CN100427558C - GMA fluorocarbon acrylic acid powdery paints and its preparation method - Google Patents
GMA fluorocarbon acrylic acid powdery paints and its preparation method Download PDFInfo
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- CN100427558C CN100427558C CNB2006100427553A CN200610042755A CN100427558C CN 100427558 C CN100427558 C CN 100427558C CN B2006100427553 A CNB2006100427553 A CN B2006100427553A CN 200610042755 A CN200610042755 A CN 200610042755A CN 100427558 C CN100427558 C CN 100427558C
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Abstract
The present invention relates to GMA fluorocarbon acrylic acid powdery paint and a preparation method thereof. The GMA fluorocarbon acrylic acid powdery paint comprises components of the following weight percentage: 55.0% to 86.0% of GMA fluorocarbon acrylic resin, 0% to 20.0% of polyester resin, 6.5% to 19.0% of dicarboxylic acid, 0.5% to 5.0% of levelling agent, 0.2% to 0.3% of degassing agent, 0.02% to 0.05% of curing catalyst, 5.0% to 30.0% of titanium white powder, 5.0% to 30.0% of deposited barium sulphate and 0% to 10.0% of light calcium carbonate. In the preparation method, materials are prepared according to the components with the compounding ratio and then are mixed in a high speed for 1 to 2 minutes, and the degassing agent, the curing catalyst, the titanium white powder, the deposited barium sulphate and the light calcium carbonate are added and mixed with each other for 3 to 5 minutes; mixtures of all the components are molten and extruded in an extruding machine, and the temperature of a feeding section is from 80 to 92 DEG C; the temperature of a melting section is from 95 to 105 DEG C, and the temperature of a mixing section is from 110 to 120 DEG C; the temperature of a discharging section is from 100 to 110 DEG C. Molten materials are pressed into sheets by a tablet press, and the sheets are sent into a flour mill after being cooled and pulverized for pulverization in different grades; ultrafine powder is separated and is sieved to obtain products.
Description
Technical field
The present invention relates to a kind of preparation method of acrylic powder coating, particularly GMA fluorocarbon acrylic acid process for preparing resins.
Technical background
The coating that acrylic powder coating is a kind of ornamental, weathering resistance, guarantor's light tint retention is good, have " 4E " characteristics (high-performance, environmental friendliness, province's energy, high-level efficiency), can be widely used in the application in fields such as refrigerator, washing machine, bike, motorcycle, its use properties obviously is better than epoxide powder coating, epoxy-polyester powder coating etc.
The research of acrylic powder coating has two comparatively active routes in the world, a kind of is the Hydroxylated acrylic resin-blocked isocyanate route in Europe, the type coating can be emitted irritant gas when solidifying, aggravating working environment also has influence on film ornamental simultaneously; Another is that the U.S., Japan are the route of film forming matter with epoxy group(ing) vinylformic acid-diprotic acid, and the type has ornamental high advantage, but because cross-linking density is not high, and mechanical property does not increase, the modification of coating is devoted in therefore a lot of work.
Open among clear 50-158621 and the clear 50-159518 of Te Kai as the Japanese Patent spy and to have introduced acrylic powder coating, the film forming matter that uses is formed by (methyl) acrylate that contains epoxy group(ing), (methyl) alkyl acrylate and other monomer copolymerizations, use with other mixed with resin that contain glyceryl ester simultaneously, to increase cross-linking density, the performance powder coating that this method obtains is good, but the modified resin price is higher, has limited applying of powder coating.
