CN102653595B - Preparation method of polyester modified hydroxyl polyacrylate, and paint containing polyester modified hydroxyl polyacrylate - Google Patents
Preparation method of polyester modified hydroxyl polyacrylate, and paint containing polyester modified hydroxyl polyacrylate Download PDFInfo
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- CN102653595B CN102653595B CN 201210131938 CN201210131938A CN102653595B CN 102653595 B CN102653595 B CN 102653595B CN 201210131938 CN201210131938 CN 201210131938 CN 201210131938 A CN201210131938 A CN 201210131938A CN 102653595 B CN102653595 B CN 102653595B
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Abstract
The invention relates to a polyester modified hydroxyl polyacrylate and to the field of organic polymer compounds; the modified hydroxyl polyacrylate is prepared by a method comprising the following steps of: (1) mixing hydroxyl polyester and anhydride-containing hydroxyl polyacrylate at the weight ratio of 1:(2-4), carrying out reaction at 150-180 DEG C for 1.5-6 hours until the acid value of the polyester modified hydroxyl polyacrylate is less than 15mg KOH/g, and cooling; and (2) distilling for removing a solvent, and adjusting the solid content to be 70-80%, thus obtaining the polyester modified hydroxyl polyacrylate with high solid content. The polyester modified hydroxyl polyacrylate has the advantages of polyester and polyacrylate, and has excellent pigment wetting dispersing performance. Double-component paint prepared by the polyester modified hydroxyl polyacrylate is rapid in drying speed, high in coating hardness and excellent in chemical resistance and weather resistance; the solid content is high, so that the fullness of coating is improved, and the construction cost is saved; and the paint can be used for coating and finishing automobile paint and car refinishing paint, and is also used for plastic paint, leather finishing agent, adhesive agent and ink.
Description
Technical field
The invention belongs to the organic high molecular compound field, relate to the macromolecular compound that the reaction of esterification and carbon-to-carbon unsaturated bond obtains, be specifically related to polyacrylic ester.
Background technology
Along with the enhancing of people's environmental consciousness and perfecting of environmental regulation, the use of volatile organic compounds (VOC) and hazardous air pollutants (HAP) more and more is restricted in the conventional solvent type coating, and high solid coating is subjected to people and more and more pays close attention to.It films the dual-component coating that hydroxyl polyacrylic ester and polyurethane curing agent are formed and has excellent weathering resistance and chemical mediator-resitant property, is widely used in particularly car paint field of high-grade paint.The solids content of the hydroxyl polyacrylic ester of Shi Yonging low (40-65%) in the market, wetting dispersive ability to color stuffing is poor, poor with the consistency of polyurethane curing agent, its film ply adhesion and poor in flexibility have limited it in the particularly application in the automobile finish of high-grade car paint; And contain a large amount of organic solvents in the coating and in use evaporate in the atmosphere, both contaminate environment was wasted resource again; Therefore, need to carry out modification to existing hydroxyl polyacrylic ester, to improve the solids content of resin, promote itself and the consistency and raising film performance of solidifying agent.
Obtaining highly filled hydroxyl polyacrylic ester method commonly used has the suitable initiator of selection, improves initiator concentration, and the rising temperature of reaction adopts the chain-transfer agent of high density etc., as Chinese patent application 03131971.8.These methods can cause monomer conversion low, and residual monomer and chain-transfer agent pollute the environment, and influence durability of products, improve synthetic cost, increase the unsafe factor on producing.Adopt the method for blend as adopting blending and modifying Hydroxylated acrylic resins such as urethane, polyester, polyethers, oxazolidine and organosilicon polymer, though can improve the execution of coating solid content, exist comixing compatibility poor, the poor transparency of filming reduces the decorative effect of filming.Adopt the method for modification by copolymerization to be conducive to obtain high-performance and highly filled hydroxyl polyacrylic ester, the vibrin of general earlier synthetic carbon-carbon double bonds is as the copolyreaction of macromonomer participation Acrylic Acid Monomer, as patent application 200710031047.4.In the described scheme of above-mentioned patent application 200710031047.4, though the consistency between resin Composition is more effective than the blending and modifying, but because the reactive behavior of the sterically hindered carbon-carbon double bond that makes macromonomer is not as good as the small molecules acrylic ester monomer, the transformation efficiency that macromonomer participates in copolyreaction is not high; In addition, because of the existence of macromonomer, the transformation efficiency of the rate of polymerization of acrylate monomer and final monomer must reduce, and contains a large amount of residual monomers in the polymerisate and pollutes the environment in the reaction system of described scheme.
