CN108368253B - Polymer-modified silane containing fluoropolyether group, surface treatment agent and article - Google Patents
Polymer-modified silane containing fluoropolyether group, surface treatment agent and article Download PDFInfo
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- CN108368253B CN108368253B CN201680071632.4A CN201680071632A CN108368253B CN 108368253 B CN108368253 B CN 108368253B CN 201680071632 A CN201680071632 A CN 201680071632A CN 108368253 B CN108368253 B CN 108368253B
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- 150000004756 silanes Polymers 0.000 title claims abstract description 64
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 148
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 9
- 125000000962 organic group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 43
- 125000002947 alkylene group Chemical group 0.000 claims description 42
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 9
- 125000000732 arylene group Chemical group 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000005375 organosiloxane group Chemical group 0.000 claims description 3
- 125000006681 (C2-C10) alkylene group Chemical group 0.000 claims 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims 1
- -1 silylene group Chemical group 0.000 abstract description 50
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000077 silane Inorganic materials 0.000 abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 92
- 239000000243 solution Substances 0.000 description 82
- 150000001336 alkenes Chemical group 0.000 description 61
- 150000001875 compounds Chemical class 0.000 description 48
- 150000003961 organosilicon compounds Chemical class 0.000 description 45
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 28
- 229910052731 fluorine Inorganic materials 0.000 description 28
- 239000011737 fluorine Substances 0.000 description 28
- 239000002253 acid Substances 0.000 description 27
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 150000002222 fluorine compounds Chemical class 0.000 description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 14
- 238000006459 hydrosilylation reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 10
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000005871 repellent Substances 0.000 description 9
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 8
- SQEGLLMNIBLLNQ-UHFFFAOYSA-N 1-ethoxy-1,1,2,3,3,3-hexafluoro-2-(trifluoromethyl)propane Chemical compound CCOC(F)(F)C(F)(C(F)(F)F)C(F)(F)F SQEGLLMNIBLLNQ-UHFFFAOYSA-N 0.000 description 8
- DJXNLVJQMJNEMN-UHFFFAOYSA-N 2-[difluoro(methoxy)methyl]-1,1,1,2,3,3,3-heptafluoropropane Chemical compound COC(F)(F)C(F)(C(F)(F)F)C(F)(F)F DJXNLVJQMJNEMN-UHFFFAOYSA-N 0.000 description 8
- FNUBKINEQIEODM-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentanal Chemical compound FC(F)(F)C(F)(F)C(F)(F)CC=O FNUBKINEQIEODM-UHFFFAOYSA-N 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- 150000001265 acyl fluorides Chemical class 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 150000001735 carboxylic acids Chemical class 0.000 description 8
- 238000006356 dehydrogenation reaction Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 230000003373 anti-fouling effect Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- 230000000269 nucleophilic effect Effects 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000007809 chemical reaction catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004210 ether based solvent Substances 0.000 description 5
- 229920002313 fluoropolymer Polymers 0.000 description 5
- 239000004811 fluoropolymer Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000013557 residual solvent Substances 0.000 description 5
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- QKAGYSDHEJITFV-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane Chemical compound FC(F)(F)C(F)(F)C(F)(OC)C(F)(C(F)(F)F)C(F)(F)F QKAGYSDHEJITFV-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910020388 SiO1/2 Inorganic materials 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000005796 dehydrofluorination reaction Methods 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 125000005429 oxyalkyl group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 2
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 2
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 2
- 229910000105 potassium hydride Inorganic materials 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 210000002374 sebum Anatomy 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IBOKZQNMFSHYNQ-UHFFFAOYSA-N tribromosilane Chemical compound Br[SiH](Br)Br IBOKZQNMFSHYNQ-UHFFFAOYSA-N 0.000 description 2
- UCSBCWBHZLSFGC-UHFFFAOYSA-N tributoxysilane Chemical compound CCCCO[SiH](OCCCC)OCCCC UCSBCWBHZLSFGC-UHFFFAOYSA-N 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- DNAPJAGHXMPFLD-UHFFFAOYSA-N triiodosilane Chemical compound I[SiH](I)I DNAPJAGHXMPFLD-UHFFFAOYSA-N 0.000 description 2
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 2
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 2
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000282575 Gorilla Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910020447 SiO2/2 Inorganic materials 0.000 description 1
- 229910020487 SiO3/2 Inorganic materials 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical group C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229940104873 methyl perfluorobutyl ether Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane 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)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- AQZYBQIAUSKCCS-UHFFFAOYSA-N perfluorotripentylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AQZYBQIAUSKCCS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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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
- C09D171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polyethers (AREA)
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polymer-modified silane containing a fluoropolyether group, which can form a waterproof and oilproof layer with excellent sliding property, a surface treatment agent containing the silane, and an article of a surface treatment object (namely, a cured coating film with the surface treatment agent on the surface) surface-treated by the surface treatment agent. A polymer-modified silane containing a fluoropolyether group represented by the following formula (1) (Rf is a 1-or 2-valent fluorooxyalkylene group-containing polymer residue, Y is a 2-to 6-valent hydrocarbon group which may have a siloxane bond and/or a silylene group, R is a 1-to 4-carbon alkyl group or phenyl group, X is a hydroxyl group or a hydrolyzable group, Q is a 2-valent organic group which may have a siloxane bond and/or a silylene group, R' is a 1-valent fluoroalkyl group, a 1-valent fluorooxyalkylene group-containing polymer residue, a 1-to 4-carbon alkyl group or phenyl group, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.).
Description
Technical Field
The present invention relates to a fluoropolyether group-containing polymer-modified silane, and more particularly, to a fluoropolyether group-containing polymer-modified silane which forms a film excellent in sliding properties, a surface treatment agent comprising the silane, and an article surface-treated with the surface treatment agent (i.e., having a cured film of the surface treatment agent on the surface).
Background
In recent years, the touch panel of a screen has been accelerated, including a display of a mobile phone. However, the touch panel is in a state of a bare screen, and there are many opportunities for direct contact of fingers, cheeks, and the like, and there is a problem that dirt such as sebum is likely to adhere. Therefore, in order to improve the appearance and visibility, the demand for a technique for making it difficult to apply fingerprints to the surface of a display and a technique for making dirt easily fall off have increased year by year, and development of materials that can satisfy these demands has been desired. In particular, since fingerprint stains are easily attached to the surface of the touch panel display, it is desirable to provide a water-and oil-repellent layer. However, the conventional oil-and water-repellent layer has a high water-and oil-repellency and an excellent dirt-wiping property, but has a problem that the antifouling performance is deteriorated during use.
In general, a fluoropolyether group-containing compound has water-and oil-repellency, chemical resistance, lubricity, releasability, antifouling property, and the like because the surface free energy thereof is very small. By utilizing its properties, the composition is industrially widely used as a water-and oil-repellent antifouling agent for paper and fiber, a lubricant for magnetic recording media, an oil-repellent agent for precision equipment, a release agent, a cosmetic, a protective film, and the like. However, the properties mean both non-adhesiveness and non-adhesiveness to other substrates, and it is difficult to make the coating film adhere to the surface of the substrate even if the coating film can be applied to the surface of the substrate.
On the other hand, silane coupling agents are known as coupling agents for bonding organic compounds to the surface of a substrate such as glass or cloth, and are widely used as coating agents for the surface of various substrates. The silane coupling agent has an organic functional group and a reactive silyl group (generally, a hydrolyzable silyl group such as an alkoxysilyl group) in 1 molecule. The hydrolyzable silyl group undergoes a self-condensation reaction due to moisture or the like in the air to form a coating film. The coating film is chemically-physically bonded to the surface of glass, metal, or the like via the hydrolyzable silyl group, and thus is a durable and strong coating film.
Therefore, there have been disclosed compositions in which a fluoropolyether group-containing polymer-modified silane having a hydrolyzable silyl group introduced into a fluoropolyether group-containing compound is used to facilitate adhesion to the surface of a base material and to form a coating film having water-and-oil repellency, chemical resistance, lubricity, mold release property, stain resistance and the like on the surface of the base material (patent documents 1 to 5: Japanese patent application laid-open No. 2008-534696, Japanese patent application laid-open No. 2008-537557, Japanese patent application laid-open No. 2012-072272, Japanese patent application laid-open No. 2012-157856, Japanese patent application laid-open No. 2013-136833).
The lens surface-treated with the composition containing the fluoropolyether group-containing polymer-modified silane having a hydrolyzable silyl group introduced into the fluoropolyether group-containing compound is excellent in abrasion resistance and mold release property of the antireflection film, but insufficient in sliding property.
Documents of the prior art
Patent document
Patent document 1: japanese Kokai publication No. 2008-534696
Patent document 2: japanese Kokai publication No. 2008-537557
Patent document 3: japanese laid-open patent publication No. 2012 and 072272
Patent document 4: japanese laid-open patent publication No. 2012-157856
Patent document 5: japanese patent laid-open publication No. 2013-136833
Patent document 6: japanese patent laid-open publication No. 2015-199906
Disclosure of Invention
Problems to be solved by the invention
As a fluoropolyether group-containing compound having excellent abrasion resistance, the present inventors have proposed a compound represented by the following formula
[ solution 1]
(wherein Rf is a 1-valent fluorooxyalkyl group-containing polymer residue or a 2-valent fluorooxyalkylene group-containing polymer residue, Y is a 2-to 6-valent hydrocarbon group which may have a siloxane bond and a silylene group, R is independently a C1-4 alkyl group or a phenyl group, X is independently a hydrolyzable group, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.)
The polymer-modified silane containing a fluoropolyether group (patent document 6: Japanese patent laid-open No. 2015-199906) shows high water-and oil-repellency and abrasion resistance of a coating film formed from a surface treatment agent containing the polymer-modified silane containing a fluoropolyether group and/or a partial hydrolysis condensate thereof. However, the slidability is still not improved.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a polymer-modified silane containing a fluoropolyether group, which is capable of forming a water-and oil-repellent layer having excellent sliding properties, a surface treatment agent containing the silane, and an article surface-treated with the surface treatment agent (that is, having a cured film of the surface treatment agent on the surface).
Means for solving the problems
The present inventors have intensively studied to solve the above-mentioned object and, as a result, found that: among the above fluoropolyether group-containing polymer-modified silanes, those represented by the following general formula (1) wherein the hydroxyl group is protected with the following-Q-R' group can form a water-and oil-repellent layer excellent in sliding properties, weather resistance and storage stability, and the present invention has been completed.
Accordingly, the present invention provides the following polymer-modified silane containing a fluoropolyether group, a surface treatment agent and an article.
