CN103193920A - Normal temperature cured type fluorine-silicon copolymerization coating resin and preparation method thereof - Google Patents
Normal temperature cured type fluorine-silicon copolymerization coating resin and preparation method thereof Download PDFInfo
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- CN103193920A CN103193920A CN2013101409209A CN201310140920A CN103193920A CN 103193920 A CN103193920 A CN 103193920A CN 2013101409209 A CN2013101409209 A CN 2013101409209A CN 201310140920 A CN201310140920 A CN 201310140920A CN 103193920 A CN103193920 A CN 103193920A
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Abstract
The invention relates to a normal temperature cured type fluorine-silicon copolymerization coating resin, and particularly relates to a normal temperature cured type fluorine-silicon copolymerization coating resin which is synthesized through solution polymerization by taking a fluorine-containing olefin monomer and organic silicon as main comonomers. The normal temperature cured type fluorine-silicon copolymerization coating resin comprises the following raw materials in percentage by weight: 30%-45% of trifluorochloroethylene, 5%-20% of organic silicon monomers, 10%-35% of ester monomers, 5%-8% of hydroxyalkyl olefin ethers, 1%-7% of undecylenic acid, 35%-45% of organic solvents and 0.5%-1% of initiating agents. The normal temperature cured type fluorine-silicon copolymerization coating resin disclosed by the invention can be cured at normal temperature by being matched with a polyurethane curing agent and also be cured in a heating way, has lowered surface, enhances self cleaning and is low in friction coefficient after being formed into a film compared with FEVE (Fluoro Ethylene-Vinyl Ether copolymer) type fluorine-carbon coating because fluorine-containing olefin and the organic silicon are copolymerized, keeps excellent adhesive force, has the advantages of preeminent weather resistance, water resistance and grease resistance and enhances the contamination resistant property of coating.
Description
Technical field
The invention belongs to the coating raw material technical field, relate to a kind of fluorine-silicon copolymer coating resin, particularly a kind of is main comonomer with fluoroolefin and organosilane monomer, the synthetic normal temperature cured type fluorine-silicon copolymer coating resin by solution polymerization.
Background technology
Fluoro-resin has the premium properties of many uniquenesses, low surface energy, high thermostability and chemical stability, be the best outdoor coating of finding so far of weathering resistance, durable years is at (the vinylformic acid polyurethane coating of general high-decoration, high-weatherability, vinylformic acid organosilicon coating more than 20 years, durable years was generally 5 ~ 10 years, and organosilicon polyester coating is the highest also to have only 10 ~ 15 years).
Silicone resin is main chain with the Si-O key, its particular structure, the performance that has had both inorganic materials and organic materials, it is low to have surface tension, temperature coefficient of viscosity is little, the compressibility height, essential propertys such as gas permeability height, and has a high-low temperature resistant, resistance to oxidation stability, difficult combustion, corrosion-resistant, excellent specific properties such as nonpoisonous and tasteless and physiology inertia, be widely used in aerospace, electric, building, transportation, weaving, food, light industry, industries such as medical treatment, wherein organosilicon is mainly used in sealing, bonding, lubricated, coating, surfactivity, the demoulding, froth breaking, press down bubble, waterproof, moistureproof, inertia filling etc., but the film forming properties of silicone resin is relatively poor, solidification value is higher, sticking power to ground is relatively poor, comparatively speaking, its fuel oil resistance and resistant to chemical media are still not as good as the organic fluorine superpolymer.And the resistance toheat of fluoro-resin, resistance to low temperature and hydrophobicity are still not as good as the organosilicon superpolymer.
And organic fluorine, silicon copolymer resins organically are combined in organic fluorine and organosilicon in the same resin, and performance strong point is separately developed the normal temperature cured type coating novel material of excellent combination property, becomes the technical problem that needs to be resolved hurrily.In the prior art, rarely has the exploitation of this type of material.
