CN112851947A - Preparation method and application of polyhydroxy silicone oil - Google Patents
Preparation method and application of polyhydroxy silicone oil Download PDFInfo
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- CN112851947A CN112851947A CN202110039368.9A CN202110039368A CN112851947A CN 112851947 A CN112851947 A CN 112851947A CN 202110039368 A CN202110039368 A CN 202110039368A CN 112851947 A CN112851947 A CN 112851947A
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- silicone oil
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- polyhydroxy silicone
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- 229920002545 silicone oil Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- -1 polysiloxane Polymers 0.000 claims abstract description 9
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 11
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 8
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 7
- 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 7
- 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 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000003921 oil Substances 0.000 abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 229920002529 medical grade silicone Polymers 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material 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
- 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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
- C10M155/02—Monomer containing silicon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/045—Siloxanes with specific structure containing silicon-to-hydroxyl bonds
Abstract
The invention relates to the field of organic silicon chemical industry, in order to solve the problems that the prior medical silicone oil needs to dilute and clean by utilizing fluorine-containing alkane such as Freon and the like in use due to too strong lipophilicity in the use process, the invention provides a preparation method of polyhydroxy silicone oil, which comprises the steps of firstly taking cyclosiloxane, hydrogen-containing ring bodies and an end sealing agent as raw materials and taking perfluorinated sulfonic acid resin as a catalyst to carry out polymerization reaction to obtain hydrogen-containing polysiloxane; then under the catalysis of Co-MOFs catalyst, obtaining polyhydroxy silicone oil through oxidation. Compared with the traditional silicone oil, the obtained polyhydroxy silicone oil is modified with more hydrophilic hydroxyl groups, and has the characteristics of good stability, high yield, good repeatability and the like.
Description
Technical Field
The invention relates to the field of organic silicon chemical industry, and particularly relates to a preparation method and application of polyhydroxy silicone oil.
Background
The medical silicone oil has the advantages of excellent smoothness, good physiological inertia, low viscosity-temperature coefficient, low volatility and the like, and is widely applied to occasions such as disease diagnosis, medical examination, operation treatment and the like, so that the strong pain feeling of rough surfaces to human skins when medical instruments are in contact with human organs is reduced, and the medical effect and experience feeling are improved. Because the medical silicone oil for lubrication mostly uses methyl silicone oil, is insoluble in medical alcohol, and generally needs to be used with high and low viscosity, the silicone oil needs to be diluted to meet the construction requirement. In general, a fluorine-containing solvent such as freon is used for cleaning and diluting in industry, and freon is a main cause for destroying the ozone layer and causing the greenhouse effect and can not directly act on the human body.
One of the important members of the silicone oil family is hydroxy silicone oil, which is commonly referred to as hydroxyl-terminated polysiloxane, also known as α, ω -dihydroxy polydimethylsiloxane, and has the following structure:
the liquid is colorless transparent oily liquid, the viscosity can be from several centistokes to hundreds of thousands of centistokes, and the liquid has wide application prospect. However, since the methyl groups bonded to silicon are lipophilic groups and insoluble in polar solvents, they are often washed and diluted with fluoroalkanes, so that their use as medical lubricants is greatly limited.
Disclosure of Invention
In order to solve the problems that the existing medical silicone oil needs to be diluted and cleaned by utilizing fluorine-containing alkane such as Freon and the like due to too strong lipophilicity in the using process, the invention provides a preparation method of polyhydroxy silicone oil, and compared with the traditional silicone oil, the obtained polyhydroxy silicone oil is modified with more hydrophilic hydroxyl groups, and has the characteristics of good stability, high yield, good repeatability and the like.
The polyhydroxy silicone oil obtained by the invention can be used as a lubricant and used on medical instruments. Can be directly cleaned after use without depending on fluorine-containing alkane, and has the advantages of convenient cleaning and dilution.
The invention is realized by the following technical scheme: the preparation method of the polyhydroxy silicone oil comprises the following steps: (1) taking cyclosiloxane, a hydrogen-containing ring body and a sealing agent as raw materials, and carrying out cation catalysis ring-opening polymerization reaction under the catalysis of perfluorinated sulfonic acid resin to obtain colorless and transparent hydrogen-containing polysiloxane;
the cyclosiloxane includes octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane and the like. Preferably, the cyclosiloxane is one or more selected from octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane and decamethylcyclopentasiloxane.
