CN116948081A - 一种高含氟高疏水氟碳树脂及其合成方法 - Google Patents
一种高含氟高疏水氟碳树脂及其合成方法 Download PDFInfo
- Publication number
- CN116948081A CN116948081A CN202310733355.0A CN202310733355A CN116948081A CN 116948081 A CN116948081 A CN 116948081A CN 202310733355 A CN202310733355 A CN 202310733355A CN 116948081 A CN116948081 A CN 116948081A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- fluorocarbon resin
- vinyl
- highly
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 60
- 239000011347 resin Substances 0.000 title claims abstract description 60
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 33
- 239000011737 fluorine Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 150000002085 enols Chemical class 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- QWYSJTTWCUXHQO-UHFFFAOYSA-N [F].OC(=O)C=C Chemical compound [F].OC(=O)C=C QWYSJTTWCUXHQO-UHFFFAOYSA-N 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 15
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 claims description 7
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
- 229960002703 undecylenic acid Drugs 0.000 claims description 3
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 claims description 2
- FSDGGBSMJHFROK-UHFFFAOYSA-N 2-prop-1-enoxyethanol Chemical compound CC=COCCO FSDGGBSMJHFROK-UHFFFAOYSA-N 0.000 claims description 2
- BQKZEKVKJUIRGH-UHFFFAOYSA-N 2-prop-2-enoxypropan-1-ol Chemical compound OCC(C)OCC=C BQKZEKVKJUIRGH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 2
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical compound CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- 150000001336 alkenes Chemical class 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 229920005604 random copolymer Polymers 0.000 abstract 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- 239000008096 xylene Substances 0.000 description 8
- -1 Polytetrafluoroethylene Polymers 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- SMGIMBKCWODARY-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,7,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)CC(F)(F)F SMGIMBKCWODARY-UHFFFAOYSA-N 0.000 description 1
- SCYOYBNXEWFQHR-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,7,7,7-dodecafluoroheptyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)OC(=O)C=C SCYOYBNXEWFQHR-UHFFFAOYSA-N 0.000 description 1