Patent ZL200810138508.2 provides a kind of normal temperature cured type tetrafluoroethylene fluorocarbon coating resin and preparation method thereof, only provided tetrafluoroethylene monomer, with monomer copolymerizations such as tertiary ethylene carbonates, make the fluorocarbon coating resin, make with its resin and to film, surface energy is also higher, and the antiseized effect of being stained with is relatively poor.And patent ZL200610042148.7 silicon fluoride super-amphiphobic non-stick coating material, it is the method that adopts cold assembly to mix with fluorocarbon resin and silicone resin, these two kinds of resin compatibilities are relatively poor, variant with the speed of response of solidifying agent, the easy layering of the coating that makes, organosilicon easily floats to film coated surface, causes filming easily being covered with dust.
Summary of the invention
The present invention is in order to overcome the deficiency of above technology, a kind of normal temperature cured type fluorine-silicon copolymer coating resin is provided, be with vinyl organosilicon and fluoroolefin copolymerization, and the esters monomer of cooperation certain percentage, end contains hydroxyl and carboxylic monomer is comonomer, is initiator with the azo-bis-isobutyl cyanide, in polymeric kettle, the pressure and temperature of control polymerization is polymerized.
The present invention realizes by following measure:
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention is to adopt the solvent-borne type copolymerization to form by the raw material of following weight part:
Trifluorochloroethylene: 30 ~ 45
Organosilane monomer: 5～15
Esters monomer: 10 ~ 30
Hydroxyalkyl alkene ether: 5 ~ 8
Undecylenic acid: 1～7
Organic solvent: 35 ~ 45
Initiator: 0.5 ~ 1
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention, described trifluorochloroethylene monomer is no color or smell gas; Fusing point-157.5 ℃, boiling point-26.2 ℃, product purity is not less than 99.5%.
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention, described organosilane monomer is the straight chain type organosilane monomer, both-end respectively has a vinyl, outward appearance is light yellow transparent liquid, viscosity (25 ℃) 100 ~ 500mPa.s, fugitive constituent≤3%, contents of ethylene 1～3%.
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention, described esters monomer is one or both in vinyl acetate, the tertiary ethylene carbonate.
Above-mentioned normal temperature cured type fluorine-silicon copolymer coating resin, the preferred ethylene glycol propenyl ether of described hydroxyalkyl alkene ether.
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention, described glycol monomethyl propenyl ether is colourless transparent liquid, soluble in water and chloroform, 65.5 ℃ of flash-points, purity is 99.77%.
Above-mentioned normal temperature cured type fluorine-silicon copolymer coating resin, in order further to improve resin to dispersing of pigments and paint film adhesion, described undecylenic acid preferred weight part is 1 ~ 3.
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention, described undecylenic acid are colourless or glassy yellow oily liquids or faint yellow xln, and special odor is arranged, can mix with alcohol, ether, chloroform, water-soluble hardly, proportion: 0.9072, purity is commercial grade.
Above-mentioned normal temperature cured type fluorine-silicon copolymer coating resin, described organic solvent are ester class organic solvent, organic solvent of ketone, benzene kind solvent and composition thereof; Preferred volume ratio is 1:(0.6-1.5) N-BUTYL ACETATE and the mixture of dimethylbenzene.
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention, described N-BUTYL ACETATE is colourless transparent liquid, structural formula CH
3COOC
4H
9, molecular weight 116.16 has fruit aroma.Zero pour-73.5 ℃, 126.11 ℃ of boiling points, 33 ℃ of flash-points (opening), 421 ℃ of burning-points, specific refractory power 1.3941, viscosity (20 ℃) 0.734MPas, specific heat capacity 1.91KJ/(KgK), solubility parameter δ=8.5. is dissolved in organic solvents such as alcohol, ketone, ether, is slightly soluble in water.Purity requirement is technical grade.
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention, described dimethylbenzene is colourless liquid, for p-Xylol,
O-Xylol,
M-xyleneAnd composition thereof, flash-point: 27.2-46.1 ℃, initial boiling point is 135 ~ 136.5 ℃, final boiling point is 141.5 ~ 145 ℃.Purity requirement is technical grade.
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention, described initiator is Diisopropyl azodicarboxylate, and it is white, needle-shaped crystals or powder, adds heat release nitrogen, can be dissolved in methyl alcohol, and is water insoluble, is dissolved in the acetone explosive, and purity requirement is industrial top grade product.