[1] A polymer-modified silane containing a fluoropolyether group represented by the following general formula (1)
[ solution 2]
(wherein Rf is a 1-or 2-valent fluorooxyalkylene group-containing polymer residue, Y is a 2-to 6-valent hydrocarbon group which may have a siloxane bond and/or a silylene group, R is a 1-4 carbon alkyl group or a phenyl group, X is a hydroxyl group or a hydrolyzable group, Q is a 2-valent organic group which may have a siloxane bond and/or a silylene group, R' is a 1-valent fluoroalkyl group, a 1-valent fluorooxyalkylene group-containing polymer residue, a 1-4 carbon alkyl group or a phenyl group, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.).
[2] [1] the fluoropolyether group-containing polymer-modified silane is characterized in that α in the formula (1) is 1, and the Rf group is a 1-valent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2).
[ solution 3]
(wherein p, q, r and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, each repeating unit may be straight or branched, and each repeating unit may be randomly bonded.)
[3] [1] the fluoropolyether group-containing polymer-modified silane is characterized in that α in the formula (1) is 2, and the Rf group is a 2-valent fluorooxyalkylene group-containing polymer residue represented by the following general formula (3).
[ solution 4]
(wherein p, q, r and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, each repeating unit may be straight or branched, and each repeating unit may be randomly bonded.)
[4] [1] the fluoropolyether group-containing polymer-modified silane according to any one of [1] to [3], wherein in the formula (1), Y represents at least 1 kind of group selected from a C3-10 alkylene group, a C8-16 alkylene group containing a phenylene group, a C2-10 group in which alkylene groups having 2 to 10 carbon atoms are bonded to each other via a silalkylene structure or a silarylene structure, a C2-4 group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bonding end of a linear organopolysiloxane residue having 2 to 10 silicon atoms, and a C2-4 group in which an alkylene group having 2 to 10 carbon atoms is bonded to a bonding end of a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms.
[5] [1] the fluoropolyether group-containing polymer-modified silane according to any one of [1] to [4], wherein in the formula (1), X is independently selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms and a halogen atom.
[6] [1] the fluoropolyether group-containing polymer-modified silane according to any one of [1] to [5], wherein Q is a 2-valent organic group represented by the following formula (4) in the formula (1).
[ solution 5]
(wherein R' is an alkylene group having 1 to 10 carbon atoms and optionally having one of a ketone, ester, amide, ether, thioether, amine and phenylene group, or a carbonyl group, W is a group having 2 to 40 carbon atoms and optionally having 2 valences selected from a linear 2-valent organic (poly) siloxane residue, a linear silalkylene group having 3 to 40 silicon atoms and optionally having a siloxane bond, which is bonded via a C1-4 alkylene group, and a linear silarylene group having 3 to 40 silicon atoms and optionally having a siloxane bond, which is bonded via a C1-4 alkylene group, each of the organic (poly) siloxane residue, the silalkylene group and the silarylene group may be singly or in combination, β is 0 or 1, γ is 0 or 1, and β + γ is 1 or 2.)
[7] The fluoropolyether group-containing polymer-modified silane according to any one of [1] to [6], wherein the polymer-modified silane represented by the formula (1) is represented by the following formula.
[ solution 6]
[ solution 7]
(wherein p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1+ q1 is an integer of 10 to 105.)
[8] A surface treatment agent comprising the fluoropolyether group-containing polymer-modified silane according to any one of [1] to [7 ].
[9] An article having a cured coating film of the surface treatment agent according to [8] on the surface thereof.
ADVANTAGEOUS EFFECTS OF INVENTION
The surface treatment agent containing the fluoropolyether group-containing polymer-modified silane in which the hydroxyl group bonded to the carbon atom is blocked with the above-mentioned-Q-R' group of the present invention can form a water-and oil-repellent layer excellent in sliding properties.
Detailed Description
The polymer-modified silane containing a fluoropolyether group of the present invention is represented by the following general formula (1).
[ solution 8]
(wherein Rf is a 1-or 2-valent fluorooxyalkylene group-containing polymer residue, Y is a 2-to 6-valent hydrocarbon group which may have a siloxane bond and/or a silylene group, R is a 1-4 carbon alkyl group or phenyl group, X is a hydroxyl group or a hydrolyzable group, Q is a 2-valent organic group which may have a siloxane bond and/or a silylene group, R' is a 1-valent fluoroalkyl group, a 1-valent fluorooxyalkylene group-containing polymer residue, a 1-4 carbon alkyl group or phenyl group, n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.)
The polymer-modified silane containing a fluoropolyether group of the present invention is a 1-or 2-valent fluorooxyalkylene group-containing polymer residue (Rf), a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group (-Si (R))3-n(X)n) A structure in which a hydrocarbon chain (Y) having a valence of 2 to 6 and a carbon atom, which may have a siloxane bond and/or a silylene group, are bonded to each other through a carbon atom, and further through an organic group (Q) having a valence of 2, which may have a siloxane bond and/or a silylene group, as a linking group, an alkylene group or a carbonyl group (R') having 1 to 10 carbon atoms, which may preferably have a ketone, an ester, an amide, an ether, a thioether, an amine, or a phenylene group, or an organopolysiloxane residue, a silylene group, or a silylene group (W), wherein a fluoroalkyl group having a valence of 1, a fluorooxyalkylene group-containing polymer residue having a valence of 1, or a C1 OCP having a carbon number of 1The alkyl group or phenyl group (R') of 4 or the like is introduced into a hydroxyl group bonded to a carbon atom in the polymer as an intermediate, thereby forming a water-and oil-repellent layer having excellent sliding properties.
In the above formula (1), when α is 1, Rf is preferably a 1-valent fluorooxyalkylene group-containing polymer residue (hereinafter, sometimes referred to as a fluorooxyalkyl group) represented by the following general formula (2).
[ solution 9]
(wherein p, q, r and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, each repeating unit may be straight or branched, and each repeating unit may be randomly bonded.)
In the above formula (1), when α is 2, Rf is preferably a 2-valent fluorooxyalkylene group-containing polymer residue represented by the following general formula (3) (hereinafter may be referred to as fluorooxyalkylene group).
[ solution 10]
(wherein p, q, r and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, each repeating unit may be straight or branched, and each repeating unit may be randomly bonded.)
In the above formulas (2) and (3), p, q, r and s are each an integer of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, r is an integer of 0 to 100, s is an integer of 0 to 100, p + q + r + s is an integer of 3 to 200, preferably 10 to 100, and each repeating unit may be straight or branched, and the repeating units may be randomly bonded. More preferably, p + q is an integer of 10 to 105, particularly an integer of 15 to 60, and r-s-0. If p + q + r + s is smaller than the above upper limit, the adhesiveness and curability are good, and if it is larger than the above lower limit, the characteristics of the fluoropolyether group can be sufficiently exhibited, which is preferable.
In addition, t is an integer of 1 to 3, preferably 1 or 2, CtF2tThe polymer may be linear or branched.
Specific examples of Rf (a residue of a fluorooxyalkylene group-containing polymer having a valence of 1 or 2) include the following groups.
[ solution 11]
F(CF2O)pCF2-
F(CF2O)p′(CF2CF2O)q′CF2-
F(CF2O)p′(CF2CF2O)q′(CF2CF2CF2O)r′CF2-
F(CF2O)p′(CF2CF2O)q′(CF2CF2CF2CF2O)s′CF2-
F(CF2O)p′(CF2CF2O)q′(CF2CF2CF2O)r′(CF2CF2CF2CF2O)s′CF2-
F(CF2CF2O)q′CF2-
F(CF2CF2CF2O)r′CF2CF2-
-CF2O(CF2O)p′CF2-
-CF2O(CF2O)p′(CF2CF2O)q′CF2-
-CF2O(CF2O)p′(CF2CF2O)q′(CF2CF2CF2O)r′CF2-
-CF2O(CF2O)p′(CF2CF2O)q′(CF2CF2CF2CF2O)s′CF2-
-CF2O(CF2O)p′(CF2CF2O)q′(CF2CF2CF2O)r′(CF2CF2CF2CF2O)s′CF2-
-CF2CF2O(CF2CF2CF2O)r′CF2CF2-
[ solution 12]
(wherein p ', q', r ', s' are each an integer of 1 or more, and the upper limit is the same as the upper limit of p, q, r, s.u is an integer of 1 to 24, v is an integer of 1 to 24, and is a number satisfying u + v.r.the repeating units may be randomly combined.)
In the formula (1), Y is a 2-6-valent, preferably 2-4-valent, and more preferably 2-valent hydrocarbon group which may have a siloxane bond ((di) organosiloxane unit or the like) and/or a silylene (diorganosilylene group), and a linking group (ether bond or the like) having low bond energy is not contained in the molecule, whereby a coating film having excellent weather resistance and abrasion resistance can be provided.
Specific examples of Y include alkylene groups having 3 to 10 carbon atoms such as propylene (trimethylene group, methylethylene group), butylene (tetramethylene group, methylpropylene group), hexamethylene group, etc., alkylene groups containing arylene groups having 6 to 8 carbon atoms such as phenylene group (for example, alkylene-arylene groups having 8 to 16 carbon atoms, etc.), groups having 2 to 10 carbon atoms bonded to each other via a silylene structure (a structure in which both ends of the alkylene group are terminated with diorganosilylene groups) or a silylene structure (a structure in which both ends of the arylene group are terminated with diorganosilylene groups), groups having 2 to 6, preferably 2 to 4, valences in which alkylene groups are bonded to the bonding ends of linear organopolysiloxane residues having 2 to 10, preferably 2 to 5, silicon atoms, groups having 2 to 6, preferably 2 to 4, alkylene groups bonded to the bonding ends of branched or cyclic organopolysiloxane residues having 3 to 10, preferably 3 to 5, silicon atoms, etc, Preferably 2 to 4 valent groups, more preferably C3 to 10 alkylene groups, C8 to 16 alkylene groups containing phenylene groups, C2 to 10 alkylene groups bonded to each other via a silalkylene structure or silarylene structure, C2 to 4 valent groups in which C2 to 10 alkylene groups are bonded to the bonding ends of 2 to 10, preferably 2 to 5 linear organopolysiloxane residues, or C2 to 4 valent groups in which C2 to 10 alkylene groups are bonded to the bonding ends of 3 to 10, preferably 3 to 5 branched or cyclic organopolysiloxane residues, and C3 to 6 alkylene groups are more preferably used.
Among them, examples of the silylene structure and the silylene structure include the following structures.