- BPGPBRLNHUNDRY-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropyl prop-2-enoate Chemical compound FC(F)(F)CC(F)OC(=O)C=C BPGPBRLNHUNDRY-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- TVFJAZCVMOXQRK-UHFFFAOYSA-N ethenyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OC=C TVFJAZCVMOXQRK-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/24—Trifluorochloroethene
- C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
- C08F214/247—Trifluorochloroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
- C08F216/20—Monomers containing three or more carbon atoms in the unsaturated aliphatic radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种高含氟高疏水氟碳树脂及其合成方法,其采用含氟烯烃、烷基乙烯基单体、丙烯酸氟酯、烯醚、烯醇和引发剂,以甲苯类或乙酸酯类的一种或两种的混合物做溶剂,通过高分子共聚工艺合成多元无规共聚物。制备时,向真空反应釜中加入提前配好的溶剂、引发剂和配方量的烷基乙烯基单体、丙烯酸氟酯、烯醇、烯酸,然后向反应釜中压入氟烯烃,开动搅拌并升温至预设温度,反应结束后回收残余气体,降至室温出料,经过适当后处理得到氟碳树脂。本发明的高含氟高疏水氟碳树脂是通过自由基溶液共聚合成,氟碳树脂具有高氟含量、疏水且可以制备常温固化氟碳树脂涂料,具有良好的市场应用前景。
Description
技术领域
本发明涉及一种高含氟高疏水氟碳树脂及其合成方法,氟碳树脂具有高氟含量、疏水且可以制备常温固化氟碳树脂涂料。
背景技术
由于聚四氟乙烯(PTFE)、聚偏氟乙烯(PVDF)树脂的熔点较高、常规有机溶剂不溶的特性极大的限制了氟树脂的应用领域,因而制备溶剂可溶、可常温固化型的FEVE氟碳树脂受到了越来越多的关注。同时由于氟碳树脂是以C-F键为主链,因而其成膜后耐候性,耐沾污等性能均较好,而且其涂层的综合性能也不亚于PTFE、PVDF树脂涂层,从而扩宽了氟碳树脂的应用领域。
众所周知,氟碳树脂中氟原子密集包围着碳-碳主链时,会形成一个螺旋形结构,保护C-C键不被冲击,不被化学介质浸入破坏。中国专利CN101104663A公开了一种含氟烯烃、烷基乙烯基醚、乙烯基脂肪族羧酸酯、不饱和羧酸、含羟基的乙烯基单体,在55-65℃下聚合16-20h得五元共聚氟碳树脂,该氟碳树脂聚合温度低,聚合时间相对较长。JimingBian课题组以三氟氯乙烯(CTFE)、醋酸乙烯(VAc)、丙烯酸正丁酯(BA)、新癸酸乙烯酯(Veova 10)和丙烯酸(AA)为原料,制备水性含氟聚合物乳液(Hongzhu Liu,Jiming Bian,Zhonggang Wang and ChuanJin Hou,Molecules 2017,22,184),该含氟聚合物中氟含量基本在12%左右,最高仅为17.79%。山东科技大学寇新秀的硕士学位论文中所用的青岛润昊的型号为3X的FEVE氟碳树脂的接触角仅为67.5°(寇新秀.氟碳/二氧化硅复合超疏水涂层的制备及性能研究[D].山东科技大学,2020),相对较低。因此,氟含量的高低,会制约氟树脂自身的亲疏水性,影响树脂的耐候等性能,从而限制FEVE型氟碳树脂的应用领域。
发明内容
本发明针对FEVE型氟碳树脂的合成,提供了一种高含氟高疏水氟碳树脂及其合成方法。
本发明采用的技术方案如下:
一种高含氟高疏水氟碳树脂,各组分如下:
1)摩尔分数为35%-60%氟烯烃;
2)摩尔分数为20%-30%烷基乙烯基单体;
3)摩尔分数为3%-20%丙烯酸氟酯;
上述组分,可以加入摩尔分数不超过18%烯醇;
上述组分,可以加入摩尔分数不超过12%烯酸。
氟烯烃作为氟碳树脂的主单体,赋予树脂优异的耐候、耐久、耐腐蚀性能。通常选用偏氟氯乙烯、四氟乙烯、三氟氯乙烯或六氟丙烯的一种或多种。其中三氟氯乙烯和四氟乙烯较为适宜,以三氟氯乙烯合成的树脂填料相容性及与基材的附着力较好,同时C-Cl键的存在能够赋予树脂优异的湿气阻隔性。
烷基乙烯基单体用于降低树脂的结晶度,提高树脂在有机溶剂中的溶解性,同时赋予树脂良好的透明性、光泽、硬度和柔韧性。可选用的烷基乙烯基单体有乙基乙烯基醚、异丁基乙烯基醚、环乙基乙烯基醚、缩水甘油基乙烯基醚、羟丁基乙烯基醚、乙酸乙烯酯、丁酸乙烯酯、己酸乙烯酯或叔碳酸乙烯酯中的一种或多种。
丙烯酸氟酯的作用降低氟树脂的表面能,同时引入更多的C-F键,提高氟含量的同时能赋予氟树脂更优异的耐候等性能。选用的丙烯酸氟酯有甲基丙烯酸十二氟庚酯、丙烯酸六氟丁酯、丙烯酸十二氟庚酯、甲基丙烯酸三氟乙酯或丙烯酸四氟丙酯中的一种或多种。
烯醇的作用是为共聚物提供交联点,使共聚物在常温下能与固化剂反应,交联固化成膜,同时对提高涂膜的附着力也起关键作用。选用的烯醇有羟丁基乙烯基醚、乙二醇单烯丙基醚、丙二醇单烯丙基醚、丙烯醇或羟乙基丙烯基醚中的一种或多种。
烯酸的作用是提高树脂的颜料润湿分散性,提高氟碳树脂色漆的储存稳定性。选用的烯酸有巴豆酸、十一烯酸或丙烯酸中的一种或多种。
引发剂选自偶氮类或有机过氧化物类中的一种或多种,优先选用偶氮二异丁腈或过氧化苯甲酰。
溶剂选自芳香族苯类和脂肪族乙酸酯类中的一种或多种。优先选用二甲苯或乙酸丁酯或二者的混合物。