CN1123302A has introduced acrylic powder coating, its base-material is the acrylic resin that contains epoxy group(ing), only use 3 kinds of monomer copolymerizations to form, has low, the advantage of simple technology of cost, but its solidifying agent is a diprotic acid, and cross-linking density is still on the low side, because the consistency of diprotic acid and acrylic resin system is not very desirable, form separating out of diprotic acid easily on the surface, have influence on the gloss of filming.Ornamental not high, and bake out temperature higher (180 ℃/20 minutes).CN1592772A relates to the composition of acrylic powder coating: 1) second-order transition temperature is 45～100 ℃, the glycidyl acrylic resin of Mn=2500～5000, GMA content 60%～90% (wt), 2) second-order transition temperature-50～30 ℃, the glycidyl acrylic resin of Mn=5000～20000, GMA content 5%～40% (wt), 3) the poly carboxylic acid component, the powder coating of being made up of above-mentioned 3 kinds of compositions has good curability at low temperatures and good storage stability.But this coating has used 2 kinds of acrylic resin collocation with high and low second-order transition temperature, and technology is numerous and diverse, and therefore, the GMA acrylic powder coating still has improved necessity and space.
In addition, patents such as above patent and EP-A-0038635, JP52077137, EP-A-0544206, US4988767, CN1443817A all do not relate to fluorocarbon acrylic acid powdery paints.
Summary of the invention
The objective of the invention is to improve ornamental, weathering resistance, the low-temperature curing performance of GMA fluorocarbon acrylic acid powdery paints, improve its physical and mechanical properties in addition, impact property is simplified its technology.
The GMA fluorocarbon acrylic acid powdery paints, by weight percentage, its component is:
GMA fluorocarbon acrylic acid resin 55.0%～82.0%
Vibrin 0%～20.0%
Di-carboxylic acid 6.5%～19.0%
Flow agent 0.5%～5.0%
Air release agent 0.2%～0.3%
Curing catalysts 0.02%～0.05%
Titanium dioxide 5.0%～30.0%
Process white 5.0%～30.0%
With light calcium carbonate 0%～10.0%.
Above-mentioned each amounts of components sum is 100%;
The feed composition of GMA fluorocarbon acrylic acid resin is in the above-described GMA fluorocarbon acrylic acid powdery paints:
Fluoro-acrylate monomer 4.0%～10.0%
Glycidyl methacrylate 11.25%～15.75%
Vinylbenzene 0%～6.75%
Methyl methacrylate 9.0%～21.6%
Butyl acrylate 4.0%～10.0%
Dodecyl mercaptans 1%～2.0%
Dimethylbenzene 26.7%
N-BUTYL ACETATE 18.3%
With dibenzoyl peroxide 0.5%.
Above-mentioned each amounts of components sum is 100%.
In the above-described GMA fluorocarbon acrylic acid powdery paints, the component of vibrin is:
Phthalic anhydride 49.8%～54.9%
M-phthalic acid 8.5%～16.8%
With TriMethylolPropane(TMP) 33.4%～36.7%.
The preparation method of GMA fluorocarbon acrylic acid powdery paints gets the raw materials ready by the above component and proportioning thereof, the steps include:
A. with GMA fluorocarbon acrylic acid resin, vibrin, di-carboxylic acid and flow agent high-speed mixing 1～2 minute, add air release agent, curing catalysts, titanium dioxide, process white and light calcium carbonate and mixed 3～5 minutes, obtain mixture;
B. the said mixture material is added forcing machine and melt extrude, obtain molten materials, the feeding section temperature is 80～92 ℃, and the melt zone temperature is 95～105 ℃, and the mixing section temperature is 110～120 ℃, 100～110 ℃ of discharging section temperature; The mixture average retention time is no more than 60 seconds;
C. with above-mentioned molten materials through the tabletting machine compressing tablet, control thickness is sent into crushing and classification in the pulverizing mill at 1～3mm through cooling off fragmentation, with meticulous powder separation, obtains product through the powder sieving of cyclonic separation by cyclonic separator.
