CN101519479B - Method for preparing self-cross linking type water-based fluorine-contained acrylic resin and polyurethane hybrid - Google Patents
Method for preparing self-cross linking type water-based fluorine-contained 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 fluorine-contained acrylic resin and polyurethane hybrid, comprising the following process: (1) unsaturated hydroxylThe invention relates to a method for preparing self-cross linking type water-based fluorine-contained acrylic resin and polyurethane hybrid, comprising the following process: (1) unsaturated hydroxyl-terminated polyester is synthesized after the polycondensation of the double-linked polyhydric alcohol and polybasic acid; (2) the unsaturated hydroxyl-terminated polyester is used as the soft segmen-terminated polyester is synthesized after the polycondensation of the double-linked 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, production of the reaction is neutralized, and water is added to tt of polyurethane, dihydric alcohol, hydrophilic monomer and isocyanate are added to the polyurethane to react with the polyurethane, production of the reaction is neutralized, and water is added to the resultant of reaction for chain extension so as to prepare unsaturated double-linked water-based polyurethane; and (3) the water-based fluorine-contained acrylic resin and polyurethane hybrid in nuhe resultant of reaction for chain extension so as to prepare unsaturated double-linked water-based polyurethane; and (3) the water-based fluorine-contained 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 fluorine-contained acrylic resin and acrylic resin by emulsifier-frcleocapsid structure is polymerized from the unsaturated double-linked water-based polyurethane used as surface active agent and the fluorine-contained acrylic resin and acrylic resin 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 ee 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 fluorocarbon resin and polyurethane resin and can be widely applied to building coating, woodenware coating and metal coating. performance of both fluorocarbon resin and polyurethane resin and can be widely applied to building coating, woodenware 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-based perfluoroalkyl acrylate resin-polyurethane hybrid body of base materials such as cement, timber, metal.This invention is by introducing unsaturated double-bond on urethane, make itself and fluorinated monomer class monomer copolymerization, synthesized a kind of novel aqueous fluoro-resin with nucleocapsid structure, of many uses, high performance-price ratio.
Background technology:
Though external watersoluble fluorine paint is through 20 years of development, kind is still more single so far, and coating property also has much room for improvement.Though China has obtained certain progress, and abroad compare, be that coating variety or coating property all have big gap.Fluorocarbon resin makes fluorocarbon polymer have low surface energy because middle F-C key key polarity is little, compares with other resins, has excellent water resistance, oil repellent, anti-stain characteristic and weathering resistance.Traditional solvent-borne type or water-based fluororesin all use tetrafluoroethylene, trifluorochloroethylene, vinylidene fluoride, perfluoro propylene as fluorine monomer, need high pressure in the building-up process, technological process more complicated, equipment requirements height, cause resin price very high, simultaneously in construction process, there are a large amount of organic solvents to evaporate in the air, cause pollution environment.
At present, also useful perfluoroalkyl acrylate class monomer is by the report of the synthetic water-based fluororesin of emulsion copolymerization, but synthetic resin cost is higher, and needs to add fluorine-containing emulsifier, not only influence the performance of resin, and the emulsifying agent that has has carcinogenesis to human body.Also have report with the long chain fluorine-containing dibasic alcohol as raw material, synthesized aqueous fluorine-containing urethane, avoided the use fluorine-containing emulsifier, but this fluoro-resin costs an arm and a leg, do not have actual should value.
Summary of the invention:
The present invention is directed to the shortcoming of the above water-based fluororesin, water-based fluororesin is carried out modification, avoided the expensive shortcoming of water-based fluororesin, come in the chemical property of urethane excellence is compound simultaneously by aqueous polyurethane.Aqueous polyurethane and water-based fluororesin heterozygosis not only make fluoro-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 perfluoroalkyl acrylate class monomer polymerization, need not add emulsifying agent, adopt the method for soap-free polymerization to make the perfluoroalkyl acrylate esters monomer carry out copolymerization well in urethane inside.The present invention had both avoided using deleterious fluorine-containing emulsifier, and the reaction conditions gentleness, owing to there is not the existence of small molecules type emulsifying agent in the product, resin property also improves a lot.