The present invention adopts and is prepared as follows the method preparation:
1) organosilane monomer, esters monomer, hydroxyalkyl alkene ether, undecylenic acid and organic solvent are joined in the little dissolving tank, start and stir, mix, under agitation slowly add initiator, stir and make it dissolving;
2) polymeric kettle is vacuumized, making vacuum tightness is 97kPa, nitrogen replacement, makes gauge pressure be 0.05Mpa, vacuumize, and the vacuum with in the polymeric kettle is drawn into polymeric kettle with mixing solutions, and polymeric kettle vacuumizes again, and opens and stir.Open trifluorochloroethylene monomer groove valve and add trifluorochloroethylene;
3) by Controlling System polymeric kettle is heated up, 70 ± 2 ℃ of control temperature of reaction, the initial pressure in the polymeric kettle is 800Kpa, and pressure was 500 Kpa when reaction finished, and the reaction times is 18-22 hour;
4) sampling qualified after, be cooled to normal temperature;
5) stop to stir, inciting somebody to action not by MONOMER RECOVERY alkene, the MONOMER RECOVERY of complete reaction arrives accumulator tank.
The normal temperature cured type fluorine-silicon copolymer coating resin that the present invention is prepared into has following performance index: color: colourless transparent liquid; Solid content: 〉=60%; Fluorine content: 〉=18%; Hydroxyl value: 35-85mgKOH/g; Acid number: 0-15 mgKOH/g; Molecular weight: 12000 ~ 25000.
Normal temperature cured type fluorine-silicon copolymer coating resin of the present invention, realized that with fluoroolefin monomers and vinyl organosilicon monomer be main comonomer, the synthetic fluorine-silicon copolymer coating resin by solution polymerization, owing to be molecular backbone chain and organosilicon copolymerization by fluoroolefin, greatly improved the weathering resistance of coating, and reduced the surface energy of filming, this resin film forming rear surface energy is low, self-cleaning is strong, frictional coefficient is low and kept good sticking power, have remarkable weathering resistance, water-repellancy and grease proofness, improved the polluting proofing property energy of coating.
Embodiment
Embodiment 1
With tertiary ethylene carbonate VV9,200 grams, both-end vinyl organosilicon monomer 100 grams, glycol monomethyl propenyl ether 80 grams, undecylenic acid 30 grams, N-BUTYL ACETATE 240 grams, dimethylbenzene 220 grams join in the little dissolving tank, startup mixes, under agitation slowly add initiator (Diisopropyl azodicarboxylate) 12 grams, stir and make it dissolving.2.5 liters polymeric kettle is vacuumized (vacuum tightness is 97kPa), nitrogen replacement to gauge pressure 0.05Mpa, vacuumize again, with the vacuum in the polymeric kettle, the mixing solutions of monomer, initiator is drawn into polymeric kettle, polymeric kettle vacuumizes again, and open and stir, open trifluorochloroethylene monomer groove valve and add trifluorochloroethylene monomer 560 grams.By Controlling System polymeric kettle is heated up, the control temperature is carried out polyreaction under (70 ± 2) ℃, and the initial pressure in the still is 800Kpa, and reaction is 500 Kpa when finishing, and the reaction times is about 20 hours.After reaction finished, unreacted monomer was extracted in decompression out, obtains resin of the present invention.
Get resin 100 grams of the present invention, the mixed solution that adds butylacetate and dimethylbenzene, after the tripolymer of solidifying agent hexa-methylene two isocyano-acid esters (Bayer 3390) mixes in proportion, spraying, solidify, be worth fluorocarbon coating varnish model, the static contact angle of test and water carries out 180 ° of peel strength tests of Pressuresensitive Tape with reference to the GB/T2792 method.