[ solution 13]
(in the formula, R1Is alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, etc., or aryl group having 6 to 10 carbon atoms such as phenyl group, R1May be the same or different. R2Is an alkylene group having 1 to 4 carbon atoms such as methylene, ethylene, propylene (trimethylene, methylethylene) or an arylene group having 6 to 10 carbon atoms such as phenylene. )
Examples of the linear organopolysiloxane residue having 2 to 10, preferably 2 to 5, silicon atoms and the branched or cyclic 2 to 6-valent organopolysiloxane residue having 3 to 10, preferably 3 to 5, silicon atoms include the following groups.
[ solution 14]
-((R1)3-kSiOk/2)(O1/2Si(R1)2)k-
[ solution 15]
k＝1 -(R1 2SiO1/2)(R1 2SiO1/2)-
k＝2 -(R1SiO2/2)(R1 2SiO1/2)-
k＝3 -(SiO3/2)(R1 2SiO1/2)-
(in the formula, R1As described above. g is an integer of 1 to 9, preferably 1 to 4, h is an integer of 2 to 6, preferably 2 to 4, j is an integer of 0 to 8, preferably 0 or 1, h + j is an integer of 3 to 10, preferably 3 to 5, and k is an integer of 1 to 3, preferably 2 or 3. )
Specific examples of Y include the following groups.
[ solution 16]
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2CH2-
In the formula (1), X is a hydroxyl group or a hydrolyzable group which may be different from each other. Examples of such X include hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy and other alkoxy groups having 1 to 10 carbon atoms, methoxymethoxy, methoxyethoxy and other alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, acetoxy and other acyloxy groups having 2 to 10 carbon atoms, isopropenoxy and other alkenyloxy groups having 2 to 10 carbon atoms, chlorine atoms, bromine atoms, iodine atoms and other halogen atoms. Among them, preferred are methoxy group, ethoxy group, isopropenyloxy group, and chlorine atom.
In the formula (1), R is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc., or a phenyl group, and among them, a methyl group is preferable.
n is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 from the viewpoint of reactivity and adhesion to a substrate.
m is an integer of 1 to 5, but if less than 1, the adhesion to the substrate is reduced, and if 6 or more, the terminal alkoxy group value is too high, which adversely affects the performance, and therefore an integer of 1 to 3 is preferable, and 1 is particularly preferable.
In the formula (1), Q is a 2-valent organic group which may have a siloxane bond and/or a silylene group, and a 2-valent organic group represented by the following formula (4) is particularly preferable.
[ solution 17]
(wherein R' is an alkylene group having 1 to 10 carbon atoms and optionally having a ketone, ester, amide, ether, thioether, amine or phenylene group, W is a group having 2 to 40 carbon atoms and optionally having 2 valences selected from a linear 2-valent organic (poly) siloxane residue having 2 to 40 silicon atoms, a linear silalkylene group having 3 to 40 silicon atoms and optionally having a siloxane bond bonded via an alkylene group having 1 to 4 carbon atoms, and a linear silarylene group having 3 to 40 silicon atoms and optionally having a siloxane bond bonded via an alkylene group having 1 to 4 carbon atoms, and each of the organic (poly) siloxane residue, the silalkylene group and the silarylene group may be singly or mixedly used, and beta is 0 or 1, gamma is 0 or 1, and beta + gamma is 1 or 2.)
In the formula (4), R' is specifically a group having a valence of 2 in which methylene, ethylene, propylene (trimethylene, methylethylene), butylene (alkylene having 1 to 10 carbon atoms such as tetramethylene, methylpropylene, hexamethylene, etc., alkylene having 1 to 10 carbon atoms are bonded to each other via an arylene group such as a ketone, ester, amide, ether, thioether, amine, phenylene having 6 to 8 carbon atoms, etc., or a carbonyl group, and is preferably an alkylene having 1 to 4 carbon atoms, a group having a valence of 2 in which alkylene having 1 to 4 carbon atoms are bonded to each other via an ether, or a carbonyl group.
Specific examples of R "include the following groups.
[ solution 18]
-CH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2-
-CH2CH2-O-CH2-
-CH2CH2CH2-O-CH2-
-CH2CH2CH2-S-CH2-
In the formula (4), examples of the linear silylene group, the silylene group structure in the linear silylene group, and the silylene group structure of W include the following structures.
[ solution 19]
(in the formula, R1Is alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, etc., or aryl group having 6 to 10 carbon atoms such as phenyl group, R1May be the same or different. R2Is an alkylene group having 1 to 4 carbon atoms such as methylene, ethylene, propylene (trimethylene, methylethylene) or an arylene group having 6 to 10 carbon atoms such as phenylene. )
Examples of the linear 2-valent organopolysiloxane residue having 2 to 40, preferably 3 to 10 silicon atoms include the following groups.
[ solution 20]
(in the formula, R1As described above. f is an integer of 1 to 39, preferably an integer of 2 to 9. )
Examples of W include the following groups.
[ solution 21]
In the formula (1), R' is a fluoroalkyl group having a valence of 1 (e.g., a fluoroalkyl group having 1 to 6 carbon atoms), a polymeric residue having a valence of 1 and containing a fluorooxyalkylene group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, or the like, or a phenyl group, among which a polymeric residue having a valence of 1 and containing a fluorooxyalkylene group and an alkyl group having 1 to 4 carbon atoms are preferable, and a polymeric residue having a valence of 1 and containing a fluorooxyalkylene group is particularly preferable.
In the above formula (1), when R 'is a 1-valent fluorooxyalkylene group-containing polymer residue, the 1-valent fluorooxyalkylene group-containing polymer residue represented by the following general formula (2) is preferable as R'.
[ solution 22]
(wherein p, q, r and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, each repeating unit may be straight or branched, and each repeating unit may be randomly bonded.)
The fluoropolyether group-containing polymer-modified silane represented by the above formula (1) may be exemplified by a fluoropolyether group-containing polymer-modified silane represented by the following formula. In each formula, the number of repetition (or the degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group or the fluorooxyalkylene group may be any number satisfying the above formulas (2) and (3).
[ solution 23]
[ solution 24]
[ solution 25]
(wherein p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1+ q1 is an integer of 10 to 105.)
Examples of the method for producing the fluoropolyether group-containing polymer-modified silane represented by the formula (1) below, wherein α is 1, include the following methods.
A fluorooxyalkyl group-containing polymer having 2 olefin moieties at one terminal of the molecular chain (i.e., a polymer having a fluorooxyalkylene group-containing polymer residue having a valence of 1 and having 2 olefin moieties at one terminal of the molecular chain) is dissolved in a solvent such as a fluorine-based solvent (e.g., 1, 3-bis (trifluoromethyl) benzene), and an organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, such as trimethoxysilane, is subjected to a hydrosilylation addition reaction in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid/vinylsiloxane complex at a temperature of 40 to 120 ℃, preferably 60 to 100 ℃, more preferably about 80 ℃, and under conditions of 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours, and is cured.
Further, as another method for producing the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) wherein α is 1, for example, the following method can be mentioned.
A polymer containing a fluorooxyalkyl group having 2 olefin moieties at one terminal end of the molecular chain is dissolved in a solvent such as a fluorine-based solvent (e.g., 1, 3-bis (trifluoromethyl) benzene), an organosilicon compound having an SiH group and a hydrolyzable terminal group (e.g., a halogen atom bonded to a silicon atom such as a chlorine atom) in the molecule, such as trichlorosilane, is subjected to a hydrosilylation addition reaction at a temperature of 40 to 120 ℃, preferably 60 to 100 ℃, more preferably about 80 ℃ for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours in the presence of a hydrosilylation reaction catalyst such as a toluene solution of a chloroplatinic acid/vinylsiloxane complex, and after the reaction is cured, the substituent group (halogen atom or the like) on the silyl group is converted to a hydrolyzable group such as an alkoxy group (e.g., a methoxy group).
Further, in the case of using an SiH group-containing organosilicon compound having no hydrolyzable terminal group instead of the above-described organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, an organosilicon compound having 2 or more SiH groups and having no hydrolyzable terminal group in the molecule may be used as the organosilicon compound. In this case, a fluorooxyalkyl group-containing polymer having 2 olefin moieties at one end of the molecular chain and an organosilicon compound having 2 or more SiH groups and having no hydrolyzable end group in the molecule are subjected to a hydrosilylation addition reaction in an equimolar or more manner as in the above-mentioned method to produce a reaction product (intermediate) having 2 residual SiH groups at one end of the molecular chain, and then the SiH group at the end of the polymer of the reaction product (intermediate) and an organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule, such as allyltrimethoxysilane, are reacted in the presence of a hydrosilylation catalyst, such as a toluene solution of chloroplatinic acid/vinylsiloxane complex, at a temperature of 40 to 120 ℃, preferably 60 to 100 ℃, more preferably about 80 ℃, for 1 to 72 hours, preferably 20 to 36 hours, More preferably about 24 hours, while allowing the hydrosilylation addition reaction to proceed.
Among them, examples of the fluorooxyalkyl group-containing polymer having 2 olefin sites at one end of the molecular chain include a fluorooxyalkyl group-containing polymer represented by the following general formula (5).
[ solution 26]
(wherein Rf, Q, and R' are the same as defined above and Z is a 2-valent hydrocarbon group.)
In the formula (5), Z is a 2-valent hydrocarbon group, preferably a 2-valent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, and specifically, it includes an alkylene group having 1 to 8 carbon atoms such as methylene, ethylene, propylene (trimethylene and methylethylene), butylene (tetramethylene and methylpropylene), hexamethylene and octamethylene, and an alkylene group containing an arylene group having 6 to 8 carbon atoms such as phenylene (for example, an alkylenearylene group having 7 to 8 carbon atoms), and the like. Z is preferably a C1-4 linear alkylene group.
The fluorooxyalkyl group-containing polymer represented by the formula (5) is preferably a polymer shown below. In each of the formulae, the number of repetition (or polymerization degree) of each repeating unit constituting the fluorooxyalkyl group may be any number satisfying the formula (2) in the above Rf.
[ solution 27]
[ solution 28]
(wherein r1 is an integer of 1 to 100, and p1, q1 and p1+ q1 are the same as defined above.)
As a method for producing the fluorooxyalkyl group-containing polymer represented by the above formula (5), for example, a fluorooxyalkyl group-containing polymer having a hydroxyl group and 2 olefin sites at one terminal of the molecular chain (i.e., a polymer having a fluorooxyalkylene group-containing polymer residue having a valence of 1 and having 2 olefin sites and a hydroxyl group at one terminal of the molecular chain) and a hydrosilane are subjected to a dehydrogenation reaction in the presence of a dehydrogenation catalyst using a solvent at a temperature of 0 to 60 ℃, preferably 15 to 35 ℃, more preferably about 25 ℃ for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.
