CN107936183A - A kind of good environment-protecting polyurethane acrylic resin of weatherability and preparation method thereof - Google Patents
A kind of good environment-protecting polyurethane acrylic resin of weatherability and preparation method thereof Download PDFInfo
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- CN107936183A CN107936183A CN201711283829.7A CN201711283829A CN107936183A CN 107936183 A CN107936183 A CN 107936183A CN 201711283829 A CN201711283829 A CN 201711283829A CN 107936183 A CN107936183 A CN 107936183A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present 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, neutralizer 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
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 non-ionic 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, the 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 there are water resistance for waterborne cation polyurethane
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 waterborne cation polyurethane, with regard to that can accomplish to maximize favourable factors and minimize unfavourable ones, obtains performance 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.
Solvent-borne type cation polyurethane-acrylic resin traditional at the same time 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 the construction process,
It is easy to cause the pollution of environment.
The content of the invention
The present 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 improves 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 is compounded with water-compatible amino resin or water-based more caprolactam curing agent, excellent combination property, ageing-resistant performance
It is prominent, exceed the similar product of the country, reduced the gap with oiliness two-component resin cation, in environmental-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, polymerization inhibitor etc. adds
Equipped with thermometer, water knockout drum and condenser pipe, in four mouthfuls of reactors with stirring, are heated to beginning with condenser pipe with electric jacket
When flowing back, and droplet is begun with water knockout drum, when insulation reaction 1 is small, being then to slowly warm up to 210 DEG C, (heating-up time is small for 5
When), when 210 DEG C of insulation reactions 0.5 are small after, start measure acid number, when acid number is down to 5mgKOH/g resins, on 100 DEG C of left sides
Right vacuum deviates from dimethylbenzene, and in vacuum >=0.045Kpa, when vacuum decompression drying 1~2 is small, temperature is 50~80 DEG C, to obtain the final product
To unsaturated 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 neutralizers, stirs 0.5~1h, are added acetone and are adjusted
Viscosity, cools to 30~40 DEG C, under stirring, adds 3800~4500 parts of deionized waters, acetone and acetone are sloughed in decompression
Just obtain unsaturated waterborne cation polyurethane；
C) the unsaturated waterborne cation polyurethane prepared in the above-mentioned steps b) of mass parts 1300~2200 is taken to be put into instead
Answer in container, at 40~60 DEG C, first add 600~1200 acrylic ester monomers, 15~20 cross-linking monomer, 14~25 draw
5%~40% of gross mass part in the mixed solution of agent is sent out, then is warming up to 80~90 DEG C, drips remaining mixed solution, instead
0.5~2h is answered, just obtains 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；Neutralizer is acetic acid, one kind in 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), tetrahydrophthalic anhydride, succinic acid, glutaric acid, ethanedioic acid, fumaric acid, dimeric dibasic acid, hexahydrophthalic anhydride and oneself two
One or more in acid.
Caprolactam monomer of the present invention for 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, is acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylic acid second without hydroxy-acrylate monomer
Ester, ethyl methacrylate, 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 vinyltrimethoxysilane, vinyltriethoxysilane, acrylic front three
Oxysilane, 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 2~20% that its dosage is acrylic ester monomer quality；Initiator for azodiisobutyronitrile, azobisisoheptonitrile,
Dibenzoyl peroxide, potassium peroxydisulfate, tert-butyl hydroperoxide, 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, 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 to have obtained low-temperature impact resistance, ageing-resistant, good weatherability, water-tolerant and chemistry
Qualitatively hydroxyl waterborne cation polyurethane-acrylic resin, and the resin is easily compounded 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
Glycol, 6 parts are put into methylol methyl phenyl ethers anisole with stirring, thermometer, nitrogen gas-guide tube, condenser pipe, four mouthfuls of reactions of water knockout drum
In device, 140 DEG C are slowly warming up to, starts stirring, is to slowly warm up to 210 DEG C (heating-up time 5h).0.5h is kept the temperature at 210 DEG C
Afterwards, start to measure acid number, when acid number is down to 5mgKOH/g resins, vacuum abjection dimethylbenzene, vacuum 0.045Kpa, vacuum
1h is dried under reduced pressure, up to unsaturated hydroxyl telechelic polyester.
