CN107629170A - A kind of good environment-protecting polyurethane acrylic resin of weatherability and preparation method thereof - Google Patents

Abstract

The invention provides a kind of preparation method of hydroxyl waterborne cation polyurethane acrylic resin, this method comprises the following steps：A) hydroxyl telechelic polyester containing unsaturated double-bond is obtained by reaction；B) using the product of gained in step a) as raw material, addition component design than dihydric alcohol, caprolactam, hydrophilic monomer, catalyst, end-capping reagent, nertralizer etc., obtain unsaturated waterborne cation polyurethane；(3) using the product of gained in step b) as reaction raw materials, with component design than acrylate monomer react and just obtain the good environment-protecting polyurethane acrylic resin of weatherability.End-capping reagent is added in step b), double bond monomer end-blocking is carried out to waterborne cation polyurethane resin prepolymer, further improves the grafting rate of acrylic resin；The reaction condition is gentle, and not additional emulsifying agent has obtained the waterborne cation polyurethane Hydroxylated acrylic resin of performance improvement, greatly expands the application field of resin.

Description

A kind of good environment-protecting polyurethane-acrylic resin of weatherability and preparation method thereof

Technical field

The present invention relates to resin art, and in particular to the preparation method of the good environment-protecting polyurethane-acrylic resin of weatherability.

Background technology

Aqueous polyurethane is divided into ionic and nonionic according to whether dispersed particle is powered, and the water-based poly- ammonia of ionic Ester can be divided into anionic, cationic and amphoteric ion type again according to the powered property in polyurethane backbone, at present on the market Application for anion aqueous polyurethane is more, and reason is that quaternary ammonium salt cationic aqueous polyurethane will be pre- in preparation process The process of aggressiveness quaternization is more complicated, and cost is higher, and prepare cation product store sometimes it is unstable；Compared to Anion-type water-thinned polyurethane, the research report of cationic is less at present, while waterborne cation polyurethane has water resistance The shortcomings of difference, gloss are low, poor solvent resistance, slow drying speed；But due to being carried on the strand of cation-type water-thinned polyurethane Positive electricity, it has good wellability to hydrophobic polyester, fabric fibre, while insensitive to the hardness of water, can be in acidity Under the conditions of use, therefore it is with a wide range of applications in fields such as weaving, leather, woodwork coating and papermaking；Water-based hydroxyl third Olefin(e) acid resin has the advantages that high mechanical strength, ageing-resistant, good weatherability and water-tolerant, but it equally exists hot sticky cold crisp Shortcoming；Hydroxy acrylate is modified to waterborne cation polyurethane, with regard to that can accomplish to maximize favourable factors and minimize unfavourable ones, performance is obtained and is changed Kind waterborne cation polyurethane-Hydroxylated acrylic resin；And the resin is convenient and amino resins compounds, and prepares waterborne cation Amino-stoving varnish；It can also be compounded with water-based more caprolactam curing agent, prepare the double groups of normal temperature self-drying type waterborne cation polyurethane Part resin, the resin after compounding can significantly improve the performance such as its hardness, water-fast, shock resistance, greatly expand cation tree The application field of fat.

Simultaneously traditional solvent-borne type cation polyurethane-acrylic resin is all to use acetone or acetone method, organic solvent Use need to be removed by the way of distillation, technique is cumbersome, while has substantial amounts of organic solvent to evaporate into air in work progress, Easily cause the pollution of environment.

The content of the invention

The invention provides a kind of method for preparing the good environment-protecting polyurethane-acrylic resin of weatherability, synthesizes first Hydroxyl telechelic polyester containing unsaturated double-bond, while double bond monomer envelope has been carried out to waterborne cation polyurethane resin prepolymer End, further improve the grafting rate of acrylic resin；When preparation weatherability good environment-protecting polyurethane-acrylic resin, Using the method for soap-free polymerization, introduce hydroxyl acrylic resin and it is modified, keep the poly- ammonia of waterborne cation While ester intrinsic excellent properties, high mechanical strength, ageing-resistant, good weatherability and water-tolerant of acrylic resin etc. are introduced Advantage.After the resin compounds with water-compatible amino resin or water-based more caprolactam curing agent, excellent combination property, ageing-resistant performance It is prominent, exceed the like product of the country, reduced the gap with oiliness two-component resin cation, in environment-friendly society With extraordinary market-oriented prospect.

