of respectively that above-mentioned steps (4) is prepared persulfate aqueous solution, in the even dropwise reaction device of peristaltic pump, the dropping time is 4.5h; When the dropping time is 3h, in reactor, splash into the molecular weight regulator Stearyl mercaptan of 0.3g; Continue then to drip seed miniemulsion and persulfate aqueous solution, the dropping time is 1.5h; The controlling reactor temperature is 78 ℃ in the dropping process;
(6) slaking: after the semicontinuous dropping polyreaction of step (5) finishes, reactor is warming up to 88 ℃, adds remaining 20% initiator solution, insulation 2h obtains the slaking reaction thing;
(7) cooling discharge: after step (6) slaking is finished, temperature of reactor is reduced to 40 ℃, filter the slaking reaction thing with 200 order filter clothes, discharging, it is 57% self-cross linking type styrene-acrylic emulsion surface sizing agent that the filtrate that obtains is solid content.
The quality of compound emulsifying agent be equivalent to add 2.5% of monomer total mass.
Embodiment 4
(1) preparation monomer pre-emulsion:
In reactor, add the 40g deionized water, 1g Sodium dodecylbenzene sulfonate and polyoxyethylene nonylphenol ether compound emulsifying agent (Sodium dodecylbenzene sulfonate wherein: the mass ratio of polyoxyethylene nonylphenol ether=3:1), disperse 13min to dissolve fully to emulsifying agent through agitator, obtain water, the 2.5g acrylamide is soluble in the aqueous phase; 46g butyl acrylate, 23 vinyl acetate g, 27g methyl methacrylate, 3g methacrylic acid are mixed with the 2.5g hexadecanol, obtain oil phase; Oil phase is joined aqueous phase,, obtain pre-emulsion through the pre-emulsification 25min of agitator;
(2) preparation monomer miniemulsion:
The 10min that again pre-emulsion of gained homogenized in processor for ultrasonic wave obtains about 140ml monomer miniemulsion;
(3) preparation seed miniemulsion:
With 0.5g compound emulsifying agent, 0.2g buffer reagent NaHCO
3, 0.1g initiator ammonium persulfate, 20g deionized water in the reactor that has condensing works, temperature indicating device, stir 20min with 160rpm and make it to be uniformly dispersed, form water; Heating in water bath feeds nitrogen flooding oxygen; Temperature is raised to 78 ℃ in the question response device, and 11ml joins aqueous phase with the preparation-obtained monomer miniemulsion of step (2); Again agitator speed is reduced to 10rpm, polyreaction 2min obtains the sufficient seed miniemulsion of blue light;
(4) preparation initiator solution:
With the 0.3g ammonium persulphate, obtain ammonium persulfate aqueous solution with the 6.5g deionized water dissolving; Wherein 80% ammonium persulfate aqueous solution is as dripping material, and remaining 20% as the material of adding after the polymerization end;
(5) semicontinuous dropping polyreaction:
The seed miniemulsion of 80% and step (3) preparation of respectively that above-mentioned steps (4) is prepared ammonium persulfate aqueous solution is with in the even dropwise reaction device of peristaltic pump, and the control rate of addition dropwises at 4.5h; After dripping 3h, in reactor, splash into the molecular weight regulator lauryl mercaptan of 0.3g; Continue to drip seed miniemulsion and ammonium persulfate aqueous solution, the dropping time is 1.5h again, and dripping the process control temperature of reactor is 78 ℃;
(6) slaking: after the semicontinuous dropping polyreaction of step (5) finishes, reactor is warming up to 89 ℃, adds remaining 20% initiator solution, insulation 2h obtains the slaking reaction thing;
(7) cooling discharge: after step (6) slaking is finished, temperature of reactor is reduced to 40 ℃, filter the slaking reaction thing with 200 order filter clothes, discharging, the filtrate that obtains is solid content at the self-cross linking type styrene-acrylic emulsion surface sizing agent that is 56%.
The quality of compound emulsifying agent be equivalent to add 0.99% of monomer total mass.
