CN107022084B - Fluorosilicone polymer, preparation method thereof and surface treating agent containing polymer - Google Patents
Fluorosilicone polymer, preparation method thereof and surface treating agent containing polymer Download PDFInfo
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- CN107022084B CN107022084B CN201710255560.5A CN201710255560A CN107022084B CN 107022084 B CN107022084 B CN 107022084B CN 201710255560 A CN201710255560 A CN 201710255560A CN 107022084 B CN107022084 B CN 107022084B
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- silane
- perfluoroalkyl
- bis
- aminoethyl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title abstract description 11
- -1 amino alkoxy silane Chemical compound 0.000 claims abstract description 77
- 229910000077 silane Inorganic materials 0.000 claims abstract description 35
- 239000003921 oil Substances 0.000 claims abstract description 28
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001265 acyl fluorides Chemical class 0.000 claims abstract description 18
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007112 amidation reaction Methods 0.000 claims abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 30
- 239000012756 surface treatment agent Substances 0.000 claims description 27
- 239000002335 surface treatment layer Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 18
- 229920001774 Perfluoroether Polymers 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical group FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 6
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical group FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 claims description 5
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- WVFYUJTYLBWLOM-UHFFFAOYSA-N 2-[[diethoxy(methyl)silyl]methyl]butane-1,4-diamine Chemical compound CCO[Si](C)(OCC)CC(CN)CCN WVFYUJTYLBWLOM-UHFFFAOYSA-N 0.000 claims description 4
- JABCKXBEMZTLNI-UHFFFAOYSA-N 2-[[dimethoxy(methyl)silyl]methyl]butane-1,4-diamine Chemical compound CO[Si](C)(OC)CC(CN)CCN JABCKXBEMZTLNI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- BHFJBHMTEDLICO-UHFFFAOYSA-N Perfluorooctylsulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O BHFJBHMTEDLICO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 4
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical group CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 4
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 3
- KWXGJTSJUKTDQU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-iodooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I KWXGJTSJUKTDQU-UHFFFAOYSA-N 0.000 claims description 3
- PBYTYWNQFMFABP-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-iododecane Chemical compound CC(I)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PBYTYWNQFMFABP-UHFFFAOYSA-N 0.000 claims description 3
- BULLJMKUVKYZDJ-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-iodohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I BULLJMKUVKYZDJ-UHFFFAOYSA-N 0.000 claims description 3
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 claims description 3
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical group FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 claims description 3
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical group FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 claims description 3
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical group FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 claims description 3
- QUGUFLJIAFISSW-UHFFFAOYSA-N 1,4-difluorobenzene Chemical group FC1=CC=C(F)C=C1 QUGUFLJIAFISSW-UHFFFAOYSA-N 0.000 claims description 3
- IQMYXIKJKHXPMS-UHFFFAOYSA-N 2-(triethoxysilylmethyl)butane-1,4-diamine Chemical compound CCO[Si](OCC)(OCC)CC(CN)CCN IQMYXIKJKHXPMS-UHFFFAOYSA-N 0.000 claims description 3
- HEXHLHNCJVXPNU-UHFFFAOYSA-N 2-(trimethoxysilylmethyl)butane-1,4-diamine Chemical compound CO[Si](OC)(OC)CC(CN)CCN HEXHLHNCJVXPNU-UHFFFAOYSA-N 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 3
- WLKJPTNYLNKNMG-UHFFFAOYSA-N 3-diethoxysilyl-n-(3-diethoxysilylbutyl)butan-1-amine Chemical compound CCO[SiH](OCC)C(C)CCNCCC(C)[SiH](OCC)OCC WLKJPTNYLNKNMG-UHFFFAOYSA-N 0.000 claims description 3
- NLUBWVOYYFNGKI-UHFFFAOYSA-N 3-dimethoxysilyl-N-(3-dimethoxysilylbutyl)butan-1-amine Chemical compound CO[SiH](OC)C(C)CCNCCC(C)[SiH](OC)OC NLUBWVOYYFNGKI-UHFFFAOYSA-N 0.000 claims description 3
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 claims description 3
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- GHBRMZFUMLMOKO-UHFFFAOYSA-N 5-[diethoxy(methyl)silyl]pentane-1,3-diamine Chemical compound CCO[Si](C)(OCC)CCC(N)CCN GHBRMZFUMLMOKO-UHFFFAOYSA-N 0.000 claims description 3
- ZOTKGMAKADCEDH-UHFFFAOYSA-N 5-triethoxysilylpentane-1,3-diamine Chemical compound CCO[Si](OCC)(OCC)CCC(N)CCN ZOTKGMAKADCEDH-UHFFFAOYSA-N 0.000 claims description 3
- KNSYYXUWMIZVIO-UHFFFAOYSA-N CC([SiH](OC)OC)NCCN Chemical compound CC([SiH](OC)OC)NCCN KNSYYXUWMIZVIO-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- LCKPYBMEBRESRM-UHFFFAOYSA-N diethoxy-ethyl-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecan-2-yloxy)silane Chemical compound FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)C(C)O[Si](OCC)(OCC)CC LCKPYBMEBRESRM-UHFFFAOYSA-N 0.000 claims description 3
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 claims description 3
- XKRPWHZLROBLDI-UHFFFAOYSA-N dimethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OC)OC XKRPWHZLROBLDI-UHFFFAOYSA-N 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 3
- MGTPBBCWEXQCOQ-UHFFFAOYSA-N ethoxy-ethyl-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecan-2-yloxy)-methylsilane Chemical compound CCO[Si](C)(CC)OC(C)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MGTPBBCWEXQCOQ-UHFFFAOYSA-N 0.000 claims description 3
- QTECILHCKMCIFT-UHFFFAOYSA-N ethyl-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononoxy)-dimethoxysilane Chemical compound CC[Si](OC)(OC)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTECILHCKMCIFT-UHFFFAOYSA-N 0.000 claims description 3
- DYJLRIXZVOPGSJ-UHFFFAOYSA-N ethyl-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononoxy)-methoxy-methylsilane Chemical compound FC(C(C(C(C(C(C(F)(F)CO[Si](OC)(C)CC)(F)F)(F)F)(F)F)(F)F)(F)F)(C(F)(F)F)F DYJLRIXZVOPGSJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 3
- OQTSOKXAWXRIAC-UHFFFAOYSA-N tetrabutan-2-yl silicate Chemical compound CCC(C)O[Si](OC(C)CC)(OC(C)CC)OC(C)CC OQTSOKXAWXRIAC-UHFFFAOYSA-N 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- BCLLLHFGVQKVKL-UHFFFAOYSA-N tetratert-butyl silicate Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BCLLLHFGVQKVKL-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- QBUATDNGCWHUGM-UHFFFAOYSA-N N'-(3-dimethoxysilylbutyl)ethane-1,2-diamine Chemical compound CC(CCNCCN)[SiH](OC)OC QBUATDNGCWHUGM-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 150000004292 cyclic ethers Chemical class 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims 1
- QMIREOCYHAFOPK-UHFFFAOYSA-N n,n'-bis(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCNCCC[Si](OCC)(OCC)OCC QMIREOCYHAFOPK-UHFFFAOYSA-N 0.000 claims 1
- 230000006103 sulfonylation Effects 0.000 claims 1
- 238000005694 sulfonylation reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 40
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 230000003373 anti-fouling effect Effects 0.000 abstract description 11
- 238000005299 abrasion Methods 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000009435 amidation Effects 0.000 abstract 2
- 239000002585 base Substances 0.000 description 36
- 238000000576 coating method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000009832 plasma treatment Methods 0.000 description 8
- KSOCRXJMFBYSFA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,6,6,6-tridecafluoro-5-(1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluorohexan-2-yloxy)hexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KSOCRXJMFBYSFA-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- PGISRKZDCUNMRX-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-(trifluoromethoxy)butane Chemical compound FC(F)(F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F PGISRKZDCUNMRX-UHFFFAOYSA-N 0.000 description 5