Preparation process of the present invention is as follows：

A) under the protection of nitrogen, by component design than polyalcohol, polyacid, solvent xylene, the addition such as polymerization inhibitor is equipped with Thermometer, water knockout drum and condenser pipe, in four mouthfuls of reactors with stirring, it is heated to beginning with back in condenser pipe with electric jacket When flowing, and the globule is begun with water knockout drum, insulation reaction 1 hour, 210 DEG C (heating-up time is 5 hours) are then to slowly warm up to, After 210 DEG C of insulation reactions 0.5 hour, start to determine acid number, it is true at 100 DEG C or so when acid number is down to 5mgKOH/g resins Sky abjection dimethylbenzene, in vacuum >=0.045Kpa, vacuum decompression is dried 1~2 hour, and temperature is 50~80 DEG C, that is, is obtained not Saturation hydroxyl telechelic polyester.

B) mass parts are pressed, the unsaturated hydroxyl telechelic polyester and 200~300 that will be prepared in 400~600 parts of above-mentioned steps a) Part dihydric alcohol be put into reaction vessel, under vacuum >=0.060Kpa, first vacuum is drawn water 0.5~1.5h, cool to 55~ 65 DEG C, 650~850 parts of acetone and 1150~1450 parts of caprolactams are added, react 0.5~1.5h, cool to 50~40 DEG C, then 150~300 parts of hydrophilic monomers are added dropwise, react 0.5~1.5h, are warming up to 65~80 DEG C, add 4~10 parts of organic metal class catalysis NCO content≤4.6% in agent to system, then 55~63 DEG C are cooled to, 150~400 parts of end-capping reagents are added, are reacted into system NCO content is close to 0；40~50 DEG C are cooled to again, adds 70~150 parts of nertralizers, stirs 0.5~1h, add acetone regulation Viscosity, 30~40 DEG C are cooled to, under stirring, add 3800~4500 parts of deionized waters, acetone and acetone are sloughed in decompression Just obtain unsaturated waterborne cation polyurethane；

C) take the unsaturated waterborne cation polyurethane prepared in the above-mentioned steps b) of mass parts 1300~2200 to be put into reaction to hold In device, at 40~60 DEG C, 600~1200 acrylic ester monomers, 15~20 cross-linking monomer, 14~25 initiators are first added Mixed solution in gross mass part 5%~40%, then be warming up to 80~90 DEG C, drip remaining mixed solution, reaction 0.5 ~2h, just obtain the good environment-protecting polyurethane-acrylic resin of weatherability.

Polymerization inhibitor of the present invention is preferably methylol methyl phenyl ethers anisole.

End-capping reagent of the present invention is senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl One in ester, methacrylic acid-β-hydroxypropyl acrylate, acrylic acid -2- hydroxyl -3- phenoxy-propyls, methacrylic acid-β-hydroxypropyl acrylate Kind；Nertralizer is one kind in acetic acid, propionic acid, butyric acid.

Polyalcohol of the present invention is the dihydric alcohol that carbon number is 1~12 and trimethylolpropane, trimethylolpropane At least two in mono allyl ether；Polyacid is maleic anhydride, 1,4 cyclohexanedicarboxylic acid, fumaric acid, phthalic anhydride, isophthalic Dioctyl phthalate, terephthalic acid (TPA), THPA, succinic acid, glutaric acid, ethanedioic acid, fumaric acid, dimeric dibasic acid, HHPA and oneself two One or more in acid.

Caprolactam monomer of the present invention be toluene dicaprolactam, the own dicaprolactams of 1,6-, isophorone two oneself Lactams, phenylenedimethylidyne dicaprolactam, two cyclohexyl methane dicaprolactams, methylcyclohexyl dicaprolactam, hexichol One or more in methylmethane -4,4- dicaprolactams；Hydrophilic monomer is diethanol amine, triethanolamine, N- methyl diethyls Hydramine, N- ethyldiethanolamines, N- propyl group diethanol amine, N butyl diethanol amine, tertiarybutyldiethanolamine, dimethyl ethanol Amine, N, N- dihydroxy ethyls aniline, N, one kind in N- dihydroxypropyl aniline.

Acrylic ester monomer of the present invention includes the acrylate monomer of not hydroxyl, the acrylate list of hydroxyl Body, it is acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylic acid second without hydroxy-acrylate monomer Ester, EMA, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, n-propyl, acrylic acid Different monooctyl ester, lauryl acrylate, lauryl methacrylate, styrene, acrylic acid octadecyl, methacrylic acid octadecyl alcolol At least one of ester, lauryl methacrylate, phenyl methacrylate, benzyl methacrylate, acrylamide, and Dosage is the 60~98% of acrylic ester monomer quality, and hydroxy acryl acid ester monomer is senecioate-hydroxyl ethyl ester, methyl-prop Olefin(e) acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, acrylic acid -2- hydroxyl -3- phenoxy-propyls, methacrylic acid-β-hydroxypropyl acrylate At least one of, its dosage is the 2~40% of acrylic ester monomer quality.

Cross-linking monomer of the present invention is vinyltrimethoxy silane, VTES, acrylic front three TMOS, γ-methacryloxy trimethoxy silane, 3- methacryloxypropyl trimethoxy silanes, triphen Ethoxy ethylene base silane, vinyl three (2- methoxy ethoxies) silane, γ-methyl propylene acryloxypropylethoxysilane trimethoxy silicon In alkane, vinyl silane triisopropoxide, 3- (isobutene acyl-oxygen) propyl trimethoxy silicane, vinyl trichlorosilane at least One kind, and its dosage is the 2~20% of acrylic ester monomer quality；Initiator be azodiisobutyronitrile, ABVN, Dibenzoyl peroxide, potassium peroxydisulfate, TBHP, ammonium persulfate, ferrous salt, isopropyl benzene hydroperoxide, sulfurous acid At least one of hydrogen sodium, sodium thiosulfate, rongalite, dosage are the 0.1~5% of acrylic ester monomer quality.

Hydroxy acrylate is just incorporated into polyurethane resin by the present invention only by 3 steps, this method operation letter It is single, it is easy to implement, while the excellent chemical property of Hydroxylated acrylic resin is introduced, avoid waterborne cation polyurethane resin The distinct disadvantages such as poor water resistance, gloss is low, it is steady low-temperature impact resistance, ageing-resistant, good weatherability, water-tolerant and chemistry are obtained Qualitatively hydroxyl waterborne cation polyurethane-acrylic resin, and the resin easily compounds with amino resins, prepares it is water-based it is positive from Sub- amino-stoving varnish；It can also be compounded with water-based more caprolactam curing agent, it is double to prepare normal temperature self-drying type waterborne cation polyurethane Components resin, the resin after compounding can significantly improve the performance such as its hardness, water-fast, shock resistance, greatly expand cation The application field of resin.

Embodiment

Technical scheme is described with reference to specific embodiment

Embodiment 1

(1) under nitrogen protection, by 120 parts of maleic anhydrides, 130 parts of trimethylolpropanes, 480 parts of adipic acids, 550 parts oneself two Alcohol, 6 parts are put into methylol methyl phenyl ethers anisole with stirring, thermometer, nitrogen airway tube, condenser pipe, four mouthfuls of reactors of water knockout drum In, 140 DEG C are slowly warming up to, starts stirring, is to slowly warm up to 210 DEG C (heating-up time 5h).After 210 DEG C are incubated 0.5h, Start to determine acid number, when acid number is down to 5mgKOH/g resins, vacuum deviates from dimethylbenzene, vacuum 0.045Kpa, and vacuum subtracts Dry 1h is pressed dry, produces unsaturated hydroxyl telechelic polyester.