Embodiment 5
(1) preparation monomer pre-emulsion:
In reactor, add the 30g deionized water, 3.5g compound emulsifying agent sodium lauryl sulphate and polyoxyethylene nonylphenol ether (sodium lauryl sulphate wherein: the mass ratio of polyoxyethylene nonylphenol ether=1:3), disperse 13min to dissolve fully to emulsifying agent through agitator, obtain water, the 3gN-n-methylolacrylamide is soluble in the aqueous phase; 48g butyl acrylate, 25g vinylbenzene, 22g vinyl acetate, 0.5g vinylformic acid are mixed with the 3g n-Hexadecane, obtain oil phase; Oil phase is joined aqueous phase,, obtain pre-emulsion through the pre-emulsification 25min of agitator;
(2) preparation monomer miniemulsion:
The 15min that again pre-emulsion of gained homogenized in processor for ultrasonic wave obtains about 130ml monomer miniemulsion;
(3) preparation seed miniemulsion:
With 1.75g compound emulsifying agent, 0.4g buffer reagent NaHCO
3, 0.2g initiator ammonium persulfate, 10g deionized water in the reactor that has condensing works, temperature indicating device, stir 20min with 160rpm and make it to be uniformly dispersed, form water; Heating in water bath feeds nitrogen flooding oxygen; Temperature is raised to 78 ℃ in the question response device, and 10.5ml joins aqueous phase with the preparation-obtained monomer miniemulsion of step (2); Again agitator speed is reduced to 10rpm, polyreaction 2min obtains the sufficient seed miniemulsion of blue light;
(4) preparation initiator solution:
With the 0.6g ammonium persulphate, obtain ammonium persulfate aqueous solution with the 3.4g deionized water dissolving; Wherein 80% ammonium persulfate aqueous solution is as dripping material, and remaining 20% as the material of adding after the polymerization end;
(5) semicontinuous dropping polyreaction:
With the seed miniemulsion and the prepared ammonium persulphate of step (4) of above-mentioned (2) preparation, in the even dropwise reaction device of peristaltic pump, the control rate of addition dropwises at 4h respectively; When the dropping time is 3h, in reactor, drip the molecular weight regulator Stearyl mercaptan of 0.4g; Continue to drip seed miniemulsion and ammonium persulfate aqueous solution then, drip time 1h; Dripping the process control temperature of reactor is 78 ℃;
(6) slaking: after the semicontinuous dropping polyreaction of step (5) finishes, reactor is warming up to 89 ℃, adds remaining 20% initiator solution, insulation 2h obtains the slaking reaction thing;
(7) cooling discharge: after step (6) slaking is finished, temperature of reactor is reduced to 40 ℃, filter the slaking reaction thing with 200 order filter clothes, discharging, the filtrate that obtains is solid content at 65% self-cross linking type styrene-acrylic emulsion surface sizing agent.
The quality of compound emulsifying agent be equivalent to add 3.55% of monomer total mass.
Embodiment 6
(1) preparation monomer pre-emulsion:
In reactor, add the 30g deionized water, 2g Sodium palmityl sulfate and polyoxyethylene nonylphenol ether compound emulsifying agent (sodium lauryl sulphate wherein: the mass ratio of polyoxyethylene nonylphenol ether=1:1), disperse 13min to dissolve fully to emulsifying agent through agitator, obtain water, the 1.25g acrylamide is soluble in the aqueous phase; 50g ethyl propenoate, 48g methyl methacrylate, 1g methacrylic acid, 1g vinylformic acid are mixed with the 1g n-Hexadecane, obtain oil phase; Oil phase is joined aqueous phase,, obtain pre-emulsion through the pre-emulsification 25min of agitator;
(2) preparation monomer miniemulsion:
The 10min that again pre-emulsion of gained homogenized in processor for ultrasonic wave obtains about 136ml monomer miniemulsion;
(3) preparation seed miniemulsion:
With 1g compound emulsifying agent, 0.2g buffer reagent NaHCO
3, 0.1g initiator ammonium persulfate, 25g deionized water in the reactor that has condensing works, temperature indicating device, stir 20min with 160rpm and make it to be uniformly dispersed, form water; Heating in water bath feeds nitrogen flooding oxygen; Temperature is raised to 78 ℃ in the question response device, and 11ml joins aqueous phase with the preparation-obtained monomer miniemulsion of step (2); Again agitator speed is reduced to 10rpm, polyreaction 2min obtains the sufficient seed miniemulsion of blue light;
(4) preparation initiator solution:
With the 0.3g Potassium Persulphate, obtain persulfate aqueous solution with the 6.5g deionized water dissolving; Wherein 80% persulfate aqueous solution is as dripping material, and remaining 20% as the material of adding after the polymerization end;
(5) semicontinuous dropping polyreaction:
With the seed miniemulsion and the prepared Potassium Persulphate of step (4) of above-mentioned (2) preparation, in the even dropwise reaction device of peristaltic pump, the control rate of addition dropwises at 3.8h respectively; The dropping time drips the molecular weight regulator Stearyl mercaptan of 0.3g when being 3h in reactor; Continue then to drip seed miniemulsion and persulfate aqueous solution, the dropping time is 0.8h; Dripping the process control temperature of reactor is 78 ℃;
(6) slaking: after the semicontinuous dropping polyreaction of step (5) finishes, reactor is warming up to 89 ℃, adds remaining 20% initiator solution, insulation 2h obtains the slaking reaction thing;
(7) cooling discharge: after step (6) slaking is finished, temperature of reactor is reduced to 40 ℃, filter the slaking reaction thing with 200 order filter clothes, discharging, it is 64% self-cross linking type styrene-acrylic emulsion surface sizing agent that the filtrate that obtains is solid content.
The quality of compound emulsifying agent be equivalent to add 1.98% of monomer total mass.
Claims (9)
1. the fine emulsion polymerization of high solids content, self-cross linking type styrene-acrylic emulsion surface sizing agent, it is characterized in that: in mass fraction, concrete steps are as follows:
(1) preparation monomer pre-emulsion: in reactor, add 20 parts～60 parts deionized waters, 0.5 part～4 parts compound emulsifying agents, obtain water behind dispersed with stirring 10min～30min; 0.5 part～3 parts cross-linking monomers are dissolved in above-mentioned water, obtain the aqueous solution; With 25 parts～50 parts soft monomers, 25 parts～50 parts hard monomers, 0.5 part～3 parts function monomers, mix, obtain oil phase with 0.5 part～4 parts co-stabilizers; Again with oil phase and aqueous solution, stir pre-emulsification 20min～30min after, obtain pre-emulsion;
(2) preparation monomer miniemulsion: behind above-mentioned pre-emulsion supersound process 5min～25min, obtain the monomer miniemulsion;
(3) preparation seed miniemulsion: 0.25 part～2 parts compound emulsifying agents, 0.1 part～0.4 part buffer reagent, 0.05 part～0.2 part initiator, 10 parts～30 parts deionized waters are added in the reactor, rotating speed with 120 rpm～280 rpm stirs 5 min～15min, forms water; With water heating in water bath to 75 ℃～85 ℃, feed rare gas element then again, get 5%～10% of the prepared monomer miniemulsion of step (2) again and join aqueous phase; Reduce stirring velocity to 5 rpm～50rpm, polyreaction 1 min～10min obtains the seed miniemulsion;
(4) preparation initiator solution: 0.15 part～0.6 part initiator with 3.4 parts～10 parts deionized water dissolvings, is obtained initiator solution;
(5) semicontinuous dropping polyreaction: the prepared seed miniemulsion of 80% and step (3) of the initiator solution that step (4) is prepared drops in the reactor simultaneously, and the dropping time is 3.5h～4.5h; When the dropping time is 3h, in reactor, add 0.1 part～0.4 part molecular weight regulator again; Continue then to drip seed miniemulsion and initiator solution, the dropping time is 0.5h～1.5h, and the temperature of controlling reactor is 75 ℃～85 ℃ in the dropping process;
(6) slaking: after the semicontinuous dropping polyreaction of completing steps (5), again reactor is warming up to 85 ℃～90 ℃, and adds remaining 20% initiator solution, be incubated 1.5 h～2.5h, obtain the slaking reaction thing;
(7) cooling discharge: after completing steps (6) slaking, temperature of reactor is reduced to 40 ℃～50 ℃, with the filter cloth filtration slaking reaction thing of 100 orders～300, the filtrate of gained is the self-cross linking type styrene-acrylic emulsion surface sizing agent.
2. fine emulsion polymerization according to claim 1 is characterized in that: described hard monomer is more than one in vinylbenzene, methyl methacrylate or the vinyl acetate; Described soft monomer is an alkyl acrylate; Described function monomer is the mixture of vinylformic acid, methacrylic acid or vinylformic acid and methacrylic acid; Described cross-linking monomer is a kind of in N hydroxymethyl acrylamide, acrylamide or the Methacrylamide.
3. fine emulsion polymerization according to claim 2 is characterized in that: described alkyl acrylate is butyl acrylate or ethyl propenoate.
4. fine emulsion polymerization according to claim 3 is characterized in that: described co-stabilizer is hexadecanol or n-Hexadecane.
5. fine emulsion polymerization according to claim 4 is characterized in that: described compound emulsifying agent comprises anionic emulsifier and nonionic emulsifying agent; Described anionic emulsifier is a kind of in sodium lauryl sulphate, Sodium palmityl sulfate, the Sodium dodecylbenzene sulfonate; Described nonionic emulsifying agent is a kind of in polyoxyethylene nonylphenol ether, the alkylphenol polyoxyethylene; The mass ratio of described anionic emulsifier and nonionic emulsifying agent is 1:3～3:1.
6. fine emulsion polymerization according to claim 5 is characterized in that: described initiator is Potassium Persulphate or ammonium persulphate.
7. fine emulsion polymerization according to claim 6 is characterized in that: described molecular weight regulator is lauryl mercaptan or Stearyl mercaptan.
8. fine emulsion polymerization according to claim 7 is characterized in that: described buffer reagent is a sodium bicarbonate.
9. fine emulsion polymerization according to claim 8 is characterized in that: described rare gas element is a kind of in helium, argon gas or the nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110116559 CN102225982B (en) | 2011-05-06 | 2011-05-06 | Miniemulsion polymerization method of high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110116559 CN102225982B (en) | 2011-05-06 | 2011-05-06 | Miniemulsion polymerization method of high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102225982A true CN102225982A (en) | 2011-10-26 |
| CN102225982B CN102225982B (en) | 2013-08-28 |
Family
ID=44806983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110116559 Expired - Fee Related CN102225982B (en) | 2011-05-06 | 2011-05-06 | Miniemulsion polymerization method of high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102225982B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103103820A (en) * | 2012-12-19 | 2013-05-15 | 上海奇想青晨新材料科技股份有限公司 | Polyacrylate binder for pigment printing and preparation method of polyacrylate binder |
| CN104693345A (en) * | 2015-03-30 | 2015-06-10 | 河北工业大学 | Polymer dispersion and preparation method thereof |
| CN108359049A (en) * | 2018-02-05 | 2018-08-03 | 苏州大乘环保新材有限公司 | A kind of aqueous EAU technologies interpenetrating networks pure acrylic latex and preparation method |
| CN109577085A (en) * | 2018-12-12 | 2019-04-05 | 上海东升新材料有限公司 | A kind of preparation method and applications of water-resistant type paper surface sizing agent |
| CN109867752A (en) * | 2017-12-01 | 2019-06-11 | 徐州市贾汪区韵谨工贸有限公司 | A kind of cement water reducing agent |
| CN109867740A (en) * | 2017-12-01 | 2019-06-11 | 徐州市贾汪区韵谨工贸有限公司 | A kind of antifreeze agent for concrete |
| CN109867753A (en) * | 2017-12-01 | 2019-06-11 | 徐州市贾汪区韵谨工贸有限公司 | A kind of cement water reducing agent |
| CN111072845A (en) * | 2019-12-20 | 2020-04-28 | 珠海展辰新材料股份有限公司 | Emulsion and method for producing the same |
| CN111794012A (en) * | 2020-06-24 | 2020-10-20 | 杭州华旺新材料科技股份有限公司 | High-strength water-resistant flame-retardant plain colored paper and preparation method thereof |
