CN116217938A - Long-chain alkyl fluorine-containing vinyl silicone oil and preparation method thereof - Google Patents
Long-chain alkyl fluorine-containing vinyl silicone oil and preparation method thereof Download PDFInfo
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- 229920002545 silicone oil Polymers 0.000 title claims abstract description 56
- -1 alkyl fluorine Chemical compound 0.000 title claims abstract description 46
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 39
- 239000011737 fluorine Substances 0.000 title claims abstract description 39
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 38
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000009833 condensation Methods 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 238000010992 reflux Methods 0.000 claims abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 claims description 2
- VNZPVCQQJPXKNQ-UHFFFAOYSA-N dimethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[SiH](OC)OC VNZPVCQQJPXKNQ-UHFFFAOYSA-N 0.000 claims description 2
- NFBBUTYICQQBJG-UHFFFAOYSA-N dimethoxy-methyl-tetradecylsilane Chemical compound CCCCCCCCCCCCCC[Si](C)(OC)OC NFBBUTYICQQBJG-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- KEBRDNWIYNXRKR-UHFFFAOYSA-N dodecyl(dimethoxy)silane Chemical compound CCCCCCCCCCCC[SiH](OC)OC KEBRDNWIYNXRKR-UHFFFAOYSA-N 0.000 claims description 2
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 2
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 2
- AILBOMWJRYLVFG-UHFFFAOYSA-N dodecyl-diethoxy-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(OCC)OCC AILBOMWJRYLVFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 238000006386 neutralization reaction Methods 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
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000000576 coating method Methods 0.000 description 5
- CWNXOPXKENEODI-UHFFFAOYSA-N C[SiH]1O[SiH](C)O[Si](C)(CCC(F)(F)F)O1 Chemical compound C[SiH]1O[SiH](C)O[Si](C)(CCC(F)(F)F)O1 CWNXOPXKENEODI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—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
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a long-chain alkyl fluorine-containing vinyl silicone oil and a preparation method thereof, comprising the following steps: (1) adding long-chain alkoxy siloxane, fluorine-containing cyclosiloxane monomer, vinyl siloxane monomer, methyl cyclosiloxane monomer and end capping agent into a reaction kettle with a thermometer, a stirrer and a condensation reflux device, setting stirring speed to 300-600 r/min, stirring for 10-20 min, adding a catalyst, heating to 80-85 ℃, and hydrolyzing and condensing the system under the action of the catalyst; (2) after reacting for 2-4 hours, heating the reaction system to 130-145 ℃, and reacting for 6-8 hours at a temperature; (3) and after the ring-opening polymerization reaction is finished, cooling down and neutralizing the catalyst, filtering and neutralizing the generated salt, and then removing a micromolecular product in vacuum at a high temperature state to obtain the silicone oil. The long-chain alkyl fluorine-containing vinyl silicone oil introduces active groups, namely vinyl and fluoroalkyl, and has the advantages of low preparation cost, easily available raw materials, simple preparation, stable reaction process and great application prospect.
Description
Technical Field
The invention relates to the technical field of modified silicone oil, in particular to long-chain alkyl fluorine-containing vinyl silicone oil and a preparation method thereof.
Background
Silicone oil is a kind of organopolysiloxane product, which is composed of a polymer with Si-O bond as main chain and silicon atom connected with organic group as side chain, and has good film forming property, low surface energy, heat resistance, biocompatibility, hydrophobicity, electrical insulation, chemical inertness and other properties. Because of its excellent physical and chemical properties, silicone oil products are now widely used in many fields such as chemical, aviation, medicine, etc.
The long-chain alkyl modified silicone oil is prepared by replacing part of methyl in a polysiloxane side chain structure with long-chain alkyl, and the addition of the long-chain alkyl ensures that the organic silicone oil has better demolding property, lipophilicity, lubricity, defoaming property and anti-tackiness, and expands the application range of the silicone oil. At present, most of commercially available long-chain alkyl silicone oil is dimethyl silicone oil without active groups, and the silicone oil is mostly used as an inert component in the subsequent application, so that the advantages of long-chain alkyl are difficult to develop. In addition, the synthesis of long-chain alkyl silicone oil mostly adopts a hydrosilylation method, and the platinum catalyst adopted by hydrosilylation is difficult to remove after the reaction is finished while the silicone oil is inactive, so that the subsequent practical use is also affected to a certain extent.