In sum, the problem of present following several respects of hydroxyl polyacrylic ester ubiquity: (1) solid content is low, generally all at 40-60%; (2) resin is bad to the wetting generation performance of color stuffing; (3) consistency of hydroxyl polyacrylic ester and isocyanate curing agent is poor, and bad with the two-pack appearance of film of its preparation, gloss is low, the difficult user demand of satisfying car paint.(4) residual acrylic acid esters monomer content height, production cost height, production security are bad etc.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of polyester modification hydroxyl polyacrylic ester, the solid content height of the polyester modification hydroxyl polyacrylic ester of this method preparation.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of preparation method of polyester modification hydroxyl polyacrylic ester, this method is made up of following steps:
(1) with hydroxyl polyester and the hydroxyl polyacrylic ester that contains acid anhydrides by hydroxyl polyester: hydroxyl polyacrylic ester=1 that contains acid anhydrides: the weight ratio of 3-6 is mixed, 150-180 ℃ of backflow polycondensation to the acid number of polyester modification hydroxyl polyacrylic ester less than 15mgKOH/g, be cooled to 140 ℃;
(2) distillation removes solvent to adjust solid content is more than 75%, is down to room temperature and gets final product;
In the above-mentioned steps (1), the hydroxyl mass percent of described hydroxyl polyester is 0.5-3.5%, by dibasic alcohol, trivalent alcohol, diprotic acid and unit are sour by dibasic alcohol: trivalent alcohol: diprotic acid: the weight ratio of unit acid=28-40: 5-10: 43-52: 5-19 prepares by the following method: with dibasic alcohol, trivalent alcohol, diprotic acid and unit acid join in the reactor, at 150-180 ℃ of decompression condensation polymerization 2-5h, be cooled to 140 ℃ then, add dibasic alcohol, trivalent alcohol, the dimethylbenzene of diprotic acid and unit acid gross weight 8-15%, react acid number to hydroxyl polyester less than 20mgKOH/g at 180-230 ℃, be cooled to 140 ℃, adding dimethylbenzene, to be diluted to solids content be 70%; Wherein,
Described dibasic alcohol is 1, ammediol, 1,4-butyleneglycol, glycol ether, 1,6-hexylene glycol, cyclohexanedimethanol, 2,2, one or more in 4-neopentyl glycol, glycol ether and the neopentyl glycol;
Described trivalent alcohol is one or both in glycerine and the TriMethylolPropane(TMP);
Described diprotic acid is one or more in hexanodioic acid, nonane diacid, Tetra hydro Phthalic anhydride, m-phthalic acid and the hexahydrophthalic acid anhydride;
The acid of described unit is one or more in phenylformic acid, p-tert-butyl benzoic acid, hydroabietic acid and the maleopimaric acid;
In the above-mentioned steps (1), the described hydroxyl polyacrylic ester that contains acid anhydrides is prepared by the following method by the initiator of Acrylic Acid Monomer, Acrylic Acid Monomer weight 2.0-6.0w% and Acrylic Acid Monomer weight 0.5-1.0 (W/W) times organic solvent: the 1-80w% that adds organic solvent in reactor, under 120-150 ℃, drip Acrylic Acid Monomer, initiator and residue organic solvent in the 3-6h, insulation 1h; Be cooled to room temperature; Wherein said Acrylic Acid Monomer is made up of 35-75 weight part (methyl) alkyl acrylate, 9-50 parts by weight of styrene, 10-20 weight part (methyl) acrylic acid hydroxy alkyl ester and 2-5 weight part cis-butenedioic anhydride; Wherein,
Described (methyl) alkyl acrylate is a kind of or two or more in methyl methacrylate, Jia Jibingxisuanyizhi, (methyl) butyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, tert-butyl methacrylate, (methyl) isobornyl acrylate and (methyl) vinylformic acid cyclohexyl ester;
Described (methyl) crylic acid hydroxy ester is one or more in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate and the methacrylic acid-2-hydroxy propyl ester;
Described organic solvent is one or more in N-BUTYL ACETATE, dimethylbenzene, 1-Methoxy-2-propyl acetate, propylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the dipropylene glycol monobutyl ether acetate;
Described initiator is one or more in tert-butyl hydroperoxide acetic ester, tert butyl peroxy benzoate, benzoyl peroxide, t-amyl peroxy acetic ester and the dicumyl peroxide.