Embodiment 2
With vinyl acetate 170 grams, both-end vinyl organosilicon monomer 140 grams, glycol monomethyl propenyl ether 80 grams, undecylenic acid 20 grams, N-BUTYL ACETATE 260 grams, dimethylbenzene 300 grams join in the autoclave, closed reactor, under agitation slowly add initiator (Diisopropyl azodicarboxylate) 10 grams, stir and make it dissolving.With reaction kettle for vacuumizing (vacuum tightness is 97kPa), charge into nitrogen then to gauge pressure 0.05Mpa, vacuumize again--get rid of the oxygen in the reactor.After air displacement finishes in the still, rely on from pressing the trifluorochloroethylene in the storage tank is joined 580 grams in the polymeric kettle gradually, the control temperature is carried out polyreaction under (70 ± 2) ℃, and the initial pressure in the still is 800Kpa, reaction is 500 Kpa when finishing, and the reaction times is about 20 hours.After reaction finished, unreacted monomer was extracted in decompression out, obtains resin of the present invention.
Get resin 100 grams of the present invention, the mixed solution that adds butylacetate and dimethylbenzene, after the tripolymer of solidifying agent hexa-methylene two isocyano-acid esters (Bayer 3390) mixes in proportion, spraying, solidify, be worth fluorocarbon coating varnish model, the static contact angle of test and water carries out 180 ° of peel strength tests of Pressuresensitive Tape with reference to the GB/T2792 method.
Embodiment 3
With tertiary ethylene carbonate VV10,100 grams, vinyl acetate 80 grams, both-end vinyl organosilicon monomer 120 grams, glycol monomethyl propenyl ether 90 grams, undecylenic acid 20 grams, N-BUTYL ACETATE 320 grams, dimethylbenzene 280 grams join in the little dissolving tank, startup mixes, under agitation slowly add initiator (Diisopropyl azodicarboxylate) 10 grams, stir and make it dissolving.2.5 liters polymeric kettle is vacuumized (vacuum tightness is 97kPa), nitrogen replacement to gauge pressure 0.05Mpa, vacuumize again, with the vacuum in the polymeric kettle, the mixing solutions of monomer, initiator is drawn into polymeric kettle, polymeric kettle vacuumizes again, and open and stir, open trifluorochloroethylene monomer groove valve and add trifluorochloroethylene monomer 620 grams.By Controlling System polymeric kettle is heated up, the control temperature is carried out polyreaction under (70 ± 2) ℃, and the initial pressure in the still is 800Kpa, and reaction is 500 Kpa when finishing, and the reaction times is about 20 hours.After reaction finished, unreacted monomer was extracted in decompression out, obtains resin of the present invention.
Get resin 100 grams of the present invention, the mixed solution that adds butylacetate and dimethylbenzene, after the tripolymer of solidifying agent hexa-methylene two isocyano-acid esters (Bayer 3390) mixes in proportion, spraying, solidify, be worth fluorocarbon coating varnish model, the static contact angle of test and water carries out 180 ° of peel strength tests of Pressuresensitive Tape with reference to the GB/T2792 method.
Embodiment 4
With tertiary ethylene carbonate VV9,100 grams, vinyl acetate 60 grams, both-end vinyl organosilicon monomer 100 grams, glycol monomethyl propenyl ether 90 grams, undecylenic acid 20 grams, N-BUTYL ACETATE 280 grams, dimethylbenzene 280 grams join in the autoclave, closed reactor, under agitation slowly add initiator (Diisopropyl azodicarboxylate) 15 grams, stir and make it dissolving.With reaction kettle for vacuumizing (vacuum tightness is 97kPa), charge into nitrogen then to gauge pressure 0.05Mpa, vacuumize again--get rid of the oxygen in the reactor.After air displacement finishes in the still, rely on from pressing the trifluorochloroethylene in the storage tank is joined 600 grams in the reactor gradually, the control temperature is carried out polyreaction under (70 ± 2) ℃, and the initial pressure in the still is 800Kpa, reaction is 500 Kpa when finishing, and the reaction times is about 20 hours.After reaction finished, unreacted monomer was extracted in decompression out, obtains resin of the present invention.
Get resin 100 grams of the present invention, the mixed solution that adds butylacetate and dimethylbenzene, after the tripolymer of solidifying agent hexa-methylene two isocyano-acid esters (Bayer 3390) mixes in proportion, spraying, solidify, be worth fluorocarbon coating varnish model, the static contact angle of test and water carries out 180 ° of peel strength tests of Pressuresensitive Tape with reference to the GB/T2792 method.