Chinese patent publication No. CN 105295052A discloses a long-chain alkyl phenyl fluorosilicone oil and a preparation method thereof, and aims to synthesize a silicone oil with excellent heat stability and friction performance, but can only be used as inert oil to be added into a system; the Chinese patent with publication number of CN 105295052A discloses a low-viscosity vinyl silicone oil and a preparation method thereof, which improves the use benefit of the vinyl silicone oil, but has complicated actual process flow and is not beneficial to application. Compared with the two, the long-chain alkyl fluorine-containing vinyl silicone oil has stronger active groups, can better exert the advantages of long-chain alkyl, and has simple process flow.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the long-chain alkyl fluorine-containing modified silicone oil with the active group, and simultaneously provides a novel synthetic method, which can prevent the silicone oil from being influenced by the catalyst remained in the hydrosilylation during subsequent use.
In order to solve the technical problems, the invention provides the following technical scheme:
a long-chain alkyl fluorine-containing vinyl silicone oil, which has the following chemical structural formula:
wherein R is 1 Is a fluorine-containing alkyl group; r is R 2 Is long chain alkyl; r is R 3 Is alkoxy or methyl; n is n 1 The value of (2) is 5-30; n is n 2 The value of (2) is 5-20; n is n 3 The value of (2) is 5-20; n is n 4 The value of (2) is 20-60.
Preferably, the fluoroalkyl group is: - (CH) 2 ) m CF 3 M has a value of 0 to 5.
Preferably, the long chain alkyl group is C 6 ～C 18 The alkoxy is ethoxy or methoxy.
The invention also discloses a preparation method of the long-chain alkyl fluorine-containing vinyl silicone oil, which comprises the following steps:
adding long-chain alkoxy siloxane, fluorine-containing cyclosiloxane monomer, vinyl siloxane monomer, methyl cyclosiloxane monomer and end capping agent into a reaction kettle with a thermometer, a stirrer and a condensation reflux device, setting stirring speed to 300-600 r/min, stirring for 10-20 min, adding a catalyst, heating to 80-85 ℃, and hydrolyzing and condensing the system under the action of the catalyst;
step two, after 2 to 4 hours of reaction, heating the reaction system to 130 to 145 ℃, and reacting for 6 to 8 hours with heat preservation;
and thirdly, after the ring-opening polymerization reaction is finished, cooling down and neutralizing the catalyst, filtering and neutralizing the generated salt, and then removing a micromolecular product in vacuum at a high temperature state to obtain the silicone oil.
Preferably, the long chain alkoxy siloxane in step one is one or more of a trialkoxysiloxane or a dialkoxysiloxane. Including but not limited to n-hexyltriethoxysilane, n-octyltriethoxysilane, n-hexyltrimethoxysilane, n-decyltriethoxysilane, n-dodecyltriethoxysilane, n-dodecylmethyldiethoxysilane, dodecyltrimethoxysilane, dodecyldimethoxysilane, n-tetradecylmethyldimethoxysilane, n-tetradecylmethyldiethoxy, hexadecyltrimethoxysilane, octadecyldimethoxysilane.
Preferably, the vinyl-containing siloxane monomer in the first step is tetramethyl tetravinyl cyclotetrasiloxane, the fluorine-containing cyclosiloxane monomer is a monomer with a structural formula shown in the following figure,
wherein R is 2 Is C 1 ～C 6 One of the alkyl groups; m is 0-5, and p is 2-5.
Preferably, in the first step, the methyl cyclosiloxane monomer is one or more of octamethyl cyclotetrasiloxane, hexamethylcyclotrisiloxane and cyclosiloxane mixed monomer (DMC), and the end capping agent is H2O or hydroxyl end capped small molecular silicone oil.
Preferably, the catalyst in the first step is one or more of sodium hydroxide and potassium hydroxide.
Preferably, the catalyst neutralization raw material in the third step is one or more of acetic acid, phosphoric acid and propionic acid. The high temperature is 170-180 ℃, the vacuum state is less than 0.1Mpa, and the time for removing small molecular products is not less than 2h.
The beneficial effects of the invention are as follows: compared with the prior art, the preparation method prepares the long-chain alkyl fluorine-containing vinyl silicone oil containing active groups, and solves the problem that the long-chain alkyl modified silicone oil is inactive. Meanwhile, from the aspect of the preparation process, the preparation method avoids the influence of the residual catalyst of hydrosilylation in subsequent use, and is simple in process, easy in raw material acquisition and expected to be used for large-scale production.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
FIG. 1 is a schematic diagram of the synthesis process of example 1 of the present invention.
FIG. 2 is an infrared spectrum of the product of examples 2 and 4 of the present invention.
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the drawings.
Example 1
60 parts of n-octyl triethoxysilane, 103 parts of tetramethyl tetravinyl cyclotetrasiloxane, 374 parts of trifluoropropyl trimethyl cyclotrisiloxane, 475 parts of octamethyl cyclotrisiloxane and 2.1 parts of end-capping agent water are put into a reaction kettle with a stirrer and a thermometer, the rotation speed of the stirrer is set to 300r/min, and the stirring is maintained for 20min. After the materials are uniformly mixed, 150ppm of potassium hydroxide catalyst is added, and the system is heated to 80 ℃ for heat preservation reaction for 2 hours.
After the one-step reaction is finished, the temperature of the system is raised to 140 ℃, the temperature is kept for reaction for 6 hours, and meanwhile, the viscosity change is observed. After the viscosity rises, the rotating speed of the stirring paddle is increased to 500r/min, and the stirring is maintained until the reaction is finished. Cooling, adding propionic acid to neutralize the catalyst, stirring for 4h, and filtering to neutralize the generated salt to obtain the liquid initial product. And (3) removing small molecular low-boiling substances from the initial product in a low-pressure environment with the vacuum degree of-0.1 Mpa and the system temperature of 170 ℃, cooling after removing for 4 hours, and discharging to obtain the long-chain alkyl fluorine-containing vinyl silicone oil with the yield of 86.6%. The product obtained was colorless in appearance, clear in solution and had a viscosity of 603 mpa.s.
Example 2
60 parts of n-octyl triethoxysilane, 103 parts of tetramethyl tetravinyl cyclotetrasiloxane, 374 parts of trifluoropropyl trimethyl cyclotrisiloxane, 475 parts of octamethyl cyclotrisiloxane and 1.5 parts of end-capping agent water are put into a reaction kettle with a stirrer and a thermometer, the rotation speed of the stirrer is set to 300r/min, and the stirring is maintained for 20min. After the materials are uniformly mixed, 150ppm of potassium hydroxide catalyst is added, and the system is heated to 80 ℃ for heat preservation reaction for 2 hours.
After the one-step reaction is finished, the temperature of the system is raised to 140 ℃, the temperature is kept for reaction for 6 hours, and meanwhile, the viscosity change is observed. After the viscosity rises, the rotating speed of the stirring paddle is increased to 600r/min, and the stirring is maintained until the reaction is finished. Cooling, adding propionic acid to neutralize the catalyst, stirring for 4h, and filtering to neutralize the generated salt to obtain the liquid initial product. And (3) removing small molecular low-boiling substances from the initial product in a low-pressure environment with the vacuum degree of-0.1 Mpa and the system temperature of 170 ℃, cooling after removing for 4 hours, and discharging to obtain the long-chain alkyl fluorine-containing vinyl silicone oil with the yield of 87.1%. The product obtained was colorless in appearance, clear in solution and had a viscosity of 1326mpa.s.
The infrared spectrum of the long-chain alkyl fluorine-containing vinyl silicone oil is shown in figure 2.
Example 3
120 parts of n-octyl triethoxysilane, 104 parts of tetramethyl tetravinyl cyclotetrasiloxane, 120 parts of trifluoropropyl trimethyl cyclotrisiloxane, 480 parts of octamethyl cyclotrisiloxane and 1 part of end-capping agent water are put into a reaction kettle with a stirrer and a thermometer, the rotation speed of the stirrer is set to 300r/min, and stirring is maintained for 20min. After the materials are uniformly mixed, 150ppm of potassium hydroxide catalyst is added, and the system is heated to 80 ℃ for heat preservation reaction for 2 hours.
After the one-step reaction is finished, the temperature of the system is raised to 140 ℃, the temperature is kept for reaction for 6 hours, and meanwhile, the viscosity change is observed. After the viscosity rises, the rotating speed of the stirring paddle is increased to 600r/min, and the stirring is maintained until the reaction is finished. Cooling, adding propionic acid to neutralize the catalyst, stirring for 4h, and filtering to neutralize the generated salt to obtain the liquid initial product. And (3) removing small molecular low-boiling substances from the initial product in a low-vacuum degree of-0.1 Mpa and a system temperature of 170 ℃ in a low-removal environment, cooling after removing for 4 hours, and discharging to obtain the long-chain alkyl fluorine-containing vinyl silicone oil. The product obtained has a yield of 86.9%, a pale yellow appearance, a clear solution and a viscosity of 1750mpa.s.
Example 4
120 parts of n-octyl triethoxysilane, 104 parts of tetramethyl tetravinyl cyclotetrasiloxane, 120 parts of trifluoropropyl trimethyl cyclotrisiloxane, 480 parts of octamethyl cyclotrisiloxane and 2 parts of end-capping agent water are put into a reaction kettle with a stirrer and a thermometer, the rotation speed of the stirrer is set to 300r/min, and stirring is maintained for 20min. After the materials are uniformly mixed, 150ppm of potassium hydroxide catalyst is added, and the system is heated to 80 ℃ for heat preservation reaction for 2 hours.