Among the preparation method of the present invention, the hydroxyl polyester is to adopt the decompression condensation polymerization to obtain, and the best vacuum tightness of the polycondensation of wherein reducing pressure is to carry out under the condition of 0.02-0.1Mpa.
Among the preparation method of the present invention, the described distillating method of step 2 is this area distillating method commonly used, can be distillation commonly used, can also be underpressure distillation.Distillating method of the present invention better is underpressure distillation, is that 100-120 ℃ and vacuum tightness are to carry out under the condition of 0.02-0.1Mpa in temperature preferably.
Polyester modification hydroxyl polyacrylic ester of the present invention can be mixed with two-component coating with isocyanate curing agent.
A kind of acrylic coating, polyester modification hydroxyl polyacrylic ester and the isocyanate curing agent of this coating the method for the invention preparation, wherein the amount of substance of the OH group in the NCO group in the isocyanate curing agent and the polyester modification hydroxyl polyacrylic ester is than being 1.0-1.5: 1.
Isocyanate curing agent of the present invention is this area solidifying agent commonly used, can be hexamethylene diisocyanate.Isocyanate curing agent of the present invention better is the L-75 of Beyer Co., Ltd, the N-75 of Beyer Co., Ltd, the military field D268 of the N3390 of Beyer Co., Ltd and Mitsui wherein one or more.
Acrylic coating of the present invention can also contain this area coatings additive(s) commonly used, for example defoamer, flow agent, pigment wetting dispersing agent etc.
Described defoamer can be silicone based polymkeric substance, as the BYK-052 of German BIC Corp, BYK-060N, BYK-141 and BYK-392 wherein one or more.
Described flow agent is the methyl phenyl silicone base polymer, as the BYK-300 of state BIC Corp, BYK-306, BYK-356, BYK-358N wherein one or more.
Described pigment wetting dispersing agent is the BYK-9076 of German BIC Corp, DisperBYK-161, DisperBYK-163, DisperBYK-2050 wherein one or more.
Two components are filmed and are had more high gloss and excellent appearance.Film and have excellent physics and chemical property simultaneously, comprise advantages such as cross-linking density height, hardness height, the chemical mediator-resitant property of filming are good, Heat stability is good, the fast and easy polishing of rate of drying, can be used as various vehicle paint bases, finish paint and retouching paint, also can make plastics, hide finishes.
Ultimate principle of the present invention: this patent adopts the decompression condensation polymerization method synthesis of hydroxy polyester that combines with the solvent refluxing condensation polymerization method, reduce on the one hand and avoid losing with reflux solvent of in condensation polymerization process polyvalent alcohol, influence the quality of polyester, increase the cost of polyester.Adopt the synthetic polyacrylic ester that contains acid anhydrides of free radical solution polymerization method, similar with the highly filled hydroxyl polyacrylic ester of routine synthetic method, comprise preferred initiator, improve initiator concentration, rising polymeric reaction temperature etc., different is to adopt cis-butenedioic anhydride to replace (methyl) vinylformic acid, the synthetic polyacrylic ester that contains acid anhydrides.According to suitable proportion hydroxyl polyester is mixed with polyacrylic ester then, the low temperature ring-opening reaction by acid anhydrides is grafted on the polyacrylic ester chain polyester to greatest extent, obtains highly filled hydroxyl polyacrylic ester.This polyester modification hydroxy acrylate not only compatibility between components is good, and with the consistency of solidifying agent might as well.This polyester modification hydroxy acrylate combines the color stuffing wettability of polyester excellence, improves the hydroxyl polyacrylic ester to the wetting dispersive ability of color stuffing, and the two-pack of preparation films particularly that colored paint has high gloss and excellent appearance.Filming has excellent physics and chemical property simultaneously, can be used as various vehicle paint bases, finish paint and retouching paint, also can make water-based plastic, hide finishes.