(2) by 500 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 230 parts of BDOs, add with agitator, thermometer, Nitrogen airway tube, condenser pipe four mouthfuls of reactors in, under the conditions of 110 DEG C, first vacuum is drawn water 1h, makes the vacuum be 0.060Kpa；Then be cooled to 60 DEG C, add 740 parts of acetone, be passed through nitrogen protection, start to be added dropwise 1300 parts of isophorones two oneself Lactams, 1h are added dropwise；Then 50 DEG C are cooled to, starts that 190 parts of N methyldiethanol amines are added dropwise, 1h is added dropwise, and is incubated 1h；Then 70 DEG C are warming up to, adds 6 parts of dibutyl tin laurates, makes NCO content for 4.5% (according to experimental design, raw material NCO content when middle hydroxyl reacts completely accounts for the percentage of resin total amount), during which with acetone regulation system viscosity；It is cooled to 60 DEG C, 316 parts of hydroxypropyl acrylates are added, insulation reaction, make system NCO content close to 0；50 DEG C are cooled to, adds 95 parts of second Acid；After stirring 0.5h；40 DEG C are cooled to, 4145 parts of deionized waters are added dropwise in the state of quick stirring, continues scattered 0.5h, 60 DEG C decompression abjection acetone and acetone, produces translucent yellowish-brown unsaturation waterborne cation polyurethane (solid content about 35%).

(3) above-mentioned 2000 parts of waterborne cation polyurethanes and 1035 parts of deionized waters are taken to add with agitating device, temperature Meter, condenser pipe and constant pressure funnel four mouthfuls of reactors in, take 210 parts of butyl acrylate, 588 parts of methyl methacrylate, 16.8 parts of vinyltrimethoxy silane, 25.2 parts of hydroxyethyl methacrylate mix with 16.8 parts of azodiisobutyronitriles, take 171 The above-mentioned mixed solution of part adds reactor, and temperature control stirs 0.5h swelling micelles at 40 DEG C, and remaining list is added dropwise from dropping funel Body and initiator mixed solution, at 85 DEG C, 3h is added dropwise temperature control, is added dropwise depending on monomers flow back speed in condenser pipe to control Speed；Continue to react 1h at 85 DEG C；Be finally cooled to 40 DEG C, 300 mesh net filtrations, that is, obtain the good environment-protecting polyurethane of weatherability- Acrylic resin (A) (solid content about 40%).

Embodiment 2：

(1) under nitrogen protection, by 120 parts of maleic anhydrides, 300 parts of trimethyolol propane monoallyl ethers, 480 parts of adipic acids, 650 parts of 2- ethyl -2- butyl 1,3-PDs, 8 parts are put into methylol methyl phenyl ethers anisole with stirring, thermometer, nitrogen airway tube, Condenser pipe, in four mouthfuls of reactors of water knockout drum, 140 DEG C are slowly warming up to, starts stirring, is to slowly warm up to 210 DEG C of (heating-up times For 5h)；After 210 DEG C are incubated 0.5h, start to determine acid number, when acid number is down to 5mgKOH/g resins, vacuum abjection dimethylbenzene, After the completion of reaction, vacuum 0.045Kpa, vacuum decompression 1.5h, unsaturated hydroxyl telechelic polyester is produced.

(2) by 400 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 280 parts of BDOs, add with agitator, thermometer, Nitrogen airway tube, condenser pipe four mouthfuls of reactors in, under the conditions of 110 DEG C, first vacuum is drawn water 1h, vacuum 0.060Kpa； Then 60 DEG C are cooled to, adds 803 parts of acetone；Nitrogen protection is passed through, starts that 1460 parts of isophorone dicaprolactams, 1h is added dropwise It is added dropwise；Then 50 DEG C are cooled to, starts that 210 parts of N methyldiethanol amines are added dropwise, 1h is added dropwise, and is incubated 1h；Then rise Temperature adds 5 parts of dibutyl tin laurates to 70 DEG C.Making NCO content, (according to experimental design, hydroxyl is complete in raw material for 4.4% NCO content during reaction accounts for the percentage of resin total amount), during which with acetone regulation system viscosity；60 DEG C are cooled to, adds 341 Part hydroxypropyl acrylate, insulation reaction, makes system NCO content close to 0；45 DEG C are cooled to, adds 105 parts of acetic acid；Stirring After 0.5h；40 DEG C are cooled to, 4410 parts of deionized waters are added dropwise in the state of quick stirring, continues scattered 0.5h, 60 DEG C of decompressions Deviate from acetone and acetone, produce translucent yellowish-brown unsaturation waterborne cation polyurethane (B) (solid content about 35%).

(3) above-mentioned 1500 parts of waterborne cation polyurethanes and 1258 parts of deionized waters are taken to add with agitating device, temperature Meter, condenser pipe and constant pressure funnel four mouthfuls of reactors in, take 236 parts of butyl acrylate, 662 parts of methyl methacrylate, 18.9 parts of vinyltrimethoxy silane, 28.4 parts of hydroxypropyl acrylate mix with 18.9 parts of azodiisobutyronitriles, take above-mentioned mixed 193 parts of addition reactors of solution are closed, temperature control stirs 0.5h swelling micelles at 40 DEG C, is added dropwise from dropping funel remaining single Body and initiator mixed solution, temperature control were added dropwise in 85 DEG C, 3 hours, were controlled depending on monomers flow back speed in condenser pipe Rate of addition；Continue to react 1h at 85 DEG C；40 DEG C are finally cooled to, 300 mesh net filtrations, that is, obtains the poly- ammonia of the good environment-friendly type of weatherability Ester-acrylic resin (solid content about 40%).

Embodiment 3：

(1) under nitrogen protection, by 90 parts of maleic anhydrides, 270 parts of trimethyolol propane monoallyl ethers, 500 parts of adipic acids, 670 parts of 2- ethyl -2- butyl 1,3-PDs, 8 parts are put into methylol methyl phenyl ethers anisole with stirring, thermometer, nitrogen airway tube, Condenser pipe, in four mouthfuls of reactors of water knockout drum, 140 DEG C are slowly warming up to, starts stirring, is to slowly warm up to 210 DEG C of (heating-up times For 5h).After 210 DEG C are incubated 0.5h, start to determine acid number, when acid number is down to 5mgKOH/g resins, vacuum abjection dimethylbenzene, After the completion of reaction, vacuum 0.045Kpa, vacuum decompression is dried 2 hours, produces unsaturated hydroxyl telechelic polyester.

(2) by 560 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 230 parts of BDOs, add with agitator, thermometer, Nitrogen airway tube, condenser pipe four mouthfuls of reactors in, under the conditions of 110 DEG C, first vacuum is drawn water 1h, vacuum 0.060Kpa； Then 60 DEG C are cooled to, adds 813 parts of acetone；Nitrogen protection is passed through, starts that 1410 parts of isophorone dicaprolactams, 1h is added dropwise It is added dropwise；Then 50 DEG C are cooled to, starts that 240 parts of N methyldiethanol amines are added dropwise, 1h is added dropwise, and is incubated 1 hour；Then 70 DEG C are warming up to, adds 5 parts of dibutyl tin laurates.Make NCO content for 4.25% (according to experimental design, hydroxyl in raw material NCO content when reacting completely accounts for the percentage of resin total amount), during which with acetone regulation system viscosity；60 DEG C are cooled to, is added 249 parts of hydroxyethyl methacrylates, insulation reaction, make system NCO content close to 0；50 DEG C are cooled to, adds 120 parts of acetic acid； After stirring 0.5h；40 DEG C are cooled to, 4403 parts of deionized waters are added dropwise in the state of quick stirring, continues scattered 0.5h, 60 DEG C Decompression abjection acetone, acetone, produce translucent yellowish-brown unsaturation waterborne cation polyurethane (solid content about 35%).

(3) above-mentioned 1500 parts of waterborne cation polyurethanes and 1258 parts of deionized waters are taken to add with agitating device, temperature In four mouthfuls of reactors of meter, condenser pipe and constant pressure funnel, 236 parts of Isooctyl acrylate monomer, 595 parts of styrene, vinyl are taken 18.9 parts of triethoxysilane, 94.5 parts of hydroxyethyl methacrylate mix with 18.9 parts of azodiisobutyronitriles, take 193 parts of additions Reactor, temperature control stir 0.5h swelling micelles at 40 DEG C, and residual monomer is added dropwise from dropping funel and initiator mixing is molten Liquid, at 85 DEG C, 3h is added dropwise temperature control, and rate of addition is controlled depending on monomers flow back speed in condenser pipe；In 85 DEG C of continuation React 1h；Be finally cooled to 40 DEG C, 300 mesh net filtrations, that is, obtain the good environment-protecting polyurethane-acrylic resin of weatherability (admittedly contain Amount is about 40%).

Embodiment 4：

(1) under nitrogen protection, by 90 parts of maleic anhydrides, 270 parts of trimethyolol propane monoallyl ethers, 500 parts of adipic acids, 460 parts of hexylene glycols, 7 parts to methylol methyl phenyl ethers anisole be put into stirring, thermometer, nitrogen airway tube, condenser pipe, the four of water knockout drum In mouth reactor, 140 DEG C are slowly warming up to, starts stirring, is to slowly warm up to 210 DEG C (heating-up time 5h).In 210 DEG C of insulations After 0.5h, start to determine acid number, when acid number is down to 5mgKOH/g resins, vacuum abjection dimethylbenzene, after the completion of reaction, vacuum For 0.045Kpa, vacuum decompression dries 2h, produces unsaturated hydroxyl telechelic polyester.

(2) by 480 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 210 parts of BDOs, add with agitator, thermometer, Nitrogen airway tube, condenser pipe four mouthfuls of reactors in, under the conditions of 110 DEG C, first vacuum is drawn water 1h, vacuum 0.060Kpa； Then 60 DEG C are cooled to, adds 740 parts of acetone；Nitrogen protection is passed through, starts that 1290 parts of isophorone dicaprolactams, 1h is added dropwise It is added dropwise；Then 50 DEG C are cooled to, starts that 240 parts of N methyldiethanol amines are added dropwise, 1h is added dropwise, and is incubated 1h；Then rise Temperature adds 5 parts of dibutyl tin laurates to 70 DEG C.Making NCO content, (according to experimental design, hydroxyl is complete in raw material for 3.77% NCO content during full response accounts for the percentage of resin total amount), during which with acetone regulation system viscosity；60 DEG C are cooled to, is added 201 parts of hydroxyethyl methacrylates, insulation reaction, make system NCO content close to 0；50 DEG C are cooled to, adds 120 parts of acetic acid； After stirring 0.5h；40 DEG C are cooled to, 3979 parts of deionized waters are added dropwise in the state of quick stirring, continues scattered 0.5h, 60 DEG C Decompression abjection acetone, acetone, produce translucent yellowish-brown unsaturation waterborne cation polyurethane (solid content about 35%).

(3) above-mentioned 1800 parts of waterborne cation polyurethanes and 1510 parts of deionized waters are taken to add with agitating device, temperature In four mouthfuls of reactors of meter, condenser pipe and constant pressure funnel, 284 parts of Isooctyl acrylate monomer, methyl methacrylate 714 are taken Part, 22.6 parts of VTES, 11.3 parts of hydroxy-ethyl acrylate mixes with 22.7 parts of azodiisobutyronitriles, takes 231 Part adds reactor, and temperature control stirs 0.5h swelling micelles at 40 DEG C, and residual monomer is added dropwise from dropping funel and initiator mixes Solution is closed, at 85 DEG C, 3h is added dropwise temperature control, and rate of addition is controlled depending on monomers flow back speed in condenser pipe；At 85 DEG C Continue to react 1h；40 DEG C are finally cooled to, 300 mesh net filtrations, that is, obtains the good environment-protecting polyurethane-acrylic resin of weatherability (solid content about 40%).

Embodiment 5：

(1) under nitrogen protection, by 90 parts of maleic anhydrides, 270 parts of trimethylolpropanes, 530 parts of adipic acids, 430 parts of hexylene glycols, 7 parts are put into methylol methyl phenyl ethers anisole with stirring, thermometer, nitrogen airway tube, condenser pipe, in four mouthfuls of reactors of water knockout drum, 140 DEG C slowly are warming up to, stirring is started, is to slowly warm up to 210 DEG C (heating-up time 5h).After 210 DEG C are incubated 0.5h, start Acid number is determined, when acid number is down to 5mgKOH/g resins, vacuum abjection dimethylbenzene, after the completion of reaction, vacuum 0.045Kpa, Vacuum decompression dries 1h, produces unsaturated hydroxyl telechelic polyester.

