CN1268658C - Water dispersion type emulsion of crylic acid, preparation method and usage - Google Patents
Water dispersion type emulsion of crylic acid, preparation method and usage Download PDFInfo
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- CN1268658C CN1268658C CNB2004100265013A CN200410026501A CN1268658C CN 1268658 C CN1268658 C CN 1268658C CN B2004100265013 A CNB2004100265013 A CN B2004100265013A CN 200410026501 A CN200410026501 A CN 200410026501A CN 1268658 C CN1268658 C CN 1268658C
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Abstract
The present invention relates to water dispersion type crylic acid emulsion with functional groups on the emulsion surface, a preparation method thereof and an application method thereof. The water dispersion type crylic acid emulsion is composed of 100 portions of acrylic acid, 180-400 portions of butyl acrylate, 80 to 160 portions of methyl methacrylate, 10 to 20 portions of vinyl acetate, 0 to 10 portions of acrylonitrile, 250 to 780 portions of deionized water and 0.5 to 3 portions of free radical initiators by weight through reaction polymerization. The preparation method has the steps that 1/3 to 2/5 of mixed monomers carry out preemulsification; then, the pH value is regulated to 4 to 6, and the temperature is raised to 74 to 83 DEG C; the initiators of parts of free radicals initiate the reaction; then, the rest mixed monomers are dripped in batch; simultaneously, the initiators are added in the mixed monomers for the reaction. When the dispersion type crylic acid emulsion is coated, reactive membranes adhere reactive acrylic resin, and the reactive acrylic resin covers on the surface of a carrier to form materials with the ion exchange function. The ion exchange performance does not influenced by the carrier performance, and the materials have the advantages of low cost and no environment pollution.
Description
Invention field
The present invention relates to water-dispersed acrylic emulsion of a kind of latex surface band functional group and its production and use.
Background of invention
Present coated film forming is used for the acrylic resin of ion-exchange and does not also see bibliographical information, the carrier of ion-exchange matrix material is used polystyrene-divinylbenzene often, glass pellet and Mierocrystalline cellulose etc., ion exchange functional groups often needs to receive on the monomer by the chemical reaction of complexity, or adds linking agent in addition and bond on the carrier.Yet there are no the similar report that on general purpose material, just can make ion exchange resin by the simple method of coating filmform.Present existing ion-exchange material and moulding process are divided into:
1, polymer (as Mierocrystalline cellulose) is a carrier, connects reactive functionality by graft copolymerization thereon.The shortcoming of this method is that the pre-treatment of graft reaction is loaded down with trivial details, and percentage of grafting is low and inhomogeneous.
2, the interpolymer of vinylbenzene-divinylbenzene, and on the phenyl ring of interpolymer, connect ion exchange functional groups by chemical reaction: sulfonic group, amino etc.Using the widest Zeo-karb at present is the method that Small introduces, the quick sulfonation of high temperature on the interpolymer bead of vinylbenzene-divinylbenzene.The shortcoming of this material is: exchange capacity is low, has only 0.005-0.05meq/g, the environmental pollution of containing benezene polymer production, and this material has certain photodegradation, is unsuitable for outdoor a large amount of uses (as water treatment).
3, nineteen eighty-two Stevens has improved the method for Small.Absorption excellent anionic exchange resin makes compound ion exchange resin on the styrene-divinyl benzene resin of Dowex-50*35.The limitation of this method is that desorption process makes the exchange resin of absorption easily by solvent elution.And this separator column back will connect suppressor column and just can carry out Sensitive Detection.
4, with the granulated glass sphere being carrier, is tackiness agent with the pyroxylin (e) cement in the volatile solvent, positively charged ion (negatively charged ion) exchange resin is adhered on the little granulated glass sphere substrate sphere of 15-20 μ m.Or adding vinylbenzene-divinylbenzene monomer and initiator on the bead surface, initiated polymerization forms exchange resin on the surface.The shortcoming of this method is that the use of volatile solvent is unfavorable for environmental protection.At the inconsistent particle size uniformity that also influences resin of the polymerization degree on surface.
5, silicon alkyl reaction is introduced SiO with ion-exchange group
2The surface of granulated glass sphere.Its shortcoming is that the silica gel skeleton has dissolution phenomena in acidity or basic solution, and the PH of application is range limited.
6, people such as Igaula adds silica gel in the solution of polymeric N-N-methyl-2-2-pyrrolidone N-of dibenzo 18-hat-6-ether, removes then and desolvates.The thinking of this method is similar to the adsorption method of Stevens, but the usage quantity of organic solvent is big, the poor solvent resistance of resin itself.
Summary of the invention
The water-dispersed acrylic emulsion that the purpose of this invention is to provide a kind of latex surface band functional group, it is the high and controlled reactive acroleic acid emulsion of latex surface carboxyl-content, it has good adhesivity to carrier, and loading capacity is greater than the ion exchange resin of identical cost.
Also purpose of the present invention provides the purposes of this ACRYLIC EMULSION, and emulsion especially can adhere to routine and cheap environment-friendly materials surface, does the back film forming and just makes novel ion-exchange material, has environment friendly.
The water-dispersed acrylic emulsion of this latex surface band functional group is counted by weight, is formed by reactive polymeric by following component:
Vinylformic acid 100,
Butyl acrylate 180-400,
Methyl methacrylate 80-160
Vinyl acetate 10-20,
Vinyl cyanide 0-10,
Deionized water 250-780,
Radical initiator 0.5-3.
The water-dispersed acrylic emulsion of a kind of more preferably latex surface band functional group is counted by weight, is formed by reactive polymeric by following component:
Vinylformic acid 100,
Butyl acrylate 180-340,
Methyl methacrylate 90-140,
Vinyl acetate 13-16,
Vinyl cyanide 1-7,
Deionized water 300-600,
Radical initiator 0.7-2.8.
Wherein radical initiator can be selected from persulfate initiators such as Potassium Persulphate, ammonium persulphate, initiator system of ammonium persulfate.
Its preparation method comprises the steps: it is earlier Acrylic Acid Monomer to be mixed with other comonomer, the 1/3-2/5 that gets the mix monomer total amount is equipped with 100-150 part deionized water, stir 50-60min and carry out pre-emulsification, regulating pH then is 4-6, be warming up to 74-83 ℃, add the initiation reaction of 0.2-0.9 part radical initiator, and insulated and stirred 50-100min, reaction is not till have a monomers flow back, and this moment, product was blue light; Drip remaining mix monomer and deionized water again, the control rate of addition drips off in 1-2h in batches, temperature of reaction goes back up to 74-83 ℃, adds 0.48-1.9 part initiator simultaneously, and regulating pH subsequently is 7-9, at 70-80 ℃ of insulation 1-3h, stirring velocity is controlled at 80-100 rev/min; Add remaining initiator at last and kill residual monomer, cooling discharge.
Wherein the pH regulator agent can be selected from mineral alkali, comprises highly basic and weak base, and is commonly used as NaOH, KOH, NH
4OH, NaHCO
3Deng, preferred NaHCO
3
This ACRYLIC EMULSION is coated in the organic materials surface filming as ion-exchange material, especially adheres to surfaces such as vegetable fibre, industrial waste, does the back film forming and just makes novel ion-exchange material.
Organic materials can be the particle of common reprocessed plastic(s), depleted disposable fast food bowls and chopsticks, agricultural waste plastic film etc., even can utilize the material that cheaply is easy to get to do the surface of carrier such as waste crop materials, industrial waste etc.
The invention belongs to utilization and make the ACRYLIC EMULSION of different carboxyl-contents, can utilize the material that cheaply is easy to get to do the surface of carrier such as waste crop materials, soil, industrial waste etc. with novel process.Only need coating, just can make the reactive acroleic acid resin is that reactive membrane adheres to and be wrapped in carrier surface, forms the material with ion exchanging function.The emulsion solid content that obtains is 45%-51%, and viscosity＜1Pa.s, minimum film-forming temperature can reach about 2 ℃.The apparent carboxyl-content of micelle is greater than 0.295mol/kg.Resin can be bonded on the carrier well when utilizing butyl acrylate segmental adhesiveproperties; The methyl methacrylate segment has certain rigid, can make resin in use not yielding; Carboxyl on the vinylformic acid segment is hydrophilic functional group, can come up along with the surface that moisture evaporated is brought to exchange membrane, makes lip-deep exchange activity point as much as possible.
Waste part with farm crop is divided into carrier, and as Pericarppium arachidis hypogaeae, the milling particle of husk in the emulsion behind the immersion dilute with water, takes out nature and dries, and latex is got final product in the carrier surface film forming.Can be carrier with the polymeric particles material that reclaims, its ion-exchange performance be subjected to the carrier Effect on Performance yet.
The advantage of this invention is: the feasibility that reactive emulsion is produced; Emulsion is produced and the environment friendly of use, and the method for surface coatings is to be different from the past in matrix surface graft copolymerization or to be prepared the novel method of ion-exchange material by single-material.But the profile various ways of material can be decided according to the needs of concrete use as lamelliform, column etc.Used carrier can be the regenerate of waste or used plastics, also can make the rough-wrought product of the discarded shell, bar etc. of natural farm crop, and overall cost is cheap, is convenient to promote.
Embodiment
Following umber all by weight.
Embodiment 1
Earlier 100 parts of Acrylic Acid Monomers are mixed with 195 parts of butyl acrylates, 97 parts of methyl methacrylates, 14 parts of four kinds of monomers of vinyl acetate, 1/3 the mix monomer of getting its total amount is equipped with 120 parts of deionized waters, and stirring 50-60min carries out pre-emulsification.Regulate the about 4-6 of PH with sodium bicarbonate.Be warming up to 78 ℃, add 0.3 part of ammonium persulphate initiation reaction, and insulated and stirred 50min, react to product and be blue light, do not have till the monomers flow back.In reactor, drip remaining mix monomer and 200 parts of deionized waters in batches, the control rate of addition drips off in 1-2h, add 1 part of initiator ammonium persulfate when temperature of reaction goes back up to 78 ℃, regulate 72 ℃ of about 7.5 insulations of PH at any time, stirring velocity is 80-100r/min.
Add 005 part of initiator at last and kill residual monomer, cooling discharge.
Make the emulsion that apparent carboxyl-content is 16% (mol ratio), film forming on filter paper.Since the wetting ability of carboxyl, and almost do not have the strong band electric group, can not make responsive biochemical substances sex change, so can be used for making bioactive moleculess such as ion exchange paper, chromatographic separation protein or amino acid.
Embodiment 2
20 parts of monomers of 100 parts of Acrylic Acid Monomers, 270 parts of butyl acrylates, 100 parts of methyl methacrylates, 4 parts of vinyl cyanide, vinyl acetate are mixed, and 1/3 the mix monomer of getting its total amount is equipped with 170 parts of deionized waters, stirs 60min and carries out pre-emulsification.
Regulate the about 4-6 of PH with sodium bicarbonate.Add 0.7 part of Potassium Persulphate initiation reaction when being warming up to 81 ℃, and insulated and stirred 70min, reaction does not have till the monomers flow back, and this moment, product was blue light.Drip remaining mixed monomer and 380 parts of deionized waters in reactor, the control rate of addition drips off in 1-2h in batches, and temperature of reaction goes back up to 80 ℃ and adds 1.5 initiator parts simultaneously, and it is about 7 to regulate PH at any time, is incubated 76 ℃, and stirring velocity is 80r/min.
Add 0.08 initiator at last and kill residual monomer, cooling discharge.
With husk, Pericarppium arachidis hypogaeae or nut-shell milling are soaked in the emulsion that is diluted to 15wt% into about 20 purpose particles, and the particle after will handling is dry under field conditions (factors).Particle drying to hand is pinched and is represented that the latex film forming gets final product when not agglomerating.This ion-exchange material has the good adsorption effect to heavy metal such as chromium, lead etc., is packed into the water body that sewage treatment tower is used to handle heavy metal contamination.Exchange material after the use is without aftertreatment, the paver that can be used for sidewalk not only has certain elasticity, even the carrier crude substance is by microbiological degradation, its macromolecular coating still can the bonding heavy metal ion and is rubber-like, can not bring secondary pollution because of regeneration and aftertreatment.
Embodiment 3
Earlier 100 parts of Acrylic Acid Monomers are mixed with 300 parts of butyl acrylates, 140 parts of methyl methacrylates, 9 parts of vinyl cyanide, 19 parts of monomers of vinyl acetate, 1/3 the mix monomer of getting its total amount is equipped with 200 parts of deionized waters, and stirring 60min carries out pre-emulsification.
Regulate the about 4-6 of PH with sodium bicarbonate.Heating up 80 ℃ adds 0.5 part of ammonium persulphate initiation reaction, and insulated and stirred 70min, and reaction is not till have a monomers flow back, and this moment, product was blue light.In reactor, drip remaining 2/3 mix monomer and 400 parts of water simultaneously in batches, the control rate of addition drips off in 1-2h, adds 2 parts of initiators when temperature of reaction goes back up to 80 ℃, and regulating PH at any time with sodium hydroxide is 8.5, be incubated 80 ℃, stirring velocity is 90r/min.
Add 0.05 part of initiator at last and kill residual monomer, cooling discharge.
Emulsion with above-mentioned high-carboxyl-content is coated in fabric face, and the fabric baking is done, and makes dying industrial wastewater repeatedly by filtration membrane, can carry out adsorption treatment to nitrogen-containing pollutant.For reducing the floor space that the chemical process decontamination is handled.Can make waste water can in few space of trying one's best, be filled purification with waste water by the treating column of multilayer filter membrane is housed.
Claims (9)
1, the water-dispersed acrylic emulsion of the surperficial band of a kind of latex functional group is counted by weight, is formed by reactive polymeric by following component:
Vinylformic acid 100,
Butyl acrylate 180-400,
Methyl methacrylate 80-160
Vinyl acetate 10-20,
Vinyl cyanide 0-10,
Deionized water 250-780,
Radical initiator 0.5-3,
The emulsion solid content that obtains is 45%-51%, viscosity＜1Pa.s.
2, the emulsion of claim 1 is counted by weight, is formed by reactive polymeric by following component:
Vinylformic acid 100,
Butyl acrylate 180-340,
Methyl methacrylate 90-140,
Vinyl acetate 13-16,
Vinyl cyanide 1-7,
Deionized water 300-600,
Radical initiator 0.7-2.8.
3, claim 1 or 2 emulsion, wherein radical initiator is selected from persulphate.
4, the emulsion of claim 3, wherein radical initiator is an ammonium persulphate.
5, the preparation method of the arbitrary emulsion of claim 1～4, comprise the steps: earlier Acrylic Acid Monomer to be mixed with other comonomer, the 1/3-2/5 that gets the mix monomer total amount is equipped with 100-150 part deionized water, stir 50-60min and carry out pre-emulsification, regulating pH then is 4-6, is warming up to 74-83 ℃, add the initiation reaction of 0.2-0.9 part radical initiator, and insulated and stirred 50-100min, reaction is not till have a monomers flow back, and this moment, product was blue light; Drip remaining mix monomer and deionized water again, the control rate of addition drips off in 1-2h in batches, temperature of reaction goes back up to 74-83 ℃, adds 0.48-1.9 part initiator simultaneously, and regulating pH subsequently is 7-9, at 70-80 ℃ of insulation 1-3h, stirring velocity is controlled at 80-100 rev/min; Add remaining initiator at last and kill residual monomer, cooling discharge.
6, the method for claim 5, wherein the pH regulator agent is selected from mineral alkali.
7, the method for claim 6, wherein the pH regulator agent is NaHCO
3
8, the arbitrary emulsion of claim 1～4 is coated in the organic materials surface filming and uses as ion-exchange material.
9, the purposes of claim 8, wherein emulsion is coated in vegetable fibre, the industrial waste surface filming is used as ion-exchange material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100265013A CN1268658C (en) | 2004-03-17 | 2004-03-17 | Water dispersion type emulsion of crylic acid, preparation method and usage |
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| CNB2004100265013A CN1268658C (en) | 2004-03-17 | 2004-03-17 | Water dispersion type emulsion of crylic acid, preparation method and usage |
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| CN1268658C true CN1268658C (en) | 2006-08-09 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1295286C (en) * | 2005-04-15 | 2007-01-17 | 宁波广用纳米涂料有限公司 | Emulsion for environmental protection type latex paint and preparation method |
| CN101089023B (en) * | 2006-06-14 | 2010-05-12 | 产协企业股份有限公司 | Resin composition for making vibrating diaphragm of loudspeaker |
| CN101338005B (en) * | 2008-03-11 | 2011-03-30 | 郑勇 | Process for synthesizing acrylic ester copolymer of ultra-high molecular mass |
| CN101880349B (en) * | 2010-08-16 | 2012-05-02 | 上海东和胶粘剂有限公司 | Cross linking type methyl acrylate and vinyl acetate emulsion and preparation method thereof |
| CN102746446B (en) * | 2011-04-22 | 2015-04-29 | 常州华威新材料有限公司 | Preparation method of ylate emulsion plant glue used for reflective membrane |
| CN102321375B (en) * | 2011-08-04 | 2012-11-21 | 宁波家联塑料科技有限公司 | Bagasse polypropylene bioplastics and preparation method thereof |
| CN103224584B (en) * | 2013-04-28 | 2015-09-16 | 徐州众恒淀粉科技有限公司 | A kind of water-soluble copolymer synthetic slurry and synthetic method thereof |
| CN105732875A (en) * | 2016-02-28 | 2016-07-06 | 吉林建筑大学 | Multifunctional quaternary soap-free vinyl acetate-acrylic emulsion and preparation method thereof |
| CN117051596A (en) * | 2022-07-08 | 2023-11-14 | 常熟威怡科技有限公司 | Polydopamine coated nano microsphere, preparation method thereof and structural chromogenic cellulose fabric |
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