The preparation method of above-described GMA fluorocarbon acrylic acid powdery paints gets the raw materials ready by the component and the proportioning of above-described GMA fluorocarbon acrylic acid resin, and fluoro-acrylate monomer, acrylic ester monomer and vinylbenzene pre-mixing are obtained mix monomer; Mixed solvent is made up of dimethylbenzene and N-BUTYL ACETATE, and wherein the mass ratio of dimethylbenzene and N-BUTYL ACETATE is 7: 3; At first in reaction vessel, drop into 10% mix monomer and partially mixed solvent, start and stir and intensification, mixture heating up to 120～130 a ℃ insulation refluxed 30 minutes, drip the residue mix monomer then, partially mixed solvent and initiator, dripped in 120～150 minutes, insulation refluxed 30 minutes, drip residue mixed solvent and initiator at last, dripped in about 30 minutes, insulation refluxed 150～180 minutes, surveyed below the free monomer content to 0.6%, and underpressure distillation is steamed and desolventized, emit GMA fluorocarbon acrylic acid resin after the degassing while hot, cooling obtains faint yellow fragility GMA fluorocarbon acrylic acid resin.
Preparation method according to the above GMA fluorocarbon acrylic acid powdery paints, component and proportioning by vibrin are got the raw materials ready, TriMethylolPropane(TMP) is dropped in the reaction vessel, add backflow dimethylbenzene, the quality of backflow dimethylbenzene is a phthalic anhydride, m-phthalic acid, 5% of the mixture quality of forming with TriMethylolPropane(TMP), in water trap, fill it up with dimethylbenzene, be heated to 120 ℃ and open stirring, be warming up to 140 ℃ of dehydrations 30 minutes, add phthalic anhydride, dissolve fully down to phthalic anhydride, continue elevated temperature to 180 ℃ 140～150 ℃ of temperature, reacted 30 minutes, be warming up to 230～240 ℃ with 10 ℃/10 minutes speed then, reaction is to theoretical dehydrating amount, and acid value is to 10mgKOH/g, be cooled to 200 ℃ and add m-phthalic acids, react to acid number is qualified and stop heating.
The invention has the advantages that this acrylic powder coating has ornamental height, has excellent weather resistance, the characteristics of low-temperature curable, and have good physical and mechanical properties, impact property is good, can satisfy the requirement of automobile A level overprint coating.The GMA fluorocarbon acrylic acid powdery paints has that technology is simple, raw material is easy to get, the characteristics of stable performance, is fit to large-scale commercial production.
GMA fluorocarbon acrylic acid powdery paints of the present invention has been introduced fluorinated acrylate monomer in resin, because the F-C bond energy is big, given coating good weathering resistance, weather resistance, and filming simultaneously has the advantage of low surface energy, and polluting proofing property can be good.Solidifying agent is the mixture of diprotic acid and high carboxyl polyester resin, and diprotic acid has been given the coating high reaction activity and high, and vibrin has given coating good bending property, simultaneously-and the existence of COOH improved the pigment wetting performance of resin.The ornamental height of the present invention meets the requirement of automobile A level coating varnish.Can be widely used in the application of automobile, household electrical appliances, bike, motorcycle.
Embodiment
Embodiment 1:
The GMA fluorocarbon acrylic acid powdery paints with the prescription of GMA fluorocarbon acrylic acid resin is: by weight percentage:
Vinylformic acid hexafluoro butyl ester 10.0%
Methyl methacrylate 15.0%
Butyl acrylate 8.0%
Glycidyl methacrylate 12.0%
Vinylbenzene 5.0%
Dimethylbenzene 26.7%
N-BUTYL ACETATE 18.3%
With dibenzoyl peroxide 0.5%.