The hydrogen-containing ring body comprises tetramethylhydrogencyclotetrasiloxane, pentamethylhydrogencyclopentasiloxane and the like, the using amount of the hydrogen-containing ring body is 2.5-25% of the total mass of the raw materials, the total mass of the raw materials is the sum of the mass of the cyclosiloxane, the hydrogen-containing ring body and the end sealing agent, and preferably, the hydrogen-containing ring body is selected from one or more of the tetramethylhydrogencyclotetrasiloxane and the pentamethylhydrogencyclopentasiloxane.
The end sealing agent comprises hexamethyldisiloxane, tetramethyldihydrodisiloxane and the like, and the using amount of the end sealing agent is 0.5-2% of the total mass of the raw materials. Preferably, the end capping agent is one or more selected from hexamethyldisiloxane and tetramethyldihydrodisiloxane.
The catalyst is perfluorosulfonic acid resin, the using amount of the catalyst is 0.5-5% of the total mass of the raw materials, and preferably, the using amount of the catalyst is 1-5% of the total mass of the raw materials.
Preferably, the polymerization reaction is carried out in a reaction vessel equipped with a stirrer and a thermometer probe;
preferably, the polymerization reaction temperature is 30-80 ℃, and the polymerization time is 2-8 hours, preferably 2-4 hours.
Removing low-boiling-point substances and a catalyst from a product obtained after the polymerization reaction to obtain colorless and transparent hydrogen-containing silicone oil; the temperature for removing low-boiling-point substances is 80-130 ℃, and the vacuum degree is-0.05 to-0.095 MPa; preferably, the temperature for removing low boiling substances is 110 to 130 ℃, and the vacuum degree is-0.05 to-0.095M Pa.
(2) Under the catalysis of Co-MOFs catalyst, the hydrogenous polysiloxane product in the step (1) is oxidized by oxidant to obtain polyhydroxy silicone oil.
Adding hydrogen-containing silicone oil obtained by the polymerization reaction into catalyst Co-MOFs and divalent cobalt (Co) in the Co-MOFs2+) The hydrogen-containing silicone oil is oxidized into trivalent cobalt by hydrogen peroxide and the like, the trivalent cobalt has strong oxidability and better affinity with a silicon-hydrogen bond, silicon-hydrogen can be selectively oxidized into silicon hydroxyl, the trivalent cobalt is reduced into divalent cobalt, the divalent cobalt returns to an initial state, catalytic circulation is completed, and the trivalent cobalt continuously participates in reaction in the presence of the hydrogen peroxide, so that the hydrogen-containing silicone oil is efficiently oxidized to obtain the polyhydroxy silicone oil.
The dosage of the Co-MOFs catalyst is 1-5% of the weight of the hydrogen-containing silicone oil, and preferably, the dosage of the Co-MOFs catalyst is 2-5% of the weight of the hydrogen-containing silicone oil.
The Co-MOFs is a novel metal organic framework porous material, is in a periodic crystal structure formed by coordination and connection of metal ions and organic ligands, and has the characteristics of porosity, high specific surface area and adjustable pore size morphology. The divalent cobalt salt includes cobalt chloride, cobalt acetate, cobalt sulfate, etc. The terephthalic acid includes 1, 4-phthalic acid and 2, 5-dihydroxyterephthalic acid.
The oxidant comprises hydrogen peroxide and the like, preferably hydrogen peroxide, and the using amount of the oxidant is 0.1-5% of hydrogen-containing polysiloxane.
The reaction temperature is 20-50 ℃, and the reaction time is 2-8 hours.
The invention starts from molecular design, selects raw materials such as organosiloxane and the like, and prepares the high-performance polyhydroxy silicone oil by controlling and converting the molecular structure of the organosiloxane. The prepared polyhydroxy silicone oil has the advantages of good transparency, high yield and the like. When used as a medical lubricant, the polyhydroxy silicone oil solves the problems of water insolubility, difficult cleaning and the like when used as a medical lubricant.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polyhydroxy silicone oil prepared by the invention has the characteristics of good hydrophilicity, good stability, high yield, good repeatability and the like.
(2) When the polyhydroxy silicone oil of the invention is used as a medical lubricant instead of conventional methyl silicone oil, the main chain structure of the silicone oil molecule is not changed, so that good lubricating property can still be maintained; meanwhile, the introduction of a plurality of hydroxyl groups improves the hydrophilicity of the silicone oil, is convenient to clean and remove, can avoid the use of a fluorine-containing alkane cleaning agent, and is beneficial to the safety of human bodies.
Detailed Description
The present invention will be described in further detail with reference to examples, but is not limited thereto. The starting materials used in the examples are either commercially available or prepared by conventional methods.
Example 1:
(1) 200Kg of cyclosiloxane (octamethylcyclotetrasiloxane), 25Kg of hydrogen-containing ring body (tetramethylhydrogencyclotetrasiloxane), 2Kg of bis-end-block (hexamethyldisiloxane) and 2.27Kg of acidic resin (perfluorosulfonic acid resin) are added into a 500L reaction kettle, the temperature is controlled at 50 ℃, the stirring reaction is carried out for 8 hours, after the acidic resin is filtered and removed, the temperature is raised to 110 ℃, the vacuum degree is controlled to be more than-0.095 MPa, and low molecular weight substances are removed, so that about 215Kg of clear and transparent hydrogen-containing silicone oil is obtained.
(2) Weighing 100Kg of the product, 5Kg of Co-MOFs and 2Kg of hydrogen peroxide, placing the mixture in a 200L reaction kettle, heating to 50 ℃, reacting for 5 hours, filtering to remove the catalyst, and obtaining clear and transparent polyhydroxy silicone oil with the conversion rate of about 99.9%.
Example 2:
(1) 200Kg of cyclosiloxane (hexamethylcyclotrisiloxane), 5.25Kg of hydrogen-containing ring body (pentamethyl hydrogen cyclopentasiloxane), 4Kg of double seal head (tetramethyl dihydro disiloxane) and 1.05Kg of acid resin (perfluorosulfonic acid resin) are added into a 500L reaction kettle, the temperature is controlled at 30 ℃, the stirring reaction is carried out for 8 hours, after the acid resin is filtered and removed, the temperature is raised to 130 ℃, the vacuum degree is controlled to be more than-0.095 MPa, and low molecular weight substances are removed, so that about 195Kg of clear and transparent hydrogen-containing silicone oil is obtained.
(2) Weighing 100Kg of the product, 1Kg of Co-MOFs and 0.1Kg of hydrogen peroxide, placing the materials in a 200L reaction kettle, heating to 20 ℃, reacting for 8 hours, filtering to remove the catalyst, and obtaining clear and transparent polyhydroxy silicone oil with the conversion rate of about 99.8%.
Example 3:
(1) 200Kg of cyclosiloxane (octamethylcyclotetrasiloxane), 68Kg of hydrogen-containing ring body (pentamethylhydrogencyclopentasiloxane), 4Kg of bis-end-cap (hexamethyldisiloxane) and 13.6Kg of acidic resin (perfluorosulfonic acid resin) are added into a 500L reaction kettle, the temperature is controlled at 80 ℃, the stirring reaction is carried out for 2 hours, after the acidic resin is filtered and removed, the temperature is raised to 115 ℃, the vacuum degree is controlled to be more than-0.095 MPa, and low molecular weight substances are removed, so that about 259Kg of clear and transparent hydrogen-containing silicone oil is obtained.
(2) Weighing 100Kg of the product, 2Kg of Co-MOFs and 5Kg of hydrogen peroxide, placing the mixture in a 200L reaction kettle, heating to 35 ℃, reacting for 2 hours, filtering to remove the catalyst, and obtaining clear and transparent polyhydroxy silicone oil with the conversion rate of about 99.7%.
Example 4:
(1) 200Kg of cyclosiloxane (octamethylcyclotetrasiloxane), 20Kg of hydrogen-containing ring body (pentamethyl hydrogen cyclopentasiloxane), 2Kg of double-end socket (tetramethyl dihydrodisiloxane) and 4.5Kg of acidic resin (perfluorosulfonic acid resin) are added into a 500L reaction kettle, the temperature is controlled at 60 ℃, the stirring reaction is carried out for 3 hours, after the acidic resin is filtered and removed, the temperature is raised to 110 ℃, the vacuum degree is controlled to be more than-0.05 MPa, and low molecular weight substances are removed, so that about 210Kg of clear and transparent hydrogen-containing silicone oil is obtained.
(2) Weighing 100Kg of the product, 3Kg of Co-MOFs and 2Kg of hydrogen peroxide, placing the mixture in a 200L reaction kettle, heating to 40 ℃, reacting for 5 hours, filtering to remove the catalyst, and obtaining clear and transparent polyhydroxy silicone oil with the conversion rate of about 99.6%.