- 239000004566 building material Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000413 hydrolysate Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- HXLVCCRPDYIRRX-UHFFFAOYSA-N iodoamine Chemical compound IN HXLVCCRPDYIRRX-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical class CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- NOPJRYAFUXTDLX-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane Chemical compound COC(F)(F)C(F)(F)C(F)(F)F NOPJRYAFUXTDLX-UHFFFAOYSA-N 0.000 description 2
- QIROQPWSJUXOJC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6-undecafluoro-6-(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F QIROQPWSJUXOJC-UHFFFAOYSA-N 0.000 description 2
- HCBRSIIGBBDDCD-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane Chemical compound FC(F)C(F)(F)COC(F)(F)C(F)F HCBRSIIGBBDDCD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NCLLGBXHAWDVEP-UHFFFAOYSA-N N,N'-bis(3-dimethoxysilylbutyl)ethane-1,2-diamine Chemical compound CC(CCNCCNCCC(C)[SiH](OC)OC)[SiH](OC)OC NCLLGBXHAWDVEP-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003666 anti-fingerprint Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005831 deiodination reaction Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000003958 fumigation Methods 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 2
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 229960004624 perflexane Drugs 0.000 description 2
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000005920 sec-butoxy group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- DHDZJALPNRIMOQ-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,10,10,10-henicosafluoro-9-iododecane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(I)C(F)(F)F DHDZJALPNRIMOQ-UHFFFAOYSA-N 0.000 description 1
- IQSVJXQJXBCPBX-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoroheptoxy-(1,1,2,2,2-pentafluoroethyl)-bis(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(C(F)(F)C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F IQSVJXQJXBCPBX-UHFFFAOYSA-N 0.000 description 1
- BCLLRNVMLZXSMM-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorocyclooctane Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F BCLLRNVMLZXSMM-UHFFFAOYSA-N 0.000 description 1
- RAGOGQITHBODEI-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-5-(2,2,3,3,4,4,5,5-octafluoropentoxy)pentane Chemical class FC(F)C(F)(F)C(F)(F)C(F)(F)COCC(F)(F)C(F)(F)C(F)(F)C(F)F RAGOGQITHBODEI-UHFFFAOYSA-N 0.000 description 1
- YCGMGHXWRSUDOM-UHFFFAOYSA-N 2-[2-[dimethoxy(methyl)silyl]oxyethyl]butane-1,4-diamine Chemical compound NCCC(CCO[Si](OC)(OC)C)CN YCGMGHXWRSUDOM-UHFFFAOYSA-N 0.000 description 1
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- MUIFHANLBSCLFJ-UHFFFAOYSA-N [SiH4].S(=O)(=O)(N)N Chemical compound [SiH4].S(=O)(=O)(N)N MUIFHANLBSCLFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- UBCPEZPOCJYHPM-UHFFFAOYSA-N dimethoxy-methyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(OC)OC UBCPEZPOCJYHPM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention provides a fluorine-silicon polymer, a preparation method thereof and a surface treating agent containing the polymer, and relates to the technical field of fluorine-silicon polymer synthesis, wherein the fluorine-silicon polymer provided by the invention has a structural formula (1), and the structure of the formula (1) is shown in the attached drawing of the abstract. The fluorine-silicon polymer is prepared by cohydrolysis of amino alkoxy silane and tetraalkoxy silane or alkyl alkoxy silane or alkoxy silane containing perfluoroalkyl substituent, and then amidation of the co-hydrolysis and perfluoropolyether acyl fluoride, or amidation of the co-hydrolysis and perfluoroalkyl iodide or perfluoroalkyl sulfonyl fluoride and then perfluoropolyether acyl fluoride. The invention also provides a surface treating agent containing the fluorine-silicon polymer, and the molecular weight of the treating agent can be improved by adopting the technology of the invention, and more alkoxy groups are introduced into the main chain, so that the adhesive force between the surface treating agent and the surface of the base material is further improved, and a film layer with water drawing property, oil drawing property, antifouling property and high abrasion resistance durability can be formed.
Description
Technical Field
The invention belongs to the technical field of synthesis of fluorosilicone polymers, and particularly relates to a fluorosilicone polymer, a preparation method thereof, a surfactant containing the polymer, and a preparation method for forming a surface treatment layer on a base material by using the fluorosilicone polymer or the surfactant.
Background
In recent years, touch panels of screens are becoming popular, and more traditional technology companies are accelerating the conversion to single-chip microcomputer touch screens. However, the touch panel is exposed and easily contaminated with fingerprints, skin oil, sweat, cosmetics, and the like during use, and thus the appearance and the use feeling are affected. Therefore, in order to improve such a situation, it is required that the surface of the product has not only a good water-and oil-repellent and stain-resistant layer but also good abrasion resistance, since the surface is not easily damaged during wiping. Therefore, the surface of the product is often required to be sprayed with the anti-fingerprint agent.
In the case of other materials, for example, base materials such as metals, ceramics, and building materials, the surface of the base material is easily abraded and stained during use, and it is also necessary to coat the surface of the base material with a treatment layer having excellent stain resistance, water resistance, and abrasion resistance.
The fluorine-silicon polymer has lower surface tension, and in the aspect of coating, the organic fluorine coating prepared by adopting the fluorine-silicon polymer has very excellent characteristics in the aspects of mechanical property, stain resistance, weather resistance, chemical resistance and the like. When the organic fluorine coating prepared from the fluorine-silicon polymer is applied to a base material, a surface treatment layer with excellent water repellency, oil repellency and antifouling property can be formed. Therefore, the coating is widely applied to the surfaces of various substrates such as glass, fiber, resin, metal, ceramic, building materials and the like, and the service life of the substrate is prolonged.
At present, the surface treating agent prepared by the fluorine-silicon polymer on the market has stable antifouling effect, but has larger dosage and higher cost; moreover, fluorine-containing groups are introduced into the organic silicon polymer to prepare the fluorine-silicon polymer, the molecular weight of the surface treatment agent prepared from the fluorine-silicon polymer is small, the adhesive force between the surface treatment layer prepared from the surface treatment agent and the base material is small, and the performances of water repellency, oil repellency, antifouling property, high abrasion resistance and durability and the like can not meet the use requirements.
Disclosure of Invention
One object of the present invention is to provide a fluorosilicone polymer, which combines the hydrophobic and oleophobic properties of perfluoropolyether and the smooth and smooth properties of silicone; another object of the present invention is to provide a method for preparing the fluorosilicone polymer, by which the molecular weight of the surface treatment agent can be increased, and more alkoxy groups are introduced into the main chain, thereby further improving the adhesion to the surface of the base material, and forming a surface treatment layer having excellent water repellency, oil repellency, antifouling property and high wear-resistant durability; the third object of the present invention is to provide a surface treating agent prepared from the fluorosilicone polymer; it is a fourth object of the present invention to provide an article comprising a base material and a surface-treated layer formed on the surface of the base material using the above-mentioned fluorosilicone polymer or surface-treating agent.