By formula ratio fluoro-acrylate monomer, acrylic ester monomer and vinylbenzene pre-mixing are obtained mix monomer; Mixed solvent is made up of dimethylbenzene and N-BUTYL ACETATE, and the weight ratio of dimethylbenzene and N-BUTYL ACETATE is 7: 3; The assembling reaction unit, check heating, stir, condensation, after temperature control system is errorless, in reaction vessel, drop into 10% mix monomer and partially mixed solvent, start and stir and intensification, mixture heating up to 120～130 a ℃ insulation refluxed 30 minutes, drip the residue mix monomer, partially mixed solvent and initiator, dripped in 120～150 minutes, insulation refluxed 30 minutes, dripped residue mixed solvent and initiator, dripped in about 30 minutes, insulation refluxed 150～180 minutes, surveyed below the free monomer content to 0.6%, and underpressure distillation is steamed and desolventized, emit GMA fluorocarbon acrylic acid resin after the degassing while hot, cooling obtains faint yellow fragility GMA fluorocarbon acrylic acid resin.
Embodiment 2-3
GMA fluorocarbon acrylic acid resin synthetic prescription is as shown in table 1, and other are identical with embodiment 1.
The prescription of table 1, GMA fluorocarbon acrylic acid resin
Embodiment 4
The prescription of vibrin is: by weight percentage:
Phthalic anhydride 54.9%
M-phthalic acid 8.5%
With TriMethylolPropane(TMP) 36.6%.
By formula ratio TriMethylolPropane(TMP) is dropped into there-necked flask, add backflow dimethylbenzene, the quality of backflow dimethylbenzene is a phthalic anhydride, m-phthalic acid, 5% of the mixture quality of forming with TriMethylolPropane(TMP), in water trap, fill it up with dimethylbenzene, be heated to 120 ℃ and open stirring, be warming up to 140 ℃ of dehydrations 30 minutes, add phthalic anhydride, 140～150 ℃ dissolve fully to phthalic anhydride, continue elevated temperature to 180 ℃, reacted 30 minutes, be warming up to 230～240 ℃ with 10 ℃/10 minutes speed then, reaction is to theoretical dehydrating amount, and acid value is to 10mgKOH/g, be cooled to 200 ℃ and add m-phthalic acids, react to acid number is qualified and stop heating.
Embodiment 5-6
Vibrin synthetic prescription is as shown in table 2, and other are identical with embodiment 4.
The prescription of table 2, fluorocarbon acrylic acid resin
Embodiment 7
The demonstrated preparation method of GMA fluorocarbon acrylic acid powdery paints of the present invention of present embodiment.
To mix 2 minutes in GMA fluorocarbon acrylic acid resin 55.0kg, vibrin 20.0kg, di-carboxylic acid 6.0kg and the flow agent 2.0kg adding high-speed mixer, add air release agent 0.2kg, curing catalysts 0.02kg, light calcium carbonate 0.5kg, titanium dioxide 14.0kg and process white 2.3kg, high-speed mixing 3 minutes obtains mixture; Mixture adds twin screw extruder and melt extrudes, 88 ℃ of feeding section temperature, 100 ℃ of melt zone temperature, 110 ℃ of mixing sections, 100 ℃ of discharging sections, the twin screw extruder rotating speed is controlled at 70rpm, compressing tablet on air-cooled track type compressing tablet crusher, cooling, broken, compressing tablet thickness 2mm is broken into the thin slice of 5～10mm, in the ACM mill through pulverizing, classification, cyclonic separator separates and screening obtains product, 7000 rev/mins of ACM mill rotating speeds, removed fine powder by cyclonic separation, product granularity control: 150 μ m oversize powders≤3%, 250 μ m oversize powder≤0.2%.
Embodiment 8～9:
The prescription such as the table 3 of GMA fluorocarbon acrylic acid powdery paints, other are identical with embodiment 7.