Comparative example (common FEVE fluorocarbon resin) is with vinyl acetate 310 grams, glycol monomethyl propenyl ether 80 grams, undecylenic acid 20 grams, N-BUTYL ACETATE 260 grams, dimethylbenzene 300 grams join in the autoclave, closed reactor, under agitation slowly add initiator (Diisopropyl azodicarboxylate) 10 grams, stir and make it dissolving.With reaction kettle for vacuumizing (vacuum tightness is 97kPa), charge into nitrogen then to gauge pressure 0.05Mpa, vacuumize again--get rid of the oxygen in the reactor.After air displacement finishes in the still, rely on from pressing the trifluorochloroethylene in the storage tank is joined 580 grams in the reactor gradually, the control temperature is carried out polyreaction under (70 ± 2) ℃, and the initial pressure in the still is 800Kpa, reaction is 500 Kpa when finishing, and the reaction times is about 20 hours.After reaction finished, unreacted monomer was extracted in decompression out, obtains resin of the present invention.
Get resin 100 grams of the present invention, the mixed solution that adds butylacetate and dimethylbenzene, after the tripolymer of solidifying agent hexa-methylene two isocyano-acid esters (Bayer 3390) mixes in proportion, spraying, solidify, be worth fluorocarbon coating varnish model, the static contact angle of test and water carries out 180 ° of peel strength tests of Pressuresensitive Tape with reference to the GB/T2792 method.
Above-described embodiment fluorine-silicon copolymer resin and comparative example fluorocarbon resin and coating thereof have been carried out performance test, and data are as follows:
Can obviously find out by above experimental data: be the major function monomer with trifluorochloroethylene and vinyl organosilicon monomer, cooperate other function monomers, the resin that synthesizes with solution polymerization process, after polyurethanes solidifying agent film forming, more common FEVE fluorocarbon resin has had bigger increase at the contact angle with water; With 180 ° of stripping strengths of sealing tape significant reduction has been arranged, fluorine-silicon copolymer resin and common FEVE fluorocarbon resin film forming are described after, surface energy has had significant reduction.
Claims (10)
1. a normal temperature cured type fluorine-silicon copolymer coating resin is characterized in that, adopts the solvent-borne type copolymerization to form by the raw material of following weight part:
Trifluorochloroethylene: 30 ~ 45;
Organosilane monomer: 5～20;
Esters monomer: 10 ~ 35;
Hydroxyalkyl alkene ether: 5 ~ 8;
Undecylenic acid: 1～7;
Organic solvent: 35 ~ 45;
Initiator: 0.5 ~ 1.
2. normal temperature cured type fluorine-silicon copolymer coating resin according to claim 1 is characterized in that, described resin is colourless transparent liquid; Solid content 〉=60%; Fluorine content 〉=18%; Hydroxyl value 35-85mgKOH/g; Acid number 0-15 mgKOH/g; Molecular weight 12000 ~ 25000.
3. normal temperature cured type fluorine-silicon copolymer coating resin according to claim 1 is characterized in that, described organosilane monomer is straight chain type vinyl organosilicon monomer.
4. normal temperature cured type fluorine-silicon copolymer coating resin according to claim 1 is characterized in that, described esters monomer is one or both in vinyl acetate, the tertiary ethylene carbonate.
5. normal temperature cured type fluorine-silicon copolymer coating resin according to claim 1 is characterized in that, described hydroxyalkyl alkene ether is the glycol monomethyl propenyl ether.
6. normal temperature cured type fluorine-silicon copolymer coating resin according to claim 1 is characterized in that, the content of described undecylenic acid is 1～3%.
7. normal temperature cured type fluorine-silicon copolymer coating resin according to claim 1 is characterized in that, described organic solvent is a kind of or its mixture in ester class organic solvent, organic solvent of ketone, the benzene class organic solvent.
8. according to claim 1 or 7 described normal temperature cured type fluorine-silicon copolymer coating resins, it is characterized in that described organic solvent is that volume ratio is 1:(0.6-1.5) N-BUTYL ACETATE and the mixture of dimethylbenzene.