| CN112574354A (en) * | 2020-12-10 | 2021-03-30 | 巴斯夫新材料有限公司 | Emulsion polymerization process |
| CN115637087A (en) * | 2022-10-31 | 2023-01-24 | 广东银洋环保新材料有限公司 | Ink-absorbing coating emulsion and preparation method thereof |
| CN117903356A (en) * | 2024-03-19 | 2024-04-19 | 四川省纺织科学研究院有限公司 | Double-crosslinking phenol-free aldehyde-free color fixing agent, and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006111184A1 (en) * | 2005-04-21 | 2006-10-26 | Topchim N.V. | Water dispersible composition for treating paper |
| JP2007114775A (en) * | 2005-10-17 | 2007-05-10 | Xerox Corp | Emulsion aggregation toner incorporating aluminized silica as coagulating agent |
| CN101538341A (en) * | 2009-04-24 | 2009-09-23 | 北京化工大学 | Room temperature self-crosslinking styrene-acrylic emulsion and preparation technique thereof |
| CN101544717A (en) * | 2009-04-27 | 2009-09-30 | 华南理工大学 | Styrene-acrylic microemulsion surface sizing agent with high solid content and core shell structure and preparation method and application thereof |
| CN101671416A (en) * | 2009-10-12 | 2010-03-17 | 佛山市顺德区巴德富实业有限公司 | Styrene-acrylate emulsion with excellent leveling property |
| CN101768895A (en) * | 2009-01-07 | 2010-07-07 | 湖北大学 | Styrene-acrylate emulsion type high effective surface sizing agent and preparation method thereof |
| CN101838371A (en) * | 2010-01-14 | 2010-09-22 | 湖北大学 | Method for preparing high-solid-content and low-viscosity core-shell structure styrene-acrylic emulsion |
-
2011
- 2011-05-06 CN CN 201110116559 patent/CN102225982B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006111184A1 (en) * | 2005-04-21 | 2006-10-26 | Topchim N.V. | Water dispersible composition for treating paper |
| JP2007114775A (en) * | 2005-10-17 | 2007-05-10 | Xerox Corp | Emulsion aggregation toner incorporating aluminized silica as coagulating agent |
| CN101768895A (en) * | 2009-01-07 | 2010-07-07 | 湖北大学 | Styrene-acrylate emulsion type high effective surface sizing agent and preparation method thereof |
| CN101538341A (en) * | 2009-04-24 | 2009-09-23 | 北京化工大学 | Room temperature self-crosslinking styrene-acrylic emulsion and preparation technique thereof |
| CN101544717A (en) * | 2009-04-27 | 2009-09-30 | 华南理工大学 | Styrene-acrylic microemulsion surface sizing agent with high solid content and core shell structure and preparation method and application thereof |
| CN101671416A (en) * | 2009-10-12 | 2010-03-17 | 佛山市顺德区巴德富实业有限公司 | Styrene-acrylate emulsion with excellent leveling property |
| CN101838371A (en) * | 2010-01-14 | 2010-09-22 | 湖北大学 | Method for preparing high-solid-content and low-viscosity core-shell structure styrene-acrylic emulsion |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103103820A (en) * | 2012-12-19 | 2013-05-15 | 上海奇想青晨新材料科技股份有限公司 | Polyacrylate binder for pigment printing and preparation method of polyacrylate binder |
| CN104693345A (en) * | 2015-03-30 | 2015-06-10 | 河北工业大学 | Polymer dispersion and preparation method thereof |
| CN109867753A (en) * | 2017-12-01 | 2019-06-11 | 徐州市贾汪区韵谨工贸有限公司 | A kind of cement water reducing agent |
| CN109867752A (en) * | 2017-12-01 | 2019-06-11 | 徐州市贾汪区韵谨工贸有限公司 | A kind of cement water reducing agent |
| CN109867740A (en) * | 2017-12-01 | 2019-06-11 | 徐州市贾汪区韵谨工贸有限公司 | A kind of antifreeze agent for concrete |
| CN108359049A (en) * | 2018-02-05 | 2018-08-03 | 苏州大乘环保新材有限公司 | A kind of aqueous EAU technologies interpenetrating networks pure acrylic latex and preparation method |
| CN109577085A (en) * | 2018-12-12 | 2019-04-05 | 上海东升新材料有限公司 | A kind of preparation method and applications of water-resistant type paper surface sizing agent |
| CN111072845A (en) * | 2019-12-20 | 2020-04-28 | 珠海展辰新材料股份有限公司 | Emulsion and method for producing the same |