The above purpose of the invention is realized by the following technical scheme:
according to an object of the present invention, there is provided a fluorosilicone polymer represented by the following formula (1), wherein the number average molecular weight is greater than 1 × 10, referring to FIG. 14，
In the formula (1), the reaction mixture is,
R1、R2、R7an alkyl group having 1 to 4 carbon atoms, typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl;
R4、R5、R8an alkyl group or an alkoxy group having 1 to 4 carbon atoms, typically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group;
R3、R6the hydrocarbon group is typically an alkyl group having 1 to 18 carbon atoms, a vinyl group, an allyl group, a phenyl group, a phenethyl group, an α -methylphenylethyl group or the like, and may be an alkoxysilylethyl group represented by the following formulae (2-a) and (2-b):
R9is hydrogen or R10，R10Is a perfluoroalkyl group selected from the following formula (3-a), a perfluoroalkylethyl group selected from the following formula (3-b), and a perfluoroalkylsulfonyl group selected from the following formula (3-c):
-CkF2k+1(3-a)
-CH2CH2-CkF2k+1(3-b)
R11is hydrogen or R12Or R13，
R12Is R13Or a perfluoroalkyl group selected from the group consisting of a perfluoroalkyl group represented by the following formula (3-a), a perfluoroalkylethyl group represented by the following formula (3-b), and a perfluoroalkylsulfonyl group represented by the following formula (3-c):
-CkF2k+1(3-a)
-CH2CH2-CkF2k+1(3-b)
R13is a perfluoropolyether group selected from the group consisting of those represented by the following formula (4):
a. b, c, d, e and f are 0 or positive integers, d is more than or equal to 1,
h is an integer of 1 to 3, k is a positive integer of 1 to 10, m is an integer of 1 to 6, n is 0 or a positive integer,
w, x, y and z are 0 or positive integers, and w + x + y + z is more than or equal to 1.
The fluorosilicone polymer prepared according to the present invention can exhibit excellent water repellency, oil repellency, stain resistance, and durability.
Another object of the present invention is to provide a method for preparing the fluorosilicone polymer, which comprises the following steps: the fluorine-silicon polymer is prepared by firstly carrying out cohydrolysis on amino alkoxy silane and tetraalkoxy silane or alkyl alkoxy silane or alkoxy silane containing perfluoroalkyl substituent groups and then carrying out amidation reaction on the amino alkoxy silane and the tetraalkoxy silane or alkyl alkoxy silane or alkoxy silane containing perfluoroalkyl substituent groups and perfluoropolyether acyl fluoride, or firstly carrying out amino substitution reaction on perfluoroalkyl iodide or carrying out sulfonylamination reaction on the amino iodide and the perfluoroalkyl sulfonyl fluoride and then carrying out amidation reaction on the amino iodide and the perfluoropolyether acyl fluoride.
Wherein the aminoalkoxysilane is preferably aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane, bis (trimethoxysilylpropyl) ammonia, bis (triethoxysilylpropyl) ammonia, bis (methyldimethoxysilylpropyl) ammonia, bis (methyldiethoxysilylpropyl) ammonia, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane, N '-bis (trimethoxysilylpropyl) ethylenediamine, N' -bis (triethoxysilylpropyl) ethylenediamine, or a mixture, N, N '-bis (methyldimethoxysilylpropyl) ethylenediamine, N' -bis (methyldiethoxysilylpropyl) ethylenediamine, 3- (2- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2- (2-aminoethyl) aminopropylmethyldiethoxysilane, 3- (2-aminoethyl) aminomethyltrimethoxysilane, N' -bis (methyldimethoxysilylmethyl) ethylenediamine, 3- (2- (2-aminoethyl) aminomethyltrimethoxysilane, etc.; the tetraalkoxysilane is preferably tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane; the hydrocarbyl alkoxy silane is preferably dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, methyl propyl dimethoxy silane, methyl vinyl dimethoxy silane, long-chain alkyl methyl dimethoxy silane with 4-18 carbon atoms, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane, vinyl trimethoxy silane, propyl trimethoxy silane or long-chain alkyl trimethoxy silane with 4-18 carbon atoms; the alkoxy silane containing perfluoroalkyl substituent is preferably nonafluorobutylethyldimethoxysilane, nonafluorobutylethyltrimethoxysilane, tridecafluorohexylethylmethyldimethoxysilane, tridecafluorohexylethyltrimethoxysilane, heptadecafluorooctylethylmethyldimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, nonafluorobutylethylmethyldiethoxysilane, nonafluorobutylethyltriethoxysilane, tridecafluorohexylethylmethyldiethoxysilane, tridecafluorohexylethyltriethoxysilane, heptadecafluorooctylethylmethyldiethoxysilane, heptadecafluorooctylethyltriethoxysilane; the perfluoroalkyl iodide is preferably nonafluorobutyl iodide, tridecafluorohexyl iodide, heptadecafluorooctyl iodide, nonafluorobutyl ethyl iodide, tridecafluorohexyl ethyl iodide and heptadecafluorooctyl ethyl iodide; the perfluoroalkyl sulfonyl fluoride is preferably nonafluorobutyl sulfonyl fluoride, tridecafluorohexyl sulfonyl fluoride or heptadecafluorooctyl sulfonyl fluoride; the perfluoropolyether acyl fluoride is preferably a polymer represented by the following general formula (5):
in the formula (5), h is an integer of 1-3, k is a positive integer of 1-10, w, x, y and z are 0 or positive integers, and w + x + y + z is more than or equal to 1.
The preparation method comprises the following steps of carrying out amino substitution reaction, sulphonamide amination reaction and amidation reaction on amino and perfluoroalkyl iodide on amino alkoxy silane, perfluoroalkyl sulfonyl fluoride or perfluoropolyether acyl fluoride, carrying out deiodination hydrogen or hydrogen fluoride by using tertiary amine (typical tertiary amine comprises triethylamine, dimethylethyl amine, dimethylpropyl amine, dimethylcyclohexylamine, pyridine, N-methylpiperidine, N-methylmorpholine, triethylene diamine and the like) or active metal powder (typical tertiary amine comprises magnesium powder, aluminum powder, zinc powder and iron powder) in a solvent to form hydroiodide or hydrofluoride, filtering to remove byproduct hydroiodide or hydrofluoride, and distilling to remove the solvent; the solvent is one or more than two of toluene, dimethylbenzene, fluorobenzene, o-difluorobenzene, m-difluorobenzene, p-difluorobenzene, trifluorobenzene, pentafluorobenzene, trifluoromethylbenzene, bis (trifluoromethyl) benzene, fluoroalkyl chain ether and fluoroalkyl cyclic ether.
A third object of the present invention is to provide a surface treatment agent which can impart water repellency, oil repellency, stain resistance, and abrasion resistance to the surface of a base material and can be suitably used as a stain-resistant coating agent or the like. The surface treating agent prepared from the fluorosilicone polymer consists of A, B, C three components; the component A is the fluorine-silicon polymer; the component B is fluoroether oil; the component C is a solvent; wherein the mass ratio of the A, B, C three components is 1: 1-1000: 0-10000;
the component B, namely the fluoroether oil, is a polymer shown as a following formula (6),
CuF2u+1-(OC4F8)p-(OC3F6)q-(OC2F4)s-(OCF2)t-CvF2v+1(6)
wherein u and v are integers of 1-10; p, q, s and t are integers of 0-300, and p + q + s + t is more than or equal to 1.
