CN1322766A - Self-emulsified polyacrylate emulsion with high solid content and its prepn process - Google Patents

Self-emulsified polyacrylate emulsion with high solid content and its prepn process Download PDF

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Publication number
CN1322766A
CN1322766A CN 01129201 CN01129201A CN1322766A CN 1322766 A CN1322766 A CN 1322766A CN 01129201 CN01129201 CN 01129201 CN 01129201 A CN01129201 A CN 01129201A CN 1322766 A CN1322766 A CN 1322766A
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China
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self
acid
emulsifying
solid content
initiator
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CN 01129201
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CN1133666C (en
Inventor
张邦华
唐广粮
宋谋道
郭天瑛
郝广杰
张育英
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Nankai University
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Nankai University
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Abstract

The polyacrylate emulsion consists of water 70-100 weight portions, methyl methacrylate 30-70 weight portions, acrylic ester 30-60 weight portions, acrylic acid 2-5 weight portions and initiator 0.1-0.6 weight portions. In the presence of initiator and self-emulsifying copolymerization monomer, emulsion polymerization is performed at 70-95 deg.c to produce self-emulsified emulsion with high solid content, clear surface, homogeneous dispersion, high stability, and no any solvent pollution to environment. The emulsion is superior to conventional soap water emulsion and may be used widely in printing industry, building decoration, automobile, etc.

Description

Self-emulsified polyacrylate emulsion with high solid content and preparation method thereof
The present invention relates to print the preparation of the self-emulsified polyacrylate emulsion with high solid content that uses with coating.
Along with pay attention to day by day to environment, especially print and coating industry, the water-base emulsion of development nontoxic pollution-free is the polyreaction of medium with water, more and more seems important with water to replace organic solvent.The conventional emulsion polymerization reaction is carried out at aqueous phase, and is very big but the existence of emulsifying agent can influence emulsion film forming post polymerization rerum natura, the water-intake rate height, and mechanical property is low, and emulsifying agent also can slowly discharge the pollution that causes environment.Adopt the self-emulsifying emulsion polymerisation process that does not add emulsifying agent, can obviously improve water tolerance, bonding strength and other physicochemical property of material, and eliminate pollution environment.
The purpose of this invention is to provide a kind of self-emulsified polyacrylate emulsion with high solid content and preparation method thereof, can obtain solid content height, surface cleaning, be uniformly dispersed, the water miscible liquid that stability is high does not have any solvent environment is polluted.Over-all properties of the present invention is better than having the soap water miscible liquid, has broad application prospects in fields such as printing industry, high-grade indoor and outdoor decoration and automobiles.Processing step of the present invention is simple, easy handling control.
The present invention is that water is the polyreaction that medium carries out with methyl methacrylate, acrylate, vinylformic acid, self-emulsifying comonomer and initiator, makes high-solid content acrylic acid ester water miscible liquid.
Composition of the present invention and weight (umber) proportioning is as follows:
Water 70.0-100
Self-emulsifying comonomer 1-4
Methyl methacrylate 30-70
Acrylate 30-60
Vinylformic acid 2-5
Initiator 0.1-0.6
Wherein, methyl methacrylate (MMA); Acrylate is butyl acrylate (BA), Jia Jibingxisuanyizhi (EMA), butyl methacrylate (BMA) or Propenoic acid, 2-methyl, isobutyl ester (IBMA); Vinylformic acid is vinylformic acid (AA) or methacrylic acid (MMA); The self-emulsifying comonomer is Sodium styrene sulfonate (NaSS), methylpropene sodium sulfonate (NaMS), methacrylic acid propyl sulfonic acid sodium ester (SPM), methacrylic acid ethylsulfonic acid sodium ester (NaSEM), 3-allyloxy-2-hydroxyl-propanesulfonic acid sodium (AHPS), 2-acryloxy propionic (AOPA) or they and uses; Initiator is Potassium Persulphate (KPS) or ammonium persulphate (APS).
The present invention preferably consists of: initiator is a Potassium Persulphate, and the self-emulsifying comonomer is 3-allyloxy-2-hydroxyl-propanesulfonic acid sodium, and monomer is methyl methacrylate, butyl acrylate and vinylformic acid.
The present invention is in the there-necked flask that agitator, prolong, nitrogen protection and feeding device are housed, and adds the mixture of water medium, self-emulsifying comonomer, initiator, vinylformic acid and the acrylate of metering, gets final product in 6.5-10 hour 70 ℃-95 ℃ reactions.Specifically: the water, initiator and the self-emulsifying comonomer that in reactor, add metering, add the vinylformic acid of metering 1/10th and the monomer mixture of acrylate again, at 70 ℃ of polyreaction 0.5-1 hours, and then add residual monomers mixture, polyreaction 4-5 hour.Then water is warming up to 80 ℃ of reactions 1-2 hour, is warming up to 95 ℃ of reactions 1-2 hour at last, be cooled to room temperature.
Salient features of the present invention is as follows:
Solid content 50-60%
Latex particle size 0.3-0.5 μ m
Apparent viscosity 0.025-0.030PaS
Stability in storage>one year
Stripping strength 380-420N/m
Film forming tensile strength 5-6MPa
Elongation 800-900%
The present invention is a kind of solid content height, surface cleaning, is uniformly dispersed, the water miscible liquid that stability is high, and over-all properties is better than having soap water miscible liquid, environmentally safe.Have broad application prospects in fields such as printing industry, high-grade indoor and outdoor decoration and automobiles.Processing step of the present invention is simple, easy handling control.
Substantive distinguishing features that the present invention gives prominence to and unusual effect can be embodied from following embodiment, but they are not that the present invention is imposed any restrictions.
Embodiment 1.
Be equipped with in the there-necked flask of agitator, prolong, nitrogen protection and feeding device at 500ml, add deionized water 70ml and NaSS 2g, heating in water bath to 70 ℃.Add KPS 0.5g, the mix monomer that adds MMA 65g, BA 32g, AA 3g then is a small amount of, after 0.5 hour, drips the residual monomers mixture again, polyreaction 3.5 hours 70 ℃ of reactions.Be warming up to 80 ℃ of reactions 1.5 hours then, be warming up to 95 ℃ of reactions 1.5 hours, be cooled to room temperature.The solid content 60% of gained self-emulsifying water miscible liquid, latex particle size 0.46 μ m, apparent viscosity 0.028PaS, stripping strength 400N/m, package stability>one year, film forming tensile strength 6.0MPa, elongation 850%.
Embodiment 2.
Be equipped with in the there-necked flask of agitator, prolong, nitrogen protection and feeding device at 500ml, add deionized water 70ml and NaSS 2g, heating in water bath to 70 ℃.Add KPS 0.5g, the mix monomer that adds MMA 30g, EMA 20g, BA 48g, AA 2g then is a small amount of, after 0.5 hour, drips the residual monomers mixture again, polyreaction 3.5 hours 70 ℃ of reactions.Be warming up to 80 ℃ of reactions 1.5 hours then, be warming up to 95 ℃ of reactions 1.5 hours, be cooled to room temperature.The solid content 60% of gained self-emulsifying water miscible liquid, latex particle size 0.50 μ m, apparent viscosity 0.025PaS, stripping strength 390N/m, package stability>one year, film forming tensile strength 5MPa, elongation 900%.
Embodiment 3.
Be equipped with in the there-necked flask of agitator, prolong, nitrogen protection and feeding device at 500ml, add deionized water 70ml and NaMS 2g, heating in water bath to 70 ℃.Add KPS 0.5g, the mix monomer that adds MMA 35g, EMA20g, BA 43g, AA 2g then is a small amount of, after 0.5 hour, drips the residual monomers mixture 70 ℃ of polyreactions again, polyreaction 3.5 hours.Be warming up to 80 ℃ of reactions 1.5 hours then, be warming up to 95 ℃ of reactions 1.5 hours at last, be cooled to room temperature.The solid content 60% of gained self-emulsifying water miscible liquid, latex particle size 0.50 μ m, apparent viscosity 0.030PaS, stripping strength 390N/m, package stability>one year, film forming tensile strength 5.5MPa, elongation 800%.
Embodiment 4.
Be equipped with in the there-necked flask of agitator, prolong, nitrogen protection and feeding device at 500ml, add deionized water 70ml and SPM 2g, heating in water bath to 70 ℃.Add KPS 0.5g, the mix monomer that adds MMA 32g, IBMA 20g, BA 46g, AA 2g then is a small amount of, after 0.5 hour, drips the residual monomers mixture, polyreaction 3.5 hours 70 ℃ of polyreactions.Be warming up to 80 ℃ of reactions 1.5 hours, be warming up to 95 ℃ of reactions 1.5 hours at last, be cooled to room temperature.The solid content 60% of gained self-emulsifying water miscible liquid, latex particle size 0.50 μ m, apparent viscosity 0.028PaS, stripping strength 400N/m, package stability>one year, film forming tensile strength 5MPa, elongation 850%.
Embodiment 5
Be equipped with in the there-necked flask of agitator, prolong, nitrogen protection and feeding device at 500ml, add deionized water 70ml and AHPS 2g, heating in water bath to 70 ℃.Add KPS 0.5g, the mix monomer that adds MMA 46g, BA 51g, AA 3g then is a small amount of, after 0.5 hour, drips the residual monomers mixture, polyreaction 3.5 hours 70 ℃ of polyreactions.Be warming up to 80 ℃ of reactions 1.5 hours then, be warming up to 95 ℃ of reactions 1.5 hours at last, be cooled to room temperature.The solid content 60% of gained self-emulsifying water miscible liquid, latex particle size 0.45 μ m, apparent viscosity 0.028PaS, stripping strength 410N/m, film forming tensile strength 6.0MPa, elongation 800%.

Claims (3)

1. a class self-emulsified polyacrylate emulsion with high solid content is characterized in that its composition and weight (umber) joins
Such as following:
Water 70.0-100
Self-emulsifying comonomer 1-4
Methyl methacrylate 30-70
Acrylate 30-60
Vinylformic acid 2-5
Initiator 0.1-0.6 wherein, acrylate is butyl acrylate, Jia Jibingxisuanyizhi, butyl methacrylate or Propenoic acid, 2-methyl, isobutyl ester; Vinylformic acid is acrylic or methacrylic acid; The self-emulsifying comonomer is Sodium styrene sulfonate, methylpropene sodium sulfonate, methacrylic acid propyl sulfonic acid sodium ester, methacrylic acid ethylsulfonic acid sodium ester, 3-allyloxy-2-hydroxyl-propanesulfonic acid sodium, 2-acryloxy propionic or they and uses; Initiator is Potassium Persulphate or ammonium persulphate.
2, according to the self-emulsified polyacrylate emulsion with high solid content described in the claim 1, it is characterized in that described consisting of: initiator is a Potassium Persulphate, the self-emulsifying comonomer is 3-allyloxy-2-hydroxyl-propanesulfonic acid sodium, and monomer is methyl methacrylate, butyl acrylate and vinylformic acid.
3, the preparation method of the self-emulsifying high-solid content acrylic acid ester water miscible liquid described in the claim 1, it is characterized in that it comprises the steps: to add water, initiator and the self-emulsifying comonomer of metering in reactor, add the vinylformic acid of metering 1/10th and the monomer mixture of acrylate again, at 70 ℃ of polyreaction 0.5-1 hours, and then adding residual monomers mixture, polyreaction 4-5 hour.Then water is warming up to 80 ℃ of reactions 1-2 hour, is warming up to 95 ℃ of reactions 1-2 hour at last, be cooled to room temperature.
CNB011292016A 2001-06-14 2001-06-14 Self-emulsified polyacrylate emulsion with high solid content and its prepn process Expired - Fee Related CN1133666C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102304262A (en) * 2010-05-28 2012-01-04 中山大学 Self-crosslinked polyacrylate latex and preparation method thereof, and water-based paper ink
CN101085817B (en) * 2006-06-07 2012-11-21 上海侨茂建筑防水材料有限公司 High solid content core-shell structure nano acrylic ester micro-emulsion and synthetic method thereof
CN102002125B (en) * 2009-08-31 2013-04-24 无锡市金箭造漆有限公司 Acrylic resin emulsion for fingerprint-resistant paint and preparation method thereof
CN103468179A (en) * 2013-09-26 2013-12-25 佛山市奥雅图胶粘实业有限公司 Casting polypropylene protection film pressure-sensitive adhesive, casting polypropylene protection film and their preparation methods
CN109535904A (en) * 2018-11-29 2019-03-29 杭州高雅涂料有限公司 A kind of coating and preparation method thereof
CN116333548A (en) * 2023-03-31 2023-06-27 河南大学 KH550 modified nano silicon dioxide@hydrotalcite/quadripolymer composite leather finishing agent and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101870793B (en) * 2010-05-28 2011-09-28 中山大学 Self-crosslinking polyacrylate rubber latex, preparation method thereof and water-based paper printing ink

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101085817B (en) * 2006-06-07 2012-11-21 上海侨茂建筑防水材料有限公司 High solid content core-shell structure nano acrylic ester micro-emulsion and synthetic method thereof
CN102002125B (en) * 2009-08-31 2013-04-24 无锡市金箭造漆有限公司 Acrylic resin emulsion for fingerprint-resistant paint and preparation method thereof
CN102304262A (en) * 2010-05-28 2012-01-04 中山大学 Self-crosslinked polyacrylate latex and preparation method thereof, and water-based paper ink
CN102304262B (en) * 2010-05-28 2013-06-19 中山大学 Self-crosslinked polyacrylate latex and preparation method thereof, and water-based paper ink
CN103468179A (en) * 2013-09-26 2013-12-25 佛山市奥雅图胶粘实业有限公司 Casting polypropylene protection film pressure-sensitive adhesive, casting polypropylene protection film and their preparation methods
CN103468179B (en) * 2013-09-26 2015-05-27 佛山市奥雅图胶粘实业有限公司 Casting polypropylene protection film pressure-sensitive adhesive, casting polypropylene protection film and their preparation methods
CN109535904A (en) * 2018-11-29 2019-03-29 杭州高雅涂料有限公司 A kind of coating and preparation method thereof
CN116333548A (en) * 2023-03-31 2023-06-27 河南大学 KH550 modified nano silicon dioxide@hydrotalcite/quadripolymer composite leather finishing agent and preparation method thereof
CN116333548B (en) * 2023-03-31 2024-02-02 河南大学 KH550 modified nano silicon dioxide@hydrotalcite/quadripolymer composite leather finishing agent and preparation method thereof

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