Example 5:
(1) 200Kg of cyclosiloxane (decamethylcyclopentasiloxane), 30Kg of hydrogen-containing ring body (pentamethyl hydrogen cyclopentasiloxane), 3.5Kg of double seal head (tetramethyl dihydrodisiloxane) and 5Kg of acidic resin (perfluorosulfonic acid resin) are added into a 500L reaction kettle, the temperature is controlled at 50 ℃, the stirring reaction is carried out for 4 hours, after the acidic resin is filtered and removed, the temperature is raised to 125 ℃, the vacuum degree is controlled to be more than-0.095 MPa, and low molecular weight substances are removed, so that about 218Kg of clear and transparent hydrogen-containing silicone oil is obtained.
(2) Weighing 100Kg of the product, 4Kg of Co-MOFs and 2.5Kg of hydrogen peroxide, placing the mixture in a 200L reaction kettle, heating to 45 ℃, reacting for 3 hours, filtering to remove the catalyst, and obtaining clear and transparent polyhydroxy silicone oil with the conversion rate of about 99.8%.
Example 6:
(1) 200Kg of cyclosiloxane (decamethylcyclopentasiloxane), 35Kg of hydrocycles (tetramethylhydrocyclotetrasiloxane), 2Kg of bis-end-caps (hexamethyldisiloxane) and 10Kg of acidic resin (perfluorosulfonic acid resin) are added into a 500L reaction kettle, the temperature is controlled at 70 ℃, the mixture is stirred and reacts for 7 hours, after the acidic resin is filtered and removed, the temperature is raised to 115 ℃, the vacuum degree is controlled to be more than-0.095 MPa, and low molecular weight substances are removed, so that about 230Kg of clear and transparent hydrogenous silicone oil is obtained.
(2) Weighing 100Kg of the product, 2.5Kg of Co-MOFs and 3Kg of hydrogen peroxide, placing the mixture in a 200L reaction kettle, heating to 30 ℃, reacting for 7 hours, filtering to remove the catalyst, and obtaining clear and transparent polyhydroxy silicone oil with the conversion rate of about 98.7%.
Example 7:
(1) 200Kg of cyclosiloxane (hexamethylcyclotrisiloxane), 40Kg of hydrogen-containing ring body (tetramethylhydrogencyclotetrasiloxane), 2.5Kg of double-end socket (tetramethyldihydrodisiloxane) and 10Kg of acidic resin (perfluorosulfonic acid resin) are added into a 500L reaction kettle, the temperature is controlled at 60 ℃, the stirring reaction is carried out for 5 hours, after the acidic resin is filtered and removed, the temperature is raised to 130 ℃, the vacuum degree is controlled to be more than-0.095 MPa, and low molecular weight substances are removed, so that about 235Kg of clear and transparent hydrogen-containing silicone oil is obtained.
(2) Weighing 100Kg of the product, 3.5Kg of Co-MOFs and 3.5Kg of hydrogen peroxide, placing the materials in a 200L reaction kettle, heating to 50 ℃, reacting for 6 hours, filtering to remove the catalyst, and obtaining clear and transparent polyhydroxy silicone oil with the conversion rate of about 97.9%.
Example 8:
(1) 200Kg of cyclosiloxane (hexamethylcyclotrisiloxane), 45Kg of hydrosphere (pentamethyl hydrosyclopentasiloxane), 3Kg of bis-end-cap (hexamethyldisiloxane) and 5Kg of acid resin (perfluorosulfonic acid resin) are added into a 500L reaction kettle, the temperature is controlled at 70 ℃, the stirring reaction is carried out for 6 hours, after the acid resin is filtered and removed, the temperature is raised to 120 ℃, the vacuum degree is controlled to be more than-0.05 MPa, and the low molecular weight substances are removed, so that about 233Kg of clear and transparent hydrosilicone oil is obtained.
(2) Weighing 100Kg of the product, 4.5Kg of Co-MOFs4, and 0.5Kg of hydrogen peroxide, placing in a 200L reaction kettle, heating to 40 ℃, reacting for 5 hours, filtering to remove the catalyst, and obtaining clear and transparent polyhydroxy silicone oil with the conversion rate of about 99.2%.