其制备工艺是:向真空反应釜中加入提前配好的溶剂、引发剂和配方量的烷基乙烯基单体、丙烯酸氟酯、烯醇、烯酸,然后向反应釜中压入氟烯烃,开动搅拌并升温至预设温度,反应结束后回收残余气体,降至室温出料,经过适当后处理得到氟碳树脂。
本发明的氟碳树脂是通过自由基溶液共聚合成,氟碳树脂具有高氟含量、疏水且可以制备常温固化氟碳树脂涂料,具有良好的市场应用前景。
具体实施方式
实施例1
向反应釜中加入摩尔分数为35%的三氟氯乙烯,26%异丁基乙烯基醚,3%甲基丙烯酸十二氟庚酯,质量分数为30%的二甲苯和乙酸丁酯混合溶剂,1%偶氮二异丁腈做引发剂,开动搅拌,升温至60±0.5℃,恒温反应6h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量30.87%、2.47×104g/mol。
实施例2
使用与实施例1相同的方法,向反应釜中加入摩尔分数为35%的三氟氯乙烯,25%乙酸乙烯酯,3.75%甲基丙烯酸十二氟庚酯,质量分数为30%的乙酸丁酯溶剂,1.2%偶氮二异丁腈做引发剂,开动搅拌,升温至60±0.5℃,恒温反应7h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量32.87%、分子量2.22×104g/mol。
实施例3
使用与实施例1相同的方法,向反应釜中加入摩尔分数为40%的三氟氯乙烯,20%异丁基乙烯基醚,10%甲基丙烯酸十二氟庚酯,质量分数为35%的二甲苯和乙酸丁酯的混合溶剂,1.3%偶氮二异丁腈做引发剂,开动搅拌,升温至70±0.5℃,恒温反应6h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量35.68%、分子量2.61×104g/mol。
实施例4
使用与实施例1相同的方法,向反应釜中加入摩尔分数为45%的三氟氯乙烯,22%乙酸乙烯酯,15%甲基丙烯酸十二氟庚酯,质量分数为30%的二甲苯和乙酸丁酯的混合溶剂,1.5%偶氮二异丁腈做引发剂,开动搅拌,升温至65±0.5℃,恒温反应8h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量44.19%、分子量3.38×104g/mol。
实施例5
使用与实施例1相同的方法,向反应釜中加入摩尔分数为50%的三氟氯乙烯,20%乙酸乙烯酯,20%甲基丙烯酸十二氟庚酯,质量分数为45%的二甲苯和乙酸丁酯的混合溶剂,2%偶氮二异丁腈做引发剂,开动搅拌,升温至60±0.5℃,恒温反应8h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量50.94%、分子量3.82×104g/mol。
实施例6
使用与实施例1相同的方法,向反应釜中加入摩尔分数为60%的三氟氯乙烯,30%乙酸乙烯酯,15%甲基丙烯酸十二氟庚酯,质量分数为30%的二甲苯和乙酸丁酯的混合溶剂,1.5%偶氮二异丁腈做引发剂,开动搅拌,升温至60±0.5℃,恒温反应8h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量46.19%、分子量3.48×104g/mol。
实施例7
使用与实施例1相同的方法,向反应釜中加入摩尔分数为45%的三氟氯乙烯,20%乙酸乙烯酯,8%甲基丙烯酸十二氟庚酯,6%乙二醇单烯丙基醚,质量分数为45%的二甲苯和乙酸丁酯的混合溶剂,2%偶氮二异丁腈做引发剂,开动搅拌,升温至60±0.5℃,恒温反应8h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量42.29%、分子量3.28×104g/mol。
实施例8
使用与实施例1相同的方法,向反应釜中加入摩尔分数为50%的三氟氯乙烯,20%异丁基乙烯基醚,12.5%甲基丙烯酸十二氟庚酯,6%乙二醇单烯丙基醚,质量分数为45%的二甲苯和乙酸丁酯的混合溶剂,2%偶氮二异丁腈做引发剂,开动搅拌,升温至60±0.5℃,恒温反应8h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量43.36%、分子量3.12×104g/mol。
实施例9
使用与实施例1相同的方法,向反应釜中加入摩尔分数为45%的三氟氯乙烯,24%异丁基乙烯基醚,16%甲基丙烯酸十二氟庚酯,6%羟丁基乙烯基醚,质量分数为50%的二甲苯和乙酸丁酯的混合溶剂,1.5%偶氮二异丁腈做引发剂,开动搅拌,升温至60±0.5℃,恒温反应8h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量42.07%、分子量3.32×104g/mol
实施例10
使用与实施例1相同的方法,向反应釜中加入摩尔分数为45%的三氟氯乙烯,20%异丁基乙烯基醚,13%甲基丙烯酸十二氟庚酯,8%羟丁基乙烯基醚,5%十一烯酸,质量分数为50%的二甲苯和乙酸丁酯的混合溶剂,2.5%偶氮二异丁腈做引发剂,开动搅拌,升温至60±0.5℃,恒温反应10h,反应结束后降至室温,除去反应残留气体,出料得到氟碳树脂。检测所得粘稠液体的性能指标如下:氟含量42.15%、分子量3.66×104g/mol。
实施例11
将实施例1-10中所制备的氟碳树脂涂在玻璃片或钢板上制成氟碳树脂清漆涂层,并检测涂层的润湿性能及耐溶剂性能。氟碳树脂清漆涂层的性能测试结果,如下表1所示:
Claims (10)
1.高含氟高疏水氟碳树脂,其特征在于采用如下配方制备而成:
1)摩尔分数为35%-60%氟烯烃;
2)摩尔分数为20%-30%烷基乙烯基单体;
3)摩尔分数为3%-20%丙烯酸氟酯。
2.根据权利要求1的高含氟高疏水氟碳树脂,其特征在于,加入烯醇,摩尔分数不超过18%。