| CN111794012A (en) * | 2020-06-24 | 2020-10-20 | 杭州华旺新材料科技股份有限公司 | High-strength water-resistant flame-retardant plain colored paper and preparation method thereof |
| CN112574354A (en) * | 2020-12-10 | 2021-03-30 | 巴斯夫新材料有限公司 | Emulsion polymerization process |
| CN115637087A (en) * | 2022-10-31 | 2023-01-24 | 广东银洋环保新材料有限公司 | Ink-absorbing coating emulsion and preparation method thereof |
| CN117903356A (en) * | 2024-03-19 | 2024-04-19 | 四川省纺织科学研究院有限公司 | Double-crosslinking phenol-free aldehyde-free color fixing agent, and preparation method and application thereof |
| CN117903356B (en) * | 2024-03-19 | 2024-05-31 | 四川省纺织科学研究院有限公司 | Double-crosslinking phenol-free aldehyde-free color fixing agent, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102225982B (en) | 2013-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102225982B (en) | Miniemulsion polymerization method of high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent | |
| CN104277174B (en) | Polyacrylamide nanometer microballoon system and preparation method thereof | |
| AU670855B2 (en) | Preparation of an aqueous polymer dispersion | |
| CN106832106A (en) | A kind of water polyacrylic acid emulsion and preparation method thereof | |
| CN104277175B (en) | Polyacrylamide reverse microemulsion transfer drive system | |
| CN103613700B (en) | A kind of Pickering emulsion polymerization prepares the method for polyacrylic ester/Nano-ZnO Hybrid Coatings printing adhesive | |
| CN102604006B (en) | Preparation method for acidic silica sol in-situ modified acrylate emulsion | |
| CN107118650B (en) | Silica sol/polyacrylate emulsion containing hydroxyl-amino resin baking varnish and preparation method thereof | |
| CN101775093B (en) | Method for preparing copolymer miniemulsion by stabilizing and modifying reactive co-stabilizer | |
| JP2000514485A (en) | Method for producing aqueous polymer dispersion | |
| CN105732885A (en) | Method for preparing indoor temperature self-crosslinking acrylate emulsion of core-shell structure | |
| CN102516448A (en) | Fluorosilicone-containing acrylate copolymer emulsion prepared with reactive emulsifier and method thereof | |
| CN101838371A (en) | Method for preparing high-solid-content and low-viscosity core-shell structure styrene-acrylic emulsion | |
| CN101092470A (en) | Method for preparing microemulsion with high solid content of crosslinked polystyrene and acrylic (ester) | |
| CN102408853A (en) | Water-based body flame-resistant acrylate adhesive and preparation method thereof | |
| CN105602490A (en) | Dual-component emulsion polyacrylate pressure-sensitive adhesive and preparation method and application thereof | |
| CN102382235B (en) | Acrylic emulsion, preparation method and application thereof | |
| CN100344692C (en) | Method for preparing aqueous nano SiO2 acrylic acid composite emulsion | |
| CN104672741A (en) | High-solid-content anionic self-emulsified water-borne epoxy resin emulsion and preparation method thereof | |
| CN106496426A (en) | A kind of preparation method of hud typed acrylic cationic resin | |
| CN111995708A (en) | Based on amphiphilic Janus SiO2Nano particle fluorine-containing polyacrylate finishing agent and preparation method thereof | |
| CN103628316A (en) | Novel preparation method of paper fiber fabric coating finishing agent microemulsion | |
| Gong et al. | Silicone acrylate dispersion based on semi-continuous seed emulsion polymerization using polymerizable emulsifiers | |
| CN1974619A (en) | Prepn and application of reactive polyacrylate microgel | |
| CN103012692B (en) | Method for preparing soybean protein copolymer emulsion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130828 Termination date: 20210506 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |