CN1133666C - 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
CN1133666C
CN1133666C CNB011292016A CN01129201A CN1133666C CN 1133666 C CN1133666 C CN 1133666C CN B011292016 A CNB011292016 A CN B011292016A CN 01129201 A CN01129201 A CN 01129201A CN 1133666 C CN1133666 C CN 1133666C
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China
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self
emulsifying
acid
acrylic acid
water
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CNB011292016A
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CN1322766A (en
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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 present invention relates to a preparation method for self-emulsified polyacrylate water emulsion with high solid content for printing and paint. The polyacrylate water emulsion is composed of components of the following proportion by weight portions: 70 to 100 portions of water, 30 to 70 portions of methyl methacrylate, 30 to 60 portions of acrylic ester, 2 to 5 portions of acrylic acid and 0.1 to 0.6 portions of initiating agent. Under the condition that the initiating agent and self-emulsified co-monomers exist, the components have an emulsion polymerization reaction at 70 to 95 DEG C, and obtained self-emulsified water emulsion has the advantages of high solid content, clean surface, uniform dispersion and high stability, and no solvents have pollution to environment. The all round performance of the self-emulsified water emulsion is superior to that of conventional water emulsion with soap, and thus, the self-emulsified water emulsion has wide application prospect to the fields of printing industry, high-grade indoor and outdoor decoration, automobiles, etc.

Description

Self-emulsified polyacrylate emulsion with high solid content and preparation method thereof
Technical field
The present invention relates to print the preparation of the self-emulsified polyacrylate emulsion with high solid content that uses with coating.
Background technology
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.
Summary of the invention
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
Esters of acrylic acid 30-60
Acrylic acid or the like 2-5
Initiator 0.1-0.6
Wherein, methyl methacrylate (MMA); Esters of acrylic acid is butyl acrylate (BA), Jia Jibingxisuanyizhi (EMA), butyl methacrylate (BMA) or Propenoic acid, 2-methyl, isobutyl ester (IBMA); Acrylic acid or the like is vinylformic acid (AA) or methacrylic acid (MA); 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; the mixture that adds water medium, self-emulsifying comonomer, initiator, methyl methacrylate, vinylformic acid and the acrylate of metering got final product 70 ℃-95 ℃ reactions in 6.5-10 hour.Specifically: in reactor, add water, initiator and the self-emulsifying comonomer of metering, add the monomer mixture of metering 1/10th again,, and then add residual monomers mixture, polyreaction 4-5 hour at 70 ℃ of polyreaction 0.5-1 hours.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
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-emulsifying acrysol is characterized in that its composition and weight (umber) proportioning are as follows:
Water 70.0-100
Self-emulsifying comonomer 1-4
Methyl methacrylate 30-70
Esters of acrylic acid 30-60
Acrylic acid or the like 2-5
Initiator 0.1-0.6
The salient features of described self-emulsifying acrysol is as follows:
Solid content 50-60%
Latex particle size 0.3-0.5 μ m
Apparent viscosity 0.025-0.030PaS wherein, esters of acrylic acid is butyl acrylate, Jia Jibingxisuanyizhi, butyl methacrylate or Propenoic acid, 2-methyl, isobutyl ester, or butyl acrylate and Jia Jibingxisuanyizhi, butyl methacrylate or Propenoic acid, 2-methyl, isobutyl ester and usefulness; Acrylic acid or the like 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; Initiator is Potassium Persulphate or ammonium persulphate.
2, according to the self-emulsifying acrysol 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 acrylate 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, the mix monomer methyl methacrylate, esters of acrylic acid and the acrylic acid or the like thing that add metering 1/10th again, at 70 ℃ of polyreaction 0.5-1 hours, and then add remaining above-mentioned mix monomer, 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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101870793A (en) * 2010-05-28 2010-10-27 中山大学 Self-crosslinking polyacrylate rubber latex, preparation method thereof and water-based paper printing ink

Families Citing this family (6)

* 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
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
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
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101870793A (en) * 2010-05-28 2010-10-27 中山大学 Self-crosslinking polyacrylate rubber latex, preparation method thereof and water-based paper printing ink

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