Polyester modification hydroxyl polyacrylic ester of the present invention compared with prior art has the following advantages:
(1) the low temperature ring-opening reaction by acid anhydrides is grafted on the polyacrylic ester chain polyester to greatest extent, ensure polyester modification hydroxy acrylate compatibility between components, the consistency of raising and solidifying agent strengthens the hydroxyl polyacrylic ester to the wetting dispersive ability of color stuffing.
(2) film and have excellent physics and chemical property simultaneously, comprise that cross-linking density height, hardness height, the chemical mediator-resitant property of filming are good, Heat stability is good, rate of drying is fast and easy advantage such as polishing, can be used as various vehicle paint bases, finish paint and retouching paint.
(3) this polyester modification hydroxy acrylate solids content height, the content of total volatile organic compound (TVOC) is less than 400g/L in the product.Satisfy the requirement of environmental labelling product authentication techniques fully, belong to Green Product.
Embodiment
Below be specific embodiments of the invention, but be not limited to described embodiment.
Embodiment 1
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.02MPa and 180 ℃ decompression polycondensation 5h down in vacuum tightness, lower the temperature then below 140 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 8% dimethylbenzene, 230 ℃ react to the hydroxyl polyester acid number be 18mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 70% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 50w%, under 120 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 3h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester mixing that contains acid anhydrides that the hydroxyl polyester that 20g step 1 is obtained and 100g step 2 obtain at the acid number 14.5mgKOH/g of 150 ℃ of backflow 6h to the polyester modification hydroxy acrylate, is cooled to room temperature;
(b) be that 120 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.06Mpa in temperature then, adjusting solid content is 75%, and cooling filters and packages.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 78%; Viscosity: 3000mpas; OH%=2.60%; Number-average molecular weight Mn=4300, dispersity=3.2;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
The mol ratio 1.5: 1 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent N3390 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
Show the over-all properties of highly filled polyester modification polyacrylic ester dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 2
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.1MPa and 150 ℃ decompression polycondensation 2h down in vacuum tightness, lower the temperature then below 140 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 15% dimethylbenzene, 220 ℃ react to acid number be 15mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 70% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 80w%, under 135 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 3h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 16g step 1 is obtained and 96g step 2 obtain mixes, and is 14.0mgKOH/g at 150 ℃ of backflow 3h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 100 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.1Mpa in temperature then, adjusting solid content is 82%, cooling, filter, packing.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 82%; Viscosity: 2500mpas; OH%=3.0%; Number-average molecular weight Mn=5500, dispersity=2.8;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
The mol ratio 1.2: 1 of NCO group and polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent N-75 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
The over-all properties of the highly filled polyester modification polyacrylic ester of table 2 dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 3
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.08MPa and 160 ℃ decompression polycondensation 4h down in vacuum tightness, lower the temperature then below 140 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 12% dimethylbenzene, 210 ℃ react to the acid number of hydroxyl polyester be 16mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 80% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 50w%, under 150 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 4h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 30g step 1 is obtained and 90g step 2 obtain mixes, and is 13.5mgKOH/g at 150 ℃ of backflow 4h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 110 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.08Mpa in temperature then, adjusting solid content is 80%.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 80%; Viscosity: 2800mpas; OH%=2.50%; Number-average molecular weight Mn=6300, dispersity=2.4;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
The mol ratio 1.0: 1.0 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent D268 (Japanese military field) according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
Show the over-all properties of highly filled polyester modification polyacrylic ester dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 4