In addition, as another method of the method for producing the fluorooxyalkyl group-containing polymer represented by the above formula (5), a fluorooxyalkyl group-containing polymer having a hydroxyl group at one terminal of the molecular chain and 2 olefin sites (that is, a polymer having a fluorooxyalkylene group-containing polymer residue having a valence of 1 and having 2 olefin sites and a hydroxyl group at one terminal of the molecular chain) and, for example, a fluorooxyalkyl group-containing polymer having an acyl fluoride at one terminal of the molecular chain are subjected to dehydrohalogenation (dehydrofluorination) reaction in the presence of a base using a solvent at a temperature of 0 to 100 ℃, preferably 25 to 80 ℃, more preferably 60 ℃ for 1 to 48 hours, preferably 5 to 36 hours, more preferably about 20 hours.
In addition to the above-mentioned acid fluoride, other acid halides (for example, acid chloride), acid anhydrides, esters (for example, alkyl esters such as methyl ester), carboxylic acids, and the like can be used as the group at one terminal of the molecular chain of the fluorooxyalkyl group-containing polymer having the acid fluoride at one terminal of the molecular chain.
Specific examples of the perfluorooxyalkyl group-containing polymer having such a group (acid halide, acid anhydride, ester, carboxylic acid, etc.) at one terminal of the molecular chain include the following polymers.
[ solution 29]
(wherein p1, q1 and p1+ q1 are the same as defined above.)
The amount of the fluorooxyalkyl group-containing polymer having a functional group such as an acyl fluoride at one end of the molecular chain can be 0.5 to 1 equivalent, more preferably 0.8 to 1 equivalent, and still more preferably about 0.9 equivalent, to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain.
Examples of the base used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5) include amines, alkali metal bases, and the like, and specific examples of the amines include triethylamine, diisopropylethylamine, pyridine, DBU, imidazole, and the like. Examples of the alkali metal base include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, potassium tert-butoxide, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, and potassium bis (trimethylsilyl) amide.
The amount of the base used is 1 to 10 equivalents, preferably 1 to 3 equivalents, and more preferably about 2 equivalents, based on 1 equivalent of the reactive terminal group of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one terminal of the molecular chain.
In the preparation of the fluorooxyalkyl group-containing polymer represented by the above formula (5), the solvent to be used is preferably a fluorine-based solvent, and examples of the fluorine-based solvent include Hydrofluoroether (HFE) based solvents (Novec series, product name: manufactured by 3M company) such as 1, 3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, and perfluoro based solvents (フロリナート series, product name: manufactured by 3M company) composed of a completely fluorinated compound.
The amount of the solvent used may be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkylene group-containing polymer having 2 olefin sites at one end of the molecular chain.
Subsequently, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is washed with an organic solvent, and the solvent is distilled off to obtain a fluorooxyalkyl group-containing polymer represented by the formula (5).
Among them, as the raw material for the production of the fluorooxyalkyl group-containing polymer represented by the formula (5), a fluorooxyalkyl group-containing polymer having 2 olefin sites together with a hydroxyl group at one terminal of the molecular chain is specifically exemplified by the following polymers.
[ solution 30]
[ solution 31]
(wherein r1, p1, q1 and p1+ q1 are the same as defined above.)
The method for producing the raw material fluorooxyalkyl group-containing polymer having a hydroxyl group at one end of the molecular chain and 2 olefin moieties is, for example, a method in which a perfluorooxyalkyl group-containing polymer having an acyl fluoride group (-C (═ O) -F) at one end of the molecular chain, a grignard reagent having an olefin moiety as a nucleophilic agent, for example, 1, 3-bis (trifluoromethyl) benzene and tetrahydrofuran as a solvent are mixed and then cured at 0 to 80 ℃, preferably 50 to 70 ℃, more preferably about 60 ℃ for 1 to 6 hours, preferably 3 to 5 hours, more preferably about 4 hours, thereby causing a hydroxyl group to be present at one end of the molecular chain together with 2 olefin moieties.
Among them, the perfluorooxyalkyl group-containing polymer as a raw material used for the production of the above-mentioned fluorooxyalkyl group-containing polymer having a hydroxyl group at one terminal of the molecular chain and 2 olefin sites can use, as a group present at one terminal of the molecular chain, other acid halides (such as acid chloride), acid anhydrides, esters, carboxylic acids, amides, and the like, in addition to the above-mentioned acid fluoride.
Specific examples of the perfluorooxyalkyl group-containing polymer having these groups at one end of the molecular chain include the following polymers.
[ solution 32]
(wherein p1, q1 and p1+ q1 are the same as defined above.)
Examples of the nucleophilic agent used for the preparation of the above-mentioned fluorooxyalkyl group-containing polymer having a hydroxyl group at one terminal of the molecular chain and 2 olefin sites include allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, and 5-hexenyl magnesium halide. In addition, corresponding lithium reagents may also be used.
The amount of the nucleophilic agent to be used may be 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and still more preferably about 3 equivalents, based on 1 equivalent of the reactive end group of the above-mentioned perfluorooxyalkyl group-containing polymer.
Examples of the solvent used for the preparation of the fluorooxyalkyl group-containing polymer having a hydroxyl group at one terminal of the molecular chain and 2 olefin positions include Hydrofluoroether (HFE) solvents such as 1, 3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane (trade name: Novec series, manufactured by 3M), and perfluoro solvents composed of a completely fluorinated compound (trade name: フロリナート series, manufactured by 3M). Further, as the organic solvent, ether solvents such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used.
The amount of the solvent used may be 10 to 300 parts by mass, preferably 100 to 200 parts by mass, and more preferably about 150 parts by mass, based on 100 parts by mass of the perfluorooxyalkyl group-containing polymer.
Subsequently, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluorooxyalkyl group-containing polymer having a hydroxyl group at one terminal of the molecular chain.
Examples of the hydrosilane used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5) include a polydimethylsiloxane-terminal hydrosilane having 2 to 40 silicon atoms, one of the terminal groups of which is blocked with an alkyl group, and a polydimethylsiloxane-terminal hydrosilane having 2 to 40 silicon atoms, one of the terminal groups of which is blocked with a fluoroalkyl group or a fluorooxyalkyl group.
Specific examples of the hydrosilane used for the production of the fluorooxyalkyl group-containing polymer represented by the formula (5) include hydrosilanes as shown below.
[ solution 33]
(wherein p1, q1 and p1+ q1 are the same as defined above.)
The amount of the hydrosilane used is 1 to 5 equivalents, more preferably 1 to 2 equivalents, and still more preferably about 1.2 equivalents, relative to 1 equivalent of the reactive end group of the fluorooxyalkyl group-containing polymer having 2 olefin sites and a hydroxyl group at one end of the molecular chain.
As the dehydrogenation catalyst used for the production of the fluorooxyalkyl group-containing polymer represented by the formula (5), for example, a platinum group metal-based catalyst such as rhodium, palladium, ruthenium and the like, a boron catalyst and the like can be used, and specific examples thereof include a platinum group metal-based catalyst such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium and the like, a boron catalyst such as tris (pentafluorophenyl) borane and the like.
The amount of the dehydrogenation catalyst used is 0.01 to 0.0005 equivalent, preferably 0.007 to 0.001 equivalent, and more preferably about 0.005 equivalent to 1 equivalent of the reactive terminal group of the fluorooxyalkyl group-containing polymer having 2 olefin sites and a hydroxyl group at one end of the molecular chain.
As the solvent used for the preparation of the fluorooxyalkyl group-containing polymer represented by the formula (5), examples of the fluorine-based solvent include a fluorine-containing aromatic hydrocarbon-based solvent such as 1, 3-bis (trifluoromethyl) benzene or trifluoromethylbenzene, a Hydrofluoroether (HFE) based solvent (Novec series, trade name: manufactured by 3M company) such as methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, and a perfluoro-based solvent (フロリナート series, trade name: manufactured by 3M company) composed of a completely fluorinated compound. Further, as the organic solvent, ether solvents such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used.
The amount of the solvent used may be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkyl group-containing polymer having 2 olefin sites together with a hydroxyl group at one end of the molecular chain.
Subsequently, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain a fluorooxyalkyl group-containing polymer represented by the formula (5).
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) wherein α is 1, the solvent to be used is preferably a fluorine-based solvent, and examples of the fluorine-based solvent include Hydrofluoroether (HFE) based solvents (Novec series, product name: manufactured by 3M company), perfluoro-based solvents (フロリナート series, product name: manufactured by 3M company) such as 1, 3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, and the like.
The amount of the solvent used may be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkyl group-containing polymer having 2 olefin sites at one end of the molecular chain.
In the production of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule is preferably a compound represented by the following general formulae (6) to (9).
[ chemical 34]
(wherein R, X, n, R1、R2G, j are the same as above. R3Is a C2-C8C 2-valent hydrocarbon group. i is an integer of 2 to 9, preferably an integer of 2 to 4, and i + j is an integer of 2 to 9. )
Wherein, as R3Examples of the 2-valent hydrocarbon group having 2 to 8 carbon atoms, preferably 2 to 3 carbon atoms, include an alkylene group such as a methylene group, an ethylene group, a propylene group (a trimethylene group, a methylethylene group), a butylene group (a tetramethylene group, a methylpropylene group), a hexamethylene group, an octamethylene group, and the like, an arylene group such as a phenylene group, or a combination of 2 or more of these groups (an alkylene-arylene group and the like), and among these, an ethylene group and a trimethylene group are preferable.
Examples of the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following organosilicon compounds.
[ solution 35]
In the production of the fluoropolyether group-containing polymer-modified silane represented by formula (1) wherein α is 1, the amount of the organosilicon compound having an SiH group and a hydrolyzable end group in the molecule used in the reaction of the fluorooxyalkyl group-containing polymer having 2 olefin moieties at one end of the molecular chain with the organosilicon compound having an SiH group and a hydrolyzable end group in the molecule can be 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, and still more preferably about 3 equivalents, relative to 1 equivalent of the reactive end group of the fluorooxyalkyl group-containing polymer having 2 olefin moieties at one end of the molecular chain.
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by formula (1) wherein α is 1, the organosilicon compound having 2 or more SiH groups without a hydrolyzable terminal group in the molecule is preferably a compound represented by the following general formulae (10) to (12).
[ solution 36]
(in the formula, R1、R2G, j, i are the same as above. )
Examples of the organosilicon compound having 2 or more SiH groups without a hydrolyzable terminal group in the molecule include organosilicon compounds shown below.