The present invention comprises 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 (F) 40～49; 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 (F), 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 ℃ with electric mantle, slowly be warming up to 190 ± 5 ℃ again, heating-up time is 4 hours, after the insulation reaction 0.5～1 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 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 4～10; 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 was drawn water 1 hour, vacuum tightness 〉=0.060kPa; Be cooled to 60～80 ℃ then, feed nitrogen protection, begin to drip vulcabond (E), dropwised in 1 hour, be warmed up to 80 ℃ then, add catalyzer, continue insulation reaction after 2 hours, make NCO content reach theoretical value; Be cooled to 60 ℃, add neutralizing agent; Stir after 0.5 hour, with acetone regulation system viscosity; Be cooled to 30～40 ℃, drip deionized water under the state that stirs fast, add chainextender after 10～20 minutes powerful the dispersion, continues to disperse 0.5～1 hour, and acetone is deviate from 60 ℃ of decompressions, promptly gets translucent unsaturated aqueous polyurethane dispersion (B);
(3) synthetic self-cross linking type water-based perfluoroalkyl acrylate resin-polyurethane hybrid body:
Synthetic self-cross linking type water-based perfluoroalkyl acrylate 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 (G) 5～18; Perfluoroalkyl acrylate esters monomer (H) 6～12; Cross-linking monomer (I) 0.12～2.1; Initiator (J) 0.1～0.5, preparation technology is: aqueous polyurethane (B) and the deionized water of getting formula ratio are incorporated in the four-hole reactor that has whipping appts, thermometer, prolong and constant pressure funnel, esters of acrylic acid (G), perfluoroalkyl acrylate esters monomer (H) and cross-linking monomer (I) are mixed with initiator (J), get its 10%～30% adding reactor, temperature is controlled at 40～60 ℃, stirs 0.5 hour swelling micelle; Drip residual monomer and initiator mixing solutions from dropping funnel, dropwised in 2～4 hours, look in the prolong monomers flow back speed and control rate of addition; Continue reaction 1 hour at 70～85 ℃, 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 nylon net filters, promptly obtain self-cross linking type water-based perfluoroalkyl acrylate resin-polyurethane hybrid body resin.
The present invention, preparing the used dibasic alcohol (C) of undersaturated hydroxyl telechelic polyester (A) is: 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.Diprotic acid (F) 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 in 4-cyclohexane cyclohexanedimethanodibasic and the 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, the used dibasic alcohol (C) of the undersaturated aqueous polyurethane of described preparation (B) comprises following dibasic alcohol: 1,4-butyleneglycol, ethylene glycol, 2-ethyl-2-butyl 1, ammediol, 1,6-hexylene glycol, glycol ether, ethohexadiol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,3 propylene glycol.Wherein, 2-ethyl-2-butyl 1, ammediol, ethohexadiol etc. therefore have good water tolerance, but this type of dibasic alcohol price are higher 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 can use separately also and can mix use.
The present invention, described acrylic ester monomer (G) is: (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) vinylformic acid stearyl alcohol ester; Also comprise monomers such as acrylamide, vinylbenzene, tertiary ethylene carbonate, can use separately also and can mix use.
The present invention; described perfluoroalkyl acrylate esters monomer (H) comprises (methyl) vinylformic acid trifluoro ethyl ester; (methyl) vinylformic acid hexafluoro butyl ester; (methyl) vinylformic acid perfluoro capryl ethyl ester; (methyl) dodecafluorhe-ptylacrylate; vinylformic acid perfluoro hexyl ethyl ester; the perfluoro capryl propyl acrylate; (methyl) vinylformic acid tetrafluoro propyl ester; methacrylic acid trimethoxy silicon propyl ester; methacrylic acid trifluoroacetyl 2-ethoxyethyl acetate; N-hydroxyethyl perfluor decoylamide acrylate; (methyl) vinylformic acid octafluoro pentyl ester; the perfluoroalkyl methyl acrylate; trifluoromethyl acrylate; N-propyl group perfluoro capryl (alkylsulfonyl) amido ethyl propenoate; 2-(N-methyl PFO base alkylsulfonyl) ethyl propylene acid esters; perfluoroalkyl methacrylate (ZonylTM, CH
2=C (CH
3)-COOCH
2CH
2C
nF
2n+1(n=6-8)).Can use separately also and can mix use.
The present invention, described cross-linking monomer (I) is: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, the rare acyloxy propyl trimethoxy silicane of γ-methyl-prop, one or more mixing 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 (J) is: one or more mixing in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, Potassium Persulphate, ammonium persulphate, tertbutyl peroxide, isopropyl benzene hydroperoxide, ferrous salt, sodium bisulfite, Sulfothiorine, 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 mixing 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, described neutralizing agent is: one or more in ammoniacal liquor, triethylamine, dimethylethanolamine, diethanolamine, the tripropyl amine are used with.
The present invention is because in the process of preparation water-based fluororesin, innovation having introduced urethane has carried out modification to it, in the cost that has reduced water-based fluororesin, abandoned in traditional water-based fluororesin building-up process the unavoidable fluorine emulsifying agent of keeping away and some harsh reaction conditionss, adopt the method for soap-free polymerization, add some cross-linking monomers, also introduced the characteristic of aqueous polyurethane simultaneously.Excellent combination property behind this resin solidification, ageing-resistant performance is outstanding, has dwindled the gap with the oiliness fluoro-resin, has extraordinary market-oriented prospect in environmental friendliness society.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 2.500gMA (maleic anhydride); (29.89gAD hexanodioic acid); (22.41gNPG neopentyl glycol); 8.460g TMPME (TriMethylolPropane(TMP) mono allyl ether); 5.000gBEPD (2-ethyl-2-butyl 1; ammediol); 5.5g dimethylbenzene; 0.2592g stopper (to the methylol methyl-phenoxide) is put into the four-hole reactor that has stirring, thermometer, nitrogen airway, prolong and water trap, is warmed up to 140 ℃, stirs; slowly be warming up to 190 ℃, the heating-up time is 4 hours.190 ℃ of insulation reaction after 1 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, be cooled to 50～80 ℃ of dischargings, promptly get unsaturated hydroxyl telechelic polyester (A).
(2) with the above-mentioned unsaturated hydroxyl telechelic polyester of 23.881g (A), 4.088g1,4-butyleneglycol, 3.591g dimethylol propionic acid adds and has in the four-hole reactor of agitator, thermometer, nitrogen airway and prolong, under 110 ℃ of conditions, first vacuum was drawn water 1 hour, vacuum tightness 〉=0.060kPa; Be cooled to 70 ℃ then, add solvent N-Methyl pyrrolidone 15ml.Feed nitrogen protection, begin to drip the 26.50g 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 2.709g; Stir after 0.5 hour, with acetone regulation system viscosity; Be cooled to 40 ℃, drip 140.7g deionized water, 3.754g chainextender (quadrol) under the state that stirs fast, continue to disperse 1.5 hours, acetone is deviate from 60 ℃ of decompressions, promptly gets translucent unsaturated aqueous polyurethane dispersion (B).
(3) get the adding of big monomer 50.00g of above-mentioned aqueous polyurethane and 34.50g deionized water and have whipping appts, thermometer, in the four-hole reactor of prolong and constant pressure funnel, get hydroxyethyl methylacrylate 1.35g, vinyltrimethoxy silane 0.720g, butyl acrylate 2.850g, methyl methacrylate 3.870g, trifluoroethyl methacrylate 13.75g, 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 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 0.118g tertbutyl peroxide and 0.0950g rongalite, continue reaction 0.5 hour; Be cooled to 40 ℃ at last, add neutralizing agent (triethylamine) 0.500g adjustment pH value and be 8.0-8.5, add the 0.360g adipic dihydrazide, stirred 20 minutes; 400 order net filtrations promptly obtain self-cross linking type water-based perfluoroalkyl acrylate-polyurethane hybrid resin.
(4) technical target of the product:
The translucent oyster white water dispersion of outward appearance;
Solid content 35%;
Fluorine content 12%;
PH value 8.0-8.5;
Gloss (60 °) 85;
Pendulum-rocker hardness 0.71;
(168h) is no abnormal for water tolerance;
1 grade of sticking power (drawing circle);
(1500h) is excellent for ageing resistance;
Anti-ethanol (50%) is no abnormal.
(the ageing resistance test: adopt ZN-ultraviolet weather proofing box (spraying type) (going up Hailin Science and Technology Ltd. frequently), experiment condition is: 60 ± 2 ℃, and ultraviolet lighting 4h; 60 ± 2 ℃, condensation 4h; Every during this time 0.5h sprays once, 15s.Evaluation method: before the experiment, measure the white paint glossiness; Experiment is measured the white paint glossiness after finishing once more, calculates the loss of gloss rate, is chosen as excellent less than 10%.)
Embodiment 2:
(1) under nitrogen protection, with 3.775gPA (phthalic anhydride), 29.89gAD (hexanodioic acid); (23.710gBDO 1, the 4-butyleneglycol), 6.063gTMPME (TriMethylolPropane(TMP) mono allyl ether); 5.5g dimethylbenzene, 0.259g stopper (to the methylol methyl-phenoxide) is put into and is had stirring, thermometer; the nitrogen airway, prolong is in the four-hole reactor of water trap; be warmed up to 140 ℃; stir, slowly be warming up to 190 ℃, the heating-up time is 4 hours.190 ℃ of insulation reaction after 1 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, be cooled to 50～80 ℃ of dischargings, promptly get unsaturated hydroxyl telechelic polyester (A).
(2) with the above-mentioned unsaturated hydroxyl telechelic polyester of 25.341g (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 70 ℃ then, add solvent acetone 10ml.Feed nitrogen protection, begin to drip the 27.5g isophorone diisocyanate, dropwised in 1 hour, be incubated 1 hour; Be warmed up to 80 ℃ then, add the catalyzer (dibutyl tin laurate) of 0.0600g.Continue insulation reaction after 2 hours, begin to measure NCO content, when NCO content≤theoretical value 2.92% (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 40 ℃, drip 139.31g deionized water, 2.701g chainextender (quadrol) under the state that stirs fast, continue to disperse 1.5 hours, acetone is deviate from 60 ℃ of decompressions, promptly gets translucent unsaturated aqueous polyurethane dispersion (B).
(3) getting the adding of big monomer 60.00g of above-mentioned aqueous polyurethane and 19.00g deionized water has in the four-hole reactor of whipping appts, thermometer, prolong and constant pressure funnel; get butyl acrylate 8.14g; methyl methacrylate 3.48g; methacrylic acid hexafluoro butyl ester 21.6g; 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 9.117g and add reactor; temperature is controlled at 60 ℃, stirs 0.5 hour swelling micelle; Drip residual monomer and initiator solution from dropping funnel, temperature is controlled at 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 70 ℃, add 0.187g tertbutyl peroxide and 0.240g rongalite, continue reaction 0.5 hour; Be cooled to 40 ℃ at last, adding neutralizing agent (dimethylethanolamine) 0.7ml adjustment pH value is 8.0-8.5; 400 order net filtrations promptly obtain self-cross linking type water-based perfluoroalkyl acrylate resin-polyurethane hybrid resin.
(4) technical target of the product:
The translucent oyster white water dispersion of outward appearance;
Solid content 40%;
Fluorine content 13%;
PH value 8.0-8.5;
Gloss (60 °) 90;
Pendulum-rocker hardness 0.75;
(168h) is no abnormal for water tolerance;
1 grade of sticking power (drawing circle);
(1500h) is excellent for ageing resistance;
Anti-ethanol (50%) is no abnormal.
Embodiment 3:
(1) under nitrogen protection, with 3.775gPA (phthalic anhydride), 33.98gIPA (m-phthalic acid); (31.09gHDO 1, the 6-hexylene glycol), 7.125gTMPME (TriMethylolPropane(TMP) mono allyl ether); 5.5g dimethylbenzene, 0.3038g stopper (to the methylol methyl-phenoxide) is put into and is had stirring, thermometer; the nitrogen airway, prolong is in the four-hole reactor of water trap; be warmed up to 140 ℃; stir, slowly be warming up to 190 ℃, the heating-up time is 4 hours.190 ℃ of insulation reaction after 0.5 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, be cooled to 50～80 ℃ of dischargings, promptly get unsaturated hydroxyl telechelic polyester (A).
(2) with the above-mentioned unsaturated hydroxyl telechelic polyester of 21.351g (A), 4.088g1,6-hexylene glycol, 4.091g dimethylol propionic 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 N-Methyl pyrrolidone 10ml.Feed nitrogen protection, begin to drip the 23.50g isophorone diisocyanate, dropwised in 1 hour, be incubated 1 hour; Be warmed up to 80 ℃ then, add the catalyzer (dibutyl tin laurate) of 0.06g.Continue insulation reaction after 2 hours, begin to measure NCO content, when NCO content≤theoretical value 2.58% (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 3.086g; Stir after 0.5 hour, with acetone regulation system viscosity; Be cooled to 40 ℃, drip 117.70g deionized water, 1.975g chainextender (quadrol) under the state that stirs fast, continue to disperse 0.5 hour, acetone is deviate from 60 ℃ of decompressions, promptly gets translucent unsaturated aqueous polyurethane dispersion (B).
(3) get the adding of big monomer 70.00g of above-mentioned aqueous polyurethane and 35.10g deionized water and have whipping appts, thermometer, in the four-hole reactor of prolong and constant pressure funnel; get butyl acrylate 5.388g; methyl methacrylate 5.985g; trifluoroethyl methacrylate 11.97g; methacrylic acid hexafluoro butyl ester 11.97g; lauryl methacrylate(LMA) 1.596g; vinyl three ('beta '-methoxy oxyethyl group) silane 1.197g mixes with the 0.599g Diisopropyl azodicarboxylate; get its 12.150g and add reactor; temperature is controlled at 40-60 ℃; stirs 0.5 hour swelling micelle; from dropping funnel dropping residual monomer and initiator solution; temperature is controlled at 70-80 ℃, dropwises in 2-4 hour, look in the prolong monomers flow back speed and control rate of addition; Continue reaction 1 hour at 85 ℃, add 0.228g tertbutyl peroxide and 0.140g rongalite, continue reaction 0.5 hour; Be cooled to 40 ℃ at last, adding neutralizing agent (dimethylethanolamine) 0.7ml adjustment pH value is 8.0-8.5; 400 order net filtrations promptly obtain self-cross linking type water-based perfluoroalkyl acrylate-polyurethane hybrid resin.
(4) technical target of the product:
The translucent oyster white water dispersion of outward appearance;
Solid content 42%;
Fluorine content 16%;
PH value 8.0-8.5;
Gloss (60 °) 92;
Pendulum-rocker hardness 0.73;
(168h) is no abnormal for water tolerance;
1 grade of sticking power (drawing circle);
(1500h) is excellent for ageing resistance;
Anti-ethanol (50%) is no abnormal.
Embodiment 4:
(1) under nitrogen protection, with 5.100gMA (maleic anhydride), 24.701gNPG (neopentyl glycol); (26.80gAD hexanodioic acid), 5.000gTMPME (TriMethylolPropane(TMP) mono allyl ether), 5.5g dimethylbenzene; 0.2464g stopper (to the methylol methyl-phenoxide) is put into and is had stirring; thermometer, nitrogen airway, prolong; in the four-hole reactor of water trap; be warmed up to 140 ℃, stir, slowly be warming up to 190 ℃ (heating-up time is 4 hours).190 ℃ of insulation reaction after 1.0 hours, 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, be cooled to 50～80 ℃ of dischargings, promptly get unsaturated hydroxyl telechelic polyester (A).