9. normal temperature cured type fluorine-silicon copolymer coating resin according to claim 1 is characterized in that, described initiator is Diisopropyl azodicarboxylate.
10. the preparation method of each described normal temperature cured type fluorine-silicon copolymer thing coating resin of claim 1-9 is characterized in that, comprises the steps:
1) organosilane monomer, esters monomer, hydroxyalkyl alkene ether, undecylenic acid and organic solvent are joined in the little dissolving tank, start and stir, mix, under agitation slowly add initiator, stir and make it dissolving;
2) polymeric kettle is vacuumized, making vacuum tightness is 97kPa, nitrogen replacement, makes gauge pressure be 0.05Mpa, vacuumize, and the vacuum with in the polymeric kettle is drawn into polymeric kettle with mixing solutions, and polymeric kettle vacuumizes again, and opens and stir; Open trifluorochloroethylene monomer groove valve and add trifluorochloroethylene;
3) by Controlling System polymeric kettle is heated up, 70 ± 2 ℃ of control temperature of reaction, the initial pressure in the polymeric kettle is 800Kpa, and reaction is 500 Kpa when finishing, and the reaction times is 18-22 hour;
4) sampling qualified after, be cooled to normal temperature;
5) stop to stir, inciting somebody to action not by MONOMER RECOVERY alkene, the MONOMER RECOVERY of complete reaction arrives accumulator tank.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2013101409209A CN103193920A (en) | 2013-04-22 | 2013-04-22 | Normal temperature cured type fluorine-silicon copolymerization coating resin and preparation method thereof |
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| CN2013101409209A CN103193920A (en) | 2013-04-22 | 2013-04-22 | Normal temperature cured type fluorine-silicon copolymerization coating resin and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602121A (en) * | 2013-11-19 | 2014-02-26 | 青岛广联达精密机械有限公司 | Improved aging-resistant waterproof coating material |
| CN104448096A (en) * | 2014-11-08 | 2015-03-25 | 安徽博泰氟材料科技有限公司 | Self-cleaning fluorocarbon coating and preparation method thereof |
| CN110818903A (en) * | 2019-10-25 | 2020-02-21 | 杭州师范大学 | Low-temperature-resistant long-chain hydrocarbon-organic silicon alternating copolymer and preparation method and application thereof |
| CN113527959A (en) * | 2021-06-30 | 2021-10-22 | 宁夏星邦豹丰涂料科技有限公司 | Preparation method of anticorrosive paint for ultrafast dry cast pipe |
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| JPH11116633A (en) * | 1997-10-16 | 1999-04-27 | Central Glass Co Ltd | Aqueous dispersion of fluororesin |
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| US5859123A (en) * | 1995-11-15 | 1999-01-12 | Central Glass Company, Limited | Water-based fluorine-containing emulsion |
| JPH11116633A (en) * | 1997-10-16 | 1999-04-27 | Central Glass Co Ltd | Aqueous dispersion of fluororesin |
| CN1450091A (en) * | 2003-04-21 | 2003-10-22 | 青岛宏丰集团建材有限公司 | Ultralow surface energy type fluorocarbon resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602121A (en) * | 2013-11-19 | 2014-02-26 | 青岛广联达精密机械有限公司 | Improved aging-resistant waterproof coating material |
| CN103602121B (en) * | 2013-11-19 | 2016-05-25 | 青岛祥嘉知识产权服务有限公司 | A kind of improved anti-aging water-repellent paint |
| CN104448096A (en) * | 2014-11-08 | 2015-03-25 | 安徽博泰氟材料科技有限公司 | Self-cleaning fluorocarbon coating and preparation method thereof |
| CN110818903A (en) * | 2019-10-25 | 2020-02-21 | 杭州师范大学 | Low-temperature-resistant long-chain hydrocarbon-organic silicon alternating copolymer and preparation method and application thereof |
| CN113527959A (en) * | 2021-06-30 | 2021-10-22 | 宁夏星邦豹丰涂料科技有限公司 | Preparation method of anticorrosive paint for ultrafast dry cast pipe |
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Application publication date: 20130710 |