[ solution 37]
In the production of the fluoropolyether group-containing polymer-modified silane represented by formula (1) wherein α is 1, the amount of the organosilicon compound having 2 or more SiH groups and having no hydrolyzable end group in the molecule when the fluorinated oxyalkyl group-containing polymer having 2 olefin moieties at one end of the molecular chain is reacted with the organic silicon compound having 2 or more SiH groups and having no hydrolyzable end group in the molecule can be 5 to 20 equivalents, more preferably 7.5 to 12.5 equivalents, and still more preferably about 10 equivalents, relative to 1 equivalent of the reactive end group of the fluorinated oxyalkyl group-containing polymer having 2 olefin moieties at one end of the molecular chain.
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule is preferably a compound represented by the following general formula (13).
[ solution 38]
(wherein R, X, n is the same as above, V is a single bond or a C1-6 2-valent hydrocarbon group.)
In the formula (13), V is a single bond or a 2-valent hydrocarbon group having 1 to 6 carbon atoms, and specific examples of the 2-valent hydrocarbon group having 1 to 6 carbon atoms include alkylene groups such as methylene, ethylene, propylene (trimethylene and methylethylene), butylene (tetramethylene and methylpropylene), and hexamethylene, and phenylene. The V is preferably a single bond or a methylene group.
In the preparation of a fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, the amount of the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule when the reactant of the fluorooxyalkyl group-containing polymer having 2 olefin moieties at one end of the molecular chain and the organosilicon compound having no hydrolyzable end group and 2 or more SiH groups in the molecule is reacted with the organosilicon compound having an olefin moiety and a hydrolyzable end group in the molecule can be 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, and still more preferably about 3 equivalents, to 1 equivalent of the reactive end group of the reactant of the fluorooxyalkyl group-containing polymer having 2 olefin moieties at one end of the molecular chain and the organosilicon compound having 2 or more SiH groups in the molecule.
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 1, examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified products of chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylenic alcohols, and the like, and platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, and the like. Preferred are platinum group compounds such as vinylsiloxane complex.
The amount of the hydrosilylation catalyst used is 0.1 to 100ppm, preferably 1 to 50ppm, in terms of transition metal (mass), based on the amount of substance of a polymer containing a fluorooxyalkyl group having 2 olefin sites at one end of the molecular chain or the reaction product of the polymer and an organosilicon compound having 2 or more SiH groups and having no hydrolyzable terminal group in the molecule.
Then, the solvent and the unreacted material are distilled off under reduced pressure, whereby the target compound can be obtained.
For example, as the polymer containing a fluorooxyalkyl group having 2 olefin sites at one terminal of the molecular chain, a compound represented by the following formula is used
[ solution 39]
When trimethoxysilane is used as the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, a compound represented by the following formula is obtained.
[ solution 40]
Examples of the method for producing the fluoropolyether group-containing polymer-modified silane represented by the formula (1) below, wherein α is 2, include the following methods.
A fluorooxyalkylene group-containing polymer having 2 oxyalkylene sites at both ends of a molecular chain (that is, a polymer having 2-valent fluorooxyalkylene group-containing polymer residues and 2 olefin sites at both ends of the molecular chain) is dissolved in a solvent such as a fluorine-based solvent (e.g., 1, 3-bis (trifluoromethyl) benzene), and an organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, such as trimethoxysilane, is cured at a temperature of 40 to 120 ℃, preferably 60 to 100 ℃, more preferably about 80 ℃ for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours, in the presence of a hydrosilylation reaction catalyst such as a toluene solution of chloroplatinic acid/vinylsiloxane complex.
In addition, an SiH group-containing organosilicon compound having no hydrolyzable terminal group may be used instead of the above-described organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, and in this case, an organosilicon compound having 2 or more SiH groups and having no hydrolyzable terminal groups in the molecule may be used as the organosilicon compound. In this case, similarly to the above-mentioned method, a fluorooxyalkylene group-containing polymer having 2 olefin sites at each of both ends of the molecular chain is reacted with an organic silicon compound having 2 or more SiH groups without a hydrolyzable terminal group in the molecule in an equimolar or more ratio to produce a reactant (intermediate) having 2 residual SiH groups at each of both ends of the molecular chain, the SiH group at the polymer terminal of the reaction product (intermediate) is aged with an organosilicon compound having an olefin portion and a hydrolyzable terminal group in the molecule, such as allyltrimethoxysilane, in the presence of a hydrosilylation catalyst, for example, a toluene solution of chloroplatinic acid/vinylsiloxane complex, at a temperature of 40 to 120 ℃, preferably 60 to 100 ℃, more preferably about 80 ℃ for 1 to 72 hours, preferably 20 to 36 hours, more preferably about 24 hours.
Among them, as the fluorooxyalkylene group-containing polymer having 2 olefin portions at both ends of the molecular chain, a fluorooxyalkylene group-containing polymer represented by the following general formula (14) can be exemplified.
[ solution 41]
(wherein Rf, Z, Q and R' are the same as defined above.)
The fluorooxyalkylene group-containing polymer represented by the formula (14) is preferably a polymer shown below. In each of the formulae, the number of repetition (or polymerization degree) of each repeating unit constituting the fluorooxyalkylene group may be any number satisfying the formula (3) in the above Rf.
[ solution 42]
p1∶q1＝47∶53，p1+q1≈43
p1∶q1＝47∶53，p1+q1≈43
p1∶q1＝47∶53，p1+q1≈43
p1∶q1＝47∶53，p1+q1≈43
(wherein p1, q1 and p1+ q1 are the same as defined above.)
As a method for producing the fluorooxyalkylene group-containing polymer represented by the above formula (14), for example, a fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of a molecular chain and having 2 olefin sites at both ends of the molecular chain (i.e., a polymer having 2-valent fluorooxyalkylene group-containing polymer residues and having 2 olefin sites at both ends of the molecular chain and having hydroxyl groups) and hydrosilane are subjected to a dehydrogenation reaction in the presence of a dehydrogenation catalyst using a solvent at a temperature of 0 to 60 ℃, preferably 15 to 35 ℃, more preferably about 25 ℃ for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.
In addition, as another method of the method for producing the fluorooxyalkylene group-containing polymer represented by the above formula (14), a fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of a molecular chain and 2 olefin sites at both ends of the molecular chain (that is, a polymer having 2-valent fluorooxyalkylene group-containing polymer residues and 2 olefin sites and hydroxyl groups at both ends of the molecular chain) and, for example, a fluorooxyalkyl group-containing polymer having acyl fluoride at one end of the molecular chain are subjected to dehydrohalogenation (dehydrofluorination) reaction in the presence of a base using a solvent at a temperature of 0 to 100 ℃, preferably 25 to 80 ℃, more preferably 60 ℃, for 1 to 48 hours, preferably 5 to 36 hours, more preferably about 20 hours.
Among these, the fluorooxyalkyl group-containing polymer having an acyl fluoride at one terminal of the molecular chain may use, in addition to the above-mentioned acyl fluoride, an acid halide, an acid anhydride, an ester, a carboxylic acid or the like as a group at one terminal of the molecular chain.
Specific examples of the perfluorooxyalkyl group-containing polymer having such a group (acid halide, acid anhydride, ester, carboxylic acid, etc.) at one terminal of the molecular chain include the following polymers.
[ solution 43]
(wherein p1, q1 and p1+ q1 are the same as defined above.)
The amount of the fluorooxyalkyl group-containing polymer having an acyl fluoride at one terminal of the molecular chain can be 0.5 to 1 equivalent, more preferably 0.8 to 1 equivalent, and still more preferably about 0.9 equivalent, to 1 equivalent of the reactive terminal group (hydroxyl group) of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both terminals of the molecular chain.
Examples of the base used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (14) include amines, alkali metal bases, and the like, and specific examples of the amines include triethylamine, diisopropylethylamine, pyridine, DBU, imidazole, and the like. Examples of the alkali metal base include sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, alkyllithium, potassium tert-butoxide, lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, and potassium bis (trimethylsilyl) amide.
The amount of the base used is 1 to 10 equivalents, more preferably 1 to 3 equivalents, and still more preferably about 2 equivalents, based on 1 equivalent of the reactive terminal group of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain.
In the preparation of the fluorooxyalkylene group-containing polymer represented by the above formula (14), a fluorine-based solvent is preferred, and examples of the fluorine-based solvent include Hydrofluoroether (HFE) based solvents (Novec series, trade name, manufactured by 3M company) such as 1, 3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, and perfluoro based solvents (Novec series, manufactured by 3M company, trade name: フロリナート series, manufactured by 3M company) comprising a completely fluorinated compound.
The amount of the solvent used may be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain.
Subsequently, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off, thereby obtaining a fluorooxyalkylene group-containing polymer represented by the formula (14).
Among them, as the fluorooxyalkylene group-containing polymer having hydroxyl groups at both molecular chain terminals and having 2 olefin sites at each of both molecular chain terminals used in the production of the fluorooxyalkylene group-containing polymer represented by the formula (14), specifically, the following polymers can be exemplified.
[ solution 44]
(wherein p1, q1 and p1+ q1 are the same as defined above.)
Among them, as the above-mentioned method for producing a fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain and 2 olefin moieties at each end of the molecular chain, for example, a perfluorooxyalkylene group-containing polymer having an acyl fluoride group (-C (═ O) -F) at both ends of the molecular chain, a grignard reagent having an olefin moiety as a nucleophilic agent, for example, 1, 3-bis (trifluoromethyl) benzene and tetrahydrofuran as a solvent are mixed and then cured at 0 to 80 ℃, preferably 50 to 70 ℃, more preferably about 60 ℃ for 1 to 6 hours, preferably 3 to 5 hours, more preferably about 4 hours, to introduce the hydroxyl groups together with 2 olefin moieties to both ends of the molecular chain.
In addition to the above-mentioned acid fluoride, an acid halide, an acid anhydride, an ester, a carboxylic acid, an amide, or the like can be used as the polymer containing a perfluoroalkoxyalkylene group as a group at both ends of the molecular chain.
Specific examples of the perfluorooxyalkylene group-containing polymer having these groups at both ends of the molecular chain include the following polymers.
[ solution 45]
(wherein p1, q1 and p1+ q1 are the same as defined above.)
As the nucleophilic agent used for the preparation of the above-mentioned fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain, allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenyl magnesium halide and the like can be used. In addition, corresponding lithium reagents may also be used.
The amount of the nucleophilic agent to be used may be 4 to 10 equivalents, more preferably 5 to 7 equivalents, and still more preferably about 6 equivalents, based on 1 equivalent of the reactive end group of the above-mentioned perfluorooxyalkylene group-containing polymer.