The prescription of table 3, GMA fluorocarbon acrylic acid powdery paints
Product granularity control: 150 μ m oversize powders≤3%, 250 μ m oversize powder≤0.2%
The accessible technical indicator of GMA fluorocarbon acrylic acid powdery paints that makes by embodiment:
The performance of epoxy powder
The project quality index
Appearance of film is smooth smooth
Set time (130 ℃)/min≤20
Sticking power/level≤2
Shock strength/J 490
Hardness/H 1～2
Gloss (60 °)/% 〉=90
Contact angle/0 110～120
Salt fog resistance (300h) is passed through
Light rate 〉=50% is protected in weathering resistance outdoor exposure (1 year)
Artificial accelerated aging (500h) is protected light rate 〉=50%
Acid resistance (5%H
2SO
4) 240h passes through
Alkali resistance (5%NaOH) 240h passes through
Package stability (15～25 ℃), 6 month not conglomerations
Claims (9)
1, GMA fluorocarbon acrylic acid powdery paints, by weight percentage, its component is:
GMA fluorocarbon acrylic acid resin 55.0%～86.0%
Vibrin 0%～20.0%
Di-carboxylic acid 6.5%～19.0%
Flow agent 0.5%～5.0%
Air release agent 0.2%～0.3%
Curing catalysts 0.02%～0.05%
Titanium dioxide 5.0%～30.0%
Process white 5.0%～30.0%
With light calcium carbonate 0%～10.0%;
Above-mentioned each amounts of components sum is 100%;
Wherein: GMA fluorocarbon acrylic acid resin, by weight percentage, its feed composition is:
Fluoro-acrylate monomer 4.0%～10.0%
Glycidyl methacrylate 11.25%～15.75%
Vinylbenzene 0%～6.75%
Methyl methacrylate 9.0%～21.6%
Butyl acrylate 4.0%～10.0%
Dodecyl mercaptans 1%～2.0%
Dimethylbenzene 26.7%
N-BUTYL ACETATE 18.3%
With dibenzoyl peroxide 0.5%;
Above-mentioned each amounts of components sum is 100%.
2, GMA fluorocarbon acrylic acid powdery paints according to claim 1 is characterized in that: by weight percentage, the component of vibrin is:
Phthalic anhydride 49.8%～54.9%
M-phthalic acid 8.5%～16.8%
With TriMethylolPropane(TMP) 33.4%～36.7%.
3, GMA fluorocarbon acrylic acid powdery paints according to claim 1 is characterized in that di-carboxylic acid is an aliphatic dicarboxylic acid.
4,, it is characterized in that di-carboxylic acid is a dodecanedioic acid according to claim 1 or 4 described GMA fluorocarbon acrylic acid powdery paints.
5, GMA fluorocarbon acrylic acid powdery paints according to claim 1 is characterized in that fluoro-acrylate monomer is a vinylformic acid hexafluoro butyl ester, perhaps is vinylformic acid ten difluoro monooctyl esters, perhaps is methacrylic acid hexafluoro butyl ester.
6, GMA fluorocarbon acrylic acid powdery paints according to claim 1 is characterized in that glycidyl methacrylate, contains glycidyl 15%～25%, epoxy equivalent (weight) scope 500～1000g.
7, the preparation method of GMA fluorocarbon acrylic acid powdery paints gets the raw materials ready by described component of claim 1 and proportioning thereof, it is characterized in that:
A. with GMA fluorocarbon acrylic acid resin, vibrin, di-carboxylic acid and flow agent high-speed mixing 1～2 minute, add air release agent, curing catalysts, titanium dioxide, process white and light calcium carbonate and mixed 3～5 minutes, obtain mixture;
B. the said mixture material is added forcing machine and melt extrude, obtain molten materials, the feeding section temperature is 80～92 ℃, and the melt zone temperature is 95～105 ℃, and the mixing section temperature is 110～120 ℃, 100～110 ℃ of discharging section temperature; The mixture average retention time is no more than 60 seconds;
C. with above-mentioned molten materials through the tabletting machine compressing tablet, control thickness is sent into crushing and classification in the pulverizing mill at 1～3mm through cooling off fragmentation, with meticulous powder separation, obtains product through the powder sieving of cyclonic separation by cyclonic separator.
