CN100494294C - Thermosetting fluorine powder coating resin and its preparing method - Google Patents
Thermosetting fluorine powder coating resin and its preparing method Download PDFInfo
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- CN100494294C CN100494294C CNB2005101059770A CN200510105977A CN100494294C CN 100494294 C CN100494294 C CN 100494294C CN B2005101059770 A CNB2005101059770 A CN B2005101059770A CN 200510105977 A CN200510105977 A CN 200510105977A CN 100494294 C CN100494294 C CN 100494294C
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- 229920005989 resin Polymers 0.000 title claims abstract description 74
- 239000011347 resin Substances 0.000 title claims abstract description 74
- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 239000000843 powder Substances 0.000 title claims abstract description 69
- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 17
- 239000011737 fluorine Substances 0.000 title abstract description 17
- -1 hydroxyalkyl vinyl ether Chemical compound 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 42
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000012673 precipitation polymerization Methods 0.000 claims abstract description 12
- 230000007704 transition Effects 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 8
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 claims description 6
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims description 6
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 claims description 2
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 claims description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005292 vacuum distillation Methods 0.000 abstract description 4
- 238000009835 boiling Methods 0.000 abstract description 3
- 239000012046 mixed solvent Substances 0.000 abstract description 3
- 239000012934 organic peroxide initiator Substances 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000009736 wetting Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 7
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical group OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 7
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 241000675108 Citrus tangerina Species 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229960002703 undecylenic acid Drugs 0.000 description 5
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- BAYVWWSKYAZXRE-UHFFFAOYSA-N C(C)(=O)OC=C.C(C)(C)(C)C1=CC=C(C(=O)O)C=C1 Chemical compound C(C)(=O)OC=C.C(C)(C)(C)C1=CC=C(C(=O)O)C=C1 BAYVWWSKYAZXRE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- VGIYPVFBQRUBDD-UHFFFAOYSA-N ethenoxycyclohexane Chemical group C=COC1CCCCC1 VGIYPVFBQRUBDD-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a thermosetting fluorine powder coating resin and its preparing method. Said resin cosegment is composed of monomer chlorotrifluoroethylene, alkanoic acid vinyl ester, hydroxyalkyl vinyl ether, alkyl olefine acid. in presence of organic peroxide initiator, using solution precipitation polymerization process, choicing low boiling mixed solvent of aliphatic halogenated hydrocarbon and deoxy deionizing water, by vacuum distillation, removing and recovering the solvent to synthesize fluorine powder coating resin. The invention has advantages of applying solution precipitation polymerization system, synthesizing thermosetting fluorine powder coating resin with good storage stability, copolymerized resin hydroxyl value 35-55mg KOH/g, acid number3.0-8.0mgKOH/g,gamma transition temperature 39-70deg.C. The resin has good intermiscibility with curing agent, good wetting dispersibility with pigment and additive. The coating has good adhesive force, high hardness, high lustre, and good weathering resistance, chemical resistance and decorating.
Description
Technical field
The present invention relates to a kind of thermosetting fluoro powder coating resin and preparation method thereof.More particularly, the present invention relates to based on the thermosetting fluoro powder coating resin of trifluorochloroethylene and utilize the solution precipitation polymerization technique to make the method for described thermosetting fluoro powder coating resin.
Background technology
Powder coating does not contain solvent fully with it; can all change into and film; and the characteristics of coating efficiency height, protection and decoration good combination property; adapt to coatings industry to economizing on resources and the energy, alleviating environmental pollution and aspect requirement such as increase work efficiency; be subjected to global extensive attention, thereby obtain develop rapidly.
Solvent-borne type ambient cure or middle low-temperature bake fluorine coating are filmed because of it and are had the excellent comprehensive physical and chemical performance, comprise performances such as erosion resistance, weathering resistance, stain resistance, are widely used in fields such as building, heavy anticorrosion, industry in recent years.Along with environmental protection consciousness improves, fluororesin powder coating can satisfy the demand of decorating aspects such as maintenance, the development prospect desirable because of its excellent over-all properties.
The Chinese patent application CN1513041A that on July 14th, 2004, the invention disclosed name was called " powdered thermosetting compositions for coatings " discloses the preparation method and the application of the fluorine-containing powder paint compositions of a kind of thermoset, described fluorinated copolymer is with the fluoroolefin unit, olefin unit and cyclohexyl vinyl ether unit and p-tert-butyl benzoic acid vinyl acetate are essential structural unit, this method is by introducing p-tert-butyl benzoic acid vinyl acetate unit in copolymerization system, improved the second-order transition temperature of resin, solve the problems of stability in storage of resin, improved the paint film impact strength.But this method is owing to the easy xanthochromia of introducing in p-tert-butyl benzoic acid vinyl acetate unit, and weathering resistance is poor, makes the poor-performings such as weathering resistance of fluoro powder coating.