Further, as the solvent used for the preparation of the above-mentioned fluorooxyalkylene group-containing polymer having hydroxyl groups at both terminals of the molecular chain, there may be mentioned, as the fluorine-based solvent, a Hydrofluoroether (HFE) based solvent (Novec series, trade name: manufactured by 3M company) such as 1, 3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, methylnonafluorobutyl ether, methylnonafluoroisobutyl ether, ethylnonafluorobutyl ether, ethylnonafluoroisobutyl ether, 1, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, a perfluoro-based solvent (Novec series, manufactured by 3M company, trade name: フロリナート series) composed of a completely fluorinated compound, and the like. Further, as the organic solvent, ether solvents such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used.
The amount of the solvent used is 10 to 300 parts by mass, preferably 100 to 200 parts by mass, and more preferably about 150 parts by mass, based on 100 parts by mass of the perfluorooxyalkylene group-containing polymer.
Subsequently, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off to obtain the above-mentioned fluorooxyalkylene group-containing polymer having hydroxyl groups at both molecular chain terminals.
Examples of the hydrosilane used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (14) include a polydimethylsiloxane-terminal hydrosilane having 2 to 40 silicon atoms, one of the terminal groups of which is blocked with an alkyl group, and a polydimethylsiloxane-terminal hydrosilane having 2 to 40 silicon atoms, one of the terminal groups of which is blocked with a fluoroalkyl group or a fluorooxyalkyl group.
The amount of hydrosilane used is 1 to 5 equivalents, more preferably 1 to 2 equivalents, and still more preferably about 1.2 equivalents, relative to 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having a hydroxyl group at one end of the molecular chain and 2 olefin sites at each end of the molecular chain.
As the dehydrogenation catalyst used for the production of the fluorooxyalkylene group-containing polymer represented by the formula (14), for example, a platinum group metal-based catalyst such as rhodium, palladium, ruthenium and the like, a boron catalyst and the like can be used, and specific examples thereof include a platinum group metal-based catalyst such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium and the like, a boron catalyst such as tris (pentafluorophenyl) borane and the like.
The amount of the dehydrogenation catalyst used is 0.01 to 0.0005 equivalent, more preferably 0.007 to 0.001 equivalent, and still more preferably about 0.005 equivalent to 1 equivalent of the reactive terminal group of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain and 2 olefin sites at both ends of the molecular chain.
Examples of the solvent used for the preparation of the fluorooxyalkylene group-containing polymer represented by the formula (14) include a fluorine-containing aromatic hydrocarbon-based solvent such as 1, 3-bis (trifluoromethyl) benzene and trifluoromethylbenzene, a Hydrofluoroether (HFE) based solvent (Novec series, trade name: manufactured by 3M company) such as methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane, and a perfluoro-based solvent (フロリナート series, trade name: manufactured by 3M company) composed of a completely fluorinated compound. Further, as the organic solvent, ether solvents such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane can be used.
The amount of the solvent used may be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkylene group-containing polymer having hydroxyl groups at both ends of the molecular chain and having 2 olefin sites at each of both ends of the molecular chain.
Subsequently, the reaction was stopped, and the aqueous layer and the fluorine solvent layer were separated by a liquid separation operation. The obtained fluorine solvent layer is further washed with an organic solvent, and the solvent is distilled off, thereby obtaining a fluorooxyalkylene group-containing polymer represented by the formula (14).
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the above formula (1) wherein α is 2, the solvent to be used is preferably a fluorine-based solvent, and examples of the fluorine-based solvent include Hydrofluoroether (HFE) based solvents (Novec series, product name: manufactured by 3M company), perfluorobased solvents (product name: フロリナート series, manufactured by 3M company) composed of a completely fluorinated compound, and the like, such as 1, 3-bis (trifluoromethyl) benzene, trifluoromethylbenzene, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane.
The amount of the solvent used may be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, based on 100 parts by mass of the fluorooxyalkylene group-containing polymer having 2 olefin sites at each end of the molecular chain.
In the production of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule is preferably a compound represented by the following general formulae (6) to (9).
[ solution 46]
(in the formula, wherein,R、X、n、R1、R2、R3g, i, j are the same as described above. )
Examples of the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following organosilicon compounds.
[ solution 47]
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by formula (1) wherein α is 2, the amount of the organosilicon compound having SiH groups and a hydrolyzable end group in the molecule when the fluorooxyalkylene group-containing polymer having 2 olefin moieties at each end of the molecular chain is reacted with the organosilicon compound having SiH groups and a hydrolyzable end group in the molecule can be 2 to 6 equivalents, more preferably 2.2 to 3.5 equivalents, and still more preferably about 3 equivalents, relative to 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having 2 olefin moieties at each end of the molecular chain.
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by formula (1) wherein α is 2, compounds represented by the following general formulae (10) to (12) are preferred as the organosilicon compound having not a hydrolyzable terminal group in the molecule but having 2 or more SiH groups.
[ solution 48]
(in the formula, R1、R2G, j, i are the same as above. )
Examples of the organosilicon compound having 2 or more SiH groups without a hydrolyzable terminal group in the molecule include organosilicon compounds shown below.
[ solution 49]
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by formula (1) wherein α is 2, the amount of the silicone compound having 2 or more SiH groups and having no hydrolyzable end group in the molecule when the fluorooxyalkylene group-containing polymer having 2 or more SiH groups and having 2 or more terminal groups at both ends of the molecule chain are reacted with the silicone compound having no hydrolyzable end group in the molecule can be 5 to 20 equivalents, more preferably 7.5 to 12.5 equivalents, and still more preferably about 10 equivalents, relative to 1 equivalent of the reactive end group of the fluorooxyalkylene group-containing polymer having 2 olefin positions at both ends of the molecule chain.
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule is preferably a compound represented by the following general formula (13).
[ solution 50]
(wherein R, X, V, n is the same as defined above.)
In the preparation of a fluoropolyether group-containing polymer-modified silane represented by formula (1) wherein α is 2, the amount of the reactant (intermediate) of a fluorooxyalkylene group-containing polymer having 2 olefin moieties at both ends of the molecular chain and an organosilicon compound having 2 or more SiH groups and having no hydrolyzable terminal group in the molecule is reacted with the organosilicon compound having an olefin moiety and a hydrolyzable terminal group in the molecule, and 2 to 6 equivalents of the amount of the reactant (intermediate) of a fluorooxyalkylene group-containing polymer having 2 olefin moieties at both ends of the molecular chain and an organosilicon compound having 2 or more SiH groups and having no hydrolyzable terminal group in the molecule are used with respect to 1 equivalent of the reactive terminal group of the reactant (intermediate) of the fluorooxyalkylene group-containing polymer having 2 olefin moieties at both ends of the molecular chain and the organosilicon compound having 2 or more SiH groups in the molecule, more preferably 2.2 to 3.5 equivalents, and still more preferably about 3 equivalents.
In the preparation of the fluoropolyether group-containing polymer-modified silane represented by the formula (1) wherein α is 2, examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified products of chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylenic alcohols, and the like, and platinum group metal catalysts such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, and the like. Preferred are platinum group compounds such as vinylsiloxane complex.
The amount of the hydrosilylation catalyst used is 0.1 to 100ppm, more preferably 1 to 50ppm, in terms of transition metal (mass), based on the mass of the fluorooxyalkylene group-containing polymer having 2 olefin sites at each end of the molecular chain, or the mass of the reaction product (intermediate) of the polymer and the organosilicon compound having 2 or more SiH groups and no hydrolyzable end groups in the molecule.
Then, the solvent and the unreacted material are distilled off under reduced pressure, whereby the target compound can be obtained.
For example, as the fluorooxyalkylene group-containing polymer having 2 olefin sites at both ends of the molecular chain, a compound represented by the following formula is used
[ solution 51]
p1∶q1＝47∶53,p1+q1≈43
When trimethoxysilane is used as the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, a compound represented by the following formula is obtained.
[ solution 52]
p1∶q1＝47∶53，p1+q1≈43
The present invention also provides a surface treatment agent containing the above-mentioned polymer-modified silane containing a fluoropolyether group. The surface treatment agent may be a product obtained by partially hydrolyzing the terminal hydrolyzable group of the fluoropolyether group-containing polymer-modified silane in advance by a known method to form a hydroxyl group, that is, a product obtained by hydrolyzing a part of the hydrolyzable group of X in the fluoropolyether group-containing polymer-modified silane represented by the formula (1) to form a hydroxyl group.
The surface-treating agent may contain, as necessary, a hydrolytic condensation catalyst, for example, an organotin compound (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), an organotitanium compound (e.g., tetra-n-butyl titanate), an organic acid (e.g., acetic acid, methanesulfonic acid, or fluorine-modified carboxylic acid), and an inorganic acid (e.g., hydrochloric acid or sulfuric acid). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, and the like are particularly preferable.
The addition amount of the hydrolysis condensation catalyst is a catalyst amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, based on 100 parts by mass of the fluoropolyether group-containing polymer-modified silane.
The surface treatment agent may contain an appropriate solvent. Examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (e.g., perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (e.g., 1, 3-bis (trifluoromethyl) benzene), fluorine-modified ether solvents (e.g., methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (e.g., perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (e.g., petroleum spirit, toluene, xylene, etc.), and ketone solvents (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, fluorine-modified solvents are preferable from the viewpoint of solubility, wettability, and the like, and 1, 3-bis (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are particularly preferable.
The solvent may be a mixture of 2 or more kinds thereof, and preferably the polymer-modified silane containing a fluoropolyether group is uniformly dissolved. The optimum concentration of the fluoropolyether group-containing polymer-modified silane dissolved in the solvent varies depending on the treatment method, but may be an amount that can be easily weighed, and in the case of direct coating, the concentration is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass, based on the total mass of the solvent and the fluoropolyether group-containing polymer-modified silane, and in the case of vapor deposition treatment, the concentration is preferably 1 to 100% by mass, and more preferably 3 to 30% by mass, based on the total mass of the solvent and the fluoropolyether group-containing polymer-modified silane.
The surface treatment agent of the present invention can be applied to a substrate by a known method such as brush coating, dipping, spraying, or vapor deposition. The heating method in the vapor deposition treatment is not particularly limited, and may be any of a resistance heating method and an electron beam heating method. The curing temperature varies depending on the curing method, and is preferably in the range of 20 to 200 ℃ when applied by, for example, vapor deposition. Alternatively, it may be solidified under humidification. The thickness of the cured coating is suitably selected depending on the type of the substrate, and is usually 0.1 to 100nm, particularly 1 to 20 nm.
The substrate to be treated with the surface treatment agent of the present invention is not particularly limited, and may be a substrate made of various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, and quartz. The surface treatment agent of the present invention can impart water-and oil-repellency to the substrate. In particular, it can be suitably used as a material subjected to SiO2The surface treatment agent for glass and film to be treated is used.