After the one-step reaction is finished, the temperature of the system is raised to 140 ℃, the temperature is kept for reaction for 6 hours, and meanwhile, the viscosity change is observed. After the viscosity rises, the rotating speed of the stirring paddle is increased to 500r/min, and the stirring is maintained until the reaction is finished. Cooling, adding propionic acid to neutralize the catalyst, stirring for 4h, and filtering to neutralize the generated salt to obtain the liquid initial product. And (3) removing small molecular low-boiling substances from the initial product in a low-pressure environment with the vacuum degree of-0.1 Mpa and the system temperature of 170 ℃, cooling after removing for 4 hours, and discharging to obtain the long-chain alkyl fluorine-containing vinyl silicone oil with the yield of 85.8%. The product obtained was pale yellow in appearance, clear in solution and had a viscosity of 109mpa.s.
The infrared spectrum of the long-chain alkyl fluorine-containing vinyl silicone oil is shown in figure 2.
Infrared spectrogram analysis: referring to FIG. 2, 3366cm -1 The position is Si-OH vibration absorption peak, 2924cm -1 Is positioned at 2860cm -1 At the positions of-CH respectively 2 The antisymmetric stretching vibration peak and the symmetrical stretching vibration peak can be seen to be obviously raised after the end capping agent and the long-chain alkane monomer are increased. 1598cm -1 At 1410cm -1 At Si-ch=ch respectively 2 The stretching vibration and shear vibration absorption peak of c=c confirm the successful introduction of double bonds. 1366cm -1 At the position of-CH 2 CH 2 CF 3 Is 1314cm -1 At CH 2 —CH 2 Is 1208cm -1 at-CF 3 These several peaks confirm the introduction of fluorine-containing groups. 1260cm -1 At Si-CH 3 Bending vibration absorption peak of 1000 to 1070cm -1 The Si-O-Si telescopic vibration absorption peak is arranged. Characterization results show that the product is long-chain alkyl fluorine-containing vinyl silicone oil.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art. The generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Example 1 Performance test and evaluation
Test example 1:
10 parts by mass of the long-chain alkyl fluorine-containing vinyl silicone oil prepared in example 1, 2 parts by mass of hydrogen-containing silicone oil and 5 parts by mass of ethyl acetate are stirred at room temperature for 10 minutes and are fully and uniformly mixed. Then 1 part of silane anchoring agent and 0.1 part of inhibitor are added into the mixture, and the mixture is stirred again for 20 minutes and fully and uniformly mixed. Finally, 40ppm (calculated as platinum) of platinum catalyst was added thereto, stirred for 10min and mixed well, and coated on PET substrate at room temperature.
Curing conditions: the curing temperature was 120℃and the curing time was 2min, the resulting coating thickness was about 3. Mu.m.
Test example 2:
10 parts by mass of the long-chain alkyl fluorine-containing vinyl silicone oil prepared in example 1, 2 parts of hydrogen-containing silicone oil, 5 parts of ethyl acetate and 1 part of silane anchoring agent are stirred at room temperature for 30min and are fully and uniformly mixed. Then 40ppm (calculated as platinum) of platinum catalyst was added thereto, stirred for 10min and mixed well, and coated on a PET substrate at room temperature.
Curing conditions: at room temperature, the curing time was 30min and the resulting coating thickness was about 3 μm.
Comparative example 1:
10 parts by mass of commercially available inactive long-chain alkyl silicone oil, 2 parts of hydrogen-containing silicone oil and 5 parts of ethyl acetate are taken and stirred at room temperature for 10min, and are fully and uniformly mixed. Then 1 part of silane anchoring agent and 0.1 part of inhibitor are added into the mixture, and the mixture is stirred again for 20 minutes and fully and uniformly mixed. Finally, 40ppm (calculated as platinum) of platinum catalyst was added thereto, stirred for 10min and mixed well, and coated on PET substrate at room temperature.
Curing conditions: the curing temperature was 120℃and the curing time was 2min, the resulting coating thickness was about 3. Mu.m.
The coatings were tested separately with a peel force tester and the average test results were taken. The comparative results of example 1 are shown in table 1.