Comparative example 1: (difference from example 1 in that Co-MOFs catalyst was not added)
(1) 200Kg of cyclosiloxane (octamethylcyclotetrasiloxane), 25Kg of hydrogen-containing ring body (tetramethylhydrogencyclotetrasiloxane), 2Kg of bis-end-block (hexamethyldisiloxane) and 2.27Kg of acidic resin (perfluorosulfonic acid resin) are added into a 500L reaction kettle, the temperature is controlled at 50 ℃, the stirring reaction is carried out for 8 hours, after the acidic resin is filtered and removed, the temperature is raised to 110 ℃, the vacuum degree is controlled to be more than-0.095 MPa, and low molecular weight substances are removed, so that about 215Kg of clear and transparent hydrogen-containing silicone oil is obtained.
(2) Weighing 100Kg of the product and 2Kg of hydrogen peroxide, placing the product and the hydrogen peroxide in a 200L reaction kettle, heating to 50 ℃, reacting for 5 hours, and testing the product to find that a large amount of silicon-hydrogen bonds are not completely reacted.
Test example
(1) Water solubility test
And (3) testing conditions are as follows: the polyhydroxy silicone oils prepared in the above examples 1-8 and comparative examples were mixed with water at a ratio of 5: 100 and named examples 1, 2, 3, 4, 5, 6, 7, 8 and comparative examples, respectively. For comparison, a commercially available hydroxy silicone oil (viscocity: 20cSt (25 ℃ C.)) commonly used as a lubricant was selected as a reference, and the results are shown in Table 1:
table 1: water solubility test results:
it was found by the test examples that the polyhydroxy silicone oils prepared in examples 1-8, when formulated with water in a ratio of 5: 100, had the advantages of complete dissolution, clear appearance, long-term stability, etc. It is illustrated that the polyhydroxy silicone oil prepared in this example has a number of hydroxyl groups greater than 2 (commercially available hydroxy silicone oils are generally referred to as polysiloxanes terminated with hydroxyl groups, containing 2 hydroxyl groups).
Finally, it should be noted that the above-mentioned embodiments are only specific embodiments of the present invention, and it is obvious that the present invention is not limited to the above-mentioned embodiments, and many operation combinations are possible.
Claims (10)
1. The preparation method of the polyhydroxy silicone oil is characterized by comprising the following steps:
(1) taking cyclosiloxane, hydrogen-containing rings and a sealing agent as raw materials, and taking perfluorinated sulfonic acid resin as a catalyst to carry out polymerization reaction to obtain hydrogen-containing polysiloxane;
(2) under the catalysis of Co-MOFs catalyst, oxidizing the product of the step (1) by an oxidant to obtain polyhydroxy silicone oil.
2. The method for preparing polyhydroxysilicone oil according to claim 1, wherein the cyclosiloxane in step (1) comprises octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane.
3. The method for preparing polyhydroxy silicone oil according to claim 1, characterized in that, in step (1), the hydrogen-containing cyclic body comprises tetramethylhydrocyclotetrasiloxane and pentamethylhydrocyclopentasiloxane, and the usage amount is 2.5% -25% of the total mass of the raw materials.
4. The method for preparing polyhydroxy silicone oil according to claim 1, wherein the end sealing agent in step (1) comprises hexamethyldisiloxane and tetramethyldihydrodisiloxane, and the amount of the end sealing agent is 0.5-2% of the total mass of the raw materials.
5. The method for preparing polyhydroxy silicone oil according to claim 1, wherein the amount of perfluorosulfonic acid resin used in step (1) is 0.5-5% of the total weight of the raw materials.
6. The method for preparing polyhydroxy silicone oil according to claim 1, characterized in that the polymerization temperature in step (1) is 30-80 ℃ and the polymerization time is 2-8 hours.
7. The method for preparing polyhydroxy silicone oil according to claim 1, characterized in that the Co-MOFs catalyst in step (2) is obtained by reacting terephthalic acid and divalent cobalt salt, and the amount of the Co-MOFs catalyst is 1.0-5% of the weight of the hydrogen-containing silicone oil in step (1).
8. The method for preparing polyhydroxy silicone oil according to claim 1, characterized in that the oxidant in step (2) comprises hydrogen peroxide, and the usage amount is 0.1% -5% of the weight of hydrogen-containing polysiloxane.
9. The method for preparing polyhydroxy silicone oil according to claim 1, characterized in that in step (2), the reaction temperature is 20-50 ℃ and the reaction time is 2-8 hours.
10. Use of the polyhydroxy silicone oil obtained by the method of preparing polyhydroxy silicone oil of claims 1-9 in medical lubricants.
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