The C component solvent is selected from C5-12 perfluorinated aliphatic hydrocarbon (such as perfluorohexane, perfluoromethylcyclohexane, etc.), polyfluorinated aromatic hydrocarbon (bis (trifluoromethyl) benzene), polyfluorinated aliphatic hydrocarbon, and Hydrofluoroether (HFE) (such as perfluoropropylmethyl ether (C)3F7OCH3) Perfluorobutyl methyl ether (C)4F9OCH3) Perfluorobutylethyl ether (C)4F9OC2H5) And perfluoroalkyl alkyl ethers (the perfluoroalkyl and alkyl groups may be linear or branched)), di-polyfluoroalkyl ethers, perfluorocyclic ethers, and the like; among them, hydrofluoroethers, difluoroalkyl ethers, perfluorocyclic ethers, such as perfluorobutyl methyl ether (C), are preferred4F9OCH3) Perfluorobutylethyl ether (C)4F9OC2H5)1, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether and perfluorooctyl cyclic ether.
The fourth object of the present invention is to provide an article comprising a base material and a film layer (surface-treated layer) formed on the surface of the base material, wherein the surface-treated layer is formed of the above-mentioned fluorosilicone polymer or the above-mentioned surface-treating agent, and has water repellency, oil repellency, stain resistance and abrasion resistance, and the composition of the surface of the base material includes glass, resin, metal and ceramic.
The preparation method of the article provided by the invention comprises the following steps:
(a) forming a precursor film on the surface of the substrate, the precursor film including the fluorosilicone polymer having a hydrolyzable group bonded to a Si bond;
(b) providing moisture to the precursor film;
(c) heating the precursor film in a dry atmosphere at a temperature exceeding 100 ℃ to form a surface treatment layer containing the fluorosilicone polymer species on the surface of the substrate.
Preferably, the moisture supply in step (b) is performed in an atmosphere at a temperature of 100 to 500 ℃.
Preferably, the substrate on which the precursor film is formed in step (a) is placed in a superheated water vapor environment so that steps (b) and (c) can be continuously performed.
The invention has the beneficial effects that:
1. the fluorosilicone polymer prepared by the invention has excellent water repellency, oil repellency, antifouling property and durability, and can be used for but not limited to surface treatment agents, lubricants, antifouling coating agents and anti-fingerprint agents.
2. The surface treatment agent prepared by the invention can make the surface of the base material have water repellency, oil repellency, antifouling property and friction resistance, and can be used for but not limited to a waterproof coating agent.
3. The surface treating agent prepared by the invention has large molecular weight.
4. The surface treatment layer prepared by the invention has water repellency, oil repellency, antifouling property and friction resistance.
5. The article produced by the present invention may be, but is not limited to, an optical component, and the substrate on the article may be glass, fiber, resin, metal, ceramic, building material, and the like.
Drawings
FIG. 1 is a structural formula of the fluorosilicone polymer of the present invention.
Wherein,
R1、R2、R7an alkyl group having 1 to 4 carbon atoms, typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl;
R4、R5、R8an alkyl group or alkoxy group having 1 to 4 carbon atoms, typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxyButoxy, t-butoxy;
R3、R6the hydrocarbon group is typically an alkyl group having 1 to 18 carbon atoms, a vinyl group, an allyl group, a phenyl group, a phenethyl group, an α -methylphenylethyl group or the like, and may be an alkoxysilylethyl group represented by the following formulae (2-a) and (2-b):
R9is hydrogen or R10，R10Is a perfluoroalkyl group selected from the following formula (3-a), a perfluoroalkylethyl group selected from the following formula (3-b), and a perfluoroalkylsulfonyl group selected from the following formula (3-c):
-CkF2k+1(3-a)
-CH2CH2-CkF2k+1(3-b)
R11is hydrogen or R12Or R13，
R12Is R13Or a perfluoroalkyl group selected from the group consisting of a perfluoroalkyl group represented by the following formula (3-a), a perfluoroalkylethyl group represented by the following formula (3-b), and a perfluoroalkylsulfonyl group represented by the following formula (3-c):
-CkF2k+1(3-a)
-CH2CH2-CkF2k+1(3-b)
R13is a perfluoropolyether group selected from the group consisting of those represented by the following formula (4):
a. b, c, d, e and f are 0 or positive integers, d is more than or equal to 1,
h is an integer of 1 to 3, k is a positive integer of 1 to 10, m is an integer of 1 to 6, n is 0 or a positive integer,
w, x, y and z are 0 or positive integers, and w + x + y + z is more than or equal to 1.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
The invention provides a fluorine-silicon polymer, the number average molecular weight of which is more than 1 × 104The compound has a chemical structural formula of a formula (1), wherein the formula (1) is shown as the attached figure 1:
in the formula (1), the reaction mixture is,
R1、R2、R7an alkyl group having 1 to 4 carbon atoms, typically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl;
R4、R5、R8an alkyl group or an alkoxy group having 1 to 4 carbon atoms, typically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group;
R3、R6the hydrocarbon group is typically an alkyl group having 1 to 18 carbon atoms, a vinyl group, an allyl group, a phenyl group, a phenethyl group, an α -methylphenylethyl group or the like, and may be an alkoxysilylethyl group represented by the following formulae (2-a) and (2-b):
R9is hydrogen or R10，R10Is a perfluoroalkyl group selected from the following formula (3-a), a perfluoroalkylethyl group selected from the following formula (3-b), and a perfluoroalkylsulfonyl group selected from the following formula (3-c):
-CkF2k+1(3-a)
-CH2CH2-CkF2k+1(3-b)
R11is hydrogen or R12Or R13，
R12Is R13Or a perfluoroalkyl group represented by the following formula (3-a) or a perfluoroalkyl group represented by the following formula (3-b)
A perfluoroalkylethyl group, or a perfluoroalkylsulfonyl group represented by the formula (3-c):
-CkF2k+1(3-a)
-CH2CH2-CkF2k+1(3-b)
R13is a perfluoropolyether group selected from the group consisting of those represented by the following formula (4):
a. b, c, d, e and f are 0 or positive integers, d is more than or equal to 1,
h is an integer of 1-3, k is a positive integer of 1-10, m is an integer of 1-6, n is 0 or a positive integer, w, x, y and z are 0 or positive integers, and w + x + y + z is more than or equal to 1.
The fluorosilicone polymer provided by the present invention can exhibit excellent water repellency, oil repellency, and stain resistance, and can be used for a surface treatment agent.
The preparation method of the fluorine-silicon polymer comprises the following steps: the fluorine-silicon polymer is prepared by firstly carrying out cohydrolysis on amino alkoxy silane and tetraalkoxy silane or alkyl alkoxy silane or alkoxy silane containing perfluoroalkyl substituent groups and then carrying out amidation reaction on the amino alkoxy silane and the tetraalkoxy silane or alkyl alkoxy silane or alkoxy silane containing perfluoroalkyl substituent groups and perfluoropolyether acyl fluoride, or firstly carrying out amino substitution reaction on perfluoroalkyl iodide or carrying out sulfonylamination reaction on the amino iodide and the perfluoroalkyl sulfonyl fluoride and then carrying out amidation reaction on the amino iodide and the perfluoropolyether acyl fluoride.
Wherein the aminoalkoxysilane is preferably aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane, bis (trimethoxysilylpropyl) ammonia, bis (triethoxysilylpropyl) ammonia, bis (methyldimethoxysilylpropyl) ammonia, bis (methyldiethoxysilylpropyl) ammonia, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane, N '-bis (trimethoxysilylpropyl) ethylenediamine, N' -bis (triethoxysilylpropyl) ethylenediamine, or a mixture, N, N '-bis (methyldimethoxysilylpropyl) ethylenediamine, N' -bis (methyldiethoxysilylpropyl) ethylenediamine, 3- (2- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2- (2-aminoethyl) aminopropylmethyldiethoxysilane, 3- (2-aminoethyl) aminomethyltrimethoxysilane, N' -bis (methyldimethoxysilylmethyl) ethylenediamine, 3- (2- (2-aminoethyl) aminomethyltrimethoxysilane, etc.; the tetraalkoxysilane is preferably tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane; the hydrocarbyl alkoxy silane is preferably dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, methyl propyl dimethoxy silane, methyl vinyl dimethoxy silane, long-chain alkyl methyl dimethoxy silane with 4-18 carbon atoms, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane, vinyl trimethoxy silane, propyl trimethoxy silane or long-chain alkyl trimethoxy silane with 4-18 carbon atoms; the alkoxy silane containing perfluoroalkyl substituent is preferably nonafluorobutylethyldimethoxysilane, nonafluorobutylethyltrimethoxysilane, tridecafluorohexylethylmethyldimethoxysilane, tridecafluorohexylethyltrimethoxysilane, heptadecafluorooctylethylmethyldimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, nonafluorobutylethylmethyldiethoxysilane, nonafluorobutylethyltriethoxysilane, tridecafluorohexylethylmethyldiethoxysilane, tridecafluorohexylethyltriethoxysilane, heptadecafluorooctylethylmethyldiethoxysilane, heptadecafluorooctylethyltriethoxysilane; the perfluoroalkyl iodide is preferably nonafluorobutyl iodide, tridecafluorohexyl iodide, heptadecafluorooctyl iodide, nonafluorobutyl ethyl iodide, tridecafluorohexyl ethyl iodide and heptadecafluorooctyl ethyl iodide; the perfluoroalkyl sulfonyl fluoride is preferably nonafluorobutyl sulfonyl fluoride, tridecafluorohexyl sulfonyl fluoride or heptadecafluorooctyl sulfonyl fluoride; the perfluoropolyether acyl fluoride is preferably a polymer represented by the following general formula (5):
in the formula (5), h is an integer of 1-3, k is a positive integer of 1-10, w, x, y and z are 0 or positive integers, and w + x + y + z is more than or equal to 1.
The preparation method comprises the following steps of carrying out amino substitution reaction, sulphonamide amination reaction and amidation reaction on amino and perfluoroalkyl iodide on amino alkoxy silane, perfluoroalkyl sulfonyl fluoride or perfluoropolyether acyl fluoride, carrying out deiodination hydrogen or hydrogen fluoride by using tertiary amine (typical tertiary amine comprises triethylamine, dimethylethyl amine, dimethylpropyl amine, dimethylcyclohexylamine, pyridine, N-methylpiperidine, N-methylmorpholine, triethylene diamine and the like) or active metal powder (typical tertiary amine comprises magnesium powder, aluminum powder, zinc powder and iron powder) in a solvent to form hydroiodide or hydrofluoride, filtering to remove byproduct hydroiodide or hydrofluoride, and distilling to remove the solvent; the solvent is one or more than two of toluene, dimethylbenzene, fluorobenzene, o-difluorobenzene, m-difluorobenzene, p-difluorobenzene, trifluorobenzene, pentafluorobenzene, trifluoromethylbenzene, bis (trifluoromethyl) benzene, fluoroalkyl chain ether and fluoroalkyl cyclic ether.
The invention provides a surface treatment agent, which comprises the fluorosilicone polymer, can form a surface treatment layer with water repellency, oil repellency, antifouling property and high abrasion resistance durability, and can be used for but not limited to waterproof and antifouling coating agents.
The surface treating agent consists of A, B, C three components, wherein the component A is the fluorosilicone polymer, and the component B is a fluorine-containing polyether compound (fluoroether oil); the component C is a volatile small molecular solvent; wherein the mass ratio of the A, B, C three components is 1: 1-1000: 0-10000; the fluoroether oil has no reactive group that reacts with the substrate, and contributes to the improvement of the surface smoothness of the surface treatment layer.
The chemical formula of the fluoroether oil is shown as the formula (4):
CuF2u+1-(OC4F8)p-(OC3F6)q-(OC2F4)s-(OCF2)t-CvF2v+1(4)
u and v are integers of 1-10;
p, q, s and t are integers of 0-300, and p + q + s + t is more than or equal to 1.
In its repeating unit, - (OC)4F8) Can have various structures, such as- (OCF)2CF2CF2CF2)-、-(OCF(CF3)CF2CF2)-、-(OCF2CF(CF3)CF2)-、-(OCF2CF2CF(CF3))-、-OC(CF3)2CF2)-、-OCF2C(CF3)2)-、-OCF(CF3)CF(CF3))-、-(OCF(C2F5)CF2) -and- (OCF)2CF(C2F5) Any of these). - (OC)3F6) May be- (OCF)2CF2CF2)-、-(OCF(CF3)CF2) -and- (OCF)2CF(CF3) Any of the above-mentioned (meth) acrylate copolymers). - (OC)2F4) May be- (OCF)2CF2) -and- (OCF (CF)3) Any of the above-mentioned (meth) acrylate copolymers).
The average molecular weight of the fluoroether oil is 1000-30000, so that the surface smoothness is improved, and the spreadability of the fluorosilicone polymer on the surface of the base material is improved.
An article obtained by using the surface treatment agent or the fluorosilicone polymer is described below, which comprises a base material and the surface treatment layer formed of the fluorosilicone polymer or the surface treatment agent on the surface of the base material, and which has water repellency, oil repellency, stain resistance, and high abrasion durability and is useful as a functional film.
The preparation method of the article provided by the invention comprises the following steps:
(a) forming a precursor film on the surface of the substrate, the precursor film including the fluorosilicone polymer having a hydrolyzable group bonded to a Si bond;
(b) providing moisture to the precursor film;
(c) heating the precursor film in a dry atmosphere at a temperature exceeding 100 ℃ to form a surface treatment layer containing the fluorosilicone polymer species on the surface of the substrate.
First, the substrate, which may be, but is not limited to, glass, fiber, resin, metal, ceramic, building material, and the like, is prepared.
The surface of the base material is provided with a group which reacts with the alkoxy of the fluorine-silicon polymer provided by the invention to form a precursor film. For example, the surface of the substrate has hydroxyl groups, such as glass, metal, ceramic, semiconductor, or the like, on which a natural oxide film or a thermal oxide film is formed.
In the case of a substrate having a small number of hydroxyl groups or no hydroxyl groups, such as a resin, the hydroxyl groups can be introduced into the surface of the substrate or the number of hydroxyl groups can be increased by a pretreatment method including plasma treatment or ion beam irradiation, wherein the plasma treatment can introduce or increase the hydroxyl groups into the surface of the substrate and can clean the surface of the substrate (remove foreign substances and the like).
The substrate may be a material whose surface is composed of an organosilicon compound or contains an alkoxysilane; the shape of the substrate is not particularly limited, and the region of the substrate on which the surface treatment layer is formed includes a part or all of the surface of the substrate.
The surface treatment layer formed on the surface of the substrate is subjected to post-treatment such as steam fumigation and/or heat baking to achieve the best effect.
The surface treatment layer is typically formed by a wet coating method or a dry coating method.
The wet coating method includes dip coating, spray coating, spin coating, and the like, and the dry coating method includes vacuum evaporation, sputtering, and the like.
When a wet coating method is selected, the surface treatment agent can be diluted by the solvent and then coated on the surface of the base material, wherein when a spraying or dip coating process is adopted, in order to obtain a more uniform surface treatment layer and reduce the cost, the fluorosilicone polymer is further diluted by a small molecular solvent which has volatility and better solubility to the fluorosilicone polymer.