3.根据权利要求1或2的高含氟高疏水氟碳树脂,其特征在于,加入烯酸,摩尔分数不超过12%的烯酸。
4.根据权利要求1的高含氟高疏水氟碳树脂,其特征在于,所述的氟烯烃选自偏氟氯乙烯、四氟乙烯、三氟氯乙烯或六氟丙烯中的一种或多种。
5.根据权利要求1的高含氟高疏水氟碳树脂,其特征在于,所述的烷基乙烯基单体选自乙基乙烯基醚、异丁基乙烯基醚、环乙基乙烯基醚、缩水甘油基乙烯基醚、羟丁基乙烯基醚、乙酸乙烯酯、丁酸乙烯酯、己酸乙烯酯或叔碳酸乙烯酯中的一种或多种。
6.根据权利要求1的高含氟高疏水氟碳树脂,其特征在于,所述的丙烯酸氟酯选自甲基丙烯酸十二氟庚酯、丙烯酸六氟丁酯、丙烯酸十二氟庚酯、甲基丙烯酸三氟乙酯或丙烯酸四氟丙酯中的一种或多种。
7.根据权利要求2的高含氟高疏水氟碳树脂,其特征在于,所述的烯醇选自羟丁基乙烯基醚、乙二醇单烯丙基醚、丙二醇单烯丙基醚、丙烯醇或羟乙基丙烯基醚中的一种或多种。
8.根据权利要求3的高含氟高疏水氟碳树脂,其特征在于,所述的烯酸选自巴豆酸、十一烯酸或丙烯酸中的一种或多种。
9.根据权利要求1-8任一所述的高含氟高疏水氟碳树脂,其特征在于,所述的引发剂选自偶氮类或有机过氧化物类中的一种或多种;所述的溶剂选自芳香族苯或脂肪族乙酸酯类中的一种或多种。
10.权利要求1-9任一所述高含氟高疏水氟碳树脂的合成方法,其特征在于如下步骤:以溶液聚合方式实现了配方中各反应单体在反应温度60-70℃、反应压力在0.6-1.2MPa,反应6-10h,制得氟碳树脂。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310733355.0A CN116948081A (zh) | 2023-06-20 | 2023-06-20 | 一种高含氟高疏水氟碳树脂及其合成方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310733355.0A CN116948081A (zh) | 2023-06-20 | 2023-06-20 | 一种高含氟高疏水氟碳树脂及其合成方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116948081A true CN116948081A (zh) | 2023-10-27 |
Family
ID=88448273
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310733355.0A Pending CN116948081A (zh) | 2023-06-20 | 2023-06-20 | 一种高含氟高疏水氟碳树脂及其合成方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116948081A (zh) |
-
2023
- 2023-06-20 CN CN202310733355.0A patent/CN116948081A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI638863B (zh) | Solvent-based coating composition and fluorocopolymer | |
CN104797609B (zh) | 反式-1,3,3,3-四氟丙烯/偏二氟乙烯共聚物的合成和用途 | |
JP5796571B2 (ja) | 含フッ素オレフィン/ビニルアルコール共重合体の製造方法 | |
EP3230329A1 (en) | Copolymers of 1,3,3,3-tetrafluoropropene | |
CN103351446B (zh) | 一种高拉伸强度聚偏氟乙烯的制备方法 | |
CN101747464B (zh) | 一种具有含氟侧基或含氟支链的氟烯烃共聚氟树脂 | |
JPH0455601B2 (zh) | ||
WO1996003447A1 (en) | Aqueous fluoropolymer dispersions | |
CN1229406C (zh) | 水性氟树脂、制法及其应用 | |
CN116948081A (zh) | 一种高含氟高疏水氟碳树脂及其合成方法 | |
CN1257921C (zh) | 偏氟乙烯聚合物及其制备方法 | |
JPH07119261B2 (ja) | 含フッ素共重合体 | |
JPS63218715A (ja) | 含フツ素共重合体の製造方法 | |
JP2746412B2 (ja) | 塗料用含フッ素樹脂 | |
CN112898470A (zh) | 一种高粘结性的含氟聚合物及其制备方法、涂层 | |
JP3087286B2 (ja) | フッ化ビニリデン共重合体およびそれを含有した硬化用組成物 | |
JP3152355B2 (ja) | 塗料用樹脂組成物 | |
JP3498489B2 (ja) | 含フッ素共重合体およびそれを用いた組成物 | |
TWI596168B (zh) | 熱固性氟素共聚物及含彼之塗料組成物 | |
JP2636933B2 (ja) | 高撥水性塗料用樹脂の製造方法 | |
CN107266992B (zh) | 一种四氟氟碳粉末涂料树脂的制备方法 | |
JPH0216325B2 (zh) | ||
JP3045817B2 (ja) | 含フッ素共重合体 | |
CN118184853A (zh) | 一种耐特殊介质的高氟过氧化物硫化氟橡胶及其制备方法 | |
CN116179026A (zh) | 一种不饱和酸酐改性的含氟聚合物粉末涂料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |