CN105778103A - Vinyl fluorine-silicon resin and preparation method thereof - Google Patents
Vinyl fluorine-silicon resin and preparation method thereof Download PDFInfo
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- CN105778103A CN105778103A CN201610160228.6A CN201610160228A CN105778103A CN 105778103 A CN105778103 A CN 105778103A CN 201610160228 A CN201610160228 A CN 201610160228A CN 105778103 A CN105778103 A CN 105778103A
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- silicones
- vinyl
- vinyl fluoride
- trifluoro propyl
- monomer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011347 resin Substances 0.000 title abstract description 15
- 229920005989 resin Polymers 0.000 title abstract description 15
- VZFHJVQUHRRTII-UHFFFAOYSA-N [Si].C(=C)F Chemical compound [Si].C(=C)F VZFHJVQUHRRTII-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims abstract description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 28
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- -1 methyl ethylene dimethoxy silica Chemical compound 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 4
- WTQAKAPKTROVFY-UHFFFAOYSA-N C[SiH]1O[Si](O[Si](O1)(CCC)F)(F)F Chemical compound C[SiH]1O[Si](O[Si](O1)(CCC)F)(F)F WTQAKAPKTROVFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- MCAPDUSPBSEQQO-UHFFFAOYSA-N O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1.CC=C Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1.CC=C MCAPDUSPBSEQQO-UHFFFAOYSA-N 0.000 claims description 2
- 229910004674 SiO0.5 Inorganic materials 0.000 claims description 2
- 229910020381 SiO1.5 Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 claims description 2
- OHABWQNEJUUFAV-UHFFFAOYSA-N dichloro-methyl-(3,3,3-trifluoropropyl)silane Chemical compound C[Si](Cl)(Cl)CCC(F)(F)F OHABWQNEJUUFAV-UHFFFAOYSA-N 0.000 claims description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 2
- GFTRQZRJGBJAKX-UHFFFAOYSA-N ethoxy-methyl-propyl-(2,2,2-trifluoroethoxy)silane Chemical compound FC(CO[Si](OCC)(C)CCC)(F)F GFTRQZRJGBJAKX-UHFFFAOYSA-N 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- 229940073561 hexamethyldisiloxane Drugs 0.000 claims description 2
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 2
- GOWYWDDPOBCVFH-UHFFFAOYSA-N methoxy-methyl-propyl-(trifluoromethoxy)silane Chemical compound FC(O[Si](OC)(C)CCC)(F)F GOWYWDDPOBCVFH-UHFFFAOYSA-N 0.000 claims description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 claims description 2
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000009833 condensation Methods 0.000 abstract description 6
- 230000005494 condensation Effects 0.000 abstract description 6
- 239000003921 oil Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000005536 corrosion prevention Methods 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000004078 waterproofing Methods 0.000 abstract 1
- 239000002023 wood Substances 0.000 abstract 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000004807 desolvation Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- DIFAZFWOOGJARJ-UHFFFAOYSA-N FC(F)(F)C(C)O[Si](OCC)(OCC)CCC Chemical compound FC(F)(F)C(C)O[Si](OCC)(OCC)CCC DIFAZFWOOGJARJ-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 125000005375 organosiloxane group Chemical group 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to vinyl fluorine-silicon resin and a preparation method thereof, comprising unit M, unit D and unit T and having a specific structural molecular: (Me3SiO0.5)a1(Me2RSiO0.5)a2(MeRfSiO)b1(MeRSiO)b2(Me2SiO)b3(RfSiO1.5)c1(MeSiO1.5)c2(RSiO1.5)c3, wherein R is vinyl, Rf is trifluoropropyl, and an organic fluorine-silicon monomer is made by hydrolysis, washing, drying, condensation, neutralizing and low-boiling-point substance removal. The fluorine-silicon resin prepared herein comprises vinyl unsaturated groups, is available for crosslinking solidification, has excellent properties such as waterproofing, oil resisting, heat resisting and stain resisting, is widely applicable to production and living aspects such as outer protection for military industry equipment, outer water prevention and corrosion prevention for oil pipelines, kitchen and sanitary ware, windscreens, wood and buildings.
Description
Technical field
The invention belongs to organosilicon macromolecule technical field, particularly to a kind of vinyl fluoride silicones and preparation method thereof.
Background technology
Fluorine silicon resin not only has the characteristics such as the excellent resistance to oxidation of common methyl silicon resin, electric insulation, weather-proof, hydrophobic, fire-retardant, salt spray resistance, and due to the introducing of fluoroalkyl, give its special solvent resistant, fuel resistance energy, therefore can meet modern coatings and the growing demand of field of surface treatment, be widely used in the productive life aspects such as the outer protective of military industry equipment, the water-tight corrosion-proof of oil pipeline outer layer, kitchen guarding's apparatus, windshield, timber and building.
At present, the preparation method of fluorine silicon resin involved in patent can be roughly divided into following three classes: (1) adopts chemical graft process to receive in organosiloxane backbones by fluoropolymer or fluorochemical monomer, such as CN102643434A etc.；(2) co-hydrolysis of fluoropolymer or fluorochemical monomer and alkoxy silane, such as CN101775144A etc.；(3) catalytic condensation of fluororesin and silicones, such as CN102924734A etc., the preparation method of above fluorine silicon resin generally can relate to special construction fluorochemical monomer or special preparation process.
Summary of the invention
It is an object of the invention to overcome above-mentioned deficiency, a kind of vinyl fluoride silicones and preparation method thereof is provided, adopt the synthesis step of normal silicone: such as hydrolysis, washing, polycondensation, desolventizing synthesis of vinyl fluorine silicon resin, it is to avoid the use of special construction fluorochemical monomer and loaded down with trivial details preparation process (generally obtaining with silicones, fluorine carbon monomer for raw material carries out polycondensation in the fluorine silicon resin preparation process of prior art).Research finds；The performance of fluorine silicon resin is closely related with the kind of organic group R, when organic group is-CH=CH2Time, the curing performance of silicones can be improved and give coupled, giving fluorine silicon resin heat stability, hydrophobicity, release property, arc resistance, fuel resistance energy；When organic group is chain alkyl, the hydrophobicity of silicones can be improved.Therefore, in the present invention " use of fluorine-containing organic silicon monomer " make the synthesis of fluorine silicon resin can design different molecular structures according to different curing performances, and there is preferably characteristic and special solvent resistant, the fuel resistance energy such as resistance to oxidation, electric insulation, weather-proof, hydrophobic, fire-retardant, salt spray resistance.
For achieving the above object, the present invention adopts following technological means:
A kind of vinyl fluoride silicones, its structural formula is:
(Me3SiO0.5)a1(Me2RSiO0.5)a2(MeRfSiO)b1(MeRSiO)b2(Me2SiO)b3(RfSiO1.5)c1(MeSiO1.5)c2(RSiO1.5)c3；
Wherein, a1, a2, b1, b2, b3, c1, c2, c3 are the natural number more than 0, and R is vinyl, RfFor trifluoro propyl.
Preferably, the R/Si ratio of described vinyl fluoride silicones is 1.0～2.0, and now, the fuel resistance of resin can be best.
Preferably, molar content≤33% of described vinyl fluoride silicones medium vinyl.
The preparation method that present invention also offers a kind of vinyl fluoride silicones, with M, D, T monomer for raw material, under catalyst existence condition after hydrolysis, polycondensation and polyreaction, prepares vinyl fluoride silicones；
Wherein, described M monomer is hexamethyl disiloxane, tetramethyl divinyl disiloxane or combination；
Described D monomer is at least one in methyl trifluoro propyl cyclotrisiloxane, trifluoropropylmethyldichlorosilane, methyl trifluoro propyl dimethoxysilane, methyl trifluoro propyl diethoxy silane, methyl ethylene cyclotetrasiloxane, methylvinyldichlorosilane, methyl ethylene dimethoxy silica, methyl vinyl diethoxysilane, octamethylcy-clotetrasiloxane, dimethyldichlorosilane, dimethyldimethoxysil,ne or dimethyldiethoxysilane；
Described T monomer is at least one in trifluoro propyl trichlorosilane, trifluoro propyl trimethoxy silane, trifluoro propyl triethoxysilane, MTMS, MTES, vinyltrimethoxy silane or VTES.
Preferably, in described hydrolysis, catalyst is the mixture of concentrated hydrochloric acid and trifluoromethanesulfonic acid.
It is furthermore preferred that described concentrated hydrochloric acid is with the mixture of trifluoromethanesulfonic acid, concentrated hydrochloric acid accounts for the 3～10% of reactant, and trifluoromethanesulfonic acid accounts for the 0.1%～1.0% of reactant.
Preferably, in described polycondensation reaction, condensation temp is 80～120 DEG C
Preferably, in described polycondensation reaction, catalyst is alkali metal hydroxide.
It is furthermore preferred that described alkali metal hydroxide is at least one in Lithium hydrate, sodium hydroxide or potassium hydroxide.
It is furthermore preferred that described alkali metal hydroxide consumption accounts for the 0.1%～1.0% of reactant.
Preferably, the condition of described polyreaction be in 120～180 DEG C, under reduced pressure, the de-low 0.5～4h that boils.
It is furthermore preferred that described reduced pressure is 133～1330Pa.
Preferably, after described polycondensation reaction, add the alkali remained in weak acid and in reaction system.
It is furthermore preferred that the consumption of described weak acid accounts for the 0.1%～1.0% of reactant.
Present invention also offers a kind of preferred vinyl fluoride silicones preparation method, including:
(1) hydrolysis
M, D, T monomer mix homogeneously, dropwise at room temperature adds containing solvent, H2In the reaction bulb of O and catalyst, stirring, after dropwising, it is warming up to 60～120 DEG C, back flow reaction 2～10h, stand, layering；
(2) wash, dry
Hydrolyzed solution is washed with distilled water to pH=6～7, stands, and anhydrous calcium chloride or magnesium sulfate dry 8～24h；
(3) condensation
Water lotion desolvation, is warming up to 80～120 DEG C, catalyzing and condensing, reacts 4～8h；
(4) neutralize
Condensation liquid adds and the equimolar nertralizer of step (3) catalyst is neutralized；
(5) low boiling is taken off
Neutralizer is warming up to 120～180 DEG C, decompression, the de-low 0.5～4h that boils, and obtains vinyl fluoride silicones.
Vinyl fluoride silicones of the present invention is in modern coatings and field of surface treatment, such as the application of the outer protective of military industry equipment, the water-tight corrosion-proof of oil pipeline outer layer, kitchen guarding's apparatus, windshield, timber and building etc..
Beneficial effects of the present invention
(1) present invention adopts the synthesis step of normal silicone: such as hydrolysis, washing, polycondensation, desolventizing synthesis of vinyl fluorine silicon resin, it is to avoid the use of special construction fluorochemical monomer and loaded down with trivial details preparation process.It addition, the use of fluorine-containing organic silicon monomer makes the synthesis of fluorine silicon resin can design different molecular structures according to different curing performances in the present invention.
(2) preparation method of the present invention is simple, practical, easy to spread.
Accompanying drawing explanation
Fig. 1 vinyl fluoride silicones1HNMR schemes；
Fig. 2 vinyl fluoride silicones29SiNMR schemes.
Detailed description of the invention
By the following examples feature of present invention and other correlated characteristic are described in further detail, in order to the understanding of technical staff of the same trade:
Embodiment 1
Tetramethyl divinyl disiloxane 415g, methyl trifluoro propyl cyclotrisiloxane 780g, methyl trifluoro propyl triethoxysilane 1280g mix homogeneously, dropwise at room temperature adds containing solvent 5000g, hydrochloric acid 175g, trifluoromethanesulfonic acid 25g, H2In the hydrolytic reaction pot of O270g, stirring, after dropwising, it is warming up to 80 DEG C, back flow reaction 4h, stand, layering, hydrolyzed solution distilled water wash, to pH=6～7, stands, desolvation after the dry 12h of anhydrous calcium chloride, and add potassium hydroxide 5.0g at 80 DEG C of condensation 4h, it is cooled to room temperature, add 5.5g glacial acetic acid to neutralize, filter, be warming up to 150 DEG C, desolvation and low-boiling-point substance under 133～1330Pa, obtain the vinyl fluoride silicones of M/D/T=1/1/11HNMR with29SiNMR characterizes product molecule structure.
Embodiment 2
Repeat the step described in embodiment 1, simply M/D/T=1/1/2,1HNMR with29SiNMR characterizes product molecule structure.
Embodiment 3
Repeat the step described in embodiment 1, simply M/D/T=1/1/3,1HNMR with29SiNMR characterizes product molecule structure.
Embodiment 4
Repeat the step described in embodiment 1, simply M/D/T=1/1/4,1HNMR with29SiNMR characterizes product molecule structure.
Embodiment 5
Repeat the step described in embodiment 1, simply M/D/T=1/1/5,1HNMR with29SiNMR characterizes product molecule structure.
Comparative example 1
Repeating the step described in embodiment 1, simply D is trifluoropropylmethyldichlorosilane,1HNMR with29SiNMR characterizes product molecule structure.
Comparative example 2
Repeating the step described in embodiment 1, simply T is methyl trifluoro propyl trimethoxy silane,1HNMR with29SiNMR characterizes product molecule structure.
Finally should be noted that, the foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although the present invention being described in detail with reference to previous embodiment, for a person skilled in the art, technical scheme described in previous embodiment still can be modified by it, or wherein part is carried out equivalent replacement.All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.The specific embodiment of the present invention is described in conjunction with accompanying drawing although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme, those skilled in the art need not pay various amendments or deformation that creative work can make still within protection scope of the present invention.