The solvent is perfluorinated aliphatic hydrocarbon (such as perfluorohexane, perfluoromethylcyclohexane, etc.) with 5-12 carbon atoms; polyfluoro aromatic hydrocarbons (bis (trifluoromethyl) benzene); a polyfluoro aliphatic hydrocarbon; hydrofluoroethers (HFE) (e.g., perfluoropropyl methyl ether (C)3F7OCH3) Perfluorobutyl methyl ether (C)4F9OCH3) Perfluorobutylethyl ether (C)4F9OC2H5) And perfluoroalkyl alkyl ethers (the perfluoroalkyl group and the alkyl group may be linear or branched)), di-polyfluoroalkyl ethers, and perfluorocyclic ethers. These solvents may be used alone or in the form of a mixture of 2 or more. Among them, hydrofluoroethers, difluoroalkyl ethers, perfluorocyclic ethers, such as perfluorobutyl methyl ether (C), are preferred4F9OCH3) Perfluorobutylethyl ether (C)4F9OC2H5)1, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether and perfluorooctyl cyclic ether.
In addition, a catalyst may be added during the preparation of the surface treatment agent, and an appropriate acid or base, such as acetic acid, formic acid, trifluoroacetic acid, ammonia, organic amine, or the like, may be used as the catalyst. When a wet coating method is adopted, a catalyst can be added into a diluent of the surface treatment agent, and then the surface treatment agent is coated on the surface of the base material; in the case of the dry coating method, the surface treatment agent to which the catalyst is added may be directly subjected to vacuum deposition treatment, or the porous metal body of copper or iron impregnated with the surface treatment agent containing the catalyst may be subjected to vacuum deposition treatment.
The surface treatment layer can comprise post-treatment in the treatment process according to requirements, wherein the treatment comprises steam fumigation or (and) heating baking.
In the step (b) of the method for manufacturing the article, moisture is supplied to the precursor film, water molecules react with alkoxy groups on Si bonds of the fluorosilicone polymer, the fluorosilicone polymer undergoes a hydrolysis reaction, and the reaction pressure may be, but is not limited to, normal pressure.
Further, when the surface of the substrate is dried and heated in the step (b), the temperature may be selected from 100 to 500 ℃, and preferably, the temperature is selected from 100 to 300 ℃, and the drying is performed in an atmosphere of unsaturated water vapor pressure, and the reaction pressure may be, but is not limited to, normal pressure.
Under the temperature atmosphere, dehydration condensation reactions occur among the hydrolyzed fluorosilicone polymers and between the hydrolyzed fluorosilicone polymers and the base material, and stable chemical bonds are formed among the fluorosilicone polymers and between the fluorosilicone polymers and the base material.
Further, the supply of moisture in the step (b) and the drying heating in the step (c) may be continuously performed by using superheated steam in the step (a).
Superheated steam is a gas obtained by heating saturated steam to a temperature higher than the boiling point, and the temperature exceeds 100 ℃ and is usually lower than 500 ℃ under normal pressure. In the step (a), when the base material on which the precursor film is formed is exposed to superheated steam, condensation is formed on the surface of the precursor film due to a temperature difference between the superheated steam and the precursor film having a lower temperature, and moisture is supplied to the precursor film; after a reaction time, the temperature difference between the superheated steam and the precursor film is reduced, the moisture on the surface of the precursor film is gasified in a dry atmosphere generated by using the superheated steam, and the moisture content on the surface of the precursor film is gradually reduced; the precursor film is heated to the same temperature as the superheated steam by contacting with the superheated steam during the process in which the moisture content of the surface of the precursor film is decreased. Therefore, the base material on which the precursor film is formed is exposed to superheated water vapor, and the steps (b) and (c) can be performed continuously.
If necessary, the article may be subjected to a post-treatment step, and when no post-treatment is required, the surface treatment agent is applied to the surface of the base material and then left to stand.
The reactants were prepared as follows
Synthesis example 1 (Fluorosilicone polymer A-1)
Synthesis of fluorosilicone polymer A-1
3.04g of methyl orthosilicate, 120g of dimethyl dimethoxysilane, 41.2g of 3- (2-aminoethyl) aminopropyl methyl dimethoxysilane and 44.4g of 3- (2-aminoethyl) aminopropyl trimethoxy silane are uniformly mixed, 25.2g of pure water is dropwise added, the temperature is raised to 60-65 ℃ under the protection of nitrogen, the reaction is carried out for 4 hours under the condition of heat preservation, then the methanol generated by hydrolysis is evaporated by rotation, and 59.5g of aminosilane hydrolysate A-1-a is obtained.
Taking 6g of the silane hydrolysate A-1-a, 200ml of dehydrated redistilled toluene and 23g of perfluorooctyl ethyl iodide, performing reflux reaction for 8 hours under the protection of nitrogen, adding 20g of zinc powder, continuing the reflux reaction for 4 hours, performing rotary evaporation under reduced pressure to remove the toluene, adding 680g of dehydrated nonafluorobutyl ethyl ether and 340g of bis-trifluoromethyl benzene, adding 224g of perfluoropolyether acyl fluoride with the average molecular weight Mw of about 2800 and the average molecular formula of C3F7O (C3F6O)15(CF3) CFCOF, performing reflux reaction for 10 hours, cooling, and performing fine filtration to obtain 1268g of pale yellow solution of fluorosilicone polymer A-1 with the average molecular weight of about 127500 and the solid content of 20.3 percent.
Synthesis example 2 (Fluorosilicone polymer A-2)
Synthesis of fluorosilicone polymer A-2
1.52g of methyl orthosilicate, 179g of octadecyl methyl dimethoxysilane, 140.4g of perfluorohexyl ethyl trimethoxysilane and 20.6g of 3- (2-aminoethyl) aminopropyl methyl dimethoxysilane are uniformly mixed, 16.2g of pure water is dropwise added, the temperature is raised to 60-65 ℃ under the protection of nitrogen, the reaction is carried out for 6 hours under the condition of heat preservation, then the reaction is carried out by rotary evaporation, methanol generated by hydrolysis is evaporated, and an aminosilane hydrolysate A-2-a 300.7g is obtained.
Taking 60g of the silane hydrolysate A-2-a, introducing nitrogen for protection, adding 800g of dehydrated 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 300g of m-difluorobenzene and 5g of magnesium powder, adding 211.5g of perfluoropolyether acyl fluoride with the average molecular weight Mw of 5300 and the average molecular formula of C3F7O (C3F6O)30(CF3) CFCOF, refluxing for 12 hours, cooling, and precisely filtering to obtain 1350g of pale yellow solution of the fluorosilicone polymer A-2 with the average molecular weight of 136000 and the average structural formula below, wherein the solid content is 19.9%.
Synthesis example 3 (Fluorosilicone polymer A-3)
Synthesis of fluorosilicone polymer A-3
500ml of fluorobenzene, 25g of 3- (2- (2-aminoethyl) aminopropylmethyltrimethoxysilane, 189g of perfluorooctylsulfonyl fluoride and 80g of triethylamine were mixed uniformly, and after a reflux reaction for 12 hours, the mixture was cooled and filtered, the salt residue was washed with fluorobenzene, and the filtrate and washing liquid were combined and subjected to rotary evaporation to remove fluorobenzene, thereby obtaining 205.7g of perfluorooctylsulfonyl amino silane A-3-a.