8, the preparation method of GMA fluorocarbon acrylic acid powdery paints according to claim 7, it is characterized in that getting the raw materials ready, fluoro-acrylate monomer, acrylic ester monomer and vinylbenzene pre-mixing are obtained mix monomer by the component and the proportioning of the described GMA fluorocarbon acrylic acid of claim 1 resin; Mixed solvent is made up of dimethylbenzene and N-BUTYL ACETATE, and wherein the mass ratio of dimethylbenzene and N-BUTYL ACETATE is 7: 3; At first in reaction vessel, drop into 10% mix monomer and partially mixed solvent, start and stir and intensification, mixture heating up to 120～130 a ℃ insulation refluxed 30 minutes, drip the residue mix monomer then, partially mixed solvent and initiator, dripped in 120～150 minutes, insulation refluxed 30 minutes, drip residue mixed solvent and initiator at last, dripped in about 30 minutes, insulation refluxed 150～180 minutes, surveyed below the free monomer content to 0.6%, and underpressure distillation is steamed and desolventized, emit GMA fluorocarbon acrylic acid resin after the degassing while hot, cooling obtains faint yellow fragility GMA fluorocarbon acrylic acid resin.
9, the preparation method of GMA fluorocarbon acrylic acid powdery paints according to claim 7, it is characterized in that: get the raw materials ready by described component of claim 2 and proportioning, TriMethylolPropane(TMP) is dropped in the reaction vessel, add backflow dimethylbenzene, the quality of backflow dimethylbenzene is a phthalic anhydride, m-phthalic acid, 5% of the mixture quality of forming with TriMethylolPropane(TMP), in water trap, fill it up with dimethylbenzene, be heated to 120 ℃ and open stirring, be warming up to 140 ℃ of dehydrations 30 minutes, add phthalic anhydride, dissolve fully down to phthalic anhydride, continue elevated temperature to 180 ℃ 140～150 ℃ of temperature, reacted 30 minutes, be warming up to 230～240 ℃ with 10 ℃/10 minutes speed then, reaction is to theoretical dehydrating amount, and acid value is to 10mgKOH/g, be cooled to 200 ℃ and add m-phthalic acids, react to acid number is qualified and stop heating.
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| CN101942057A (en) * | 2010-08-20 | 2011-01-12 | 中国海洋石油总公司 | Baking self-crosslinking fluorine-containing acrylate resin for metal substrate |
| CN103012660A (en) * | 2012-12-05 | 2013-04-03 | 北京化工大学 | Fluorine-containing epoxy acrylate oligomer for photo-curing and synthetic method thereof |
| CN105802365A (en) * | 2014-12-31 | 2016-07-27 | 江苏考普乐新材料有限公司 | Production method and equipment for PVDF fluorocarbon coating |
| CN104927590A (en) * | 2015-07-09 | 2015-09-23 | 张作玮 | Preparation method for powder coating |
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| CN106381022A (en) * | 2016-08-31 | 2017-02-08 | 苏州翰晨商贸有限公司 | Weather-proof anti-corrosion highlight powdery paint |
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| CN111440501A (en) * | 2020-05-14 | 2020-07-24 | 郑州知淘信息科技有限责任公司 | Organic silicon-fluorine modified acrylic resin powder coating and preparation method thereof |
| CN111393940A (en) * | 2020-05-14 | 2020-07-10 | 郑州知淘信息科技有限责任公司 | High-weather-resistance self-cleaning acrylic resin powder coating and preparation method thereof |
| CN112592469A (en) * | 2020-12-15 | 2021-04-02 | 浙江光华科技股份有限公司 | Polyester resin for outdoor heat transfer printing matt powder coating and preparation method thereof |
| CN115612327B (en) * | 2022-10-27 | 2023-11-10 | 中昊北方涂料工业研究设计院有限公司 | Preparation method of low-odor easily-stripped optical fiber inner layer coating |
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