CN102140219A - Water-base resin for plastic and preparation method and application thereof - Google Patents
Water-base resin for plastic and preparation method and application thereof Download PDFInfo
- Publication number
- CN102140219A CN102140219A CN2010101021172A CN201010102117A CN102140219A CN 102140219 A CN102140219 A CN 102140219A CN 2010101021172 A CN2010101021172 A CN 2010101021172A CN 201010102117 A CN201010102117 A CN 201010102117A CN 102140219 A CN102140219 A CN 102140219A
- Authority
- CN
- China
- Prior art keywords
- hydrophilic
- water
- hydrophobic polymer
- resin
- monomer
- 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.)
- Pending
Links
Images
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to the technical field of coating chemical industry and particularly relates to water-base resin for plastic which has high adhesion on a plastic substrate, and a preparation method and application thereof. The preparation method comprises the following steps of: performing in-situ polymerization on a hydrophilic monomer, a comonomer and a hydrophobic polymer with the molecular weight of between 1,000 and 200,000 in an organic solvent to synthesize a hydrophilic-hydrophobic polymer solution by adopting a radical polymerization method or an addition polymerization or condensation polymerization method; and under the condition that an aqueous neutralizing agent is added or not added, adding water to prepare the water-base resin for plastic by adopting a phase reversal method. By adopting the preparation method provided by the invention, a hydrophobic polymer chain segment and a hydrophilic polymer chain segment form a uniform microphase separation structure. The water-base resin prepared by adopting the preparation method has a simple preparation process, high storage stability, high hardness, high water resistance and high surface adhesion on a plastic substrate, and can be applied to preparation of a plastic coating material with excellent preparation performance.
Description
Technical field
The invention belongs to the painting technical field, be specifically related to a kind of plastics use resin that plastic basis material is had excellent adhesive attraction and its production and application.
Background technology
Plastic prod has been compared the low density that has with it with other materials since invention, lightweight has obtained application more and more widely in industrial production.For example in automotive industry, the lighting of vehicle design helps to reduce unit consumption of energy, thereby more and more assembly is replaced by various plastics, as polypropylene, and ABS, polycarbonate etc.Such as in household electrical appliances and 3C industry, plastic component has occupied very big ratio again, and what have can reach more than 80%.The industrial coating of all types of plastic substantially all is to use solvent based coating from priming paint to the finish paint at present, and the solvent evaporates amount is big in producing and constructing, the health that has not only endangered operation and workmen, and the discharging of its volatile organic matter has also brought great environmental issue.Therefore developing the water-based plastic resin is the task of top priority.Compare with traditional solvent based coating, water-base resin and coating are to be dispersion medium with water, have do not fire, advantage such as low toxicity, low cost, easy cleaning, saved the resource and the energy.
The polycomponent water-base resin that U.S. Pat 2007059530-A1 provides a kind of consumer electronics market plastic basis material to use, this water-base resin comprises water-based aliphatic polycarbonate-polyurethane dispersing liquid, acrylic polyol resin dispersion liquid and energy while that has functional group and the 3rd component of preceding two kinds of resin crosslinks; The VOC content of this resin is very low, and can form has good sticking power to multiple plastic basis material, the filming of good moisture-proof gas and hardness, but coating is to low polarity plastic basis material poor adhesive force.The method of U.S. Pat 6184281-B2 has prepared a kind of plastic basis material of metal ion crosslinked with filming; it comprises the water base dispersion resin of the many carboxyls of amine neutral and the compound zinc ammonium salt of cross-linking set is provided; film have good snappiness, advantage such as Gao Guang, moisture-proof gas, be mainly used in the outer protection of high polarity plastic basis material.Chinese invention patent CN200610026688.6 and Chinese invention patent CN200610026686.7 have reported a kind of aqueous polyurethane coating and waterborne polyester-amino resin coating material that adopts the water nano composite polyester resin preparation, can be used for the frosting coating, but be difficult to be used in low polarity frosting.Chinese invention patent CN101006147A has reported a kind of aqueous priming paint of combination, it is made up of the water dispersion of modified polyolefin, polyol resin and pigment water-soluble or water dispersion, the paint base composition of this three component is good to the moulded goods binding property, water tolerance and solvent resistance excellence, but its matrix resin is the combination of the dispersion of two kinds of different resins, two kinds of different operational paths have increased the complicacy of its operation, have increased cost.Patent of invention CN101376684A has reported and carried out letex polymerization on the basis of modified polyolefin dispersion, and preparation coating, forms the water-borne coatings good to plastic basis material sticking power.Its modified poly carries out in two steps, has increased running cost, and the polymerizability unsaturated monomer of letex polymerization is confined to the free yl polymerizating monomer of alkene class, and its application has limitation.
Summary of the invention
The objective of the invention is to propose that a kind of preparation technology is simple, excellent storage stability, hardness height, adaptability are strong, multiple plastics are had well attached performance and water-proof plastics use resin.
Another object of the present invention is to propose the preparation method of above-mentioned plastics use resin.This water-base resin is to utilize the hydrophilic-hydrophobic polymer solution with microphase-separated to add water " phase reversion " method directly to make.Furtherly, be with hydrophilic monomer, comonomer and molecular weight 1000-200,000 hydrophobic polymer is a raw material, adopt solution free radical polymerization method or polyaddition reaction or polycondensation method to obtain to have the hydrophilic-hydrophobic polymer solution of micro phase separation structure, and this hydrophilic-hydrophobic polymer can stably be dispersed in the water adding or not adding under the situation of neutralizing agent.
A further object of the present invention is to propose the range of application and the application method thereof of above-mentioned water-base resin.
Plastics use resin proposed by the invention, be with hydrophilic monomer, comonomer and molecular weight 1000-200,000 hydrophobic polymer is a raw material, method with Raolical polymerizable or polyaddition reaction or polycondensation makes hydrophilic-hydrophobic polymer solution, this polymers soln has the structure of microphase-separated, and but stable dispersion is in water, wherein, hydrophilic-hydrophobic polymer solution by the hydrophilic monomer preparation that has the ionizable hydrophilic radical, add the water-based neutralizing agent therein and make the hydrophilic polymer ionization, add water-dispersion again and form water-base resin; Hydrophilic-hydrophobic polymer solution by the hydrophilic monomer preparation with non-ionic hydrophilic group can directly be distributed to it in water.
Plastics use resin proposed by the invention, the second-order transition temperature of wherein hydrophilic-hydrophobic polymer be-20-150 ℃, and the solid content of hydrophilic-hydrophobic polymer solution is 30-85wt%, the solid content of water-base resin is 10-60wt%.
Water-base resin proposed by the invention has good sticking power to plastic basis material such as PVC, Epoxy, ABS, PC, PS, HIPS, POM, PP, PE etc.
Of the present invention hydrophilic-second-order transition temperature of hydrophobic polymer is preferably 0-100 ℃.
Of the present invention hydrophilic-hydrophobic polymer has micro phase separation structure, the size of the microcell that is separated that it is hydrophilic or hydrophobic is less than 10 μ m.
Of the present invention hydrophilic-gravel size decision of its hydrophilic or hydrophobic microcell that is separated of hydrophobic polymer is less than 2 μ m.
Hydrophilic monomer of the present invention is selected from ionizable hydrophilic monomer, or has the hydrophilic monomer of non-ionic hydrophilic group.
Ionizable hydrophilic monomer of the present invention, be selected from have ionizable hydrophilic radical-COOH ,-SO
3H ,-PO
4H
2,-NH
2,-NH or-in vinyl monomer, alcohols monomer or the thio-alcohol monomer of SH one or both, the 5-40wt% of hydrophilic-hydrophobic polymer total amount that consumption accounts for.
Ionizable hydrophilic monomer described in the present invention, non-limiting example is a vinylformic acid, methacrylic acid, vinyl sulfonic acid, propenyl sulfonic acid, vinylbenzenesulfonic acid, vinyl phosphonate, 1,2-propadiene base phosphonic acids, phenyl vinyl-1-phosphonic acids, diallyl amine, 2, the 2-dimethylol propionic acid, dimethylolpropionic acid, 9,10-dihydroxyl stearic acid, 2, the 4-resorcylic acid, propenoic methyl carbamate, dimethylaminoethyl acrylate, 2-methyl-2-vinylformic acid-2-(dimethylamino) ethyl acetate, trolamine, 1-amino-2-propyl alcohol, Phenylpropanolamine, allyl mercaptan, the 2-diethylamino ethanethiol, 1, the 2-dithioglycol, 1, the 3-dimercaptopropane.
The hydrophilic monomer that has non-ionic hydrophilic group of the present invention, being selected from the molecular weight that can participate in polycondensation or radical polymerization is vinyl monomer, alcohols monomer or the thio-alcohol monomer that 100-50000 has non-ionic hydrophilic group such as polyoxyethylene segment, polyoxypropylene segment, sorbitan ester segment, sucrose fatty ester segment.
The hydrophilic monomer that has non-ionic hydrophilic group of the present invention is vinyl monomer, alcohols monomer or the thio-alcohol monomer that 500-10000 has non-ionic hydrophilic group such as polyoxyethylene segment, polyoxypropylene segment, sorbitan ester segment, sucrose fatty ester segment from the molecular weight that can participate in polycondensation or radical polymerization preferably.
The hydrophilic monomer that has non-ionic hydrophilic group described in the present invention, be selected from the polyethenoxy ether class that molecular weight is 100-50000, the polyoxypropylene ethers, the alkylphenol polyoxyethylene class, the high-carbon fatty alcohol polyoxyethylene ether class, the polyoxyethylene carboxylate class, the polyoxyethylene amine, the polyoxyethylate amide class, the ethylene oxide adduct of polypropylene glycol (polyether-type nonionic tensio-active agent), the ethylene oxide adduct of the polypropylene glycol of band vinyl, the polyethenoxy ether class of band edge vinyl, the polyoxypropylene ethers of band edge vinyl, arlacels, the vinyl monomer of sucrose fatty ester class hydrophilic radical, in alcohols monomer or the thio-alcohol monomer one or both, the 5-40wt% of hydrophilic-hydrophobic polymer total amount that consumption accounts for.
The hydrophilic monomer that has non-ionic hydrophilic group described in the present invention, non-limiting example are polyoxyethylene glycol, the Soxylat A 25-7 dibasic alcohol, the polyethenoxy ether dibasic alcohol, the Soxylat A 25-7 trivalent alcohol, the polyethenoxy ether trivalent alcohol, Soxylat A 25-7 two mercaptan, polyethenoxy ether two mercaptan, the castor oil polyoxyethylene ether dibasic alcohol, the polyoxyethylene polyoxypropylene glycerol, the hydrogenated castor oil polyoxyethylene ester, dodecyl primary amine polyoxyethylene fat, Methylacrylic Acid Polyoxyethylene Ester, methacrylic acid polyoxypropylene ester, the vinylformic acid polyoxyethylene ester, polyurethane-modified Soxylat A 25-7 dibasic alcohol, acrylate modified oxygen Vinyl Ether dibasic alcohol.
Comonomer of the present invention is selected from two or more in the alkene class comonomer that participates in radical polymerization or the isocyanic ester that participates in addition polymerization and alcohols monomer or participation polyester condensation polymeric acid and the alcohols monomer, the 20-75wt% of hydrophilic-hydrophobic polymer total amount that consumption accounts for.
The alkene class comonomer of the participation radical polymerization described in the present invention, non-limiting example is a vinyl acetate, acetate 2-propenyl ester, ethyl propenoate, butyl acrylate, ethyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, the methacrylic acid pentyl ester, n octyl methacrylate, methacrylic acid-2-methyl ester, Hydroxyethyl acrylate, propylene oxide acids vinyl ester, hydroxyethyl methylacrylate, vinylbenzene, alpha-methyl styrene, the 3-t-butyl styrene, 4-phenetole ethene, vinyltrimethoxy silane, vinyltriethoxysilane, ethenylphenyl dimethoxy silane, vinyl three (dimethyl siloxane) silane, 1-(trimethicone) tetrahydrobenzene, the allyl group sily oxide, methacryloxypropyl diethoxy silane and methacryloxypropyl dimethoxy silane.
The isocyanic ester comonomer of the participation urethane addition polymerization described in the present invention, non-limiting example is tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), many phenyl polymethine polyisocyanates (PAPI), naphthalene-1,5 vulcabond, aliphatics hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), isocyanic ester methoxy silane, isocyanic ester Ethoxysilane, isocyanate-containing alkyl methoxy silane and isocyanate-containing alkyl Ethoxysilane.
Participation polyester condensation polymeric polyprotonic acid comonomer described in the present invention, non-limiting example is Succinic Acid, hexanodioic acid, nonane diacid, pimelic acid, suberic acid, SL-AH, m-phthalic acid, terephthalic acid, phthalic acid, isophthalic anhydride, terephthalic anhydride, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride and 1,4 cyclohexanedicarboxylic acid.
Participation urethane addition polymerization described in the present invention or the used polyvalent alcohol of participation polyester condensation polymerization, non-limiting example is an ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 3-butyleneglycol, 1, the 6-hexylene glycol, cyclohexanedimethanol, 1, the 4-butyleneglycol, 2,2-dimethyl-1, ammediol, glycol ether, 2-ethyl-2-propyl group-1, ammediol, 1, the 4-cyclohexanediol, glycerol, TriMethylolPropane(TMP), tetramethylolmethane, polyether Glycols, polyether-tribasic alcohol, polyester diol, the polyester trivalent alcohol, the epoxy dibasic alcohol, amido polyethers and PTMG.
Hydrophobic polymer molecular weight of the present invention is 1000-200,000.
Hydrophobic polymer molecular weight of the present invention is preferably 5000-100,000.
Hydrophobic polymer of the present invention is made up of hydrophobic backbone and hydrophilic radical.
The hydrophobic backbone of hydrophobic polymer of the present invention is selected from the alkyl isocyanate of alkylsiloxane class, C3-C30 of arene, the C3-C30 of cycloalkane, the C6-C30 of olefines, the C3-C30 of alkanes, the C3-C30 of C3-C30 one or both.
The wetting ability functional group of hydrophobic polymer of the present invention is selected from hydroxyl, amino or amido, carboxyl, sulfonic acid group, phosphonyl group, the halogen group one or both, and consumption accounts for the 2-50wt% of hydrophobic polymer amount.
Hydrophobic polymer of the present invention, non-limiting example is acrylate resin, urethane resin, organic silicon-acrylate resin, epoxy-acrylate resin, organosilicon-urethane resin, vibrin, olefin-acrylic ester resin, haloolefin resin or cyclic olefin resins, the 5-40wt% of hydrophilic-hydrophobic polymer amount that consumption accounts for.
Of the present invention hydrophilic-hydrophobic polymer solution is medium with the organic solvent, solid content is 30-85wt%, organic solvent is selected from hydrophilic organic solvent, hydrophobic organic solvent or its mixture, in the time of 20 ℃, hydrophilic organic solvent and water dissolve each other or the solubleness in water greater than 14wt%, the solubleness of hydrophobic organic solvent in water is less than 6wt%.
Of the present invention hydrophilic-hydrophobic polymer solution, be with hydrophilic monomer, comonomer, molecular weight 1000-200,000 hydrophobic polymer is a raw material, obtains with free radical polymerisation process or polyaddition reaction or polycondensation method, has the structure of microphase-separated.
Of the present invention hydrophilic-solid content of hydrophobic polymer solution is 30-85wt%.
Water-base resin of the present invention has the hydrophilic-hydrophobic polymer solution of the hydrophilic monomer preparation of ionizable hydrophilic radical for employing, adds the water-based neutralizing agent therein and makes the hydrophilic polymer ionization, obtains by adding water-dispersion.
Water-based neutralizing agent of the present invention be used in equivalent or the non-equivalent and hydrophilic-hydrophobic polymer segment on ionogenic hydrophilic radical, be selected from ammonia, alkylamine, hydramine, morpholine, mercaptan, carboxylic acid, organic sulfonic acid or the organic phospho acid one or more.
Water-based neutralizing agent of the present invention: ionizable hydrophilic radical mole dosage is than being 0.4-3 in hydrophilic-hydrophobic polymer.
Water-based neutralizing agent of the present invention: ionizable hydrophilic radical mole dosage ratio is preferably 0.6-2 in hydrophilic-hydrophobic polymer.
Water-base resin of the present invention has the hydrophilic-hydrophobic polymer solution of the hydrophilic monomer preparation of non-ionic hydrophilic group for employing, can directly be distributed in the water under the situation of aquosity neutralizing agent not.
The solid content of water-base resin of the present invention is 10-60wt%.
The preparation method of plastics use resin proposed by the invention, it comprises following steps:
(1) will have hydrophilic monomer, comonomer, the molecular weight 1000-200 of ionizable hydrophilic radical, 000 hydrophobic polymer mixes in organic solvent, adopt free radical polymerisation process or polyaddition reaction or polycondensation method, the in-situ polymerization preparation has the hydrophilic-hydrophobic polymer solution of micro phase separation structure;
(2) under agitation condition, 0-100 ℃ temperature, in hydrophilic-hydrophobic polymer solution, add the water-based neutralizing agent and mix, stir under the 100-1500rpm rotating speed;
(3) under agitation condition, 0-100 ℃ temperature, add water in the mixture that under the 100-3000rpm rotating speed, in step (2), obtains, " phase reversion " obtains water-base resin.
In step (1), adopt the preparation of free radical polymerisation process or polyaddition reaction or polycondensation method to have the hydrophilic-hydrophobic polymer solution of micro phase separation structure, used organic solvent need be selected in hydrophilic organic solvent, hydrophobic organic solvent or its mixture according to polymerization.
In step (2), preferably under 0-100 ℃ temperature, in polymers soln, add the water-based neutralizing agent and mix, the 100-1500rpm rotating speed stirred 2-30 minute down, formed Ionized polymkeric substance.
In step (3), preferably under 0-100 ℃ temperature, under the 100-3000rpm rotating speed, stir ionomeric polymer solution, add entry " phase reversion " method and obtain plastics use resin.
The preparation method of plastics use resin proposed by the invention, it comprises following steps:
(1) will have hydrophilic monomer, comonomer, the molecular weight 1000-200 of non-ionic hydrophilic group, 000 hydrophobic polymer mixes in organic solvent, adopt free radical polymerisation process or polyaddition reaction or polycondensation method, the in-situ polymerization preparation has the hydrophilic-hydrophobic polymer solution of micro phase separation structure;
(2) under 0-100 ℃ temperature, hydrophilic-hydrophobic polymer solution is directly added in the entry, under the 300-5000rpm rotating speed, stirred 2-60 minute, directly it is dispersed in the water, obtain water-base resin.
In step (1), adopt the preparation of free radical polymerisation process or polyaddition reaction or polycondensation method to have the hydrophilic-hydrophobic polymer solution of micro phase separation structure, used organic solvent need be selected in hydrophilic organic solvent, hydrophobic organic solvent or its mixture according to polymerization.
In step (2), preferably under 0-100 ℃ temperature, under the 100-3000rpm rotating speed, water is added hydrophilic-hydrophobic polymer solution, stir and directly obtain plastics use resin.
When plastics use resin of the present invention is used for plastic basis material, can add in the coating after solidifying agent commonly used solidifies, be applied to the plastic basis material surface again.
When plastics use resin of the present invention is used for plastic basis material, can be mixed with water-borne coatings with auxiliary agents such as dispersion agent, defoamer, film coalescence aid and pigment, filler earlier, be applied to the plastic basis material surface again.
The preparation process of plastics use resin of the present invention does not have special requirement to pressure, as long as it can not influence the preparation process of plastics use resin of the present invention significantly unfriendly.Other processing condition of not mentioning in the preparation process of the invention described above plastics use resin and hydrophilic-hydrophobic polymer but may relating to can be with the conventional plastics use resin and the preparation condition of hydrophilic-hydrophobic polymer.
A kind of method that is equipped with plastics use resin with the phase reversion legal system that the present invention proposes, its advantage is: compared with former water-base resin synthetic method, the present invention adopts solution free radical polymerization method or polyaddition reaction or polycondensation method to obtain to have the hydrophilic-hydrophobic polymer solution of micro phase separation structure, add or do not add neutralizing agent, can directly obtain have the water-base resin of hydrophobic structure in the aqueous phase single stage method, strong with the plastic basis material surface adhesion force, hardness is high, water-tolerant.Preparation technology of the present invention is very simple, realizes suitability for industrialized production easily, can be widely used in plastic basis material surfaces such as ABS, PS, HIPS, PE, HDPE, PP, POM, PVC, can be used as the surface decoration and the protection of plastic basis material.
Unless otherwise, all per-cents used herein and ratio are all by weight.
The process that the external phase of the former finger multicomponent system of the term that this paper relates to " phase reversion " such as polymkeric substance/oil/aqueous systems transforms under certain condition mutually, as external phase by water to oil phase or from the transformation of oil phase to water, interfacial tension in external phase limited proportionality system is minimum, thereby the size minimum of disperse phase.Be a kind of method for preparing aqueous polymer dispersion in the present invention, detailed process is to add neutralizing agent to make the hydrophilic radical ionization in polymkeric substance that has hydrophilic radical and organic solution system, under certain shearing condition, in system, add entry subsequently lentamente, increase along with amount of water, whole system is progressively changed to oil-in-water by water-in-oil, forms uniform and stable water-dilutable or water dissolvable system.Perhaps, can directly be distributed in the water, form stable dispersion liquid for the polymers soln that adopts the polymerization single polymerization monomer preparation that has non-ionic hydrophilic group among the present invention.
Description of drawings
Fig. 1 is atomic force microscope (AFM) photo by a kind of hydrophilic-hydrophobic polymer of the inventive method preparation, demonstrates hydrophilic-hydrophobic polymer among the figure and has micro phase separation structure (500nm * 500nm).
Fig. 2 be a kind of water-base resin coating by the inventive method preparation attached to cross section scanning electron microscope (SEM) photo on the PP plastic basis material, demonstrate the sticking power that water-base resin coating and PP plastic basis material have excellence among the figure.
Embodiment
The following example has further described and has proved the preferred embodiment in the scope of the invention.These embodiment that given only are illustrative, and are unintelligible for being limitation of the present invention.
Below among each embodiment each step of preparation plastics use resin all under normal pressure, carry out, unless otherwise.
The plastics use resin property that the present invention makes characterizes as follows:
The phenomenon of phase separation of hydrophilic-hydrophobic polymer is observed by the SPA 300HV-DFM atomic force microscope (AFM) of Japanese Seiko company and is obtained.
The pattern that water-base resin is filmed is observed by the S-360 field emission scanning electron microscope (FE-SEM) of Britain Cambridge company and is obtained.
The sticking power test of paint film on plastic basis material adopts the cross cut test method of the paint and varnish paint film that meets GB GB/T 9286-1998 to carry out.With the quality of 0～5 grade of representative to base material sticking power, 0 grade is best, and 5 grades for the poorest.
Each test is all carried out under envrionment conditions, except as otherwise noted.
Embodiment 1:
Be equipped with in the four-hole boiling flask of thermometer, condenser, agitator, logical nitrogen at 250mL; with 10 gram molecular weights 10; 000 ethylene-acrylic acid copolymer, 20 gram butyl methacrylate, 10 gram vinylbenzene, 20 gram propenyl sulfonic acid add 40 gram sym-trimethylbenzene; under nitrogen protection, stir and be warming up to 90 ℃ of backflows, free radical copolymerization 5 hours.Polyreaction finishes postcooling, adds to mix with the triethylamine of sulfonic group equivalent, adds the deionized water that measures, and making resin solid content is 19wt%, promptly obtains plastics use resin.The sticking power of filming at PVC, ABS base material is 1 grade.
Embodiment 2:
Be equipped with in the four-hole boiling flask of thermometer, condenser, agitator, logical nitrogen at 250mL; with 20 gram molecular weights 100; 000 chlorinated polypropylene, 10 gram alpha-methyl styrenes, 15 gram lauryl methacrylate(LMA)s (LMA); 25 the gram dimethylaminoethyl acrylates join 10 the gram N-BUTYL ACETATEs, 20 the gram dimethylbenzene mixed solvent in the dissolving and mix; under nitrogen protection, stir and be warming up to 70-80 ℃, free radical copolymerization 8 hours.Polyreaction finishes postcooling, and the aqueous acetic acid that adds 12 times of amino equivalent mixes, and adds the deionized water that measures, and making resin solid content is 30wt%, promptly obtains the oyster white water-base resin.The sticking power of filming at the ABS base material is 0 grade, is 1 grade at the sticking power of PP, PE base material.
Embodiment 3:
Be equipped with in the four-hole boiling flask of thermometer, condenser, agitator at 250mL, with 5 gram molecular weights 25,000 organic silicon-acrylate resin, 10 gram Tetra hydro Phthalic anhydrides, 5 grams, 15 carbon dicarboxylic acids, 5 grams 1,6-hexylene glycol, 30 gram dimethylolpropionic acids add in 20 gram dimethyl succinates and the 25 gram Methyl glutarate mixed solvents, 150-180 ℃ of reaction 15 hours, obtain vibrin.Polyreaction finishes postcooling, adds in the N-methylmorpholine of 2 times of carboxyl equivalents and the acid in the resin, adds the deionized water that measures, and high-speed stirring is 30 minutes under the 3000rpm rotating speed, and making resin solid content is 40wt%, promptly obtains plastics use resin.Add the aqueous polyurethane solidifying agent, the sticking power of filming at the Epoxy plastic basis material that obtains is 0 grade, and the sticking power on the POM plastic basis material is 1 grade.
Embodiment 4:
Be equipped with in the four-hole boiling flask of thermometer, condenser, agitator at 250mL, with 25 gram molecular weights 40,000 ethylene-vinyl acetate resin, 30 grams 1,4-butyleneglycol, 5 gram dodecanedioic acids, 20 grams 2, the 4-resorcylic acid adds in 50 gram dimethylbenzene and the 20 gram dipropylene glycol dme mixed solvents, 120-170 ℃ of reaction 7 hours, obtain vibrin.Polyreaction finishes postcooling, adds the N of 0.8 times of carboxyl equivalent, in the N-dimethylethanolamine and the acid in the resin, adds the deionized water that measures, and making resin solid content is 55wt%, promptly obtains plastics use resin.Add titanium dioxide, talcum powder colo(u)rant dispersion then, add the aqueous polyurethane solidifying agent again, the sticking power of filming at the PS plastic basis material that obtains is 0 grade.
Embodiment 5:
Be equipped with in the four-hole boiling flask of thermometer, condenser, agitator at 250mL, with 5 gram molecular weights 50,000 epoxy-acrylate resin, 5 gram molecular weights 10,000 terpine resin, 15 gram molecular weights are that 3000 polyether Glycols, 5 gram isophorone diisocyanates, 10 gram dimethylol propionic acids add in 30 gram dimethylbenzene, the 30 gram tetrahydrofuran (THF) mixed solvents dissolving and mix, be warming up to 80 ℃ of reactions 6 hours, obtain urethane resin.Polyreaction finishes postcooling, adds in the ammoniacal liquor of 0.6 times of carboxyl equivalent and the acid in the resin, adds the deionized water that measures, and making resin solid content is 20wt%, promptly obtains plastics use resin.Add the water-compatible amino resin solidifying agent, the sticking power of filming at the ABS plastic base material that obtains is 0 grade.
Embodiment 6:
Be equipped with in the four-hole boiling flask of thermometer, condenser, agitator at 250mL, the vinyl chloride-vinyl acetate resin of 10 gram molecular weights 19000, polymerizable polyoxyethylene ether, the 20 gram methyl methacrylates, 5 that 15 gram molecular weights are 6000-8000 are restrained dissolving and mixing in the positive ethyl ester adding 20 gram dimethylbenzene of vinylformic acid, the 30 gram trimethylbenzene mixed solvents, be warming up to 70-90 ℃ of reaction 6 hours, obtain benzene-third resin.Polyreaction finishes postcooling, directly adds the deionized water that measures, and making resin solid content is 30wt%, disperses under the 4000rpm rotating speed, promptly obtains plastics use resin.The sticking power of filming at the PMMA plastic basis material that obtains is 1 grade.
Embodiment 7:
Be equipped with in the four-hole boiling flask of thermometer, condenser, agitator at 250mL, with polyurethane-acrylate resin, 10 gram molecular weights of 20 gram molecular weights 8000 is that 2000 polyoxyethylene glycol, 10 gram butyleneglycols, 30 gram phthalic acids add in the 30 gram N-BUTYL ACETATEs dissolving and mix, be warming up to 150-210 ℃ of condensation reaction 15 hours, obtain modified polyester resin.Polyreaction finishes postcooling, directly adds the deionized water that measures, and disperses under the 3800rpm rotating speed, and making resin solid content is 30wt%, promptly obtains plastics use resin.Add aqueous epoxy resins and solidify, the sticking power of filming at the PC plastic basis material that obtains is 0 grade.
Embodiment 8:
Be equipped with in the four-hole boiling flask of thermometer, condenser, agitator at 250mL, with ethylene-vinyl acetate copolymer, 30 gram molecular weights of 10 gram molecular weights 20000 is that 2800～3400 polyoxypropylene glycerol ether, 5 gram propylene glycol, 20 gram MALEIC ANHYDRIDE add in 10 gram toluene, the 25 gram Virahols dissolving and mix, be warming up to 140-160 ℃ of condensation reaction 25 hours, obtain modified polyester resin.Polyreaction finishes postcooling, directly adds the deionized water that measures, and disperses under the 5000rpm rotating speed, and making resin solid content is 40wt%, promptly obtains plastics use resin.Add wetting agent, dispersion agent, titanium dioxide, barium sulfate then and mix, disperse to stir under the 5000rpm rotating speed, add the aqueous polyurethane solidifying agent again and solidify, the sticking power of filming at the PVC plastic basis material that obtains is 1 grade.
Claims (19)
1. plastics use resin, it is characterized in that adopting free radical polymerisation process or polyaddition reaction or polycondensation method, with hydrophilic monomer, comonomer and molecular weight 1000-200,000 hydrophobic polymer in-situ polymerization in organic solvent, synthesize and have the hydrophilic-hydrophobic polymer solution of micro phase separation structure, hydrophilic-the hydrophobic polymer solution that has the hydrophilic monomer preparation of ionizable hydrophilic radical for employing, add the water-based neutralizing agent therein and make the hydrophilic polymer ionization, obtain water-base resin by adding water " phase reversion " method, hydrophilic-hydrophobic polymer solution for the hydrophilic monomer preparation of adopting non-ionic hydrophilic group directly is distributed to it and obtains water-base resin in water;
Wherein, the second-order transition temperature of hydrophilic-hydrophobic polymer is-20-150 ℃, the solid content of hydrophilic-hydrophobic polymer solution is 30-85wt%, the solid content of water-base resin is 10-60wt%.
2. plastics use resin according to claim 1, it is characterized in that described hydrophilic-second-order transition temperature of hydrophobic polymer is for-20-150 ℃, has micro phase separation structure, the size of the microcell that is separated that it is hydrophilic or hydrophobic is less than 10 μ m.
3. plastics use resin according to claim 1 is characterized in that described hydrophilic monomer is selected from ionizable hydrophilic monomer, or has the hydrophilic monomer of non-ionic hydrophilic group.
4. ionizable hydrophilic monomer according to claim 3, it is characterized in that being selected from have ionizable hydrophilic radical-COOH ,-SO
3H ,-PO
4H
2,-NH
2,-NH or-in vinyl monomer, alcohols monomer or the thio-alcohol monomer of SH one or both, the 5-40wt% of hydrophilic-hydrophobic polymer total amount that consumption accounts for.
5. the hydrophilic monomer that has non-ionic hydrophilic group according to claim 3, it is characterized in that being selected from the molecular weight that to participate in polycondensation or radical polymerization and be in vinyl monomer, alcohols monomer or the thio-alcohol monomer that 100-50000 has non-ionic hydrophilic group such as polyoxyethylene segment, polyoxypropylene segment, sorbitan ester segment, sucrose fatty ester segment one or both, the 5-40wt% of hydrophilic-hydrophobic polymer total amount that consumption accounts for.
6. plastics use resin according to claim 1, it is characterized in that described comonomer is selected from two or more in the alkene class comonomer that participates in radical polymerization or the isocyanic ester that participates in addition polymerization and alcohols monomer or participation polyester condensation polymeric acid and the alcohols monomer, the 20-75wt% of hydrophilic-hydrophobic polymer total amount that consumption accounts for.
7. plastics use resin according to claim 1 is characterized in that hydrophobic polymer is made up of hydrophobic backbone and wetting ability functional group, and molecular weight is 1000-200,000.
8. hydrophobic polymer according to claim 7 is characterized in that hydrophobic backbone is selected from one or more in the alkyl isocyanate of the alkylsiloxane class of the arene of the cycloalkane of the olefines of the alkanes of C3-C45, C3-C45, C3-C45, C6-C45, C3-C45, C3-C45.
9. hydrophobic polymer according to claim 7 is characterized in that the wetting ability functional group is selected from one or both in hydroxyl, amino or amido, carboxyl, sulfonic acid group, phosphonyl group, the halogen group.
10. hydrophobic polymer according to claim 7, it is characterized in that being selected from any one or two kinds of acrylate resin, urethane resin, organic silicon-acrylate resin, epoxy-acrylate resin, organosilicon-urethane resin, vibrin, olefin-acrylic ester resin, haloolefin resin or cyclic olefin resins, the 5-40wt% of hydrophilic-hydrophobic polymer amount that consumption accounts for.
11. plastics use resin according to claim 1, it is characterized in that hydrophilic-hydrophobic polymer solution is medium with the organic solvent, solid content is 30-85wt%, organic solvent is selected from hydrophilic organic solvent, hydrophobic organic solvent or its mixture, in the time of 20 ℃, hydrophilic organic solvent and water dissolve each other or the solubleness in water greater than 14wt%, the solubleness of hydrophobic organic solvent in water is less than 6wt%.
12. plastics use resin according to claim 1, it is characterized in that the water-based neutralizing agent that adds be used in equivalent or the non-equivalent and hydrophilic-hydrophobic polymer segment on ionogenic hydrophilic radical, be selected from ammonia, alkylamine, hydramine, morpholine, mercaptan, carboxylic acid, organic sulfonic acid or the organic phospho acid one or more.
13. water-based neutralizing agent according to claim 12 is characterized in that the water-based neutralizing agent: ionizable hydrophilic radical mole dosage is than being 0.4-3 in hydrophilic-hydrophobic polymer, and the solid content of water-base resin is 10-60wt%.
14. plastics use resin according to claim 1, it is characterized in that having the hydrophilic-hydrophobic polymer solution of the hydrophilic monomer preparation of non-ionic hydrophilic group for employing, can be under the situation of aquosity neutralizing agent not, directly be distributed in the water, the solid content of water-base resin is 10-60wt%.
15. the preparation method as plastics use resin as described in the claim 1-14, it comprises following steps:
(1) will have hydrophilic monomer, comonomer, the molecular weight 1000-200 of ionizable hydrophilic radical, 000 hydrophobic polymer mixes in organic solvent, adopt free radical polymerisation process or polyaddition reaction or polycondensation method, the in-situ polymerization preparation has the hydrophilic-hydrophobic polymer solution of micro phase separation structure;
(2) under 0-100 ℃ temperature, in hydrophilic-hydrophobic polymer solution, add the water-based neutralizing agent and mix, stir under the 100-1500rpm rotating speed;
(3) under 0-100 ℃ temperature, add water in the mixture that under the 100-3000rpm rotating speed, in step (2), obtains, " phase reversion " obtains water-base resin.
16. the preparation method as plastics use resin as described in the claim 1-14, it comprises following steps:
(1) will have hydrophilic monomer, comonomer, the molecular weight 1000-200 of non-ionic hydrophilic group, 000 hydrophobic polymer mixes in organic solvent, adopt free radical polymerisation process or polyaddition reaction or polycondensation method, the in-situ polymerization preparation has the hydrophilic-hydrophobic polymer solution of micro phase separation structure;
(2) under 0-100 ℃ temperature, hydrophilic-hydrophobic polymer solution is directly added in the entry, under the 300-5000rpm rotating speed, stirred 2-60 minute, directly it is dispersed in the water, obtain water-base resin.
17. can be applied to the protection and the decoration on plastic basis material surface according to each plastics use resin of claim 1 to 16; as Resins, epoxy (Epoxy); polycarbonate (PC); polyester (PET); polyoxymethylene (POM); polyvinyl chloride (PVC); polyethylene (PE); polypropylene (PP); polyisobutene (PIB); polystyrene (PS); acrylic (PMMA); (acrylonitrile-styrene-butadienecopolymer (ABS) and their mixed and modified plastic basis materials or based on their plastic basis material with the modification of additive method chemical process, and multiple plastic basis material wherein had good sticking power and water tolerance.
18. when being used for plastic basis material, can add after solidifying agent commonly used solidifies in the coating, be applied to the plastic basis material surface again according to each plastics use resin of claim 1 to 16.
19. when being used for plastic basis material, can be mixed with water-borne coatings with auxiliary agents such as dispersion agent, defoamer, film coalescence aid and pigment, filler earlier, be applied to the plastic basis material surface again according to each plastics use resin of claim 1 to 16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101021172A CN102140219A (en) | 2010-01-28 | 2010-01-28 | Water-base resin for plastic and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101021172A CN102140219A (en) | 2010-01-28 | 2010-01-28 | Water-base resin for plastic and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102140219A true CN102140219A (en) | 2011-08-03 |
Family
ID=44408025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101021172A Pending CN102140219A (en) | 2010-01-28 | 2010-01-28 | Water-base resin for plastic and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102140219A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104159903A (en) * | 2011-12-16 | 2014-11-19 | 3M创新有限公司 | Mercapto-containing bisanhydrohexitol derivatives and uses thereof |
| CN107406533A (en) * | 2015-02-26 | 2017-11-28 | 旭硝子株式会社 | The manufacture method of waterborne liquid containing polyvinyl and the manufacture method of waterproofing/oilproofing agent |
| EP3755753B1 (en) * | 2018-02-21 | 2022-07-27 | Basf Se | Method for producing articles coated with adhesive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611522A (en) * | 2003-10-29 | 2005-05-04 | 深圳彩虹环保建材科技有限公司 | Method for preparing water-based polyurethane |
| CN101374876A (en) * | 2006-02-02 | 2009-02-25 | 斯塔尔国际有限公司 | Process for the preparation of dispersions of cross-linking agents in water |
| CN101636418A (en) * | 2006-11-17 | 2010-01-27 | 阿克佐诺贝尔股份有限公司 | Method for producing dispersions and use thereof |
-
2010
- 2010-01-28 CN CN2010101021172A patent/CN102140219A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611522A (en) * | 2003-10-29 | 2005-05-04 | 深圳彩虹环保建材科技有限公司 | Method for preparing water-based polyurethane |
| CN101374876A (en) * | 2006-02-02 | 2009-02-25 | 斯塔尔国际有限公司 | Process for the preparation of dispersions of cross-linking agents in water |
| CN101636418A (en) * | 2006-11-17 | 2010-01-27 | 阿克佐诺贝尔股份有限公司 | Method for producing dispersions and use thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104159903A (en) * | 2011-12-16 | 2014-11-19 | 3M创新有限公司 | Mercapto-containing bisanhydrohexitol derivatives and uses thereof |
| CN104159903B (en) * | 2011-12-16 | 2016-06-29 | 3M创新有限公司 | Double; two anhydrohexitol derivants comprising sulfydryl and application thereof |
| US9388274B2 (en) | 2011-12-16 | 2016-07-12 | 3M Innovative Properties Company | Mercapto-containing bisanhydrohexitol derivatives and uses thereof |
| CN107406533A (en) * | 2015-02-26 | 2017-11-28 | 旭硝子株式会社 | The manufacture method of waterborne liquid containing polyvinyl and the manufacture method of waterproofing/oilproofing agent |
| CN107406533B (en) * | 2015-02-26 | 2020-02-18 | Ａｇｃ株式会社 | Method for producing aqueous liquid containing vinyl polymer and method for producing water and oil proofing agent |
| EP3755753B1 (en) * | 2018-02-21 | 2022-07-27 | Basf Se | Method for producing articles coated with adhesive |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Athawale et al. | Preparation and properties of urethane/acrylate composite by emulsion polymerization technique | |
| Overbeek | Polymer heterogeneity in waterborne coatings | |
| CN101421366B (en) | Aqueous primer composition | |
| CN101796149B (en) | Coating agent and method for production thereof | |
| CN102770499B (en) | Water-based coating composition and process for formation of coating film | |
| CN1131252C (en) | Acrylic modified waterborne alkyd or uralkyd dispersions | |
| JP5103390B2 (en) | Multi-component water-based paint and coating method thereof | |
| CN102020759B (en) | Preparation method of waterborne resin and water-based paint composition | |
| KR20130113965A (en) | Stable aqueous wax dispersions | |
| AU2011384369B2 (en) | Process for preparing polyurethane/acrylic hybrid dispersions | |
| WO2001002490A1 (en) | Aqueous polyester dispersion and process for producing the same | |
| CN102844390A (en) | Manganese complex drier for coating compositions | |
| JP2783679B2 (en) | Paint composition | |
| TW201843202A (en) | Polycarbodiimide compound, production method therefor, and resin composition | |
| CN101550308A (en) | Aqueous coating composition | |
| CN101333408A (en) | Aqueous primer composition and coating method using the composition | |
| DE4410557A1 (en) | Aqueous multi-component polyurethane coating agent, process for its preparation and its use in processes for producing a multi-layer coating | |
| EP3478780A1 (en) | Aqueous polymer emulsion | |
| CN102821874B (en) | Method for forming coating film | |
| CN102165027A (en) | Aqueous coating composition | |
| PL236351B1 (en) | Aqueous binder compositions | |
| CN102140219A (en) | Water-base resin for plastic and preparation method and application thereof | |
| CN1306056A (en) | Water paint compsns. | |
| CN107109116A (en) | There are the water-based paint compositions of flexible touch after drying | |
| CN102618158B (en) | Aqueous essential oil for coating soft PVC (Poly Vinyl Chloride) and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110803 |