(2) with the above-mentioned unsaturated hydroxyl telechelic polyester of 28.358g (A), 6.088g2-ethyl-2-butyl 1, ammediol, 4.693g dimethylol propionic acid adds and has agitator, thermometer, nitrogen airway, 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 N-Methyl pyrrolidone 15ml.Feed nitrogen protection, begin to drip the 28.50g isophorone diisocyanate, dropwised in 1 hour, be incubated 1 hour; Be warmed up to 80 ℃ then, add the catalyzer (dibutyl tin laurate) of 0.06g.Continue insulation reaction after 2 hours, begin to measure NCO content, when NCO content≤theoretical value 2.74% (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 (diethanolamine) of 3.680g; Stir after 0.5 hour, with acetone regulation system viscosity; Be cooled to 40 ℃, drip 150.645g deionized water, 2.752g chainextender (quadrol) under the state that stirs fast, continue to disperse 1.5 hours, acetone is deviate from 60 ℃ of decompressions, promptly gets translucent unsaturated aqueous polyurethane dispersion (B).
(3) get the adding of big monomer 50.00g of above-mentioned aqueous polyurethane and 18.53g deionized water and have whipping appts, thermometer, in the four-hole reactor of prolong and constant pressure funnel, get butyl methacrylate 2.7g, tertiary ethylene carbonate (VV-10) 4.050g, methyl methacrylate 3.240g, methacrylic acid ten difluoro heptyl ester 13.50g, (methyl) glycidyl acrylate 0.540g, vinyltrimethoxy silane 0.810g, lauryl methacrylate(LMA) 0.540g, diacetone-acryloamide(DAA) 1.080g mixes, get its 6.750g and add reactor, temperature is controlled at 40-60 ℃, stirs 0.5 hour swelling micelle, get the 0.216g Potassium Persulphate and the 15.00g deionized water mixes, get 3.804g and splash into reactor, temperature is controlled at 75-80 ℃, stirs 0.5h; Drip residual monomer and initiator solution from dropping funnel, temperature is controlled at 80-90 ℃, dropwises in 2-4 hour, looks in the prolong monomers flow back speed and controls rate of addition; Continue reaction 1 hour at 90 ℃, be cooled to 60-70 ℃, add 0.128g tertbutyl peroxide and 0.089g rongalite, continue reaction 0.5 hour; Be cooled to 40 ℃ at last, adding neutralizing agent (triethylamine) 0.5g adjustment pH value is 8.0-8.5, adds the 0.540g adipic dihydrazide, stirs 20 minutes; 400 order net filtrations promptly obtain self-cross linking type water-based perfluoroalkyl acrylate-polyurethane hybrid resin.(4) technical target of the product:
The translucent oyster white water dispersion of outward appearance;
Solid content 38%;
Fluorine content 18%;
PH value 8.0-8.5;
Gloss (60 °) 86;
Pendulum-rocker hardness 0.77;
(168h) is no abnormal for water tolerance;
1 grade of sticking power (drawing circle);
(1500h) is excellent for ageing resistance;
Anti-ethanol (50%) is no abnormal.