The Chinese patent application CN1553943A that on December 8th, 2004, the invention disclosed name was called " fluorine resin powder coating composition " discloses the preparation method and the application of the fluorine-containing powder paint compositions of a kind of thermoset, described fluorinated copolymer comprises cross-linking part more than 2 kinds, reach the curing system of the solidifying agent formation of reacting with this cross-linking part, these solidify system and independently carry out crosslinking reaction in fact respectively, and two kinds of cross-linking reaction times that solidify system differed more than 20 seconds.This method can only make unglazed fluoro powder coating resin, and polymerization technique control is complicated, and the reaction repetition rate is lower.
The Chinese patent application CN1571821A that on January 26th, 2005, the invention disclosed name was called " fluoro-resin powder coating composition " discloses the preparation method and the application of the fluorine-containing powder coating of a kind of thermoset.Described fluorine-containing copolymerization powdex with fluorine-containing interpolymer as core particle, (methyl) acrylic resin etc. that is higher than core particle with second-order transition temperature covers this particle surface and the core/shell structure of compoundization, this method makes fluoro powder coating because fluorinated copolymer and the compound core/shell structure that turns to of acrylic resin, make that coating surface is smooth, gloss is high, ornamental height, but this method is owing to being shell with the acrylic resin, and therefore making fluoro powder coating exists the relatively poor problem of weathering resistance.
The Chinese patent application CN1606573A that on April 13rd, 2005, the invention disclosed name was called " having the fluorine resin powder of solidified nature functional group and the manufacture method of coating composition thereof " discloses the manufacture method of a kind of thermoset fluorine resin powder and coating composition thereof, use the regular solution polymerization technique, add anti-gelating agent in polymerization process, aftertreatment adopts the film vacuum evaporation method to make fluoro powder coating resin.Problems such as this method exists the fluoro powder coating resin manufacturing cost that makes higher, and the resin glass temperature is lower, and the coating stability in storage is relatively poor.
The Chinese patent application CN1620484A that on May 25th, 2005, the invention disclosed name was called " fluorine resin powder coating composition and have the article of filming " discloses a kind of preparation method of thermoset fluorine resin powder coating composition, described fluorinated copolymer powdex is to be core with the fluorinated copolymer, shell is to have the nucleocapsid structure that nuclear and the shell more than 1 layer constitute, and at least 1 layer of shell and/or examine and constitute by fluoropolymer.This method makes fluoro powder coating resin and has characteristics such as remarkable weathering resistance, high gloss, impact strength height, but there is resin manufacture cost height in this method, complex process, shortcomings such as operation control difficulty.
In view of the above-mentioned defective of prior art, need a kind of preparation of exploitation easy, excellent combination property and thermosetting fluoro powder coating resin cheaply.
Summary of the invention
The purpose of this invention is to provide a kind of applying soln precipitation polymerization technology and make the method for described fluoro powder coating resin, this method synthesis technique is easy, and operation control is simple, and production cost is low.
Another object of the present invention provides a kind of multi-component copolymer thermosetting fluoro powder coating resin based on trifluorochloroethylene.This resin has good stability in storage, has excellent weathering resistance, erosion resistance, good luster, performances such as good decorative property with the fluoro powder coating of this resin manufacture.
One aspect of the present invention provides a kind of thermosetting fluoro powder coating resin based on trifluorochloroethylene, and the total mole number of pressing resin calculates, and its cosegment comprises:
(1) 47.0～55.0 mole of % is from the segment of trifluorochloroethylene;
(2) 30.0～40.0 moles of % are from the segment of paraffinic acid vinyl ester;
(3) 10.0～15.0 moles of % are from the segment of hydroxyalkyl vinyl ether;
(4) 0.5～2.5 moles of % are from the segment of alkyl olefin(e) acid;
The hydroxyl value of described copolymerization fluoro powder coating resin is 35-55mgKOH/g, and acid number is 3.0-8.0mgKOH/g, 39～70 ℃ of second-order transition temperatures.