Examples of the article treated with the surface treatment agent of the present invention include medical instruments such as car navigation, cellular phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, spectacle lenses, camera lenses, filters, sunglasses, and gastroscopes, and optical articles such as copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the above-mentioned articles, and can impart scratch resistance, and therefore, is useful particularly as a water-and oil-repellent layer for touch panel displays, antireflection films, and the like.
The surface treatment agent of the present invention is also useful as an antifouling paint for sanitary products such as bath tubs and wash tables, an antifouling paint for window glasses or tempered glass of automobiles, electric trains, aircrafts, and the like, an antifouling paint for exterior wall building materials, an antifouling paint for kitchen building materials, an antifouling and poster-proof paint for telephone boxes, a paint for providing fingerprint-proof property for art products and the like, a fingerprint-proof paint for CDs, DVDs, and the like, a mold release agent or a paint additive, a resin modifier, a fluidity modifier or a dispersibility modifier for inorganic fillers, and a lubricity improver for tapes, films, and the like.
Examples
The present invention will be described in more detail below by way of examples and comparative examples, but the present invention is not limited to the following examples.
[ example 1]
In a reaction vessel, 100g of 1, 3-bis (trifluoromethyl) benzene and 0.01g (2.0X 10) of tris (pentafluorophenyl) borane were placed- 5mol) of the following formula (A)
[ Hua 53]
The compound represented by (1) 100g (2.7X 10)-2mol) and slowly dropped into the mixture of the following formula (B)
[ solution 54]
13.6g (3.3X 10) of the indicated silane-2mol) and stirred at 25 ℃ for 1 hour. Then, water was added, and the fluorine compound layer as the lower layer was recovered by a liquid separation operation, followed by washing with acetoneAnd (3) cleaning. The cleaned fluorine compound layer as the lower layer was collected again, and the residual solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (C)
[ solution 55]
The expression "fluoropolymer having a fluoropolyether group" means 103 g.
1H-NMR
δ0-0.2(-OSi(CH 3)3)24H
δ0.5-0.7(-SiC 2HCH2CH2CH3)2H
δ0.8-1.0(-SiCH2CH2CH2C 3H)3H
δ1.2-1.4(-SiCH2C 2HC 2HCH3)4H
δ2.4-2.6(-CH 2CH＝CH2)4H
δ4.9-5.1(-CH2CH＝CH 2)4H
δ5.7-5.9(-CH2CH＝CH2)2H
The reaction vessel is prepared from the following formula (C)
[ solution 56]
90g (2.4X 10) of the compound represented-2mol), 90g of 1, 3-bis (trifluoromethyl) benzene, 9g (7.4X 10) of trimethoxysilane-2mol) and chloroplatinic acid/vinylsiloxane complex 9.0X 10 toluene solution-2g (calculated by Pt simple substance, 2.4X 10)-6mol), and aging at 80 ℃ for 24 hours. Then, the solvent and the unreacted materials were distilled off under reduced pressure to obtain 88g of a liquid product.
It was confirmed by NMR that the obtained compound had a structure represented by the following formula (D).
[ solution 57]
1H-NMR
δ0-0.2(-OSi(CH 3)3)24H
δ0.5-0.7(-SiC 2HCH2CH2CH3，-CH2CH2CH 2-Si(OCH3)3)6H
δ0.8-1.0(-SiCH2CH2CH2C 3H)3H
δ1.3-1.4(-SiCH2C 2HC 2HCH3)4H
δ1.5-1.9(-CH2CH 2CH2-Si(OCH3)3，-CH 2CH2CH2-Si(OCH3)3)8H
δ3.4-3.7(-Si(OCH 3)3)18H
[ example 2]
In a reaction vessel, 100g of 1, 3-bis (trifluoromethyl) benzene and 0.01g (2.0X 10) of tris (pentafluorophenyl) borane were placed- 5mol) of the following formula (A)
[ solution 58]
The compound represented by (1) 100g (2.7X 10)-2mol) and slowly dropped into the mixture of the following formula (E)
[ chemical 59]
Expressed silane 25.0g (3.3X 10)-2mol) and stirred at 25 ℃ for 1 hour. Is connected withThen, water was added, and the lower fluorine compound layer was collected by a liquid separation operation and washed with acetone. The cleaned fluorine compound layer as the lower layer was recovered again, and the residual solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (F)
[ solution 60]
125g of the fluoropolymer having a fluoropolyether group was represented.
1H-NMR
δ0-0.2(-OSi(CH 3)3)60H
δ0.5-0.7(-SiC 2HCH2CH2CH3)2H
δ0.8-1.0(-SiCH2CH2CH2C 3H)3H
δ1.2-1.4(-SiCH2C 2HC 2HCH3)4H
δ2.4-2.6(-CH 2CH＝CH2)4H
δ4.9-5.1(-CH2CH＝CH 2)4H
δ5.7-5.9(-CH2CH＝CH2)2H
In the reaction vessel, the reaction vessel is prepared from the following formula (F)
[ solution 61]
90g (2.4X 10) of the compound represented-2mol), 90g of 1, 3-bis (trifluoromethyl) benzene, 9g (7.4X 10) of trimethoxysilane-2mol) and chloroplatinic acid/vinylsiloxane complex 9.0X 10 in toluene-2g (calculated by Pt simple substance, 2.4X 10)-6mol) and aging at 80 ℃ for 24 hours. Then, the solvent and the unreacted materials were distilled off under reduced pressure to obtain 76g of a liquid product.
It was confirmed by NMR that the obtained compound had a structure represented by the following formula (G).
[ solution 62]
1H-NMR
δ0-0.2(-OSi(CH 3)3)60H
δ0.5-0.7(-SiC 2HCH2CH2CH3，-CH2CH2CH 2-Si(OCH3)3)6H
δ0.8-1.0(-SiCH2CH2CH2C 3H)3H
δ1.3-1.4(-SiCH2C 2HC 2HCH3)4H
δ1.5-1.9(-CH2CH 2CH2-Si(OCH3)3，-CH 2CH2CH2-Si(OCH3)3)8H
δ3.4-3.7(-Si(OCH 3)3)18H
[ example 3]
In a reaction vessel, 100g of 1, 3-bis (trifluoromethyl) benzene and 0.01g (2.0X 10) of tris (pentafluorophenyl) borane were placed- 5mol) of the formula (H)
[ solution 63]
p1∶q1＝47∶53，p1+q1≈43
The compound represented by (1) 100g (2.6X 10)-2mol) and slowly dropped with a compound represented by the following formula (B)
[ solution 64]
27.2g (6.6X 10) of the indicated silane-2mol) and stirred at 25 ℃ for 1 hour. Next, water was added, and the fluorine compound layer as the lower layer was collected by a liquid separation operation and washed with acetone. The lower layer after washing, i.e., the fluorine compound layer, was recovered again, and the residual solvent was distilled off under reduced pressure to obtain a fluorine-containing polymer represented by the following formula (I)
[ solution 65]
p1∶q1＝47∶53，p1+q1≈43
105g of the illustrated fluoropolymer having a fluoropolyether group.
1H-NMR
δ0-0.2(-OSi(CH 3)3)48H
δ0.5-0.7(-SiC 2HCH2CH2CH3)4H
δ0.8-1.0(-SiCH2CH2CH2C 3H)6H
δ1.2-1.4(-SiCH2C 2HC 2HCH3)8H
δ2.4-2.6(-CH 2CH＝CH2)8H
δ4.9-5.1(-CH2CH＝CH 2)8H
δ5.7-5.9(-CH2CH＝CH2)4H
In a reaction vessel, a reaction vessel comprising a reaction product of the following formula (I)
[ solution 66]
p1∶q1＝47∶53，p1+q1≈43
90g (2.3X 10) of the compound represented-2mol), 90g of 1, 3-bis (trifluoromethyl) benzene, trisMethoxysilane 8.4g (6.9X 10)-2mol) and chloroplatinic acid/vinylsiloxane complex 8.4X 10 in toluene-2g (calculated by Pt simple substance, contains 2.3X 10)-6mol) and aging at 80 ℃ for 24 hours. Then, the solvent and the unreacted materials were distilled off under reduced pressure to obtain 93g of a liquid product.
It was confirmed by NMR that the obtained compound had a structure represented by the following formula (J).
[ solution 67]
p1∶q1＝47∶53，p1+q1≈43
1H-NMR
δ0-0.2(-OSi(CH 3)3)48H
δ0.5-0.7(-SiC 2HCH2CH2CH3，-CH2CH2CH 2-Si(OCH3)3)12H
δ0.8-1.0(-SiCH2CH2CH2C 3H)6H
δ1.3-1.4(-SiCH2C 2HC 2HCH3)8H
δ1.5-1.9(-CH2CH 2CH2-Si(OCH3)3，-CH 2CH2CH2-Si(OCH3)3)16H
δ3.4-3.7(-Si(OCH 3)3)36H
[ example 4]
In a reaction vessel, 30g of 1, 3-bis (trifluoromethyl) benzene, a 3.0X 10 toluene solution of chloroplatinic acid/vinyl siloxane complex-2g (calculated by Pt simple substance, containing 8.2X 10)-7mol), 9.0g (4.5X 10) of tetramethyldisiloxane-2mol) and slowly dropped into the mixture of the following formula (K)
[ solution 68]
p1∶q1＝47∶53，p1+q1≈43
30g (9.0X 10) of the compound represented-3mol) and stirred at 25 ℃ for 1 hour. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 31g of a liquid product.
It was confirmed by NMR that the obtained compound had a structure represented by the following formula (L).
[ solution 69]
p1∶q1＝47∶53，p1+q1≈43
1H-NMR
δ0-0.2(-OSi(CH 3)3)12H
δ0.5-0.7(-OCH2CH2CH 2-Si)2H
δ1.6-1.8(-OCH2CH 2CH2-Si)2H
δ3.5-3.6(-OCH 2CH 2 CH2-Si)2H
δ3.7-3.8(-C2F2CH 2O-)2H
δ4.7-4.8(-Si-H)1H
In a reaction vessel, 10g of 1, 3-bis (trifluoromethyl) benzene and 2.8X 10g of tris (pentafluorophenyl) borane were placed-3g(5.4×10-5mol) of the following formula (A)
[ solution 70]
10g (2.7X 10) of the compound represented-3mol) are mixed and slowly added dropwise with a mixture of the following formula (L)
[ solution 71]
p1∶q1＝47∶53，p1+q1≈43
11.7g (2.7X 10) of the compound shown-3mol) and stirred at 25 ℃ for 1 hour. Next, water was added, and the fluorine compound layer as the lower layer was collected by a liquid separation operation and washed with acetone. The lower layer after washing, i.e., the fluorine compound layer, was recovered again, and the residual solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (M)
[ chemical formula 72]
20g of the illustrated fluoropolymer containing a fluoropolyether group.
1H-NMR
δ0-0.2(-OSi(CH 3)2)12H
δ0.5-0.7(-OCH2CH2CH 2-Si)2H
δ1.6-1.8(-OCH2CH 2CH2-Si)2H
δ2.5-2.7(-CH 2CH＝CH2)4H
δ3.4-3.6(-OCH 2CH 2 CH2-Si)2H
δ3.6-3.8(-C2F2CH 2O-)2H
δ5.0-5.2(-CH2CH＝CH 2)4H
δ5.7-5.9(-CH2CH＝CH2)2H
In the reaction vessel, the reaction vessel is prepared from the following formula (M)
[ solution 73]
15g (2.0X 10) of the compound represented-3mol), 15g of 1, 3-bis (trifluoromethyl) benzene, 0.73g (6.0X 10) of trimethoxy silane-3mol) and a 2.0X 10 toluene solution of chloroplatinic acid/vinylsiloxane complex-2g (calculated by Pt simple substance, contains 5.3X 10)-7mol) and aging at 80 ℃ for 24 hours. Then, the solvent and the unreacted materials were distilled off under reduced pressure to obtain 14g of a liquid product.
It was confirmed by NMR that the obtained compound had a structure represented by the following formula (N).
[ chemical formula 74]
1H-NMR
δ0-0.2(-OSi(CH 3)2)12H
δ0.5-0.7(-OCH2CH2CH 2-Si，-CH2CH2CH 2-Si(OCH3)3)6H
δ1.4-2.0(-OCH2C 2HCH2-Si，-C 2HC 2HCH2-Si(OCH3)3)10H
δ3.3-3.8(-C2F2CH 2O-，-OC 2HCH2CH2-Si，-Si(OCH 3)3)22H
[ example 5]
In a reaction vessel, 10g of 1, 3-bis (trifluoromethyl) benzene and 0.54g (5.4X 10) of triethylamine-3mol) of the following formula (A)
[ solution 75]
10g (2.7X 10) of the compound represented-3mol) and slowly dropped into the mixture of the following formula (O)
[ 76]
p1∶q1＝47∶53，p1+q1≈43
The compound represented by (8.1 g) (2.4X 10)-3mol) and stirred at 60 ℃ for 20 hours. Next, hydrochloric acid was added, and the lower fluorine compound layer was collected by a liquid separation operation and washed with acetone. The lower layer after washing, i.e., the fluorine compound layer, was recovered again, and the residual solvent was distilled off under reduced pressure to obtain a fluorine compound represented by the following formula (P)
[ solution 77]
The fluoropolymer was 17 g.
1H-NMR
δ2.7-3.0(-CH 2CH＝CH2)4H
δ4.9-5.1(-CH2CH＝CH 2)4H
δ5.6-5.8(-CH2CH＝CH2)2H
In the reaction vessel, the reaction vessel is prepared from the following formula (P)
[ solution 78]
15g (2.0X 10) of the compound represented-3mol), 15g of 1, 3-bis (trifluoromethyl) benzene, 0.73g (6.0X 10) of trimethoxy silane-3mol) and a 2.0X 10 toluene solution of chloroplatinic acid/vinylsiloxane complex-2g (calculated by Pt simple substance, contains 5.3X 10)-7mol) and aging at 80 ℃ for 24 hours. Then, the solvent and the unreacted materials were distilled off under reduced pressure to obtain 13g of a liquid product.
It was confirmed by NMR that the obtained compound had a structure represented by the following formula (Q).
[ solution 79]
p1∶q1＝47∶53，p1+q1≈43
1H-NMR
δ0.5-0.7(-OCH2CH2CH 2-Si)4H
δ1.7-2.1(-OCH2C 2HCH2-Si，-OC 2HCH2CH2-Si)8H
δ3.4-3.7(-Si(OCH 3)3)18H
Comparative example 1
As comparative examples, the following polymers were used.
[ solution 80]
Preparation of surface treating agent and formation of cured coating film
The fluoropolyether group-containing polymer-modified silane obtained in examples 1, 2 and 4 and the polymer of comparative example 1 were dissolved in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) so that the concentration thereof became 20 mass%, to prepare a surface treatment agent. Using 10nm SiO at the outermost surface2Treated glass (Gorilla, Corning) was vacuum-evaporated (treatment condition: pressure: 2.0X 10)-2Pa, heating temperature: at 700 ℃ C., 7mg of each surface treating agent was cured in an atmosphere of 25 ℃ and a humidity of 40% for 24 hours to form a cured coating having a thickness of 10 nm.
Evaluation of Water repellency
[ evaluation of initial Water repellency ]
The glass having the cured film formed thereon prepared as described above was measured for the contact angle with water (water repellency) using a contact angle meter Drop Master (manufactured by synechia interfacial science). Good water repellency was exhibited at the initial stage. The results are shown in table 1.
[ evaluation of coefficient of dynamic Friction ]
The glass having the cured coating film formed thereon prepared above was measured for its dynamic friction coefficient to ベンコット (manufactured by asahi chemicals co., ltd.) under the following conditions using a surface property tester 14FW (manufactured by new eastern science corporation). The results are shown in table 1.
Contact area: 10mm by 35mm
Loading: 100g
[ evaluation of slidability ]
The evaluation group 10 touched the cured film-formed glass prepared above with a finger, evaluated the feeling of use according to the following criteria, and evaluated the most numerous as the evaluation of the slidability. The results are shown in table 1.
Very good: is very good
O +: good taste
O: in general
X: difference (D)
[ Table 1]
In examples 1, 2 and 4 in which a siloxane group or a fluoropolyether group was further introduced into a molecule of a polymer containing a fluoropolyether group, the coefficient of dynamic friction was reduced and the improvement of sliding property was confirmed as compared with comparative example 1 in which a single chain was present.
Claims (9)
1. A fluoropolyether group-containing polymer-modified silane represented by the following general formula (1):
[ solution 1]
Wherein Rf is
From F- (CF)2O)p1-(C2F4O)q1-CtF2tA 1-valent fluorooxyalkylene group-containing polymer residue represented by the formula, wherein p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1+ q1 is an integer of 10 to 105, t is an integer of 1 to 3, and the repeating units may be randomly combined,
or is represented by-CtF2tO-(CF2O)p1-(C2F4O)q1-CtF2tA 2-valent fluorooxyalkylene group-containing polymer residue represented by the formula, wherein p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, p1+ q1 is an integer of 10 to 105, t is an integer of 1 to 3, and the repeating units may be randomly combined,
y is at least 1 member selected from the group consisting of C3-10 alkylene, C8-16 alkylene containing phenylene, C2-10 alkylene mutually bonded via a silalkylene structure or silarylene structure, C2-4 group having C2-10 alkylene bonded to the bonding end of linear organopolysiloxane residue having C2-10 silicon atoms, and C2-4 group having C2-10 alkylene bonded to the bonding end of branched or cyclic organopolysiloxane residue having C3-10 silicon atoms,
r is C1-4 alkyl or phenyl,
x is a hydroxyl group or a hydrolyzable group,
q is a 2-valent organic group represented by the following formula (4),
[ solution 2]
Wherein R' is an alkylene group having 1 to 10 carbon atoms which may have any one of a ketone, ester, amide, ether, thioether, amine and phenylene group, or a carbonyl group,
w is a group having a valence of 2 selected from the group consisting of a linear 2-valent organosiloxane residue or organopolysiloxane residue having 2 to 40 silicon atoms, a linear silalkylene group having a silalkylene structure which is bonded via an alkylene group having 1 to 4 carbon atoms and may have a siloxane bond having 3 to 40 silicon atoms, and a linear silarylene group having a silarylene structure which contains a phenylene group and may be bonded via an alkylene group having 1 to 4 carbon atoms and may have a siloxane bond having 3 to 40 silicon atoms, the organosiloxane residue or organopolysiloxane residue, the silalkylene group, and the silarylene group may be each independently or mixed, β is 0 or 1, γ is 0 or 1, β + γ is 1 or 2,
r' is a 1-valent fluoroalkyl group represented by the following general formula (2)
[ solution 3]
Wherein in the general formula (2), p, q, r and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, each repeating unit may be straight or branched, and the repeating units may be randomly bonded to each other,
C1-C4 alkyl group
Or a phenyl group,
wherein, in the case where Q is a carbonyl group, R' is the residue of the 1-valent fluorooxyalkylene-containing polymer,
n is an integer of 1 to 3, m is an integer of 1 to 5, and α is 1 or 2.
2. The fluoropolyether group-containing polymer-modified silane according to claim 1, wherein in the Rf group in the formula (1), t is 1.
3. The fluoropolyether group-containing polymer-modified silane according to claim 1 or 2, wherein R' in the formula (1) is represented by the following general formula (2)
[ solution 4]
A residue of a fluorooxyalkylene group-containing polymer having a valence of 1 or a butyl group,
in the general formula (2), p, q, r and s are each an integer of 0 to 200, p + q + r + s is an integer of 3 to 200, t is an integer of 1 to 3, each repeating unit may be straight or branched, and the repeating units may be randomly bonded to each other,
wherein, in the case where Q is a carbonyl group, R' is the residue of the 1-valent fluorooxyalkylene-containing polymer.
4. The fluoropolyether group-containing polymer-modified silane according to claim 1 or 2,
r' in the formula (4) is C1-4 alkylene, C1-4 alkylene mutually bonded 2-valent group via ether bond, and carbonyl.
5. The fluoropolyether group-containing polymer-modified silane according to claim 1 or 2, wherein in the formula (1), each X is independently selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms and a halogen atom.
6. The fluoropolyether group-containing polymer-modified silane according to claim 1 or 2,
the structure of the linear silylene group and the linear silylene group in W of the formula (4) is represented by the following formula,
[ solution 5]
In the formula, R1Is C1-4 alkyl or C6-10 aryl, R1Which may be the same or different, R2Is C1-C4 alkylene or C6-C10 arylene.
7. The fluoropolyether group-containing polymer-modified silane according to claim 1 or 2, wherein the polymer-modified silane represented by formula (1) is represented by the following formula:
[ solution 6]
[ solution 7]
Wherein p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1+ q1 is an integer of 10 to 105.
8. A surface treatment agent comprising the fluoropolyether group-containing polymer-modified silane according to any one of claims 1 to 7.
9. An article having a cured coating film of the surface treatment agent according to claim 8 on the surface thereof.
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| JP6119656B2 (en) * | 2014-03-31 | 2017-04-26 | 信越化学工業株式会社 | Fluoropolyether group-containing polymer |
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