Claims (5)
1. the preparation method of self-cross linking type water-based perfluoroalkyl acrylate 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 (F) 40～49; 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 (F), the TriMethylolPropane(TMP) mono allyl ether, thermometer is equipped with in dimethylbenzene and stopper adding, water trap, prolong and having in the four-hole reactor of stirring, be heated to 140 ℃ with electric mantle, slowly be warming up to 190 ± 5 ℃ again, heating-up time is 4 hours, after the insulation reaction 0.5～1 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 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 4～10; 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 was drawn water 1 hour, vacuum tightness 〉=0.060kPa; Be cooled to 60～80 ℃ then, feed nitrogen protection, begin to drip vulcabond (E), dropwised in 1 hour, be warmed up to 80 ℃ then, add catalyzer, continue insulation reaction after 2 hours, make NCO content reach theoretical value; Be cooled to 60 ℃, add neutralizing agent; Stir after 0.5 hour, with acetone regulation system viscosity; Be cooled to 30～40 ℃, under the state that stirs fast, drip deionized water, add chainextender after 10～20 minutes powerful the dispersion, continue to disperse 0.5～1 hour, acetone is deviate from 60 ℃ of decompressions, promptly gets translucent unsaturated aqueous polyurethane dispersion (B), wherein, NCO content theoretical value refers to: according to experimental design, the NCO content in the raw material during hydroxyl complete reaction accounts for the percentage ratio of resin total amount;
(3) synthetic self-cross linking type water-based perfluoroalkyl acrylate resin-polyurethane hybrid body:
Synthetic self-cross linking type water-based perfluoroalkyl acrylate 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 (G) 5～18; Perfluoroalkyl acrylate esters monomer (H) 6～12; Cross-linking monomer (I) 0.12～2.1; Initiator (J) 0.1～0.5, preparation technology is: aqueous polyurethane (B) and the deionized water of getting formula ratio are incorporated in the four-hole reactor that has whipping appts, thermometer, prolong and constant pressure funnel, esters of acrylic acid (G), perfluoroalkyl acrylate esters monomer (H) and cross-linking monomer (I) are mixed with initiator (J), get its 10%～30% adding reactor, temperature is controlled at 40～60 ℃, stirs 0.5 hour swelling micelle; Drip residual monomer and initiator mixing solutions from dropping funnel, dropwised in 2～4 hours, look in the prolong monomers flow back speed and control rate of addition; Continue reaction 1 hour at 70～85 ℃; Be cooled to 40 ℃ at last, add neutralizing agent and adjust pH value to 8.0～8.5,400 order nylon net filters, promptly obtain self-cross linking type water-based perfluoroalkyl acrylate resin-polyurethane hybrid body resin.
2. the preparation method of self-cross linking type water-based perfluoroalkyl acrylate resin according to claim 1-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 mixing 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 mixing 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. the preparation method of self-cross linking type water-based perfluoroalkyl acrylate resin according to claim 1-polyurethane hybrid body, it is characterized in that: prepare the used dibasic alcohol (C) of undersaturated aqueous polyurethane (B) and be one or more mixing 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 mixing: 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, one or more mixing in the 4-vulcabond.
4. the preparation method of self-cross linking type water-based perfluoroalkyl acrylate resin according to claim 1-polyurethane hybrid body, it is characterized in that: described acrylic ester monomer (G) is: one or more mixing in (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) vinylformic acid stearyl alcohol ester, acrylamide, vinylbenzene, the tertiary ethylene carbonate; Described perfluoroalkyl acrylate esters monomer (H) is: (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid hexafluoro butyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) dodecafluorhe-ptylacrylate, vinylformic acid perfluoro hexyl ethyl ester, the perfluoro capryl propyl acrylate, (methyl) vinylformic acid tetrafluoro propyl ester, methacrylic acid trimethoxy silicon propyl ester, methacrylic acid trifluoroacetyl 2-ethoxyethyl acetate, N-hydroxyethyl perfluor decoylamide acrylate, (methyl) vinylformic acid octafluoro pentyl ester, the perfluoroalkyl methyl acrylate, trifluoromethyl acrylate, N-propyl group perfluoro capryl (alkylsulfonyl) amido ethyl propenoate, 2-(N-methyl PFO base alkylsulfonyl) ethyl propylene acid esters, one or more mixing in the perfluoroalkyl methacrylate; Described cross-linking monomer (I) is: the mixture of one or more in vinyl three ('beta '-methoxy oxyethyl group) silane, (methyl) glycidyl acrylate, N n-methylolacrylamide, diacetone-acryloamide(DAA), lauryl methacrylate(LMA), vinyltrimethoxy silane, vinyl silane triisopropoxide, the adipic dihydrazide; Described initiator (J) 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.
5. the preparation method of self-cross linking type water-based perfluoroalkyl acrylate resin according to claim 1-polyurethane hybrid body, it is characterized in that: described neutralizing agent is: one or more mixtures in ammoniacal liquor, triethylamine, dimethylethanolamine, diethanolamine, the tripropyl amine.
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