Another aspect of the present invention provides the method for the described thermosetting fluoro powder coating resin of a kind of applying soln precipitation polymerization prepared, and it comprises the steps:
1) provides a kind of solution of forming by the mixture of aliphatic halogenated hydrocarbon and deoxidation deionized water, the ratio of deoxidation deionized water in solution is 20-75% (mass ratio), described aliphatic halogenated hydrocarbon is a Freon 113, Tetrafluoroethane, the mixture of one or more arbitrary proportions in the HFC-236fa, the consumption of this solution are following 2) participate in the 40-50% of the total moles monomer of reaction;
2) with paraffinic acid vinyl ester, hydroxyalkyl vinyl ether, alkyl acrylic monomer and above-mentioned 1) solution mixture of preparation places in the reactor, feeds trifluorochloroethylene; Monomer consumption (mole ratio) is as follows:
47.0～55.0 moles of % of trifluorochloroethylene;
30.0～40.0 moles of % of paraffinic acid vinyl ester;
10.0～15.0 moles of % of hydroxyalkyl vinyl ether;
0.5～2.5 mole of % of alkyl olefin(e) acid;
3) adopt the solution precipitation polymerization technique, under the organic peroxide evocating agent effect, under 30～60 ℃ temperature of reaction, 0.5～1.5MPa reaction initial pressure, make step 2) preparation reaction mixture polymerization 4～10hr, distillation removes the recovery solvent, make fluoro powder coating resin, in the total mole number of described resin, cosegment comprises:
(1) 47.0～55.0 mole of % is from the segment of trifluorochloroethylene;
(2) 30.0～40.0 moles of % are from the segment of paraffinic acid vinyl ester;
(3) 10.0～15.0 moles of % are from the segment of hydroxyalkyl vinyl ether;
(4) 0.5～2.5 moles of % are from the segment of alkyl olefin(e) acid;
Fluorochemical monomer is a trifluorochloroethylene in the fluoro powder coating resin of the present invention, account for 47.0～55.0 moles of % from trifluorochloroethylene segmental content in the resin, if from the segmental content of trifluorochloroethylene less than 47.0 moles of %, the weathering resistance of multipolymer will reduce, if greater than 55.0 moles of %, then the gloss of multipolymer descends, to the moisture dispersibility of pigment, auxiliary agent, solidifying agent etc. from the segmental content of trifluorochloroethylene, intermiscibility descends, and causes film performance to descend.In a preferred embodiment of the present invention, be 50.0～53.0 moles of % from the segmental content of trifluorochloroethylene.
Paraffinic acid vinyl ester segment is tertiary monocarboxylic acid vinyl ester and the mixture that is selected from vinyl-acetic ester, vinyl propionate base ester, butyric acid vinyl ester, valeric acid vinyl ester, the caproic acid vinyl ester any one in the fluoro powder coating resin of the present invention, and wherein the mol ratio of tertiary ethylene carbonate is 33.3～46.7 moles of %; From paraffinic acid vinyl ester segmental content is 30.0～40.0 moles of %, in a preferred embodiment of the present invention, paraffinic acid vinyl ester segment is the mixture of tertiary ethylene carbonate and vinyl-acetic ester, is 32.5～37.5 moles of % from paraffinic acid vinyl ester segmental content.
The commodity that the representational example of tertiary ethylene carbonate that the present invention uses has Shell Co. Ltd to produce Veova9 tertiary ethylene carbonate by name.
The present invention finds, adds tertiary ethylene carbonate in copolymerization system, utilizes the high glass-transition temperature of tertiary carbon acid esters vinyl acetate monomer on the one hand, improves the second-order transition temperature of copolymer resins, improves the stability in storage of resin.Utilize the space steric effect of large volume tertiary monocarboxylic acid group on the other hand; the straight chain alkanoic acid vinyl ester segment of fracture takes place in protection easily under UV-irradiation; in addition; tertiary ethylene carbonate and trifluorochloroethylene and other monomer have good copolymerization; make the alternately property raising of whole cosegment; improved the weathering resistance of fluoro powder coating resin, chemical resistance.
Hydroxyalkyl vinyl ether segmental content accounts for 10.0～15.0 moles of % in the fluoro powder coating resin of the present invention, and the hydroxyalkyl vinyl ether is selected from hydroxyethyl vinyl ether, hydroxypropyl vinyl ether and hydroxy butyl vinyl ether.Content is lower than 10.0 moles of %, and resin and solidifying agent degree of crosslinking are not enough, the poor-performings such as solvent resistance, snappiness of filming; Content is higher than 15.0 moles of %, and the production of resins cost improves, and coating weatherability descends.At hydroxyalkyl vinyl ether described in the preferred embodiment of the present invention is the hydroxyethyl vinyl ether, and the segment preferred content is 12.0～13.0 moles of %.