(2) by 500 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 230 parts of 1,4-butanediol, add with blender, thermometer,
Nitrogen gas-guide 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 keeps the temperature
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, makes 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, up to 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 vinyltrimethoxysilane, 25.2 parts of hydroxyethyl methacrylate are mixed 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；In 85 DEG C of the reaction was continued 1h；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 oneself two
Acid, 650 parts of 2- ethyl -2- butyl 1,3-PDs, 8 parts are put into methylol methyl phenyl ethers anisole with stirring, thermometer, nitrogen air guide
Manage, condenser pipe, in four mouthfuls of reactors of water knockout drum, be slowly warming up to 140 DEG C, start stirring, be to slowly warm up to 210 DEG C of (heatings
Time is 5h)；After 210 DEG C keep the temperature 0.5h, start to measure acid number, when acid number is down to 5mgKOH/g resins, vacuum abjection two
Toluene, after the completion of reaction, vacuum 0.045Kpa, vacuum decompression 1.5h, up to unsaturated hydroxyl telechelic polyester.
(2) by 400 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 280 parts of 1,4-butanediol, add with blender, thermometer,
Nitrogen gas-guide 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 keeps the temperature 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, up to 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 vinyltrimethoxysilane, 28.4 parts of hydroxypropyl acrylate are mixed with 18.9 parts of azodiisobutyronitriles, are taken 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 are added dropwise in 85 DEG C, 3 when small, are controlled depending on monomers flow back speed in condenser pipe
Rate of addition；In 85 DEG C of the reaction was continued 1h；40 DEG C are finally cooled to, 300 mesh net filtrations, that is, obtain 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 oneself two
Acid, 670 parts of 2- ethyl -2- butyl 1,3-PDs, 8 parts are put into methylol methyl phenyl ethers anisole with stirring, thermometer, nitrogen air guide
Manage, condenser pipe, in four mouthfuls of reactors of water knockout drum, be slowly warming up to 140 DEG C, start stirring, be to slowly warm up to 210 DEG C of (heatings
Time is 5h).After 210 DEG C keep the temperature 0.5h, start to measure acid number, when acid number is down to 5mgKOH/g resins, vacuum abjection two
Toluene, after the completion of reaction, vacuum 0.045Kpa, when vacuum decompression drying 2 is small, up to unsaturated hydroxyl telechelic polyester.
(2) by 560 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 230 parts of 1,4-butanediol, add with blender, thermometer,
Nitrogen gas-guide 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, when insulation 1 is small；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, makes 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, up to 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 are mixed 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 oneself two
Acid, 460 parts of hexylene glycols, 7 parts are put into methylol methyl phenyl ethers anisole with stirring, thermometer, nitrogen gas-guide tube, condenser pipe, water knockout drum
Four mouthfuls of reactors in, be slowly warming up to 140 DEG C, start stirring, be to slowly warm up to 210 DEG C (heating-up time 5h).At 210 DEG C
After keeping the temperature 0.5h, start to measure acid number, when acid number is down to 5mgKOH/g resins, vacuum abjection dimethylbenzene, after the completion of reaction, very
Reciprocal of duty cycle is 0.045Kpa, vacuum decompression drying 2h, up to unsaturated hydroxyl telechelic polyester.
(2) by 480 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 210 parts of 1,4-butanediol, add with blender, thermometer,
Nitrogen gas-guide 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 keeps the temperature 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, makes 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, up to 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 vinyltriethoxysilane, 11.3 parts of hydroxy-ethyl acrylate is mixed 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
The reaction was continued 1h；40 DEG C are finally cooled to, 300 mesh net filtrations, that is, obtain 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 oneself
Glycol, 7 parts are put into methylol methyl phenyl ethers anisole with stirring, thermometer, nitrogen gas-guide tube, condenser pipe, four mouthfuls of reactions of water knockout drum
In device, 140 DEG C are slowly warming up to, starts stirring, is to slowly warm up to 210 DEG C (heating-up time 5h).0.5h is kept the temperature at 210 DEG C
Afterwards, start to measure acid number, when acid number is down to 5mgKOH/g resins, vacuum abjection dimethylbenzene, after the completion of reaction, vacuum is
0.045Kpa, vacuum decompression drying 1h, up to unsaturated hydroxyl telechelic polyester.
(2) by 420 parts of above-mentioned unsaturated hydroxyl telechelic polyesters, 190 parts of 1,4-butanediol, add with blender, thermometer,
Nitrogen gas-guide 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 keeps the temperature 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, makes 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 scattered 0.5 it is small when, 60
DEG C decompression abjection acetone, acetone, up to 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 vinyltriethoxysilane, 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 of the reaction was continued 1h；40 DEG C are finally cooled to, 300 mesh net filtrations, that is, obtain 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 include the following steps：
A) mass parts are pressed, 550~650 parts of polyacids, 600~1000 parts of polyalcohols and 5~9 parts react 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 neutralizers and
3800-4500 parts of 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, neutralizer 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；Neutralizer 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, ethyl methacrylate, 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) dihydric alcohol, trimethylolpropane, trimethyolol propane monoallyl ether that polyalcohol described in is 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, tetrahydrophthalic anhydride, succinic acid, glutaric acid, ethanedioic acid, fumaric acid, dimeric dibasic acid, hexahydrophthalic anhydride 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, bis- hydroxypropyl of N, N-
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 vinyltrimethoxysilane, vinyltriethoxysilane, 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, tert-butyl hydroperoxide, 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%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192031A (en) * | 2017-12-29 | 2018-06-22 | 何俊 | A kind of preparation method of environment-protecting polyurethane-acrylic resin |
| CN109232824A (en) * | 2018-09-03 | 2019-01-18 | 武汉纺织大学 | Cation type polyurethane modified polyacrylate emulsion and preparation method thereof with cross-linked core-shell structure |
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|---|---|---|---|---|
| CN105418853A (en) * | 2015-11-27 | 2016-03-23 | 武汉仕全兴聚氨酯科技股份有限公司 | Hydroxyl type water-borne cationic polyurethane-acrylic acid resin and preparation method thereof |
| CN107629170A (en) * | 2017-09-07 | 2018-01-26 | 绵阳凤面科技有限公司 | A kind of good environment-protecting polyurethane acrylic resin of weatherability and preparation method thereof |
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2017
- 2017-12-07 CN CN201711283829.7A patent/CN107936183A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418853A (en) * | 2015-11-27 | 2016-03-23 | 武汉仕全兴聚氨酯科技股份有限公司 | Hydroxyl type water-borne cationic polyurethane-acrylic acid resin and preparation method thereof |
| CN107629170A (en) * | 2017-09-07 | 2018-01-26 | 绵阳凤面科技有限公司 | A kind of good environment-protecting polyurethane acrylic resin of weatherability and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192031A (en) * | 2017-12-29 | 2018-06-22 | 何俊 | A kind of preparation method of environment-protecting polyurethane-acrylic resin |
| CN109232824A (en) * | 2018-09-03 | 2019-01-18 | 武汉纺织大学 | Cation type polyurethane modified polyacrylate emulsion and preparation method thereof with cross-linked core-shell structure |
| CN109232824B (en) * | 2018-09-03 | 2020-11-27 | 武汉纺织大学 | Cationic polyurethane modified polyacrylate emulsion with crosslinked core-shell structure and preparation method thereof |
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