Table 1 example 1 comparative results
| Curing temperature/. Degree.C | Curing time/min | Coating thickness/. Mu.m | Peel force/gf | |
| Test example 1 | 120 | 2 | 3 | 5.4 |
| Test example 2 | 26 | 30 | 3 | 5.6 |
| Comparative example 1 | 120 | 2 | 3 | Uncured state |
It should be noted that test example 1 and test example 2 of the present invention are merely test results applied to example 1, and the application thereof is not limited in this respect. It will be apparent to those skilled in the art that various modifications, improvements, and substitutions can be made without departing from the spirit of the invention, and these are intended to be within the scope of the invention.
Claims (10)
1. The long-chain alkyl fluorine-containing vinyl silicone oil is characterized in that active groups, namely vinyl and fluoroalkyl, are introduced into the long-chain alkyl silicone oil, and the structural formula of the long-chain alkyl fluorine-containing vinyl silicone oil is shown as follows:
wherein R is 1 Is a fluorine-containing alkyl group; r is R 2 Is long chain alkyl; r is R 3 Is alkoxy or methyl; n is n 1 The value of (2) is 5-30; n is n 2 The value of (2) is 5-20;
n 3 the value of (2) is 5-20; n is n 4 The value of (2) is 20-60.
2. The long-chain alkyl fluorine-containing vinyl silicone oil according to claim 1, wherein the fluorine-containing alkyl group is: - (CH) 2 ) m CF 3 M has a value of 0 to 5.
3. The long-chain alkyl fluorine-containing vinyl silicone oil according to claim 1, wherein the long-chain alkyl group is C 6 ～C 18 The alkoxy is ethoxy or methoxy.
4. A process for the preparation of a long-chain alkyl fluorine-containing vinyl silicone oil according to any one of claims 1 to 3, comprising the steps of:
adding long-chain alkoxy siloxane, fluorine-containing cyclosiloxane monomer, vinyl siloxane monomer, methyl cyclosiloxane monomer and end capping agent into a reaction kettle with a thermometer, a stirrer and a condensation reflux device, setting stirring speed to 300-600 r/min, stirring for 10-20 min, adding a catalyst, heating to 80-85 ℃, and hydrolyzing and condensing the system under the action of the catalyst;
step two, after 2 to 4 hours of reaction, heating the reaction system to 130 to 145 ℃, and reacting for 6 to 8 hours with heat preservation;
and thirdly, after the ring-opening polymerization reaction is finished, cooling down and neutralizing the catalyst, filtering and neutralizing the generated salt, and then removing a micromolecular product in vacuum at a high temperature state to obtain the silicone oil.
5. The method for preparing a long-chain alkyl fluorine-containing vinyl silicone oil according to claim 4, wherein the long-chain alkoxy siloxane in the step one is one or more of trialkoxysiloxane and dialkoxysiloxane. Including but not limited to n-hexyltriethoxysilane, n-octyltriethoxysilane, n-hexyltrimethoxysilane, n-decyltriethoxysilane, n-dodecyltriethoxysilane, n-dodecylmethyldiethoxysilane, dodecyltrimethoxysilane, dodecyldimethoxysilane, n-tetradecylmethyldimethoxysilane, n-tetradecylmethyldiethoxy, hexadecyltrimethoxysilane, octadecyldimethoxysilane.
6. The method for preparing a long-chain alkyl fluorine-containing vinyl silicone oil according to claim 4, wherein the vinyl-containing siloxane monomer in the first step is tetramethyl tetravinyl cyclotetrasiloxane, the fluorine-containing cyclosiloxane monomer is a monomer with a structural formula shown in the following figure,
wherein R is 2 Is C 1 ～C 6 One of the alkyl groups; m is 0 to 5, and p is2～5。
7. The method for preparing a long-chain alkyl fluorine-containing vinyl silicone oil according to claim 4, wherein the methyl cyclosiloxane monomer in the first step is one or more of octamethyl cyclotetrasiloxane, hexamethylcyclotrisiloxane and cyclosiloxane mixed monomer (DMC), and the end-capping agent is H 2 O or hydroxyl end-capped small molecular silicone oil.
8. The method for preparing a long-chain alkyl fluorine-containing vinyl silicone oil according to claim 4, wherein the catalyst in the first step is one or more of sodium hydroxide and potassium hydroxide.
9. The method for preparing long-chain alkyl fluorine-containing vinyl silicone oil according to claim 4, wherein the catalyst neutralization raw material in the third step is one or more of acetic acid, phosphoric acid and propionic acid.
10. The method for preparing a long-chain alkyl fluorine-containing vinyl silicone oil according to claim 4, wherein the high temperature in the third step is 170-180 ℃, the vacuum state is less than 0.1Mpa, and the time for removing small molecular products is not less than 2h.
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