Alkyl olefin(e) acid segmental content is 0.5～2.5 mole of % in the fluoro powder coating resin of the present invention, and used alkyl olefin(e) acid is selected from vinylformic acid, methacrylic acid, butenoic acid, 10-undecylenic acid, oleic acid, fumaric acid, toxilic acid.Alkyl olefin(e) acid content is less than 0.5 mole of %, and the intermiscibility of resin and auxiliary agent, solidifying agent is relatively poor, and is relatively poor to the moisture dispersibility of pigment; Content is during greater than 2.5 moles of %, and the acid number of resin is too high, causes the decline of appearance of film and physical and mechanical properties.At alkyl olefin(e) acid described in the preferred embodiment of the present invention is the 10-undecylenic acid, better with the copolymerization of fluoroolefin, and the preferred content in cosegment is 0.5～1.5 mole of %.
Key of the present invention is the method for applying soln precipitation polymerization prepared thermosetting fluoro powder coating resin, and it comprises:
1) provide a kind of solution to form by the mixture of aliphatic halogenated hydrocarbon and deoxidation deionized water, the ratio of deoxidation deionized water in this solution is 20-75% (mass ratio), described aliphatic halogenated hydrocarbon is a Freon 113, Tetrafluoroethane, the mixture of one or more arbitrary proportions in the HFC-236fa;
2) with paraffinic acid vinyl ester, hydroxyalkyl vinyl ether, alkyl acrylic monomer and above-mentioned 1) solution of preparation mixes and to place in the reactor, feeds trifluorochloroethylene; The monomer consumption calculates with mole number:
(1) 47.0～55.0 mole of % is from the segment of trifluorochloroethylene;
(2) 30.0～40.0 moles of % are from the segment of paraffinic acid vinyl ester;
(3) 10.0～15.0 moles of % are from the segment of hydroxyalkyl vinyl ether;
(4) 0.5～2.5 moles of % are from the segment of alkyl olefin(e) acid;
3) adopt the solution precipitation polymerization technique, under the organic peroxide evocating agent effect, under 30～60 ℃ temperature of reaction, 0.5～1.5MPa reaction pressure, make step 2) preparation reaction mixture polymerization 4～10hr, distillation removes the recovery solvent, make fluoro powder coating resin, in the total mole number of described resin, cosegment comprises:
(1) 47.0～55.0 mole of % is from the segment of trifluorochloroethylene;
(2) 30.0～40.0 moles of % are from the segment of paraffinic acid vinyl ester;
(3) 10.0～15.0 moles of % are from the segment of hydroxyalkyl vinyl ether;
(4) 0.5～2.5 moles of % are from the segment of alkyl olefin(e) acid;
The solution precipitation polymerization system is adopted in copolyreaction of the present invention, and solution is the mixture of aliphatic halogenated hydrocarbon and deoxidation deionized water, and the ratio of deoxidation deionized water in this solution is 20-75% (mass ratio).Aliphatic halogenated hydrocarbon is a Freon 113, Tetrafluoroethane, the mixture of one or more in the HFC-236fa.In a preferred embodiment of the present invention, be preferably the mixture of Tetrafluoroethane and deoxidation deionized water, wherein the ratio of deoxidation deionized water in solution is 70～75% (mass ratioes), and this solution usage is preferably 42～45% of the total moles monomer of participating in reaction.
What polymerization starter of the present invention adopted is organic peroxide initiator, and they can use separately, also can two or more mix use.The indefiniteness example that can be used for organic peroxide evocating agent of the present invention is a diisobutyryl peroxide, di-cyclohexylperoxy dicarbonate, the mixture of one or more in the di-isopropyl peroxydicarbonate, preferable amount are 0.5～1.5 mole of % of reaction monomers total amount.According to different initiators, polymerization temperature of the present invention is 30～60 ℃, and polymerization pressure is 0.5～1.5MPa, polymerization reaction time 4～10hr.In better example of the present invention, described organic peroxide initiator is preferably di-cyclohexylperoxy dicarbonate, the amount of initiator that adds account for reaction mixture total mole number 0.8～1.0%, 55 ℃ of temperature of reaction, the reaction initial pressure is 1.00～1.45MPa, and polymerization reaction time is 6hr.
The synthetic of resin of the present invention is applying soln precipitation polymerization technology, select the mixed solvent of lower boiling aliphatic halogenated hydrocarbon and deoxidation deionized water for use, and low temperature high activity peroxide initiator, under 30～60 ℃ of lower temperature and lower pressure 0.5～1.5MPa, in short polymerization reaction time 4～10hr, carry out, polymerisate removes the recovery solvent by underpressure distillation, thus synthetic fluoro powder coating resin with excellent mechanical, corrosion-resistant and weather resistance.
The present invention has following advantage compared to existing technology:
1) trifluorochloroethylene of the present invention is that the multipolymer fluoro powder coating resin cosegment of main body is by the monomer A trifluorochloroethylene; B paraffinic acid vinyl ester; C hydroxyalkyl vinyl ether; D alkyl olefin(e) acid is formed; Performance is better than existing fluoro powder coating resin;
2) adopt the solution precipitation polymerization system, under than low reaction temperatures and pressure, in the short reaction times, synthesized and have superior physical properties, the fluoro powder coating resin of excellent anticorrosive and weathering resistance;
3) select the mixed solvent of lower boiling aliphatic halogenated hydrocarbon and deoxidation deionized water for use, aftertreatment has directly obtained the fluoro powder coating resin particle after by vacuum distillation recovered solvent, and synthesis technique is simple, has reduced the fluoro powder coating resin production cost;
4) hydroxyl value of synthetic fluoro powder coating resin is 35-55mgKOH/g, acid number is 3.0-8.0mgKOH/g, 39～70 ℃ of second-order transition temperatures, so the synthetic fluoro powder coating resin of the present invention has good stability in storage, 40 ℃ of constant temperature store that 7d does not feel like jelly, nondiscoloration, nothing caking;
5) powder coating that is made by the synthetic fluoro powder coating resin of the present invention has good powder coating workability.
Embodiment
Enumerate five embodiment below, the present invention is further specified, but the present invention is not only limited to these embodiment.
Embodiment 1
Adopt 2L to have the autoclave of induction stirring, be provided with chuck heating and cooling device in the still, the still outer wall is with electric heater unit.Autoclave vacuumizes deoxidation before the experiment, oxygen concentration is less than 45ppm in the still, then add the 1092.0g Freon 113,300.0g deoxidation deionized water, 123.1g vinyl butyrate, 51.0g hydroxy butyl vinyl ether, 81.1g tertiary ethylene carbonate, 7.0g methacrylic acid, replace twice with high pure nitrogen in the still, remove and reclaim residual oxygen in the solution, feed the 219.0g trifluorochloroethylene, stir on one side, one side is heat temperature raising slowly, when temperature is raised to 35 ℃, add the 3.5g diisobutyryl peroxide with high-pressure metering pump, keep temperature of reaction between 33～37 ℃, with water cooling autoclave stopped reaction, discharge residual unreacted monomer in the reactor behind the 4hr.
On autoclave, connect vacuum distillation apparatus, in still, add the 700.0g deionized water at twice, Yi Bian slowly heating, Yi Bian slowly stir, keep temperature in the kettle at 30 ℃, vacuum tightness remains on-0.1MPa in the still, and underpressure distillation removes reclaims Freon 113, afterwards, be cooled to room temperature, blowing, drying obtains granulated polymer 409.2g.
Experimental data and multipolymer physicals see Table 1.
Embodiment 2
Operation steps and equipment are with embodiment 1, and different with embodiment is: add 936.0g Freon 113,400.0g deoxidation deionized water, 61.1g vinyl-acetic ester, 53.0g hydroxypropyl vinyl ether, 84.2g tertiary ethylene carbonate, 11.0g undecylenic acid.Feed the 242.0g trifluorochloroethylene.When temperature is raised to 50 ℃, add the 15.5g di-isopropyl peroxydicarbonate with high-pressure metering pump, keep temperature of reaction between 48～52 ℃, with water cooling autoclave stopped reaction, discharge residual unreacted monomer in the reactor behind the 8hr.In still, add 600.0g deionized water, vacuum distillation recovered solvent at twice.Obtain granulated polymer 406.0g at last.Experimental data and multipolymer physicals see Table 1.
Embodiment 3
Adopt 2L to have the autoclave of induction stirring, be provided with chuck heating and cooling device in the still, the still outer wall is with electric heater unit.Autoclave vacuumizes deoxidation before the experiment, oxygen concentration is less than 45ppm, then add 750.0g deoxidation deionized water, 68.8g vinyl-acetic ester, 42.2g hydroxyethyl vinyl ether, 109.2g tertiary ethylene carbonate, 3.7g undecylenic acid, replace twice with high pure nitrogen in the still, remove and reclaim residual oxygen in the solution, feed the 250.0g Tetrafluoroethane, then feed the 233.0g trifluorochloroethylene, stir on one side, one side is heat temperature raising slowly, when temperature is raised to 55 ℃, add the 12.7g di-cyclohexylperoxy dicarbonate with high-pressure metering pump, keep temperature of reaction between 53～57 ℃, use water cooling autoclave stopped reaction behind the 6hr, under slowly stirring, slowly discharge unreacted monomer residual in the reactor and solvent, afterwards, be cooled to room temperature, blowing, drying obtains granulated polymer 420.3g.
Experimental data and multipolymer physicals see Table 1.
Embodiment 4
Operation steps and equipment are with embodiment 3, as different from Example 3: add 700.0g deoxidation deionized water, 63.6g vinyl-acetic ester, 45.8g hydroxyethyl vinyl ether, 87.4g tertiary ethylene carbonate, 11.0g undecylenic acid.Feed the 300.0g Tetrafluoroethane, then feed the 247.0g trifluorochloroethylene.When temperature is raised to 55 ℃, add the 12.7g di-cyclohexylperoxy dicarbonate with high-pressure metering pump, keep temperature of reaction between 53～57 ℃, under slowly stirring, slowly discharge unreacted monomer residual in the reactor and solvent, afterwards, be cooled to room temperature, blowing, drying obtains granulated polymer 423.0g.
Experimental data and multipolymer physicals see Table 1.
Embodiment 5
Operation steps and equipment are with embodiment 3, and different with embodiment is: add 700.0g deoxidation deionized water, 80.0g vinyl butyrate, 44.0g hydroxyethyl vinyl ether, 62.4g tertiary ethylene carbonate, 8.8g butenoic acid.Feed the 300.0g HFC-236fa, then feed the 256.3g trifluorochloroethylene.When temperature is raised to 55 ℃, add the 19.0g di-cyclohexylperoxy dicarbonate with high-pressure metering pump, keep temperature of reaction between 53～57 ℃, under slowly stirring, slowly discharge unreacted monomer residual in the reactor and solvent, afterwards, be cooled to room temperature, blowing, drying obtains granulated polymer 402.0g.
Experimental data and multipolymer physicals see Table 1.
It is 1 as follows that embodiment 1-5 experimental data and multipolymer physicals are tabulated:
Table 1, embodiment 1-5 experimental data and multipolymer physicals
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Participate in reaction monomers | |||||
| Trifluorochloroethylene (g) | 219.0 | 242.0 | 233.0 | 247.0 | 256.3 |
| Vinyl-acetic ester (g) | -- | 61.1 | 68.8 | 63.6 | -- |
| Propionate (g) | -- | -- | -- | -- | 80.0 |
| Vinyl butyrate (g) | 123.1 | -- | -- | -- | -- |
| Tertiary ethylene carbonate (g) | 81.1 | 84.2 | 109.2 | 87.4 | 62.4 |
| Hydroxyethyl Vinyl Ether (g) | -- | -- | 42.2 | 45.8 | 44.0 |
| Hydroxypropyl Vinyl Ether (g) | -- | 53.0 | -- | -- | -- |
| Hydroxyl butyl vinyl ether (g) | 51.0 | -- | -- | -- | -- |
| Methacrylic acid (g) | 7.0 | -- | -- | -- | -- |
| Butenoic acid (g) | -- | -- | -- | -- | 8.8 |
| Undecylenic acid (g) | -－ | 11.0 | 3.7 | 11.0 | -- |
| Solvent | |||||
| Freon 113 (g) | 1092.0 | 936.0 | -- | -- | -- |
| Tetrafluoroethane (g) | -- | -- | 250.0 | 300.0 | -－ |
| HFC-236fa (g) | 300.0 | ||||
| Deoxidation deionized water (g) | 300.0 | 400.0 | 750.0 | 700.0 | 700.0 |
| Initiator | |||||
| Diisobutyryl peroxide (g) | 3.5 | -- | -- | -- | -- |
| Di-isopropyl peroxydicarbonate (g) | 15.5 | ||||
| Di-cyclohexylperoxy dicarbonate (g) | -- | -- | 12.7 | 15.9 | 19.0 |
| Temperature of reaction (℃) | 33～37 | 48～52 | 53～57 | 53～ 57 | 53～57 |
| Reaction initial pressure (MPa) | 0.62 | 0.85 | 1.35 | 1.45 | 1.20 |
| Reaction terminating pressure (MPa) | 0.15 | 0.29 | 1.0 | 1.12 | 0.85 |
| Reaction times (hr) | 4 | 8 | 6 | 6 | 10 |
| Multipolymer amount (g) | 409.2g | 406.0 | 420.3 | 423.0 | 402.0 |
| Multipolymer is formed (mol%) | |||||
| Trifluorochloroethylene | 47.0 | 52.0 | 50.0 | 53.0 | 55.0 |
| Vinyl-acetic ester | -- | 18.0 | 20.0 | 18.5 | -- |
| Propionate | -- | -- | -- | -- | 20.0 |
| Vinyl butyrate | 27.0 | -- | -- | -- | -- |
| Tertiary ethylene carbonate | 13.0 | 13.5 | 17.5 | 14.0 | 10.0 |
| The hydroxyethyl Vinyl Ether | -- | -- | 12.0 | 13.0 | 12.5 |
| The hydroxypropyl Vinyl Ether | -- | 13.0 | -- | -- | -- |
| The hydroxyl butyl vinyl ether | 11.0 | -- | -- | -- | -- |
| Methacrylic acid | 2.0 | - | -- | -- | -- |
| Butenoic acid | -- | -- | -- | -- | 2.5 |
| Undecylenic acid | -- | 1.5 | 0.5 | 1.5 | -- |
| Add up to | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Hydroxyl value (mgKOH/g) | 37.0 | 55.0 | 45.0 | 48.0 | 43.0 |
| Acid number (mgKOH/g) | 6.7 | 4.8 | 3.5 | 5.4 | 7.3 |
| The multipolymer second-order transition temperature (℃) | 47 | 56 | 67 | 60 | 39 |
| The multipolymer stability in storage (40 ℃, 7d) | No change | No change | No change | No change | Slight caking is arranged, can use after the mixing |
Experimental example
The fluoro powder coating resin that embodiment 1-5 is obtained, add requirement blocked isocyanate curing agent B1530 (production of Degussa company), titanium dioxide (E.I.Du Pont Company's production), flow agent, st-yrax etc. according to calculating, in premixing tank, carry out pre-mixing, putting into twin screw extruder (east, Yantai brightness company produces) then melt extrudes, after the pulverizing, sieve with 200 eye mesh screens, obtain fluoro powder coating.The fluoro powder coating for preparing adopts the electrostatic spraying construction technology, detects every physical and chemical performance by GB making sheet, and embodiment 1-5 powder coating prescription and every performance test results see Table 2.
Table 2, embodiment 1-5 fluoro powder coating prescription and the physical and chemical performance detected result of filming
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The powder coating prescription | |||||
| Fluorine powdex (g) | 200.0 | 200.0 | 200.0 | 200.0 | 200.0 |
| B1530(g) | 34.0 | 40.0 | 50.0 | 38.0 | 37.0 |
| Flow agent (g) | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| St-yrax (g) | 1.2 | 1.2 | 1.2 | 1.2 | 1.2 |
| Performance powder coating | |||||
| The coating stability in storage (40 ℃, 7d) | No change | No change | No change | No change | Slight caking is arranged, can use after the mixing |
| The physical and chemical performance of filming | |||||
| Condition of cure | 200℃× 10min | 200℃× 10min | 200℃× 10min | 200℃×10min | 200℃× 10min |
| Thickness, μ m | 49 | 50 | 52 | 48 | 50 |
| Appearance of film | Slight tangerine line slightly grows dim | Slight tangerine line | Extremely slight tangerine line | Extremely slight tangerine line | Extremely slight tangerine line |
| Gloss (60 °) | 52 | 65 | 76 | 73 | 74 |
| Shock strength, cm | 40 | 50 | 50 | 50 | 50 |
| Sticking power, level | 2 | 1 | 1 | 1 | 1 |
| Snappiness, mm) | 3 | 1 | 1 | 1 | 1 |
| Pencil hardness | 2H | 3H | 3H | 3H | 3H |
| Chemical reagent-resistant performance | |||||
| 10％HCl(10d) | No change | No change | No change | No change | No change |
| 10％H 2S0 4(10d) | No change | No change | No change | No change | No change |
| 10％Na0H | No change | No change | No change | No change | No change |
| Dimethylbenzene (10d) | The 3d swelling | No change | No change | No change | No change |
| MEK cleans (inferior) | 50 | >100 | >100 | >100 | >100 |
| Salt-fog test (2000hr) | No change | No change | No change | No change | No change |
| Artificial accelerated aging test (3000hr protects light rate %) | 62 | 85 | 96 | 98 | 93 |
The invention provides synthetic method and prepare fluoro powder coating resin, synthetic technology of resins is easy, simple to operate, production cost is lower, synthetic fluorine powdex has good stability in storage, the powder coating application property that this resin is mixed with is good, has excellent physicals, erosion resistance, weathering resistance and high-decoration.
Claims (6)
1, a kind of thermosetting fluoro powder coating resin, by the total mole number of described resin, cosegment comprises:
(1) 47.0～55.0 mole of % is from the segment of trifluorochloroethylene;
(2) 30.0～40.0 moles of % are from the segment of paraffinic acid vinyl ester;
(3) 10.0～15.0 moles of % are from the segment of hydroxyalkyl vinyl ether;
(4) 0.5～2.5 moles of % are from the segment of alkyl olefin(e) acid;
The hydroxyl value of described thermosetting fluoro powder coating resin is 35-55mgKOH/g, and acid number is 3.0-8.0mgKOH/g, 39～70 ℃ of second-order transition temperatures;
Described paraffinic acid vinyl ester is tertiary monocarboxylic acid vinyl ester and the mixture that is selected from vinyl-acetic ester, vinyl propionate base ester, butyric acid vinyl ester, valeric acid vinyl ester, the caproic acid vinyl ester any one, and wherein to account for paraffinic acid vinyl ester segment be 33.3～46.7 moles of % to tertiary ethylene carbonate.