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.03MPa and 170 ℃ decompression polycondensation 5h down in vacuum tightness, lower the temperature then below 150 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 10% dimethylbenzene, 180 ℃ react to the acid number of hydroxyl polyester be 19mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 80% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 80w%, under 120 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 3h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 20g step 1 is obtained and 80g step 2 obtain mixes, and is 12mgKOH/g at 150 ℃ of backflow 5h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 120 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.06Mpa in temperature then, adjusting solid content is 80%.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 80%; Viscosity: 3000mpas; OH%=2.55%; Number-average molecular weight Mn=5800, dispersity=3.0;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
The mol ratio 1.3: 1 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent N3390 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
Show the over-all properties of highly filled polyester modification polyacrylic ester dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 5
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.03MPa and 180 ℃ decompression polycondensation 5h down in vacuum tightness, lower the temperature then below 150 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 8% dimethylbenzene, 230 ℃ react to the acid number of hydroxyl polyester be 16mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 80% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 50w%, under 120 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 3h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 20g step 1 is obtained and 100g step 2 obtain mixes, and is 14.5mgKOH/g at 150 ℃ of backflow 3h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 120 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.06Mpa in temperature then, adjusting solid content is 80%.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 80%; Viscosity: 3300mpas; OH%=1.50%; Number-average molecular weight Mn=3800, dispersity=3.2; Storage at normal temperature stability 1 year;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
The mol ratio 1.2: 1 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent N3390 and N 75 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
Show the over-all properties of highly filled polyester modification polyacrylic ester dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 6
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.02MPa and 180 ℃ decompression polycondensation 5h down in vacuum tightness, lower the temperature then below 140 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 8% dimethylbenzene, 220 ℃ react to the acid number of hydroxyl polyester be 18mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 70% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 50w%, under 120 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 3h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 20g step 1 is obtained and 100g step 2 obtain mixes, and is 14.5mgKOH/g at 150 ℃ of backflow 6h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 120 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.06Mpa in temperature then, adjusting solid content is 75%, and cooling filters and packages.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 78%; Viscosity: 2500mpas; OH%=2.40%; Number-average molecular weight Mn=4400, dispersity=3.4;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
Above-mentioned high solids content polyester modification hydroxyl polyacrylic ester 80g
Thinner dimethylbenzene 30g
Solidifying agent N3390 (Beyer Co., Ltd) 30g
The mol ratio 1.5: 1 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent N3390 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
Show the over-all properties of highly filled polyester modification polyacrylic ester dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 7
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.1MPa and 150 ℃ decompression polycondensation 4h down in vacuum tightness, lower the temperature then below 140 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 15% dimethylbenzene, 220 ℃ react to the acid number of hydroxyl polyester be 15mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 70% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 80w%, under 135 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 3h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 16g step 1 is obtained and 96g step 2 obtain mixes, and is 14.0mgKOH/g at 150 ℃ of backflow 3h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 100 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.1Mpa in temperature then, adjusting solid content is 82%, cooling, filter, packing.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 81%; Viscosity: 2800mpas; OH%=3.0%; Number-average molecular weight Mn=5300, dispersity=2.6;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
The mol ratio 1.2: 1 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent N-75 and N3390 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
The over-all properties of the highly filled polyester modification polyacrylic ester of table 2 dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 8
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.08MPa and 160 ℃ decompression polycondensation 4h down in vacuum tightness, lower the temperature then below 140 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 12% dimethylbenzene, 210 ℃ react to the acid number of hydroxyl polyester be 16mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 80% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 50w%, under 150 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 4h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 30g step 1 is obtained and 90g step 2 obtain mixes, and is 13.5mgKOH/g at 150 ℃ of backflow 3h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 110 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.08Mpa in temperature then, adjusting solid content is 80%.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 81%; Viscosity: 2900mpas; OH%=2.45%; Number-average molecular weight Mn=6800, dispersity=2.8;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