200g of the sulfamide silane is taken, 300ml of toluene, 2.46g of bis (trimethoxysilyl) ethane, 49.8g of methyl phenyl dimethoxy silane and 11.35g of 3- (2- (2-aminoethyl) aminopropyl methyl dimethoxy silane are added, after uniform mixing, 7.55g of pure water is added dropwise, the temperature is raised to 60-65 ℃ under the protection of nitrogen, the reaction is kept for 6 hours, and then the toluene and methanol generated by hydrolysis are evaporated by rotary evaporation to obtain 242.9g of aminosilane hydrolysate.
Taking 100g of the above silane hydrolysate, introducing nitrogen gas for protection, adding 300g of dehydrated bis (trifluoromethyl) benzene, 300g of m-difluorobenzene and 6g of triethylamine, and adding the mixture with average molecular weight Mw of about 3800 and average molecular formula of CF3O(C2F4O)20(CF2O)20CF2212.8g of perfluoropolyether acyl fluoride of COF is refluxed for 16 hours, then the solvent is removed by rotary evaporation, 1240g of perfluorocyclooctane ether is added after cooling, and fine filtration is carried out, thus obtaining 1543g of light yellow solution of fluorosilicone polymer A-3 with average structural formula as shown in the specification and average molecular weight of about 167000, and the solid content is 20.6%.
The surface-treated layer was prepared on the surface of the substrate by the following method, wherein the substrate used in the following examples and comparative examples, which was coated with chemically strengthened glass (manufactured by corning corporation, thickness 0.70mm, plane size 50mm x 100mm), was used, and the specific experimental conditions of the following examples and comparative examples are shown in table 1.
Example 1
First, a surface treatment agent D suitable for coating by a spray coating method was prepared.
0.5 part by mass of a 20% solution of fluorosilicone polymer A-1 obtained in Synthesis example 1 and 1.0 part by mass of fluoroether oil (kinematic viscosity at 25 ℃ C. of 330 mm)2S) and 98.5 parts by mass of hydrofluoroether (NovecHFE 7100 (perfluorobutyl methyl ether) manufactured by 3M) were mixed to obtain a surface-treating agent D.
Then, the base material is pretreated in a plasma treatment manner. The surface treatment agent D was uniformly sprayed (flow rate: 6ml/min) onto the plasma-cleaned substrate glass surface by means of spraying to form a precursor film. Then, the reaction was carried out at 130 ℃ for 1.5 hours under the condition of superheated steam to form a cured film. Thereby, a surface treatment layer is formed on the surface of the base material.
Example 2
First, a surface treatment agent E suitable for coating by a spray coating method was prepared.
0.5 part by mass of a 20% solution of fluorosilicone polymer A-2 obtained in Synthesis example 2 and 1.0 part by mass of fluoroether oil (kinematic viscosity at 25 ℃ C. of 330 mm)2And/s) and 98.5 parts by mass of perfluorooctyl cyclic ether were mixed to prepare a surface treating agent E.
Then, the base material was pretreated in the same manner as in example 1 by plasma treatment, and a surface-treated layer was formed on the surface of the base material by forming the precursor film in the same manner as in example 1.
Example 3
First, a surface treatment agent F suitable for vacuum evaporation coating was prepared.
25 parts by mass of a 20% solution of fluorosilicone polymer A-3 obtained in Synthesis example 3 and 75 parts by mass of fluoroether oil (kinematic viscosity at 25 ℃ of 330 mm)2And/s) mixing the components to prepare a surface treating agent F.
Then, the base material is pretreated in a plasma treatment manner.
The surface treatment agent F was added to a copper crucible container (diameter: 10mm) opened upward and placed in a vacuum coating apparatus, and the base glass was placed about 30cm above the copper crucible container (cavity inner diameter 50cm, height 50 cm). And (3) selecting the technological conditions of 12% of evaporation power and 60 seconds of evaporation time to carry out evaporation coating to form a precursor film. Then, the substrate was taken out and reacted at 130 ℃ for 1.5 hours with superheated steam to form a cured film. Thereby, a surface treatment layer is formed on the surface of the base material.
Example 4
First, a surface treatment agent G suitable for vacuum evaporation coating was prepared.
10 parts by mass of a 20% solution of the fluorosilicone polymer A-2 obtained in Synthesis example 2, 15 parts by mass of a 20% solution of the fluorosilicone polymer A-3 obtained in Synthesis example 3, and 5 parts by mass of fluoroether oil (kinematic viscosity at 25 ℃ of 330 mm)2S) and 70 parts by mass of hydrofluoroether (Novec HFE7200 (perfluorobutylethyl ether) manufactured by 3M Co.) were mixed to prepareA surface treating agent G was prepared.
Then, the base material was pretreated in the same manner as in example 3 using plasma treatment, and a surface-treated layer was formed on the surface of the base material by forming a precursor film.
Comparative example 1
And carrying out pretreatment on the base material, wherein the treatment mode is plasma treatment.
0.2 part by mass of perfluorooctylethyltrimethoxysilane and 3.0 parts by mass of fluoroether oil (kinematic viscosity at 25 ℃ of 330 mm)2S) and 96.8 parts by mass of hydrofluoroether (Novec HFE7200 (perfluorobutylethyl ether) manufactured by 3M company) were mixed to prepare a surface treatment agent H, and a surface treatment layer was formed on the surface of the base material by a spray coating method.
Comparative example 2
And carrying out pretreatment on the base material, wherein the treatment mode is plasma treatment.
25 parts by mass of a commercially available perfluoropolyether-based trimethoxysilane 20% solution and 75 parts by mass of fluoroether oil (kinematic viscosity at 25 ℃ of 330 mm)2And/s) preparing a surface treating agent K, and forming a surface treatment layer on the surface of the base material by adopting vacuum evaporation coating.
TABLE 1
Test method
For the surface treatment layers formed on the substrate surfaces in the above examples and comparative examples, the static contact angle of water was measured. First, the contact angle when the surface of the substrate was not subjected to any rubbing (the number of times of rubbing was 0) was measured as a preliminary evaluation. Then using a wire mesh with the number of 0000#, the size of 10mm, at 1000gf/cm2The glass substrate was rubbed at a rate of 60 rubs per minute under the load of (1), the contact angle and the coefficient of friction were measured every 1000 times, and when the contact angle was measured to be less than 100 degrees, the rubbing was stopped, and the test results of the application test of the surface treatment layer prepared in the above examples are shown in table 2.
TABLE 2
From the test results, compared with a certain commercial surface treating agent, the fluorosilicone polymer provided by the invention has the advantages that more methoxyl groups are introduced into the main chain, and the friction resistance and durability can be further improved. It can also be seen from the test results that the surface treatment agent may be a single fluorosilicone polymer, or a mixture of two or more thereof. The film layer obtained from the surface treatment agent of the fluorosilicone polymer is called a surface treatment layer, and can be applied to the surfaces of various substrates such as glass, fiber, resin, metal, ceramic, building materials and the like as a functional film.
