CN1294217C - Soluble fluorine-containing paint resin and method for preparing same - Google Patents
Soluble fluorine-containing paint resin and method for preparing same Download PDFInfo
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- CN1294217C CN1294217C CNB2003101093838A CN200310109383A CN1294217C CN 1294217 C CN1294217 C CN 1294217C CN B2003101093838 A CNB2003101093838 A CN B2003101093838A CN 200310109383 A CN200310109383 A CN 200310109383A CN 1294217 C CN1294217 C CN 1294217C
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- Prior art keywords
- vinyl ether
- vinyl
- ester
- alkyl
- vinyl ester
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- 229920005989 resin Polymers 0.000 title claims abstract description 61
- 239000011347 resin Substances 0.000 title claims abstract description 61
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 33
- 239000011737 fluorine Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003973 paint Substances 0.000 title abstract description 13
- -1 alkyl vinyl ether Chemical compound 0.000 claims abstract description 52
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 41
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims description 50
- 239000011248 coating agent Substances 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 claims description 8
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical group CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 8
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical group CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical group OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 claims description 4
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 4
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 4
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 claims description 4
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 claims description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 4
- MHNNAWXXUZQSNM-UHFFFAOYSA-N methylethylethylene Natural products CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 4
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 claims description 3
- YQMANMTVEHKOHX-UHFFFAOYSA-N 4-ethenoxybutan-2-ol Chemical compound CC(O)CCOC=C YQMANMTVEHKOHX-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- HJVKTYVDOZVQPA-UHFFFAOYSA-N ethenoxycyclopentane Chemical compound C=COC1CCCC1 HJVKTYVDOZVQPA-UHFFFAOYSA-N 0.000 claims description 3
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical group C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 claims description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003999 initiator Substances 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DQNSRQYYCSXZDF-UHFFFAOYSA-N 1,4-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1CCC(COC=C)CC1 DQNSRQYYCSXZDF-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000001792 White test Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000002075 anti-alcohol Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to fluorine containing paint resin, a cosegment of which comprises a chain segment of 45 to 60% of tetrafluoroethylene, a chain segment of 10 to 35% of alkyl vinyl ether, a chain segment of 15 to 22% of hydroxyalkyl vinyl ether and a chain segment of 3 to 20% of vinyl ester. A hydroxyl value of the fluorine-containing copolymer paint resin is from 70 to 100 mgKOH/g, and the inherent viscosity is from 0.3 to 0.8. The present invention also relates to a preparation method of the fluorine containing paint resin, and the method comprises :1) providing a monomer mixture which comprises the tetrafluoroethylene, the alkyl vinyl ether, the hydroxyalkyl vinyl ether and the vinyl ester; 2) polymerizing for 4 to 6 hours at 1.0 to 1.5Mpa reaction pressure under the function of an initiating agent so as to prepare the fluorine containing paint resin.
Description
Invention field
The present invention relates to a kind of solvable type fluoro-containing coating resin and preparation method thereof.More particularly, the present invention relates to coating resin that a kind of tetrafluoroethylene and vinyl ether or vinyl ester multi-component copolymer form and preparation method thereof.The coating resin that forms has higher fluorine content, fabulous weathering resistance and solvent resistance.And the reaction pressure of the inventive method is low, speed of response is fast, safe.
Background technology
The soluble fluoride coating resin except anti-patience such as weathering resistance with general fluorine coating resin, chemical-resistant, also have common coating solvent soluble and can ambient cure etc. good workability, be widely used.Known in the fluoro-containing coating resin, fluorine content is high more, and its weathering resistance is good more.
The beginning of the eighties, Japan AGC company develops the quarternary copolymerized fluorine coating resin (referring to JP58136662) of trifluorochloroethylene-alkyl vinyl ether-cycloalkyl vinyl ether-hydroxyalkyl vinyl ether, owing in multipolymer, introduced the hydroxyalkyl vinyl ether, its hydroxyl that contains is as cross-linking set, can carry out crosslinked with isocyanic ester, realized ambient cure, but its post-treatment performance of making lacquer is not enough, the poor-performing of anti-solvent toluene.
The Chinese patent application CN1145386A that on March 19th, 1997, the invention disclosed name was called " fluoro-containing coating method for making and application thereof " discloses a kind of fluoro-containing coating preparation method and application, this method is by being to introduce carboxylic acid functional in the tetrapolymer of main body at trifluorochloroethylene, it is poor to have solved the fluoro-resin pigment-dispersing, easily produce shortcomings such as lacquer disease, but there is the defective of anti-alcohols poor performance in this method.
The Chinese patent application CN1244556A that on February 16th, 2000, the invention disclosed name was called " based on the fluoric copolymer paint and the method for making thereof of tetrafluoroethylene " discloses a kind of fluoric copolymer paint and preparation method based on tetrafluoroethylene, it is fluorochemical monomer that this method adopts tetrafluoroethylene, preparation tetrafluoroethylene-aliphatic ester and/or isomeric olefine-fatty enol and/or alkene ether dibasic alcohol-fatty olefin(e) acid multiple copolymer coating resin, this coating resin has superior corrosion resistance, weathering resistance and good solvent resolvability.But coating resin that the document makes and preparation method thereof has following defective:
1) this copolymer resin uses the aliphatic ester monomer, at the monomer of aliphatic ester described in the polymerization process autohemagglutination takes place easily as everyone knows, and the result causes the content of tetrafluoroethylene monomer in the multipolymer that makes to descend, and promptly this multipolymer is difficult to have high fluorine content;
2) in the building-up process of this resin, adopt reaction under high pressure (2.0-2.8Mpa), and polymerization time long (20-22hr), not only can cause facility investment big, dangerous high, and production efficiency is lower;
3) document is not mentioned the anti-toluene performance of resin.
In view of the above-mentioned defective of prior art, need a kind of erosion resistance of exploitation, solvent resistance excellence with tetrafluoroethylene be main fluorochemical monomer multi-component copolymer coating resin and require this coating resin can be with under low pressure synthetic at a high speed.
What the purpose of this invention is to provide a kind of erosion resistance, weathering resistance, solvent resistance excellence is the coating resin of the multi-component copolymer of main fluorochemical monomer with tetrafluoroethylene.
Another object of the present invention provides a kind of method of at a high speed synthetic described coating resin under low pressure.
Summary of the invention
One aspect of the present invention provides a kind of fluorinated copolymer coating resin, and by the total mole number of resin, its cosegment comprises:
1) 45-60 mole % is from the segment of tetrafluoroethylene;
2) 10-35 mole % is from the segment of alkyl vinyl ether, and described alkyl is C
1-C
8Alkane or naphthenic hydrocarbon;
3) 15-22 mole % is from the segment of hydroxyalkyl vinyl ether, and described alkyl is C
1-C
4Straight-chain paraffin; With
4) 3-20 mole % is from the segment of vinyl ester;
The hydroxyl value of described fluorinated copolymer coating resin is 70～100mgKOH/g, and limiting viscosity is 0.3～0.8.
Another aspect of the present invention provides a kind of preparation method of described fluorinated copolymer coating resin, and it comprises the steps:
1) provide a kind of monomer mixture of being made up of tetrafluoroethylene, alkyl vinyl ether, hydroxyalkyl vinyl ether and vinyl ester, the alkyl in the described alkyl vinyl ether is C
1-C
8Alkane or naphthenic hydrocarbon, the alkyl in the described hydroxyalkyl vinyl ether is C
1-C
4Straight-chain paraffin; With
2) under action of evocating under the 1.0-1.5Mpa reaction pressure polymerization 4-6 hour, make the fluorine coating resin, in the total mole number of described resin, its cosegment comprises:
A) 45-60 mole % is from the segment of tetrafluoroethylene;
B) 10-35 mole % is from the segment of alkyl vinyl ether;
C) 15-22 mole % is from the segment of hydroxyalkyl vinyl ether;
D) 3-20 mole % is from the segment of vinyl ester, and described vinyl ester is the mixture of paraffinic acid vinyl ester and tertiary ethylene carbonate, and both mol ratios are 20: 80～80: 20.
Embodiment
The present invention relates to a kind of be fluorine-containing comonomer with tetrafluoroethylene, the fluorine coating resin that forms with alkyl vinyl ether, hydroxyalkyl vinyl ether and the vinyl ester multi-component copolymer formed by alkyl vinyl ester and tertiary monocarboxylic acid vinyl ester.Its fluorine content is 30～36 moles of %, and hydroxyl value is 70～100mgKOH/g, and limiting viscosity is 0.3～0.8dl/g (30 ℃, tetrahydrofuran (THF) (being called for short THF) is made solvent).
In the fluorine coating resin of the present invention fluorochemical monomer specific be tetrafluoroethylene, total mole number in the fluorine coating resin, segmental content from tetrafluoroethylene accounts for 45～60%, if from the content of segment in multipolymer of tetrafluoroethylene less than 45 moles of %, the weathering resistance of multipolymer will reduce, if greater than 60 moles of %, then polyreaction will become difficult from the content of segment in multipolymer of tetrafluoroethylene, solubleness descends.In a better example of the present invention, be 47～52 moles of % from the segmental content of tetrafluoroethylene.
Alkyl vinyl ether of the present invention is that carbonatoms is the alkane or the naphthenic hydrocarbon of n=1～8 in the alkyl, its illustrative example includes, but are not limited to ethyl vinyl ether, isopropyl-ethylene base ether, butyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether.In copolyreaction, these vinyl ether can use separately also can mix use.In the total mole number of fluorine coating resin, be 10～35% from the content of segment in polymkeric substance of alkyl vinyl ether.If content is lower than 10%, the paint film flexibility that polymkeric substance is made is not enough; Content is higher than 35%, and the hardness of paint film and weathering resistance will descend.In a better example of the present invention, be 15-25 mole % from the segmental content of alkyl vinyl ether.
Hydroxyalkyl vinyl ether of the present invention is the straight-chain paraffin of carbonatoms n=1～4 in the alkyl, and the example of its indefiniteness comprises hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, 3-hydroxy butyl vinyl ether and 4-hydroxy butyl vinyl ether.Be preferably the 4-hydroxy butyl vinyl ether.By the total mole number of fluorine coating resin, be 15～22% from the segmental content of hydroxyalkyl vinyl ether.Content is lower than 15%, and the degree of crosslinking of making paint film is not enough, and the solvent resistance of coating will obviously descend; Content is higher than 22%, and it is comparatively difficult that polymerization will become, and can influence the weathering resistance of coating simultaneously.
By the total mole number of fluorine coating resin, fluorine coating resin of the present invention also contains the segment of 3-20 mole % from vinyl ester, and it is paraffinic acid vinyl ester segment and tertiary ethylene carbonate segmental mixture.In a better example of the present invention, the mol ratio of two kinds of esters is 20: 80～80: 20 in the mixture of described paraffinic acid vinyl ester and tertiary ethylene carbonate.
As above described when commenting Chinese patent CN 1244556A, independent paraffinic acid vinyl ester has the part autohemagglutination in chain, certainly the party of described paraffinic acid vinyl ester descends the alternate degree of whole polymkeric substance, causes the decline of fluorine content, thus the weathering resistance of impact polymer.
If the inventor finds to add tertiary ethylene carbonate in described straight-chain ethylene base ester, promptly utilize sterically hindered big tertiary monocarboxylic acid group, the autohemagglutination that can stop paraffinic acid vinyl ester with autohemagglutination tendency, the alternate degree of whole multipolymer is improved, improve the weathering resistance of resin, utilize the degree of crystallinity of sterically hindered effective reduction multipolymer of tertiary monocarboxylic acid group simultaneously, improve the dissolving resin degree.The present invention adopts the mixture of alkyl vinyl ether and hydroxyalkyl vinyl ether as comonomer, makes the alternately property of whole multipolymer obviously improve, and has improved the content of tetrafluoroethylene in the resin effectively, has guaranteed the high-weatherability of resin.
Paraffinic acid vinyl ester of the present invention can be this area paraffinic acid vinyl ester commonly used, for example can adopt the paraffinic acid vinyl ester described in the Chinese patent CN 1244556A.In another example of the present invention, described paraffinic acid vinyl ester is C
1-C
6The paraffinic acid vinyl ester, for example: formic acid vinyl ester, vinyl-acetic ester, vinyl propionate base ester, butyric acid vinyl ester, valeric acid vinyl ester and caproic acid vinyl ester.
The tertiary ethylene carbonate that the present invention uses is this area tertiary monocarboxylic acid ethene value commonly used, and the commodity that its representational example has Shell Co. Ltd to produce are called the tertiary ethylene carbonate of Veova-9.
The invention still further relates to the preparation method of described fluorine coating resin, it comprises:
1) provide a kind of monomer mixture of being made up of tetrafluoroethylene, alkyl vinyl ether, hydroxyalkyl vinyl ether and vinyl ester, the alkyl in the described alkyl vinyl ether is C
1-C
8Alkane or naphthenic hydrocarbon, the alkyl in the described hydroxyalkyl vinyl ether is C
1-C
4Straight-chain paraffin; With
2) under action of evocating under the 1.0-1.5Mpa reaction pressure polymerization 4-6 hour, make the fluorine coating resin, in the total mole number of resin, its cosegment comprises:
A) 45-60 mole % is from the segment of tetrafluoroethylene;
B) 10-35 mole % is from the segment of alkyl vinyl ether;
C) 15-22 mole % is from the segment of hydroxyalkyl vinyl ether;
D) 3-20 mole % is from the segment of vinyl ester.
Copolyreaction of the present invention is a Raolical polymerizable, adopts solution reaction system.Its solvent is without particular limitation, can be this area solvent commonly used.In a better example of the present invention, described solvent is the mixture of aliphatics ketone and acetates.The example of described alkanones solvent has acetone, methylethylketone, methyl iso-butyl ketone (MIBK) etc., and the indefiniteness example of described acetates solvent has vinyl acetic monomer, N-BUTYL ACETATE etc.In a better example of the present invention, use the aliphatics ketone: the acetates mol ratio is the reaction solvent system of 70-60: 30-40.Consumption in the described solvent of mole serves as to participate in 40～50% of reaction monomers total mole number.
The polymerization starter that is used for polyreaction of the present invention can be any radical polymerization initiator known in the art.In a better example of the present invention, the polymerization starter of employing is organic peroxide evocating agent or azo-compound initiator, and they can use separately, also can two or more mix use.The indefiniteness example that is applicable to organic peroxide evocating agent of the present invention has the tert-butylcyclohexyl superoxide.The indefiniteness example that is applicable to azo-compound initiator of the present invention has Diisopropyl azodicarboxylate.
The consumption of initiator can be any consumption known in the art.In a better example of the present invention, the amount of the initiator of adding accounts for 0.5～3.0% of the total mole of reaction mixture.
According to different initiators, the temperature of reaction of polyreaction of the present invention is 40～100 ℃.The initiator that uses is Diisopropyl azodicarboxylate preferably in the example at one of the present invention, and temperature of reaction is 60～80 ℃.
In a better example of the present invention, the present invention adopts tetrafluoroethylene monomer initially to add method, and promptly the carrying out along with reaction progressively adds the tetrafluoroethylene monomer raw material, thereby the reaction pressure in the whole process is controlled at 1.0～1.5Mpa.Compared with prior art, adopt this method obviously to reduce reaction pressure, thereby improve security and reduce equipment cost, and the reaction process variation obviously, and control is easy, and the reaction times of entire reaction shortens greatly, generally be controlled at 4～6 hours, production efficiency is improved.
Compared with prior art, the invention has the advantages that:
1) the fluorine content height of fluorine coating resin product is 30～36%, thereby has improved its weathering resistance;
2) tetrafluoroethylene concentration modification scope is wide, 45～60%;
3) make the mechanical property excellence of paint film (varnish) behind the coating: sticking power is zero level; Hardness is 3H; Snappiness is 1mm, the paint film flawless; Impact the 50cm flawless; Gloss (60 °) 84～87;
4) solvent resistance of coating is good, and test plate (panel) soaks 20 days no changes in toluene solution; Clean＞200 times with acetone;
5) good weatherability: artificial accelerated aging 4200 hours, loss of gloss zero level, variable color one-level;
6) the used pressure of polymerization process is low, and speed of response is fast, and is safe and facility investment is low.
Below, further specify the present invention in conjunction with the embodiments.
Embodiment
Embodiment 1
Have to 2L and to add 200g N-BUTYL ACETATE, 2.5g Diisopropyl azodicarboxylate in the autoclave of induction stirring, autoclave is found time, fill nitrogen, add 126g cyclohexyl vinyl ether (being called for short CHVE), 17.2 vinyl acetates (VAC), 147.2g Veova-9,116g hydroxy butyl vinyl ether (being called for short HBVE), 300g acetone with volume pump then, feeding tetrafluoroethylene to reactor pressure then is 0.5Mpa, autoclave is heated gradually to 70 ℃, feeding tetrafluoroethylene to reactor pressure is 1.5Mpa, keep pressure, maintain the temperature at 70 ℃.Reaction times is 4.5 hours.Cooling discharge.Obtain as clear as crystal colourless or light yellow thick liquid.The solid content of this thick liquid is 55%.Get this thick liquid of part, precipitate as precipitation agent, then throw out was obtained sample in 24 hours 60 ℃ of following vacuum-dryings with sherwood oil.Fluorine content=31.03% of this sample, hydroxyl value=76.3mgKOH/g, η=0.52dl/g (30 ℃, THF makes solvent).Analyze (mol%) with nucleus magnetic resonance, find TFE: CHVE: HBVE: VAC: Veova-9=48: 15.8: 16.3: 4.4: 15.5.
Get the 100g resin solution, add the mixing solutions of N-BUTYL ACETATE and dimethylbenzene, according to the hexamethylene diisocyanate of calculated amount needs, be made into coating varnish, that regulates coating is coated with-4
#Cup viscosity is 15-17 second, makes various test plate (panel)s by GB, and tests by GB, and test result is as follows:
Sticking power (cross-hatching): 0 grade
Hardness (pencil hardness): 3H
Impact: 50cm
Pliability test: 1mm flawless
Gloss (60 °): 87
Acidproof (10% sulfuric acid): 15 days no changes of normal temperature
Alkaline-resisting (10% sodium hydroxide): 15 days no changes of normal temperature
Anti-toluene: 15 days no changes of normal temperature
Anti-acetone is wiped examination:＞200 times
Artificial accelerated aging: 4200 hours, loss of gloss zero level, variable color one-level, paint film does not have efflorescence, be full of cracks and other catabiosis.(white test plate (panel))
Embodiment 2-5
Use the method identical with embodiment 1, but be to use monomer shown in the table 1 and consumption thereof (to list in the bracket, unit is gram), make fluorine resin (in embodiment 2, adopting tert-butylcyclohexyl superoxide (TBCP, Tianjin Akzo Nobel company limited produces) to make initiator):
Table 1
*
| Alkyl vinyl ether | The hydroxyalkyl vinyl ether | The paraffinic acid vinyl ester | The tertiary monocarboxylic acid vinyl ester | |
| Embodiment 2 | Butyl vinyl ether (38.0) cyclohexyl vinyl ether (63.0) | Hydroxyethyl vinyl ether (108.0) | Valeric acid vinyl ester (45.0) | Veova-9 (92.0) |
| Embodiment 3 | Cyclohexyl vinyl ether (132.8) | Hydroxy butyl vinyl ether (169.7) | Butyric acid vinyl ester (92.5) | Veova-9 (32) |
| Embodiment 4 | Isopropyl-ethylene base ether (234.5) | Hydroxy butyl vinyl ether (125.0) | Caproic acid vinyl ester (50.0) | Veova-9 (16.0) |
| Embodiment 5 | Ethyl vinyl ether (36.0) cyclohexyl vinyl ether (63.0) | Hydroxy butyl vinyl ether (110.0) | Vinyl-acetic ester (34.1) | Veova-9 (140.0) |
*: the polymerization pressure of embodiment 2 remains on 1.0MPa, and polymerization time is 6 hours;
The polymerization pressure of embodiment 3 remains on 1.3MPa, and polymerization time is 5 hours;
The polymerization pressure of embodiment 4 remains on 1.5MPa, and polymerization time is 5.3 hours;
The polymerization pressure of embodiment 4 remains on 1.4MPa, and polymerization time is 4 hours.
The performance of the final resin that records by embodiment 1 described method is as shown in table 2 below:
Table 2
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Fluorine content (mole %) | 34.85 | 36.01 | 33.15 | 34.29 |
| Hydroxyl value (mgOH/g) | 93.9 | 98.3 | 88.9 | 73.8 |
| Viscosity (30 ℃, THF) | 0.49 | 0.42 | 0.32 | 0.30 |
| Each segmental content (mole %) | ||||
| Tetrafluoroethylene | 50.5 | 53.2 | 45.5 | 49.8 |
| Alkyl vinyl ether | 14.9 | 14.0 | 34.7 | 16.16 |
| The hydroxyalkyl vinyl ether | 19.6 | 20.5 | 15.2 | 15.33 |
| The paraffinic acid vinyl ester | 5 | 9.2 | 3.6 | 3.8 |
| The tertiary monocarboxylic acid vinyl ester | 10 | 3.1 | 1 | 14.9 |
| Sticking power (cross-hatching) | 0 grade | 0 grade | 0 grade | 0 grade |
| Hardness (pencil hardness) | 3H | 3H | 3H | 3H |
| Impact | 50cm | 50cm | 50cm | 50cm |
| Pliability test | The 1mm leakless | The 1mm leakless | The 1mm leakless | The 1mm leakless |
| Gloss (60 °) | 84 | 87 | 87 | 85 |
| Acidproof (10% sulfuric acid, normal temperature) | 15 days no changes | 15 days no changes | 15 days no changes | 15 days no changes |
| Alkaline-resisting (10%NaOH, normal temperature) | 15 days no changes | 15 days no changes | 15 days no changes | 15 days no changes |
| Anti-toluene (normal temperature) | 15 days no changes | 15 days no changes | 15 days no changes | 15 days no changes |
| Anti-acetone wiping | ＞200 times | ＞200 times | ＞200 times | ＞200 times |
Comparative example
2L has and adds 200g N-BUTYL ACETATE, 400g dimethylbenzene in the autoclave of induction stirring, 2.5g Diisopropyl azodicarboxylate, autoclave is found time, fill nitrogen, add 126g cyclohexyl vinyl ether, 17.2 vinyl acetates, 147.2g Veova-9,116g hydroxy butyl vinyl ether and 360g trifluorochloroethylene with volume pump then, autoclave is heated gradually to 70 ℃, maintain the temperature at 70 ℃, the reaction times is 10 hours.Cooling discharge.Obtain as clear as crystal colourless or light yellow thick liquid.The solid content of this thick liquid=50.2%.Get this thick liquid of part, precipitate as precipitation agent, then throw out was obtained sample in 24 hours 60 ℃ of following vacuum-dryings with sherwood oil.Fluorine content=23.2% of this sample, hydroxyl value 78.2mgKOH/g, η=0.32 (30 ℃, THF makes solvent).
Get the 100g resin solution, add the mixing solutions of N-BUTYL ACETATE and dimethylbenzene, according to the hexamethylene diisocyanate of calculated amount needs, be made into coating varnish, regulate that being coated with of coating-4# cup viscosity is 15-17 second, makes various test plate (panel)s by GB, and test by GB, test result is as follows:
Sticking power (cross-hatching): 0 grade
Hardness (pencil hardness): 3H
Impact: 50cm
Pliability test: 1mm flawless
Gloss (60 °): 85
Acidproof (10% sulfuric acid): normal temperature only can keep 10 days no changes
Alkaline-resisting (10% sodium hydroxide): normal temperature only can keep 10 days no changes
Anti-toluene: poor performance only can keep 5 days no changes under the normal temperature
Anti-acetone is wiped examination:＞100 times, but wrinkling takes place when reaching 110 times
By above-mentioned test-results as seen, fluorine coating resin of the present invention has excellent solvent tolerance and soda acid tolerance.
Claims (10)
1. fluorinated copolymer coating resin, by the total mole number of resin, its cosegment comprises:
1) 45-60% is from the segment of tetrafluoroethylene;
2) 10-35% is from the segment of alkyl vinyl ether, and described alkyl is C
1-C
8Alkane or naphthenic hydrocarbon;
3) 15-22% is from the segment of hydroxyalkyl vinyl ether, and described alkyl is C
1-C
4Straight-chain paraffin; With
4) 3-20% is from the segment of vinyl ester, and described vinyl ester is the mixture of paraffinic acid vinyl ester and tertiary ethylene carbonate, and both mol ratios are 20: 80～80: 20;
The hydroxyl value of described fluorinated copolymer coating resin is 70～100mgKOH/g, and limiting viscosity is 0.3～0.8dl/g.
2. coating resin as claimed in claim 1, the fluorine content that it is characterized in that described coating resin are 30～36 moles of %; From tetrafluoroethylene segmental content is 47～52 moles of %.
3. coating resin as claimed in claim 1 or 2 is characterized in that described alkyl vinyl ether is selected from ethyl vinyl ether, isopropyl-ethylene base ether, butyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether; From alkyl vinyl ether segmental content is 15-25 mole %.
4. coating resin as claimed in claim 1 or 2 is characterized in that described hydroxyalkyl vinyl ether is selected from hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, 3-hydroxy butyl vinyl ether and 4-hydroxy butyl vinyl ether.
5. coating resin as claimed in claim 1 or 2, it is characterized in that described paraffinic acid vinyl ester is a C1-C6 paraffinic acid vinyl ester, it is selected from formic acid vinyl ester, vinyl-acetic ester, vinyl propionate base ester, butyric acid vinyl ester, valeric acid vinyl ester and caproic acid vinyl ester.
6. the preparation method of coating resin as claimed in claim 1, it comprises:
1) provide a kind of monomer mixture of being made up of tetrafluoroethylene, alkyl vinyl ether, hydroxyalkyl vinyl ether and vinyl ester, the alkyl in the described alkyl vinyl ether is C
1-C
8Alkane or naphthenic hydrocarbon, the alkyl in the described hydroxyalkyl vinyl ether is C
1-C
4Straight-chain paraffin, described vinyl ester are the mixtures of paraffinic acid vinyl ester and tertiary ethylene carbonate, and both mol ratios are 20: 80～80: 20; With
2) under action of evocating under the 1.0-1.5Mpa reaction pressure polymerization 4-6 hour, make the fluorine coating resin, in the total mole number of resin, its cosegment comprises:
A) 45-60 mole % is from the segment of tetrafluoroethylene;
B) 10-35 mole % is from the segment of alkyl vinyl ether;
C) 15-22 mole % is from the segment of hydroxyalkyl vinyl ether;
D) 3-20 mole % is from the segment of vinyl ester, and described vinyl ester is the mixture of paraffinic acid vinyl ester and tertiary ethylene carbonate, and both mol ratios are 20: 80～80: 20.
7. method as claimed in claim 6 is characterized in that temperature of reaction is 40～100 ℃, and adopts tetrafluoroethylene monomer initially to add method.
8. as claim 6 or 7 described methods, the fluorine content that it is characterized in that described coating resin is 30～36 moles of %; From tetrafluoroethylene segmental content is 47～52 moles of %.
9. as claim 6 or 7 described methods, it is characterized in that described alkyl vinyl ether is selected from ethyl vinyl ether, isopropyl-ethylene base ether, butyl vinyl ether, cyclopentyl vinyl ether, cyclohexyl vinyl ether; Described segmental content from alkyl vinyl ether is 15-25 mole %; Described hydroxyalkyl vinyl ether is selected from hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, 3-hydroxy butyl vinyl ether and 4-hydroxy butyl vinyl ether.
10. as claim 6 or 7 described methods, it is characterized in that described paraffinic acid vinyl ester is C
1-C
6The paraffinic acid vinyl ester, it is selected from formic acid vinyl ester, vinyl-acetic ester, vinyl propionate base ester, butyric acid vinyl ester, valeric acid vinyl ester and caproic acid vinyl ester.
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| CNB2003101093838A CN1294217C (en) | 2003-12-15 | 2003-12-15 | Soluble fluorine-containing paint resin and method for preparing same |
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| CNB2003101093838A CN1294217C (en) | 2003-12-15 | 2003-12-15 | Soluble fluorine-containing paint resin and method for preparing same |
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| CN101319113B (en) * | 2008-07-18 | 2010-06-02 | 深圳市广田环保涂料有限公司 | Medium-temperature baking type fluorine-carbon paint and its use method |
| CN104829772B (en) * | 2015-05-18 | 2016-09-14 | 山东森福新材料有限公司 | A kind of normal temperature cure Fluorocoating resin and preparation method thereof |
| WO2018012577A1 (en) * | 2016-07-14 | 2018-01-18 | 旭硝子株式会社 | Fluorine-containing polymer composition, fluorine resin coating, coated article |
| CN110511628A (en) * | 2019-08-26 | 2019-11-29 | 佛山科学技术学院 | A kind of modified water-soluble FEVE fluorocarbon coating and preparation method thereof |
| CN115011157A (en) * | 2021-03-05 | 2022-09-06 | Ａｇｃ株式会社 | Coating agent for external package of battery pack |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064920A (en) * | 1989-11-17 | 1991-11-12 | Toagosei Chemical Industry Co., Ltd. | Fluorine-containing copolymer and coating composition containing the copolymer |
| JPH06100834A (en) * | 1992-09-16 | 1994-04-12 | Toagosei Chem Ind Co Ltd | Fluororesin coating composition |
| CN1117979A (en) * | 1994-06-01 | 1996-03-06 | 埃勒夫阿托化学有限公司 | Stable aqueous dispersive body of hydroxyleste fluoridated copolymer and acrylic copolymer and preparation and application as aqueous pait of same |
| CN1244556A (en) * | 1999-08-20 | 2000-02-16 | 大连塑料研究所 | Fluoric copolymer paint with PTFE as main component and its preparation |
-
2003
- 2003-12-15 CN CNB2003101093838A patent/CN1294217C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064920A (en) * | 1989-11-17 | 1991-11-12 | Toagosei Chemical Industry Co., Ltd. | Fluorine-containing copolymer and coating composition containing the copolymer |
| JPH06100834A (en) * | 1992-09-16 | 1994-04-12 | Toagosei Chem Ind Co Ltd | Fluororesin coating composition |
| CN1117979A (en) * | 1994-06-01 | 1996-03-06 | 埃勒夫阿托化学有限公司 | Stable aqueous dispersive body of hydroxyleste fluoridated copolymer and acrylic copolymer and preparation and application as aqueous pait of same |
| CN1244556A (en) * | 1999-08-20 | 2000-02-16 | 大连塑料研究所 | Fluoric copolymer paint with PTFE as main component and its preparation |
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