The mol ratio 1.0: 1.0 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent D268 (Japanese military field) and N3390 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
Show the over-all properties of highly filled polyester modification polyacrylic ester dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 9
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.06MPa and 170 ℃ decompression polycondensation 5h down in vacuum tightness, lower the temperature then below 150 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 10% dimethylbenzene, 190 ℃ react to the acid number of hydroxyl polyester be 17mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 80% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 80w%, under 120 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 3h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 20g step 1 is obtained and 80g step 2 obtain mixes, and is 15mgKOH/g at 150 ℃ of backflow 5h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 120 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.06Mpa in temperature then, adjusting solid content is 80%.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 80%; Viscosity: 3200mpas; OH%=2.55%; Number-average molecular weight Mn=6200, dispersity=3.2;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
The mol ratio 1.3: 1 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent N3390 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
Show the over-all properties of highly filled polyester modification polyacrylic ester dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 10
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.04MPa and 180 ℃ decompression polycondensation 3h down in vacuum tightness, lower the temperature then below 150 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 8% dimethylbenzene, 230 ℃ react to the acid number of hydroxyl polyester be 16mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 80% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 50w%, under 120 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 3h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 20g step 1 is obtained and 100g step 2 obtain mixes, and is 13mgKOH/g at 150 ℃ of backflow 6h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 120 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.06Mpa in temperature then, adjusting solid content is 80%.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 80%; Viscosity: 3800mpas; OH%=1.50%; Number-average molecular weight Mn=6800, dispersity=3.6;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
The mol ratio 1.2: 1 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
According to above-mentioned prescription, with polyester modification hydroxyl polyacrylic ester, flow agent, defoamer, thinner etc., suitably disperseing 15 minutes under the dispersing speed.Take by weighing solidifying agent N3390 and N 75 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
Show the over-all properties of highly filled polyester modification polyacrylic ester dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Embodiment 11
The consumption of each component of hydroxyl polyester:
Dibasic alcohol, trivalent alcohol, diprotic acid and unit acid are joined in the reactor, be 0.02MPa and 180 ℃ decompression polycondensation 5h down in vacuum tightness, lower the temperature then below 140 ℃, add dibasic alcohol, trivalent alcohol, diprotic acid and unit acid gross weight 8% dimethylbenzene, 230 ℃ react to the acid number of hydroxyl polyester be 17mgKOH/g, be cooled to 140 ℃, add dimethylbenzene and be diluted to 70% solids content.
(2) contain the hydroxyl polyacrylic ester of acid anhydrides:
The consumption that contains each component of hydroxyl polyacrylic ester of acid anhydrides:
In reactor, add the organic solvent of 50w%, under 120 ℃, drip the mixture of Acrylic Acid Monomer, initiator and residue organic solvent in the 3h, insulation 1h; Be cooled to room temperature and obtain containing the hydroxyl polyacrylic ester of acid anhydrides.
(3) preparation of high solids content polyester modification hydroxyl polyacrylic ester:
(a) the hydroxyl polyacrylic ester that contains acid anhydrides that the hydroxyl polyester that 20g step 1 is obtained and 100g step 2 obtain mixes, and is 15.5mgKOH/g at 150 ℃ of backflow 6h to the acid number of polyester modification hydroxyl polyacrylic ester, cooling;
(b) be that 120 ℃ and vacuum tightness are that underpressure distillation removes solvent under the condition of 0.06Mpa in temperature then, adjusting solid content is 75%, and cooling filters and packages.
(4) performance of high solids content polyester modification hydroxyl polyacrylic ester:
Solid content: 78%; Viscosity: 3100mpas; OH%=2.73%; Number-average molecular weight Mn=4700, dispersity=2.9;
(5) high solids content polyester modification hydroxyl polyacrylic ester two-component coating
(a) prescription
Above-mentioned high solids content polyester modification hydroxyl polyacrylic ester 80g
Solidifying agent N3390 (Beyer Co., Ltd) 30g
The mol ratio 1.5: 1 of NCO group and high solids content polyester modification hydroxyl polyacrylic ester OH group in the solidifying agent wherein.