The above embodiments are only for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may be modified or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A fluorosilicone polymer, characterized in that: the fluorine-silicon polymer is prepared by firstly cohydrolyzing amino alkoxy silane with tetraalkoxysilane or alkyl alkoxy silane or alkoxy silane containing perfluoroalkyl substituent, and carrying out amidation reaction with perfluoropolyether acyl fluoride in the first way after cohydrolysis; the second way is to perform an amidation reaction with perfluoropolyether acyl fluoride after performing an amino substitution reaction with the perfluoroalkyl iodide; the third way is to prepare the compound by carrying out the amidation reaction with perfluoropolyether acyl fluoride after carrying out the sulfonylation amination reaction with perfluoroalkyl sulfonyl fluoride;
the amino substitution reaction, the sulphonamide amination reaction and the amidation reaction are carried out on the amino alkoxy silane and perfluoroalkyl iodide, perfluoroalkyl sulfonyl fluoride or perfluoropolyether acyl fluoride in a solvent by using tertiary amine or active metal powder to remove hydrogen iodide or hydrogen fluoride to form hydriodide or hydrofluoride, and the solvent is removed by distillation after the by-product hydriodide or hydrofluoride is removed by filtration; the solvent is one or a mixture of more than two of methylbenzene, dimethylbenzene, fluorobenzene, o-difluorobenzene, m-difluorobenzene, p-difluorobenzene, trifluorobenzene, pentafluorobenzene, trifluoromethylbenzene, bis (trifluoromethyl) benzene, fluoroalkyl chain ether and fluoroalkyl cyclic ether;
the fluorosilicone polymer is represented by the following formula (1), and has a number average molecular weight of more than 1 × 104，
In the formula (1), the reaction mixture is,
R1、R2、R7an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl;
R4、R5、R8an alkyl or alkoxy group having 1 to 4 carbon atoms, which is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy;
R3、R6the hydrocarbon group is an alkyl group having 1 to 18 carbon atoms, a vinyl group, an allyl group, a phenyl group, a phenethyl group, or an α -methylphenylethyl group, and may be an alkoxysilylethyl group represented by the following formulae (2-a) and (2-b):
R9is hydrogen or R10，R10Is a perfluoroalkyl group selected from the following formula (3-a), a perfluoroalkylethyl group selected from the following formula (3-b), and a perfluoroalkylsulfonyl group selected from the following formula (3-c):
-CkF2k+1(3-a)
-CH2CH2-CkF2k+1(3-b)
R11is hydrogen or R12Or R13，
R12Is R13Or a perfluoroalkyl group selected from the group consisting of a perfluoroalkyl group represented by the following formula (3-a), a perfluoroalkylethyl group represented by the following formula (3-b), and a perfluoroalkylsulfonyl group represented by the following formula (3-c):
-CkF2k+1(3-a)
-CH2CH2-CkF2k+1(3-b)
R13is a perfluoropolyether group selected from the group consisting of those represented by the following formula (4):
a. b, c, d, e and f are 0 or positive integers, d is more than or equal to 1,
h is an integer of 1-3, k is a positive integer of 1-10, m is an integer of 1-6, n is 0 or a positive integer, w, x, y and z are 0 or positive integers, and w + x + y + z is more than or equal to 1.
2. The fluorosilicone polymer of claim 1, wherein the aminoalkoxysilane is aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane, bis (trimethoxysilylpropyl) ammonia, bis (triethoxysilylpropyl) ammonia, bis (methyldimethoxysilylpropyl) ammonia, bis (methyldiethoxysilylpropyl) ammonia, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane, N '-bis (trimethoxysilylpropyl) ethylenediamine, N' -bis (trimethoxysilylpropyl) ethylenediamine, N, N ' -bis (triethoxysilylpropyl) ethylenediamine, N ' -bis (methyldimethoxysilylpropyl) ethylenediamine, N ' -bis (methyldiethoxysilylpropyl) ethylenediamine, 3- (2- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2- (2-aminoethyl) aminopropylmethyldiethoxysilane, 3- (2- (2-aminoethyl) aminopropylmethyldiethoxysilane, 3- (2-aminoethyl) aminomethyltrimethoxysilane, N ' -bis (methyldimethoxysilylmethyl) ethylenediamine, N ' -bis (methyldimethoxysilylpropyl) ethylenediamine, 3- (2- (2-aminoethyl) aminomethyltrimethoxysilane; the tetraalkoxysilane is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane; the hydrocarbyl alkoxy silane is dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, methyl propyl dimethoxy silane, methyl vinyl dimethoxy silane, long-chain alkyl methyl dimethoxy silane with the carbon number of 4-18, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane, vinyl trimethoxy silane, propyl trimethoxy silane or long-chain alkyl trimethoxy silane with the carbon number of 4-18; the alkoxy silane containing perfluoroalkyl substituent is nonafluorobutylethyldimethoxysilane, nonafluorobutylethyltrimethoxysilane, tridecafluorohexylethylmethyldimethoxysilane, tridecafluorohexylethyltrimethoxysilane, heptadecafluorooctylethylmethyldimethoxysilane, heptadecafluorooctylethyltrimethoxysilane, nonafluorobutylethyldiethoxysilane, nonafluorobutylethyltriethoxysilane, tridecafluorohexylethylmethyldiethoxysilane, tridecafluorohexylethyltriethoxysilane, heptadecafluorooctylethylmethyldiethoxysilane, heptadecafluorooctylethyltriethoxysilane; the perfluoroalkyl iodide is nonafluorobutyl iodide, tridecafluorohexyl iodide, heptadecafluorooctyl iodide, nonafluorobutyl ethyl iodide, tridecafluorohexyl ethyl iodide and heptadecafluorooctyl ethyl iodide; the perfluoroalkyl sulfonyl fluoride is nonafluorobutyl sulfonyl fluoride, tridecafluorohexyl sulfonyl fluoride and heptadecafluorooctyl sulfonyl fluoride; the perfluoropolyether acyl fluoride is a polymer shown in the following general formula (5):
in the formula (5), h is an integer of 1-3, k is a positive integer of 1-10, w, x, y and z are 0 or positive integers, and w + x + y + z is more than or equal to 1.
3. The surface treating agent is characterized by comprising A, B, C, wherein the mass ratio of A, B, C is 1: 1-1000: 0-10000; wherein the A component is the fluorosilicone polymer of claim 1; the component B is fluoroether oil; the component C is a solvent.
4. The surface treating agent according to claim 3, wherein the fluoroether oil of the B component is a polymer represented by the formula (6):
CuF2u+1-(OC4F8)p-(OC3F6)q-(OC2F4)s-(OCF2)t-CvF2v+1(6)
in the formula (6), u and v are integers of 1-10; p, q, s and t are 0 or integers of 1-300, and p + q + s + t is more than or equal to 1.
5. The surface treating agent according to claim 4, wherein the C component solvent is one or a mixture of two or more selected from the group consisting of perfluorinated aliphatic hydrocarbons having 5 to 12 carbon atoms, polyfluorinated aromatic hydrocarbons (bis (trifluoromethyl) benzene), polyfluorinated aliphatic hydrocarbons, perfluoroalkyl alkyl ethers of Hydrofluoroethers (HFEs), difluoroalkyl ethers, and perfluorinated cyclic ethers.
6. An article comprising a substrate and a surface treatment layer formed on a surface of the substrate by the fluorosilicone polymer described in claim 1 or the surface treatment agent described in claim 3.
7. The article as recited in claim 6, wherein: the composition of the surface of the article includes glass, resin, metal, and ceramic.
8. A method of manufacturing an article as claimed in claim 6 or 7, the method comprising the steps of:
(a) forming a precursor film on the surface of the substrate, the precursor film including the fluorosilicone polymer having a hydrolyzable group bonded to a Si bond;
(b) providing moisture to the precursor film;
(c) heating the precursor film in a dry atmosphere at a temperature exceeding 100 ℃ to form the surface treatment layer containing the fluorosilicone polymer species on the surface of the substrate.
9. The method for manufacturing an article according to claim 8, wherein the moisture supply in the step (b) is performed in an atmosphere of a temperature of 100 to 500 ℃.
10. The method of manufacturing an article according to claim 8, the substrate on which the precursor film is formed in step (a) is placed in a superheated water vapor environment so that steps (b) and (c) can be continuously performed.
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