2, thermosetting fluoro powder coating resin as claimed in claim 1 is characterized in that, described segmental content from the paraffinic acid vinyl ester is 32.5～37.5 moles of %.
3, the preparation method of thermosetting fluoro powder coating resin as claimed in claim 1, it comprises following step:
1) provides a kind of solution of forming by the mixture of aliphatic halogenated hydrocarbon and deoxidation deionized water, the ratio of deoxidation deionized water in solution is 20-75% by mass, described aliphatic halogenated hydrocarbon is a Freon 113, Tetrafluoroethane, the mixture of one or more in the HFC-236fa, the consumption of this solution are following 2) participate in the 42-45% of the total moles monomer of reaction;
2) with paraffinic acid vinyl ester, hydroxyalkyl vinyl ether, alkyl acrylic monomer and above-mentioned 1) solution of preparation mixes and to place in the reactor, feeds trifluorochloroethylene; The monomer consumption is as follows by mole number:
Trifluorochloroethylene 47.0～55.0%;
Paraffinic acid vinyl ester 30.0～40.0%;
Hydroxyalkyl vinyl ether 10.0～15.0%;
Alkyl olefin(e) acid 0.5～2.5%;
3) adopt the solution precipitation polymerization technique, under the organic peroxide evocating agent effect, under 30～60 ℃ temperature of reaction, 0.5～1.5MPa reaction pressure, make step 2) preparation reaction mixture polymerization 4～10hr, by distillation solvent removal is also reclaimed, make fluoro powder coating resin, in the total mole number of described resin, cosegment comprises:
(1) 47.0～55.0 mole of % is from the segment of trifluorochloroethylene;
(2) 30.0～40.0 moles of % are from the segment of paraffinic acid vinyl ester;
(3) 10.0～15.0 moles of % are from the segment of hydroxyalkyl vinyl ether;
(4) 0.5～2.5 moles of % are from the segment of alkyl olefin(e) acid.
4, the preparation method of thermosetting fluoro powder coating resin according to claim 3, it is characterized in that described organic peroxide evocating agent is one or more the mixture in diisobutyryl peroxide, di-cyclohexylperoxy dicarbonate and the di-isopropyl peroxydicarbonate, its consumption is 0.5～1.5 mole of % of reaction monomers total mole number.
5, the preparation method of thermosetting fluoro powder coating resin according to claim 4 is characterized in that: described organic peroxide evocating agent is a di-cyclohexylperoxy dicarbonate, and its consumption is 0.8～1.0 mole of % of the total mole number of reaction monomers.
6, according to the preparation method of any described thermosetting fluoro powder coating resin among the claim 3-5, it is characterized in that: temperature of reaction is 55 ℃, and reaction pressure is 1.00～1.45MPa, and polymerization reaction time is 6hr.
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| CN101125979B (en) * | 2006-08-18 | 2010-05-12 | 无锡市雅丽涂料有限公司 | Thermosetting fluorine-carbon resin for metal coiled material and coating thereof |
| CN101955712B (en) * | 2009-09-01 | 2012-11-07 | 老虎粉末涂料制造（太仓）有限公司 | Oil-repellent thermosetting powder coating and preparation method and application thereof |
| CN103483942B (en) * | 2013-08-26 | 2016-08-24 | 广州擎天材料科技有限公司 | A kind of fluorocarbon powder paint with grain effect and preparation method thereof |
| CN104927503A (en) * | 2015-06-18 | 2015-09-23 | 巨化集团技术中心 | Thermoset fluororesin powder coating preparation method |
| CN111138956A (en) * | 2019-12-23 | 2020-05-12 | 江阴市玲珑高分子材料有限公司 | Thermosetting powder electromagnetic shielding coating |
| CN113121737A (en) * | 2021-04-30 | 2021-07-16 | 鞍山润德精细化工有限公司 | Solid polyacrylate resin containing anhydride functional group and preparation and use method thereof |
| CN115477719B (en) * | 2022-09-27 | 2023-07-18 | 大连广福新材料科技有限公司 | Chlorotrifluoroethylene-vinyl ether powder resin and preparation method thereof |
| CN115417943B (en) * | 2022-09-30 | 2023-08-01 | 大连广福新材料科技有限公司 | Chlorotrifluoroethylene-vinyl ester powder fluororesin and preparation method thereof |
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