(b) compound method and use
Take by weighing solidifying agent N3390 according to prescription, and under dispersion state, slowly add polyester modification hydroxyl polyacrylic ester, continue to disperse to obtain in 5 minutes two-component coating.
The high solids content polyester modification hydroxyl polyacrylic ester two-component coating that obtains was solidified dry 48 days at normal temperatures.
(c) preparation dual-component coating, it is as shown in the table for its performance:
Show the over-all properties of highly filled polyester modification polyacrylic ester dual-component coating
The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed.
The test of anti-ethanol is that the paint film that drying is good is immersed in the ethanolic soln, detects the gloss of paint film behind the 48h.
Anti-5%H
2SO
4Test be that the paint film that drying is good is immersed in 5%H
2SO
4Whether in the solution, observe paint film behind the 72h and exist and break, phenomenons such as foaming if do not have, think that coating passes through anti-5%H
2SO
4Test.
Whether the test of anti-5%NaOH is that the paint film that drying is good is immersed in the 5%NaOH solution, observe paint film behind the 72h and exist and break, and phenomenons such as foaming if do not have, are thought the test of coating by anti-5%NaOH.
Claims (5)
1. the preparation method of a polyester modification hydroxyl polyacrylic ester, this method is made up of following steps:
(1) hydroxyl polyester is mixed by the weight ratio that Qiang base Ju Zhi ︰ contains the hydroxyl polyacrylic ester=1:3-6 of acid anhydrides with the hydroxyl polyacrylic ester that contains acid anhydrides, 150-180 ℃ of backflow polycondensation to the acid number of polyester modification hydroxyl polyacrylic ester less than 15mgKOH/g, be cooled to 140 ℃;
(2) distillation removes solvent to adjust solid content is more than 75%, is down to room temperature and gets final product;
In the above-mentioned steps (1), the hydroxyl mass percent of described hydroxyl polyester is 0.5-3.5%, by dibasic alcohol, trivalent alcohol, diprotic acid and unit acid prepare by the following method by the weight ratio of Er Yuan Chun ︰ San Yuan Chun ︰ Er Yuan Suan ︰ unit acid=28-40 ︰ 5-10 ︰ 43-52 ︰ 5-19: with dibasic alcohol, trivalent alcohol, diprotic acid and unit acid join in the reactor, at 150-180 ℃ of decompression condensation polymerization 2-5h, be cooled to 140 ℃ then, add dibasic alcohol, trivalent alcohol, the dimethylbenzene of diprotic acid and unit acid gross weight 8-15%, react acid number to hydroxyl polyester less than 20mgKOH/g at 180-230 ℃, be cooled to 140 ℃, adding dimethylbenzene, to be diluted to solids content be 70%; Wherein,
Described dibasic alcohol is 1, ammediol, 1,4-butyleneglycol, glycol ether, 1,6-hexylene glycol, cyclohexanedimethanol, 2,2, one or more in 4-neopentyl glycol and the neopentyl glycol;
Described trivalent alcohol is one or both in glycerine and the TriMethylolPropane(TMP);
Described diprotic acid is one or more in hexanodioic acid, nonane diacid, Tetra hydro Phthalic anhydride, m-phthalic acid and the hexahydrophthalic acid anhydride;
The acid of described unit is one or more in phenylformic acid, p-tert-butyl benzoic acid, hydroabietic acid and the maleopimaric acid;
In the above-mentioned steps (1), the described hydroxyl polyacrylic ester of acid anhydrides that contains is by initiator and the Acrylic Acid Monomer weight 0.5-1.0(W/W of Acrylic Acid Monomer, Acrylic Acid Monomer weight 2.0-6.0w%) doubly organic solvent prepares by the following method: the 1-80w% that adds organic solvent in reactor, under 120-150 ℃, drip Acrylic Acid Monomer, initiator and residue organic solvent in the 3-6h, insulation 1h; Be cooled to room temperature; Wherein said Acrylic Acid Monomer is made up of 35-75 weight part (methyl) alkyl acrylate, 9-50 parts by weight of styrene, 10-20 weight part (methyl) acrylic acid hydroxy alkyl ester and 2-5 weight part cis-butenedioic anhydride; Wherein,
Described (methyl) alkyl acrylate is a kind of or two or more in methyl methacrylate, Jia Jibingxisuanyizhi, (methyl) butyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, tert-butyl methacrylate, (methyl) isobornyl acrylate and (methyl) vinylformic acid cyclohexyl ester;
Described (methyl) acrylic acid hydroxy alkyl ester is one or more in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate and the methacrylic acid-2-hydroxy propyl ester;
Described organic solvent is one or more in N-BUTYL ACETATE, dimethylbenzene, 1-Methoxy-2-propyl acetate, propylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the dipropylene glycol monobutyl ether acetate;
Described initiator is one or more in tert-butyl hydroperoxide acetic ester, tert butyl peroxy benzoate, benzoyl peroxide, t-amyl peroxy acetic ester and the dicumyl peroxide.