Claims (10)
1. a vinyl fluoride silicones, it is characterised in that its structural formula is:
(Me3SiO0.5)a1(Me2RSiO0.5)a2(MeRfSiO)b1(MeRSiO)b2(Me2SiO)b3(RfSiO1.5)c1(MeSiO1.5)c2(RSiO1.5)c3；
Wherein, a1, a2, b1, b2, b3, c1, c2, c3 are the natural number more than 0, and R is vinyl, RfFor trifluoro propyl.
2. vinyl fluoride silicones as claimed in claim 1, it is characterised in that the R/Si ratio of described vinyl fluoride silicones is 1.0～2.0.
3. vinyl fluoride silicones as claimed in claim 1, it is characterised in that molar content≤33% of described vinyl fluoride silicones medium vinyl.
4. the preparation method of a vinyl fluoride silicones, it is characterised in that with M, D, T monomer for raw material, under catalyst existence condition after hydrolysis, polycondensation and polyreaction, prepares vinyl fluoride silicones；
Wherein, described M monomer is hexamethyl disiloxane, tetramethyl divinyl disiloxane or combination；
Described D monomer is at least one in methyl trifluoro propyl cyclotrisiloxane, trifluoropropylmethyldichlorosilane, methyl trifluoro propyl dimethoxysilane, methyl trifluoro propyl diethoxy silane, methyl ethylene cyclotetrasiloxane, methylvinyldichlorosilane, methyl ethylene dimethoxy silica, methyl vinyl diethoxysilane, octamethylcy-clotetrasiloxane, dimethyldichlorosilane, dimethyldimethoxysil,ne or dimethyldiethoxysilane；
Described T monomer is at least one in trifluoro propyl trichlorosilane, trifluoro propyl trimethoxy silane, trifluoro propyl triethoxysilane, MTMS, MTES, vinyltrimethoxy silane or VTES.
5. method as claimed in claim 1, it is characterised in that in described hydrolysis, catalyst is the mixture of concentrated hydrochloric acid and trifluoromethanesulfonic acid.
6. method as claimed in claim 1, it is characterised in that in described polycondensation reaction, catalyst is alkali metal hydroxide.
7. the method for claim 1, it is characterised in that the condition of described polyreaction be in 120～180 DEG C, under reduced pressure, the de-low 0.5～4h that boils.
8. method as claimed in claim 7, it is characterised in that described reduced pressure is 133～1330Pa.
9. the method for claim 1, it is characterised in that after described polycondensation reaction, adds the alkali remained in weak acid and in reaction system.
10. the vinyl fluoride silicones described in any one of claim 1-3 is in the application of the process of the outer protective of military industry equipment, the water-tight corrosion-proof of oil pipeline outer layer, kitchen guarding's apparatus, windshield, timber and building surface and coating preparation field.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108440758A (en) * | 2018-03-23 | 2018-08-24 | 哈尔滨工业大学 | A kind of preparation method of hydrophobic fluorine silicon resin |
| CN114196215A (en) * | 2022-01-08 | 2022-03-18 | 深圳市康利邦科技有限公司 | MTQ (methyl thiazolyl tetrazolium) silicon resin, preparation method thereof, fluorine-containing organic silicon rubber, and preparation method and application thereof |
| CN116217938A (en) * | 2023-03-20 | 2023-06-06 | 浙江润禾有机硅新材料有限公司 | Long-chain alkyl fluorine-containing vinyl silicone oil and preparation method thereof |
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| CN101626893A (en) * | 2007-02-22 | 2010-01-13 | 道康宁公司 | Reinforced silicone resin films |
| CN104893301A (en) * | 2014-03-05 | 2015-09-09 | 信越化学工业株式会社 | Addition-curable silicone composition and optical device |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101626893A (en) * | 2007-02-22 | 2010-01-13 | 道康宁公司 | Reinforced silicone resin films |
| CN104893301A (en) * | 2014-03-05 | 2015-09-09 | 信越化学工业株式会社 | Addition-curable silicone composition and optical device |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440758A (en) * | 2018-03-23 | 2018-08-24 | 哈尔滨工业大学 | A kind of preparation method of hydrophobic fluorine silicon resin |
| CN114196215A (en) * | 2022-01-08 | 2022-03-18 | 深圳市康利邦科技有限公司 | MTQ (methyl thiazolyl tetrazolium) silicon resin, preparation method thereof, fluorine-containing organic silicon rubber, and preparation method and application thereof |
| CN116217938A (en) * | 2023-03-20 | 2023-06-06 | 浙江润禾有机硅新材料有限公司 | Long-chain alkyl fluorine-containing vinyl silicone oil and preparation method thereof |
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