CN101519480A - Method for preparing self-cross linking type water-based acrylic resin and polyurethane hybrid - Google Patents
Method for preparing self-cross linking type water-based acrylic resin and polyurethane hybrid Download PDFInfo
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Abstract
The invention relates to a method for preparing self-cross linking type water-based acrylic resin and polyurethane hybrid, comprising the following process: (1) unsaturated hydroxyl-terminated polyester is synthesized after the polycondensation of trimethylolpropane monoallyl ether, polyhydric alcohol and polybasic acid; (2) the unsaturated hydroxyl-terminated polyester is used as the soft segment of polyurethane, dihydric alcohol, hydrophilic monomer and isocyanate are added to the polyurethane to react with the polyurethane to prepare unsaturated double-linked water-based polyurethane; and (3) the water-based acrylic resin and polyurethane hybrid in nucleocapsid structure is polymerized from the unsaturated double-linked water-based polyurethane used as surface active agent and the acrylic resin used as monomer by emulsifier-free emulsion. The unsaturated double-linked water-based polyurethane and fluorine-contained acrylic resin are grafted innovatively, and the synthesized environmentally-friendly resin has the excellent performance of both the acrylic resin and polyurethane resin and can be widely used as the base material of water-based woodenware coating, building coating and metal coating.
Description
Technical field:
The present invention relates to a kind of preparation method who is used for the self-cross linking type water-borne acrylic resin-polyurethane hybrid body of base materials such as cement, timber, metal.By on aqueous polyurethane, introducing unsaturated double-bond, make itself and acrylic ester monomer copolymerization, synthesized a kind of novel aqueous coating resin with extensive use, high performance-price ratio with nucleocapsid structure.
Background technology:
Though external water-borne coatings is through 20 years of development, coating property also has much room for improvement.China's water-borne coatings research and development are started late, and are that coating variety or coating property all have big gap.At present, acrylic emulsions, aqueous polyurethane and water soluble acrylic acid-polyurethane hybrid body is the main product of water-base resin.ACRYLIC EMULSION is mainly used in the base-material of building coating, and aqueous polyurethane and water soluble acrylic acid-urethane resin can be used for buildings, woodenware and metal matrix water-borne coatings.Especially with water soluble acrylic acid-urethane resin because the cost performance height, have boundless application prospect.
Water soluble acrylic acid-urethane resin can prepare by blending method, but poor-performing; Water soluble acrylic acid-polyurethane hybrid body by copolymerization method preparation gets up the structure keyed jointing of acrylic resin and urethane resin, and the premium properties that can give full play to the two is latest generation water soluble acrylic acid-urethane resin.At present, the preparation of water soluble acrylic acid-polyurethane hybrid body generally adopts aqueous polyurethane to carry out the letex polymerization or the first emulsion copolymerization that synthesizes the big monomer of aqueous polyurethane of acrylate-based client and then carry out acrylic monomer of Acrylic Acid Monomer as emulsifying agent.The former is poor because of the aqueous polyurethane surfactivity, and the Acrylic Acid Monomer consumption can not be too big, and percentage of grafting is also lower simultaneously, and performance is better than co-mixing system slightly; Latter's surfactivity height, but big monomer molecule amount causes its polymerization activity lower more greatly, is not that all big monomers have all participated in copolymerization, and performance also has much room for improvement.
Summary of the invention:
The present invention is directed to the shortcoming of the above water-base resin, molecular level hydridization by water-borne acrylic resin and aqueous polyurethane is carried out modification to water-base resin, avoided the expensive shortcoming of water-base resin, simultaneously with acrylic resin with the urethane excellent physical chemistry is compound comes in.Make it have remarkable characteristics such as low-temperature impact resistance, chemical stability, elasticity, snappiness and wear resistance.This water-based heterozygosis resin can be used for building coating, and can be used for woodenware and metallic paint.
The present invention is based on aqueous polyurethane, utilize the characteristic of aqueous polyurethane anion surfactant, when carrying out the acrylic monomer polymerization, need not add emulsifying agent, adopt the method for soap-free polymerization to make acrylic monomer carry out copolymerization well in urethane inside.The present invention has promptly avoided the use emulsifying agent, and the reaction conditions gentleness, owing to there is not the existence of emulsifying agent in the product, resin property also improves a lot.What is more important is introduced polyurethane backbone with autonomous synthetic unsaturated polyester, improves the percentage of grafting of acrylic resin greatly, and resin property is significantly improved.
The present invention may further comprise the steps:
(1) synthetic undersaturated hydroxyl telechelic polyester (A):
Synthetic undersaturated hydroxyl telechelic polyester (A) comprises following component and mass ratio: dibasic alcohol (C) 25～40; Diprotic acid (H) 40～50; TriMethylolPropane(TMP) mono allyl ether 5～15; Dimethylbenzene 2～8; Stopper 0.1～0.4; Preparation technology is: under protection of nitrogen gas, according to component design with dibasic alcohol (C), diprotic acid (H), the TriMethylolPropane(TMP) mono allyl ether, thermometer is equipped with in solvent xylene and stopper adding, water trap, prolong and having in the four-hole reactor of stirring, be heated to and begin to have backflow in the prolong, and when beginning the globule is arranged in the water trap (about 140 ℃), slowly be warming up to 190 ± 5 ℃ again, heating-up time is 4 hours, 190 ± 5 ℃ of insulation reaction, 0.5 after～1 hour, begin to measure acid number, when acid number is reduced to the 5mgKOH/g resin, be cooled to 100 ℃ of left and right sides vacuum removal dimethylbenzene, vacuum tightness 〉=0.045kPa is cooled to 50～80 ℃ of dischargings, promptly gets unsaturated hydroxyl telechelic polyester (A);
(2) synthetic undersaturated aqueous polyurethane (B):
Synthetic undersaturated aqueous polyurethane (B) comprises following component and mass ratio: unsaturated hydroxyl telechelic polyester (A) 38～56; Dibasic alcohol (C) 5～15; Hydrophilic monomer (D) 4～9; Vulcabond (E) 35～52; Catalyzer 0.05～0.15; Neutralizing agent 3～8; Deionized water 200～250; Chainextender 2～10; Preparation technology is: the undersaturated hydroxyl telechelic polyester (A), the dibasic alcohol (C) that add formula ratio in the four-hole reactor that nitrogen protection is arranged that has whipping appts, hydrophilic monomer (D), under 110 ℃, material is melted, vacuum hydro-extraction 1 hour, vacuum tightness 〉=0.060kPa; Be cooled to 60～80 ℃ then, drip vulcabond (E), dripped off in 1 hour; Be warmed up to 80 ℃, add catalyzer in reactor, continue insulation reaction, NCO content is near theoretical value in reaction system; Be cooled to 60 ℃,, add neutralizing agent, stirred 0.5 hour with acetone regulation system viscosity; Be cooled to 30～40 ℃, drip deionized water, chainextender under the state that stirs fast, the powerful dispersion 0.5～1 hour, acetone is deviate from 60 ℃ of decompressions, promptly gets translucent undersaturated aqueous polyurethane (B);
(3) synthetic self-cross linking type water-borne acrylic resin-polyurethane hybrid body:
Synthetic self-cross linking type water-borne acrylic resin-polyurethane hybrid body comprises following component and mass ratio: undersaturated aqueous polyurethane (B) 9～15 (in solid); Deionized water 8～25; Acrylic ester monomer (F) 10～30; Cross-linking monomer (G) 0.12～1.5; Initiator (I) 0.1～0.5, preparation technology is: get the undersaturated aqueous polyurethane (B) of formula ratio and deionized water and be incorporated in and have whipping appts, thermometer, in the four-hole reactor of prolong and constant pressure funnel, acrylic ester monomer (F) and cross-linking monomer (G) are mixed with initiator (I), get its 5%～30% adding reactor, temperature is controlled at 40～60 ℃, stir 0.5h swelling micelle, drip residual monomer and initiator mixing solutions from dropping funnel, 2～4h dropwises, continue reaction 1h at 70～85 ℃, can add a small amount of initiator and improve monomer conversion; Be cooled to 40 ℃ at last, add neutralizing agent and adjust pH value to 8.0～8.5,400 order net filtrations, promptly obtain self-cross linking type water-borne acrylic resin-polyurethane hybrid body.
The present invention, prepare the used dibasic alcohol (C) of undersaturated hydroxyl telechelic polyester (A) and be ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1,6-hexylene glycol, 1,3-butyleneglycol, neopentyl glycol, ethohexadiol, 1,4-cyclohexanedimethanol, 2-ethyl-2-butyl 1, one or more mixing in the ammediol.Wherein, 2-ethyl-2-butyl 1, ammediol, space steric effect of ethyl, butyl can shield ester group on it, improves hydrolytic resistance, and neopentyl glycol is also often used owing to same characteristic; Preparing the used diprotic acid (H) of undersaturated hydroxyl telechelic polyester (A) is: maleic anhydride, FUMARIC ACID TECH GRADE, phthalic anhydride, m-phthalic acid, terephthalic acid, tetrahydrophthalic anhydride, Succinic Acid, pentanedioic acid, oxalic acid, fumaric acid, dimeracid, HHPA, 1, it is to be used for reducing cost that one or more mixing of 4-cyclohexane cyclohexanedimethanodibasic and hexanodioic acid, phthalic anhydride mainly act on; Prepare the used TriMethylolPropane(TMP) mono allyl ether of undersaturated hydroxyl telechelic polyester (A) and be used for introducing unsaturated double-bond, diprotic acid such as m-phthalic acid mainly are to be used for improving hydrolytic resistance.
The present invention, described undersaturated aqueous polyurethane (B) is to utilize unsaturated hydroxyl telechelic polyester (A), dibasic alcohol (C), hydrophilic monomer (D), vulcabond (E), neutralizing agent, chainextender, deionized water etc. synthetic.Dibasic alcohol recited above (C) comprises following dibasic alcohol: 1, and 4-butyleneglycol, ethylene glycol, 2-ethyl-2-butyl 1, ammediol, 1,6-hexylene glycol, glycol ether, ethohexadiol, neopentyl glycol, 1,4 cyclohexane dimethanol, 1,3 propylene glycol.Wherein, 2-ethyl-2-butyl 1, therefore ammediol, ethohexadiol etc. have good water tolerance owing to have long carbochain.Above-mentioned dibasic alcohol can use separately also can mix use.Hydrophilic monomer (D) comprising: dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), dihydroxymethyl acetate, 2-sodium sulfonate-1,4-butyleneglycol, 2,4-diamino benzene sulfonic acids etc. are preferentially selected DMBA or DMPA for use, can use separately also and can mix use.Vulcabond (E) monomer comprises: tolylene diisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, Methylcyclohexyl diisocyanate, ditan-4, the 4-vulcabond, preferentially select tolylene diisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate or its mixture can use separately also and can mix use.
The present invention, described acrylic ester monomer (F) is (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, lauryl methacrylate(LMA), acrylamide, vinylbenzene, tertiary ethylene carbonate, can use separately also and can mix use.Described cross-linking monomer (G) is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, the rare acyloxy propyl trimethoxy silicane of γ-methyl-prop, the rare acyloxy propyl group three of γ-methyl-prop (β-trimethoxy Ethoxysilane), (methyl) glycidyl acrylate, N hydroxymethyl acrylamide, diacetone-acryloamide(DAA) vinyltrimethoxy silane, vinyl silane triisopropoxide, adipic dihydrazide can use separately also and can mix use.Described initiator (I) is: one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, Potassium Persulphate, ammonium persulphate, tertbutyl peroxide, isopropyl benzene hydroperoxide, the rongalite.
The present invention, described catalyzer comprises organometallic compound and trimethylamine class, organometallic compound comprises: stannous octoate, dibutyl tin laurate, lead octoate 36, iron octoate etc.; Trimethylamine comprises: triethylamine, N, N-dimethylcyclohexylamine, triethylenediamine, N, N-dimethyl benzylamine, N, one or more of N-dimethyl butylamine etc.Preferably use organometallic compound class catalyzer among the present invention, as dibutyl tin laurate.
The present invention, described chainextender comprises diamine or the polyamine that contains amido, as quadrol, isophorone diamine, diethylenetriamine, triethylene tetramine etc. one or more, preferentially selects diamine for use, as quadrol.
The present invention, because in the process of preparation water-base resin, innovation having introduced the grafted propylene acid resin carries out modification to aqueous polyurethane, in the cost that has reduced water-base resin, over-all properties behind this resin solidification is significantly improved, in environmental friendliness society, have extraordinary market-oriented prospect.Because the synthesis material that we adopted all is some basic common raw materials, particularly we have independently synthesized unsaturated hydroxyl telechelic polyester, wherein, the TriMethylolPropane(TMP) mono allyl ether is used for introducing unsaturated double-bond, rather than depend on external, both grasp the technology of producing, reduced cost again.
Embodiment:
Embodiment 1:
(1) under nitrogen protection; with 1.500gMA (maleic anhydride); (31.89gAD hexanodioic acid); (19.41gNPG neopentyl glycol); 5.079g TriMethylolPropane(TMP) mono allyl ether; 12.50gBEPD (2-ethyl-2-butyl 1; ammediol); 5.5g dimethylbenzene; have in the reactor of stirring, thermometer, nitrogen airway, prolong and water trap 0.259g methylol methyl-phenoxide (stopper) added,, to stir with electric mantle heat temperature raising to 140 ℃; slowly be warming up to 190 ℃, the heating-up time is 4 hours.190 ℃ of insulation reaction, 0.5 after hour, begin to measure acid number, when acid number is reduced to the 5mgKOH/g resin, deviate from dimethylbenzene in 100 ℃ of left and right sides vacuum, after reaction is finished, dry 1-2 hour of vacuum decompression, vacuum tightness 〉=0.045KPa is cooled to 50～80 ℃ of dischargings, promptly gets unsaturated hydroxyl telechelic polyester (A).
(2) with the above-mentioned unsaturated hydroxyl telechelic polyester of 25.85g (A), 4.088g1,4-butyleneglycol, 3.650g dimethylol propionic acid adds and has in the reactor of agitator, thermometer, nitrogen airway, prolong, under 110 ℃ of conditions, first vacuum hydro-extraction 1 hour, vacuum tightness 〉=0.060KPa; Be cooled to 60 ℃ then, add N-Methyl pyrrolidone 15g.Feed nitrogen protection, begin to drip the 26.5g isophorone diisocyanate, dropwised in 1 hour, be incubated 1 hour; Be warmed up to 80 ℃ then, add the catalyzer (dibutyl tin laurate) of 0.0700g.Continue insulation reaction after 2 hours, begin to measure NCO content, when NCO content≤theoretical value 4.07% (according to experimental design, the NCO content in the raw material during hydroxyl complete reaction accounts for the percentage ratio of resin total amount); Be cooled to 60 ℃, add the neutralizing agent (triethylamine) of 2.710g; Stir after 0.5 hour, with acetone regulation system viscosity; Be cooled to 40 ℃, drip the 140.7g deionized water under the state that stirs fast, add 3.754g chainextender (quadrol) the powerful dispersion after 2-5 minute, continue to disperse 0.5 hour, acetone is deviate from 60 ℃ of decompressions, promptly gets translucent undersaturated aqueous polyurethane (B).
(3) get the adding of above-mentioned undersaturated aqueous polyurethane (B) 50.00g and 34.50g deionized water and have whipping appts, thermometer, in the four-hole reactor of prolong and constant pressure funnel, get hydroxyethyl methylacrylate 1.350g, vinyltrimethoxy silane 0.720g, butyl acrylate 4.850g, methyl methacrylate 15.60g, diacetone-acryloamide(DAA) 0.720g mixes with the 0.270g Diisopropyl azodicarboxylate, get its 4.568g and add reactor, temperature is controlled at 40～60 ℃, stir 0.5 hour swelling micelle, drip residual monomer and initiator solution from dropping funnel, temperature is controlled at 70～80 ℃, dropwised in 2～4 hours, and looked in the prolong monomers flow back speed and control rate of addition; Continue reaction 1 hour at 85 ℃, be cooled to 60～70 ℃, add 0.118g tertbutyl peroxide (dilution of 1.00g water) and 0.095g rongalite (1.00g water dissolution), continue reaction 0.5 hour; Be cooled to 40 ℃ at last, add neutralizing agent (triethylamine) and adjust pH value to 8.0～8.5, add 0.360g adipic dihydrazide (dilution of 1.00g water), stirred 20 minutes; 400 order net filtrations promptly obtain self-cross linking type water-borne acrylic resin-polyurethane hybrid body.
(4) technical target of the product:
The translucent oyster white water dispersion of outward appearance;
Solid content 35%;
PH value 8.0～8.5;
Gloss (60 °) 85;
Pendulum-rocker hardness 0.65;
(48h) is no abnormal for water tolerance;
Alcohol resistance (50%, V/V, 1h) no abnormal;
1 grade of sticking power (drawing lattice).
Embodiment 2:
(1) under nitrogen protection; with 3.985gHPPA (HHPA); (29.95gAD hexanodioic acid), 23.730gBDO (1, the 4-butyleneglycol); (6.063gTMPME TriMethylolPropane(TMP) mono allyl ether); 5.0g dimethylbenzene and 0.255g add methylol methyl-phenoxide (stopper) and have. the four-hole of stirring, thermometer, nitrogen airway, prolong and water trap is answered in the device, with electric mantle heat temperature raising to 140 ℃, stirs; slowly be warming up to 190 ℃ again, the heating-up time is 4 hours.190 ℃ of insulation reaction, 0.5 after hour, begin to measure acid number, when acid number is reduced to the 5mgKOH/g resin, deviate from dimethylbenzene in 100 ℃ of left and right sides vacuum, after reaction is finished, vacuum decompression drying 1～2 hour, vacuum tightness 〉=0.045Kpa is cooled to 50～80 ℃ of dischargings, promptly gets unsaturated hydroxyl telechelic polyester (A).
(2) with the above-mentioned unsaturated hydroxyl telechelic polyester of 25.741g (A), 7.029g ethohexadiol, 3.491g dimethylolpropionic acid add and have agitator, thermometer, the nitrogen airway is in the four-hole reactor of prolong, under 110 ℃ of conditions, first vacuum was drawn water 1 hour, vacuum tightness 〉=0.060Kpa; Be cooled to 60 ℃ then, add solvent acetone 10ml.Feed nitrogen protection, begin to drip the 21.56g tolylene diisocyanate, dropwised in 1 hour, be incubated 1 hour; Be warmed up to 80 ℃ then, add the catalyzer (dibutyl tin laurate) of 0.0600g.Continue insulation reaction after 2 hours, begin to measure NCO content, when NCO content≤theoretical value 3.2% (according to experimental design, the NCO content in the raw material during hydroxyl complete reaction accounts for the percentage ratio of resin total amount); Be cooled to 60 ℃, add the neutralizing agent (triethylamine) of 2.420g; Stir after 0.5 hour, with acetone regulation system viscosity; Be cooled to 30 ℃, drip the 139.307g deionized water under the state that stirs fast, add 1.301g chainextender (quadrol) the powerful dispersion after 2-5 minute, continue to disperse 0.5 hour, acetone is deviate from 60 ℃ of decompressions, promptly gets translucent undersaturated aqueous polyurethane (B).
(3) getting the adding of above-mentioned a certain amount of undersaturated aqueous polyurethane (B) 60.00g and 19.00g deionized water has in the reactor of whipping appts, thermometer, prolong and constant pressure funnel; get butyl acrylate 5.040g; methyl methacrylate 28.10g; glycidyl methacrylate 0.72g; lauryl methacrylate(LMA) 1.44g; vinyl silane triisopropoxide 1.44g mixes with the 0.504g 2,2'-Azobis(2,4-dimethylvaleronitrile); get its 9.000g and add reactor; temperature is controlled at 40-60 ℃, stirs 0.5 hour swelling micelle; Drip residual monomer and initiator solution from dropping funnel, temperature is controlled at 70-80 ℃, dropwises in 2-4 hour, looks in the prolong monomers flow back speed and controls rate of addition; Continue reaction 1 hour at 85 ℃, be cooled to 60-70 ℃, add 0.187g tertbutyl peroxide and 0.240g rongalite, continue reaction 0.5 hour; Be cooled to 40 ℃ at last, add neutralizing agent (dimethylethanolamine) and adjust batch pH value to 8.0-8.5; 400 order net filtrations promptly obtain self-cross linking type water-borne acrylic resin one polyurethane hybrid body.
(4) technical target of the product:
The translucent oyster white water dispersion of outward appearance;
Solid content 35%;
PH value 8.0-8.5;
Gloss (60 °) 85;
Pendulum-rocker hardness 0.62;
(48h) is no abnormal for water tolerance;
Alcohol resistance (50%, V/V, 1h) no abnormal;
1 grade of sticking power (drawing lattice).
Claims (4)
1, the preparation method of self-cross linking type water-borne acrylic resin-polyurethane hybrid body is characterized in that comprising following step:
(1) synthetic undersaturated hydroxyl telechelic polyester (A):
Synthetic undersaturated hydroxyl telechelic polyester (A) comprises following component and mass ratio: dibasic alcohol (C) 25～40; Diprotic acid (H) 40～50; TriMethylolPropane(TMP) mono allyl ether 5～15; Dimethylbenzene 2～8; Stopper 0.1～0.4; Preparation technology is: under protection of nitrogen gas, according to component design with dibasic alcohol (C), diprotic acid (H), the TriMethylolPropane(TMP) mono allyl ether, thermometer is equipped with in solvent xylene and stopper adding, water trap, prolong and having in the four-hole reactor of stirring, be heated to 140 ℃, slowly be warming up to 190 ± 5 ℃ again, heating-up time is 4 hours, 190 ± 5 ℃ of insulation reaction, 0.5 after～1 hour, begin to measure acid number, when acid number is reduced to the 5mgKOH/g resin, be cooled to 100 ℃ of vacuum removal dimethylbenzene, vacuum tightness 〉=0.045kPa, be cooled to 50～80 ℃ of dischargings, promptly get unsaturated hydroxyl telechelic polyester (A);
(2) synthetic undersaturated aqueous polyurethane (B):
Synthetic undersaturated aqueous polyurethane (B) comprises following component and mass ratio: unsaturated hydroxyl telechelic polyester (A) 38～56; Dibasic alcohol (C) 5～15; Hydrophilic monomer (D) 4～9; Vulcabond (E) 35～52; Catalyzer 0.05～0.15; Neutralizing agent 3～8; Deionized water 200～250; Chainextender 2～10; Preparation technology is: the undersaturated hydroxyl telechelic polyester (A), the dibasic alcohol (C) that add formula ratio in the four-hole reactor that nitrogen protection is arranged that has whipping appts, hydrophilic monomer (D), under 110 ℃, material is melted, vacuum hydro-extraction 1 hour, vacuum tightness 〉=0.060kPa; Be cooled to 60-80 ℃ then, drip vulcabond (E), dripped off in 1 hour; Be warmed up to 80 ℃, add catalyzer in reactor, continue insulation reaction, NCO content is near theoretical value in reaction system; Be cooled to 60 ℃,, add neutralizing agent, stirred 0.5 hour with acetone regulation system viscosity; Be cooled to 30～40 ℃, drip deionized water, chainextender under the state that stirs fast, the powerful dispersion 0.5～1 hour, acetone is deviate from 60 ℃ of decompressions, promptly gets translucent undersaturated aqueous polyurethane (B);
(3) synthetic self-cross linking type water-borne acrylic resin-polyurethane hybrid body:
Synthetic self-cross linking type water-borne acrylic resin-polyurethane hybrid body comprises following component and mass ratio: undersaturated aqueous polyurethane (B) 10～15, in solid; Deionized water 8～25; Acrylic ester monomer (F) 10～30; Cross-linking monomer (G) 0.12～1.0; Initiator (I) 0.025～0.180, preparation technology is: get the undersaturated aqueous polyurethane (B) of formula ratio and deionized water and be incorporated in and have whipping appts, thermometer, in the four-hole reactor of prolong and constant pressure funnel, acrylic ester monomer (F) and cross-linking monomer (G) are mixed with initiator (I), get its 5%～30% adding reactor, temperature is controlled at 40～60 ℃, stir 0.5h swelling micelle, drip residual monomer and initiator mixing solutions from dropping funnel, 2～4h dropwises, continue reaction 1h at 70～85 ℃, be cooled to 40 ℃ at last, add neutralizing agent and adjust pH value to 8.0～8.5,400 order net filtrations promptly obtain self-cross linking type water-borne acrylic resin-polyurethane hybrid body.
2, according to the preparation method of claims 1 described crosslinking type aqueous acrylic resin-polyurethane hybrid body, it is characterized in that: prepare the used dibasic alcohol (C) of undersaturated hydroxyl telechelic polyester (A) and be one or more mixtures of following dibasic alcohol: ethylene glycol, Diethylene Glycol, 1,2-propylene glycol, 1,6-hexylene glycol, 1,3-butyleneglycol, neopentyl glycol, ethohexadiol, 2-ethyl-2-butyl 1, ammediol; Diprotic acid (H) is one or more mixtures of following diprotic acid: maleic anhydride, FUMARIC ACID TECH GRADE, phthalic anhydride, m-phthalic acid, terephthalic acid, tetrahydrophthalic anhydride, Succinic Acid, pentanedioic acid, oxalic acid, fumaric acid, dimeracid, HHPA and hexanodioic acid.
3, according to the preparation method of claims 1 described self-cross linking type water-borne acrylic resin-polyurethane hybrid body, it is characterized in that: prepare the used dibasic alcohol (C) of undersaturated aqueous polyurethane (B) and be one or more mixtures of following dibasic alcohol: 1,4-butyleneglycol, ethylene glycol, 1,6-hexylene glycol, glycol ether, 2-ethyl-2-butyl 1, ammediol, ethohexadiol, neopentyl glycol, 1,3 propylene glycol; Hydrophilic monomer (D) is following monomeric one or more mixtures: dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl acetate, 2-sodium sulfonate-1,4-butyleneglycol, 2,4-diamino benzene sulfonic acid; Vulcabond (E) is a tolylene diisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, Methylcyclohexyl diisocyanate, ditan-4, the mixture of one or more in the 4-vulcabond.
4, according to the preparation method of claims 1 described self-cross linking type water-borne acrylic resin-polyurethane hybrid body, it is characterized in that: described acrylic ester monomer (F) is: the mixture of one or more in (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, lauryl methacrylate(LMA), acrylamide, vinylbenzene, the tertiary ethylene carbonate; Described cross-linking monomer (G) is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, the rare acyloxy propyl trimethoxy silicane of γ-methyl-prop, the mixture of one or more in the rare acyloxy propyl group three of γ-methyl-prop (β-trimethoxy Ethoxysilane), (methyl) glycidyl acrylate, N hydroxymethyl acrylamide, diacetone-acryloamide(DAA) vinyltrimethoxy silane, vinyl silane triisopropoxide, the adipic dihydrazide; Described initiator (I) is: the mixture of one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, Potassium Persulphate, ammonium persulphate, tertbutyl peroxide, isopropyl benzene hydroperoxide, the rongalite.
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| CN101838377A (en) * | 2010-05-11 | 2010-09-22 | 张春华 | Radiation curable multifunctional (methyl) acrylate composition |
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Address after: 515500, south side of Huaan Road, Jiedong experimental area, Guangdong, Jieyang (No. 16) Patentee after: Guangdong Tianyin Industrial Co., Ltd. Patentee after: Wuhan Institute of Technology Address before: 515500 south section of Huaan Road, Jiedong Economic Development Zone, Jiedong County, Guangdong Patentee before: Tianyin Chemical Industry Co., Ltd., Guangdong Patentee before: Wuhan Institute of Technology |