2. the preparation method of the described polyester modification hydroxyl of claim 1 polyacrylic ester is characterized in that, the decompression condensation polymerization reaction described in the hydroxyl polyester preparation method is to carry out under the 0.02-0.1MPa in vacuum tightness.
3. the preparation method of the described polyester modification hydroxyl of claim 1 polyacrylic ester is characterized in that, the distillation described in the step (2) removes solvent, and to adjust solid content be to be that 100-120 ℃ and vacuum tightness are to carry out under the condition of 0.02-0.1MPa in temperature.
4. acrylic coating, this coating contains the polyester modification hydroxyl polyacrylic ester of isocyanate curing agent and one of them described method preparation of claim 1 to 3, and wherein the amount of substance of the OH group in the NCO group in the isocyanate curing agent and the polyester modification hydroxyl polyacrylic ester is than being 1.0-1.5:1.
5. the described acrylic coating of claim 4 is characterized in that, described isocyanate curing agent is hexamethylene diisocyanate.
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| CN103756538A (en) * | 2013-12-12 | 2014-04-30 | 江苏普兰纳涂料有限公司 | Ultra-quick drying varnish used for automobiles |
| CN105037614B (en) * | 2015-09-08 | 2017-01-25 | 陕西科技大学 | High-solid-content leather finishing agent prepared on basis of miniemulsion polymerization method and method thereof |
| CN106065545B (en) * | 2016-06-03 | 2017-08-25 | 华南理工大学 | A kind of rosin based aqueous UV solidifications paper surface sizing agent of high water resistant quick-dry type and preparation method thereof |
| CN107177020A (en) * | 2017-04-24 | 2017-09-19 | 东莞市隆海新材料科技有限公司 | A kind of maleopimaric acid modified polyacrylate dispersant and preparation method thereof |
| CN107216427A (en) * | 2017-06-15 | 2017-09-29 | 中山市大涂料有限公司 | A kind of block modified polyurethane/acrylate emulsion of unsaturated polyester resin and preparation method thereof |
| CN107903854A (en) * | 2017-12-25 | 2018-04-13 | 江苏景宏新材料科技有限公司 | A kind of acrylate pressure-sensitive adhesive containing unsaturated polyester (UP) and preparation method thereof |
| CN109535409B (en) * | 2018-11-21 | 2021-05-11 | 安庆北化大科技园有限公司 | Photosensitive resin of amine modified polyester acrylate and synthetic method thereof |
| CN113372506B (en) * | 2021-06-28 | 2022-11-29 | 宁波中南联创科技有限公司 | Preparation method of polyester grafted polyacrylate macromolecule for transparent powder coating |
| CN115304757B (en) * | 2022-07-20 | 2023-08-11 | 成都托展新材料股份有限公司 | Block type ink resin and preparation method thereof |
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| CN101845118B (en) * | 2010-04-27 | 2011-08-10 | 广东天银化工实业有限公司 | Preparation method of hydroxy fluorine-containing water-based acrylic resin-polyurethane hybrid |
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