(2) by 420 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 190 parts of BDOs, add with agitator, thermometer, Nitrogen airway tube, condenser pipe four mouthfuls of reactors in, under the conditions of 110 DEG C, first vacuum is drawn water 1h, vacuum 0.060Kpa； Then 60 DEG C are cooled to, adds 690 parts of acetone；Nitrogen protection is passed through, starts that 1230 parts of isophorone dicaprolactams, 1h is added dropwise It is added dropwise；Then 50 DEG C are cooled to, starts that 230 parts of N methyldiethanol amines are added dropwise, 1h is added dropwise, and is incubated 1h；Then rise Temperature adds 5 parts of dibutyl tin laurates to 70 DEG C.Making NCO content, (according to experimental design, hydroxyl is complete in raw material for 4.43% NCO content during full response accounts for the percentage of resin total amount), during which with acetone regulation system viscosity；60 DEG C are cooled to, is added 220 parts of hydroxyethyl methacrylates, insulation reaction, make system NCO content close to 0；50 DEG C are cooled to, adds 115 parts of acetic acid； After stirring 0.5h；Be cooled to 40 DEG C, 3778 parts of deionized waters be added dropwise in the state of quick stirring, continue it is scattered 0.5 hour, 60 DEG C decompression abjection acetone, acetone, produce translucent yellowish-brown unsaturation waterborne cation polyurethane (solid content about 35%).

(3) above-mentioned 1800 parts of waterborne cation polyurethanes and 1215 parts of deionized waters are taken to add with agitating device, temperature In four mouthfuls of reactors of meter, condenser pipe and constant pressure funnel, 236 parts of Isooctyl acrylate monomer, methyl methacrylate 595 are taken Part, 18.9 parts of VTES, 94.5 parts of hydroxyethyl methacrylate is mixed with 15.2 parts of azodiisobutyronitriles, taken 192 parts of addition reactors, temperature control stir 0.5h swelling micelles at 40 DEG C, and residual monomer and initiation is added dropwise from dropping funel Agent mixed solution, at 85 DEG C, 3h is added dropwise temperature control, and rate of addition is controlled depending on monomers flow back speed in condenser pipe； 85 DEG C are continued to react 1h；40 DEG C are finally cooled to, 300 mesh net filtrations, that is, obtains the good environment-protecting polyurethane of weatherability-acrylic acid tree Fat (solid content about 40%).

Claims (10)

1. a kind of preparation method of the good environment-protecting polyurethane-acrylic resin of weatherability, it is characterised in that comprise the following steps：

A) mass parts are pressed, 550~650 parts of polyacids, 600~1000 parts of polyalcohols and 5~9 parts are reacted methylol methyl phenyl ethers anisole, Obtain unsaturated hydroxyl telechelic polyester；

B) mass parts are pressed, take the unsaturated hydroxyl telechelic polyester being prepared in 400~600 parts of above-mentioned steps a), 200~300 parts Dihydric alcohol is put into reaction vessel, sequentially adds 650~850 parts of acetone, 1150~1450 parts of caprolactams, 150~300 parts of parents Aqueous monomer, the reaction of 4~10 parts of organometallic catalysts, add 150~400 parts of end-capping reagents, 70~150 parts of nertralizers and 3800-4500 part deionized waters, decompression slough acetone, obtain unsaturated waterborne cation polyurethane；

C) the unsaturated waterborne cation polyurethane being prepared in 1300~2200 parts of above-mentioned steps b) is taken to be put into reaction vessel In, 600~1200 parts of acrylic ester monomers are added, 15~20 parts of cross-linking monomers, 14~25 parts of initiators, reaction obtains weather-proof Good environment-protecting polyurethane-the acrylic resin of property.

A kind of 2. good environment-protecting polyurethane-acrylic resin of weatherability according to claim 1, it is characterised in that：Step B) reaction temperature in is 55~65 DEG C, adds end-capping reagent, insulation reaction NCO content into system is 0, is cooled to 40~50 DEG C, nertralizer is added, is cooled to 30~40 DEG C, deionized water is added dropwise under stirring, decompression sloughs acetone, obtains unsaturation Waterborne cation polyurethane.

A kind of 3. good environment-protecting polyurethane-acrylic resin of weatherability according to claim 1, it is characterised in that：Step C) reaction temperature in is 40~60 DEG C, adds acrylic ester monomer, cross-linking monomer, initiator mixed solution 5%~ 40%, then temperature is increased to 80~90 DEG C, remaining mixed solution is added dropwise, after reacting 0.5~2h, is cooled to 35~45 DEG C, obtain the good environment-protecting polyurethane-acrylic resin of weatherability.

A kind of 4. good environment-protecting polyurethane-acrylic resin of weatherability according to claim 1 or 2, it is characterised in that：Institute End-capping reagent is stated as senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, methacrylic acid-β-hydroxyl One kind in propyl ester, acrylic acid -2- hydroxyl -3- phenoxy-propyls, methacrylic acid-β-hydroxypropyl acrylate；Nertralizer is acetic acid, third One kind in acid, butyric acid.

A kind of 5. good environment-protecting polyurethane-acrylic resin of weatherability according to claim 1, it is characterised in that：Step C) acrylic ester monomer described in includes the not acrylate monomer of the acrylate monomer of hydroxyl and hydroxyl, without hydroxyl Base acrylate monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, acrylic acid fourth Ester, butyl methacrylate, cyclohexyl acrylate, n-propyl, Isooctyl acrylate monomer, lauryl acrylate, methyl-prop Olefin(e) acid lauryl, acrylic acid octadecyl, methacrylic acid octadecyl, lauryl methacrylate, methacrylic acid At least one of phenyl ester, benzyl methacrylate and acrylamide, styrene, its dosage are acrylic ester monomer quality 60~98%；Hydroxy acryl acid ester monomer is senecioate-hydroxyl ethyl ester, methacrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxyl At least one of propyl ester, acrylic acid -2- hydroxyl -3- phenoxy-propyls, methacrylic acid-β-hydroxypropyl acrylate, its dosage is propylene The 2~40% of esters of gallic acid monomer mass.

A kind of 6. good environment-protecting polyurethane-acrylic resin of weatherability according to claim 1, it is characterised in that：Step A) polyalcohol described in is dihydric alcohol, trimethylolpropane, trimethyolol propane monoallyl ether of the carbon number from 1~12 In at least two.

A kind of 7. good environment-protecting polyurethane-acrylic resin of weatherability according to claim 1, it is characterised in that：Step A) polyacid described in is maleic anhydride, 1,4 cyclohexanedicarboxylic acid, fumaric acid, phthalic anhydride, M-phthalic acid, terephthaldehyde One kind or more in acid, THPA, succinic acid, glutaric acid, ethanedioic acid, fumaric acid, dimeric dibasic acid, HHPA and adipic acid Kind.

A kind of 8. good environment-protecting polyurethane-acrylic resin of weatherability according to claim 1, it is characterised in that：Step B) caprolactam monomer described in is toluene dicaprolactam, the own dicaprolactams of 1,6-, isophorone dicaprolactam, benzene two Methylene dicaprolactam, two cyclohexyl methane dicaprolactams, methylcyclohexyl dicaprolactam, diphenyl methane -4,4- One or more in dicaprolactam.

A kind of 9. good environment-protecting polyurethane-acrylic resin of weatherability according to claim 1, it is characterised in that：Step B) hydrophilic monomer described in is diethanol amine, triethanolamine, N methyldiethanol amine, N- ethyldiethanolamines, N- propyl group two Monoethanolamine, N butyl diethanol amine, tertiarybutyldiethanolamine, dimethylethanolamine, N, N- dihydroxy ethyls aniline, the hydroxypropyl of N, N- bis- One kind in base aniline.

A kind of 10. good environment-protecting polyurethane-acrylic resin of weatherability according to claim 1, it is characterised in that：Step C) cross-linking monomer described in is vinyltrimethoxy silane, VTES, acrylic trimethoxy silane, γ-methacryloxy trimethoxy silane, 3- methacryloxypropyl trimethoxy silanes, triple phenoxyl vinyl In silane, γ-methyl propylene acryloxypropylethoxysilane trimethoxy silane, vinyl silane triisopropoxide, vinyl trichlorosilane At least one, its dosage be acrylic ester monomer quality 2~20%；The initiator is azodiisobutyronitrile, azo Two different heptonitriles, dibenzoyl peroxide, potassium peroxydisulfate, TBHP, ammonium persulfate, ferrous salt, isopropylbenzene peroxidating At least one of hydrogen, sodium hydrogensulfite, sodium thiosulfate, rongalite, its dosage for acrylic ester monomer quality 0.1~ 5%.