CN116875065A - Preparation method of methyl phenyl silicone resin - Google Patents
Preparation method of methyl phenyl silicone resin Download PDFInfo
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- CN116875065A CN116875065A CN202310880895.1A CN202310880895A CN116875065A CN 116875065 A CN116875065 A CN 116875065A CN 202310880895 A CN202310880895 A CN 202310880895A CN 116875065 A CN116875065 A CN 116875065A
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 82
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 88
- 238000003756 stirring Methods 0.000 claims abstract description 80
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 52
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000725 suspension Substances 0.000 claims abstract description 50
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000000945 filler Substances 0.000 claims abstract description 31
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 31
- WPUJEWVVTKLMQI-UHFFFAOYSA-N benzene;ethoxyethane Chemical compound CCOCC.C1=CC=CC=C1 WPUJEWVVTKLMQI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003381 stabilizer Substances 0.000 claims abstract description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000077 silane Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 86
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 83
- 239000006229 carbon black Substances 0.000 claims description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 34
- -1 tolylene phenyldichlorosilane Chemical compound 0.000 claims description 31
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 29
- 239000005054 phenyltrichlorosilane Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000004821 distillation Methods 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 17
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 239000007970 homogeneous dispersion Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000000265 homogenisation Methods 0.000 abstract description 3
- 229940105289 carbon black Drugs 0.000 description 79
- 235000019241 carbon black Nutrition 0.000 description 79
- 239000002002 slurry Substances 0.000 description 21
- 238000005507 spraying Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 11
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical group O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- 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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of methyl phenyl silicone resin, which comprises the steps of preparing chlorosilane mixed solution; adding the octahydroxybutyl POSS into the diethyl ether-benzene mixed solution, stirring uniformly, performing ultrasonic dispersion for 20-30min to obtain a suspension, adding the chlorosilane mixed solution, and performing low-temperature ultrasonic treatment for 20-30min to obtain a suspension mixed solution; adding the mixed suspension into a reaction kettle, introducing mixed gas, standing for 2-3h, then distilling under reduced pressure, and performing ultrasonic dispersion to obtain a silane prepolymer mixture; adding modified filler into the prepolymer, dispersing at low temperature, and then reacting the catalyst at constant temperature for 2-5h to obtain prefabricated methyl phenyl silicone resin; adding the stabilizer into the prefabricated methyl phenyl silicone resin, and uniformly stirring to obtain the methyl phenyl silicone resin. According to the invention, the heat-resistant stability of the methylphenyl silicone resin is effectively improved by utilizing the modification and the silicon hydroxyl characteristics of the octahydroxybutyl POSS, and excellent compatibility with the methylphenyl silicone resin is realized by utilizing the self silicon hydroxyl homogenization structure of the octahydroxybutyl POSS.
Description
Technical Field
The invention belongs to the technical field of silicone rubber, and particularly relates to a preparation method of methyl phenyl silicone resin.
Background
The organic silicon macromolecule is a polymer which contains element silicon in a molecular structure and has an organic group connected with a silicon atom, and is also called polysiloxane. The methyl phenyl silicone resin has excellent high and low temperature resistance, irradiation resistance and electrical insulation property, is widely applied to the fields of aerospace, mechanical and electronic, building and the like, has one of the largest uses, is used for preparing organic silicone paint, especially special paint to meet the special requirements of military industry, is obviously superior to methyl silicone resin in aspects of thermoelasticity, mechanical property, cohesiveness, glossiness, coordination with organic matters and inorganic fillers and the like due to the introduction of phenyl siloxane chain links, and can be widely applied to products such as high-temperature resistant insulating paint, high-temperature resistant adhesive, high-temperature resistant molding packaging material, ablative material, trapezoid polymer, silicone resin micropowder and the like, and is one of the most used and widely applied varieties of the current silicone resin. However, the polycondensation method is the most commonly used method for the methylphenyl silicone resin, also called as condensed type methylphenyl silicone resin, and the methylphenyl silicone resin prepared by the polycondensation method has the problems of low glass transition temperature and poor heat resistance stability.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of methyl phenyl silicone resin, which solves the problem of poor thermal stability of condensed methyl phenyl silicone resin, and utilizes the modification of octahydroxybutyl POSS and the characteristic of silicon hydroxyl, thereby not only effectively improving the heat-resistant stability of the methyl phenyl silicone resin, but also utilizing the silicon hydroxyl homogenization structure of octahydroxybutyl POSS to realize excellent compatibility with the methyl phenyl silicone resin.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of methyl phenyl silicone resin comprises the following steps:
step 1, mixing methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane at a low temperature by stirring to form a chlorosilane mixed solution, wherein the volume ratio of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane is 1:1:5-7:3-5, and the stirring speed of low-temperature stirring and mixing is 100-200r/min and the temperature is 5-10 ℃; the step utilizes the physical state that methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluenephenyldichlorosilane are all liquid, and can form homogeneous dispersive mixing in a low-temperature environment;
step 2, adding the octahydroxybutyl POSS into the diethyl ether-benzene mixed solution, uniformly stirring, performing ultrasonic dispersion for 20-30min to obtain a suspension, adding the chlorosilane mixed solution, and performing low-temperature ultrasonic treatment for 20-30min to obtain the suspension mixed solution; the concentration of the octahydroxybutyl POSS in the diethyl ether-benzene mixed solution is 1-3g/L, the volume ratio of diethyl ether to benzene in the diethyl ether-benzene mixed solution is 4:1-2, and the stirring speed of uniform stirring is 200-400r/min; the ultrasonic frequency of the ultrasonic dispersion is 60-80kHz, and the temperature is 5-10 ℃; the concentration of the chlorosilane mixed solution in the suspension mixed solution is 400-600g/L, the temperature of the low-temperature ultrasonic treatment is 5-10 ℃, and the ultrasonic frequency is 50-80kHz; the method comprises the steps of putting octahydroxybutyl POSS into an ether-benzene mixed solution for uniform dispersion, carrying out ultrasonic treatment under a low-temperature environment, and uniformly dispersing octahydroxybutyl POSS in the whole system, wherein when a chlorosilane mixed solution is added, the chlorosilane mixed solution has good solubility in ether and benzene, so that the chlorosilane mixed solution in the suspension mixed solution can be uniformly dispersed in the ether-benzene mixed solution, and the octahydroxybutyl POSS forms uniform dispersion in the low-temperature ultrasonic dispersion, and ensures the suspension state of the octahydroxybutyl POSS by matching with the viscosity of the chlorosilane mixed solution;
step 3, adding the mixed suspension into a reaction kettle, introducing mixed gas, standing for 2-3 hours, then performing reduced pressure distillation, and performing ultrasonic dispersion to obtain a silane prepolymer mixture, wherein the mixed gas is formed by mixing water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 8-10:1, the introducing speed is 4-7mL/min, and the standing temperature is 5-10 ℃; the pressure of the reduced pressure distillation is 80-90% of the atmospheric pressure, and the temperature is 20-30 ℃; the ultrasonic frequency of the ultrasonic dispersion is 70-80kHz, and the temperature is 10-15 ℃; the method comprises the steps of converting the whole reaction kettle atmosphere into a water vapor-containing atmosphere by utilizing mixed gas, and effectively controlling the content of water molecules in a solution by utilizing the slightly soluble characteristic of diethyl ether and benzene on distilled water, so that the hydrolysis reaction of chlorosilane mixed solution is effectively controlled, and the chlorosilane mixed solution is converted into a prepolymer; the viscosity of the prepolymer is greatly increased, and the octahydroxybutyl POSS can be promoted to be dispersed in the whole system in a low-temperature ultrasonic mode; meanwhile, the reduced pressure distillation system can convert diethyl ether into steam for direct recovery, and convert the solvent into benzene solution;
step 4, adding modified filler into the prepolymer, dispersing at low temperature to form a homogeneous dispersion liquid, and then reacting the catalyst at constant temperature for 2-5h to obtain the prefabricated methyl phenyl silicone resin; the modified filler adopts silane modified gas-phase white carbon black, the addition amount of the modified filler is 10-20% of the mass of the chlorosilane mixed solution, the low-temperature dispersion adopts low-temperature ultrasonic treatment, the ultrasonic frequency is 60-80kHz, and the temperature is 5-10 ℃; the addition amount of the catalyst is 1-2% of the mass of the chlorosilane mixed solution, the catalyst adopts triethylene diamine, the catalyst is rapidly stirred before the constant temperature reaction, the stirring speed is 1000-2000r/min, the temperature of the constant temperature reaction is 60-65 ℃, and the vacuum degree is 0.06MPa; the step utilizes silane modified filler as solid material to be uniformly dispersed in the prepolymer to form a homogenized dispersion system; dispersing and reacting at constant temperature after adding the catalyst to realize polycondensation reaction;
and 5, adding a stabilizer into the prefabricated methyl phenyl silicone resin, and uniformly stirring to obtain the methyl phenyl silicone resin, wherein acetic acid is adopted as the stabilizer, the adding amount of the stabilizer is 0.2-0.5% of the mass of the prefabricated methyl phenyl silicone resin, and the stirring speed is 100-300r/min.
Wherein the modified filler adopts silane modified gas-phase white carbon black, and particularly adopts trihydroxy phenyl silicone resin modified gas-phase white carbon black. The gas-phase white carbon black is one of extremely important nanoscale inorganic raw materials, and has the advantages of large specific surface area, strong surface adsorption force, large surface energy, high chemical purity, good dispersion performance, thermal resistance and electric resistance because of small particle sizeThe product has specific performance in the aspects of excellent stability, reinforcement, thickening and thixotropic property. The fumed silica is based on silicon dioxide, and has certain activity on the surface, so that the connection stability is general, and the heat-resistant stability after the fumed silica is added is not obviously improved; the modification treatment of the gas-phase white carbon black is to form a stable silica shell layer on the surface of the gas-phase white carbon black, wherein the shell layer has a mesoporous structure and an active hydroxyl structure, and meanwhile, the same material is needed to be noted in the prepolymer of the mixed solution of the trihydroxy phenyl silicone resin and the chlorosilane on the surface of the structure, and a stable polycondensation reaction is formed in the subsequent catalytic polycondensation, so that a good curing effect is realized; the preparation method of the modified filler comprises the following steps: a1, adding gas-phase white carbon black into diethyl ether, uniformly stirring to form slurry, and performing ball milling treatment on the slurry for 10-20min to obtain white carbon black slurry, wherein the mass ratio of the gas-phase white carbon black to the diethyl ether is 10-12:1, the uniform stirring speed is 200-400r/min, the ball milling treatment pressure is 0.2-0.3MPa, and the temperature is 5-10 ℃; the step utilizes wet ball milling to disperse and refine the gas-phase white carbon black, thereby achieving the dispersive white carbon black slurry; a2, adding diethyl ether into the white carbon black slurry, and performing ultrasonic treatment for 20-30min to obtain white carbon black suspension, wherein the white carbon black concentration in the white carbon black suspension is 100-500g/L, the ultrasonic frequency of ultrasonic treatment is 40-60kHz, and the temperature is 5-10 ℃; the method comprises the steps of uniformly dispersing white carbon black in diethyl ether in an ultrasonic manner to form dispersion; a3, adding phenyl trichlorosilane into the white carbon black suspension, performing ultrasonic treatment for 20-30min, and then performing reduced pressure distillation to form a concentrated solution; the addition amount of the phenyl trichlorosilane is 1-2% of the mass of the gas-phase white carbon black, the ultrasonic frequency of ultrasonic treatment is 60-80kHz, and the temperature is 5-10 ℃; the pressure of the reduced pressure distillation is 80-90% of the atmospheric pressure, and the temperature is 30-35 ℃; a4, carrying out suction filtration on the concentrated solution to obtain filter residues, then spraying the filter residues into a reaction kettle for sedimentation to obtain the trihydroxyphenyl modified fumed silica, wherein the spraying speed is 5-10g/min, and the spraying area is 200-400cm 2 The atmosphere of the reaction kettle is a mixed atmosphere of nitrogen and steam, the volume ratio of the nitrogen to the steam is 10-12:1, and the temperature is 35-40 ℃; the step uses suction filtration to make diethyl etherAnd removing the redundant phenyl trichlorosilane, only depositing a liquid film on the surface of the gas-phase white carbon black, spraying the gas-phase white carbon black with the liquid film on the surface to form hydrolysis conversion of the trichlorophenyl silane, and forming the gas-phase white carbon black coated with the surface trihydroxy phenyl silicone resin. The modified gas-phase white carbon black prepared by the process utilizes the silicon hydroxyl groups on the trihydroxy phenyl silicone resin and the hydroxyl groups on the gas-phase white carbon black to form a polycondensation structure so as to achieve stable connection, and meanwhile, the trihydroxy phenyl silicone resin forms a surface film to form a trihydroxy phenyl silicone resin polycondensate rich in hydroxyl groups and phenyl groups, and the surface film modified gas-phase white carbon black can form stable connection with the hydroxyl groups in the silane prepolymer mixture, so that the overall thermal stability is improved.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of poor thermal stability of condensed methyl phenyl silicone resin, and utilizes the characteristics of the modification and the silicon hydroxyl of the octahydroxybutyl POSS to effectively improve the heat-resistant stability of the methyl phenyl silicone resin, and also utilizes the silicon hydroxyl homogenization structure of the octahydroxybutyl POSS to realize excellent compatibility with the methyl phenyl silicone resin.
2. The invention uses gas phase white carbon black as filler, forms a composite nano silicon oxide series permeation structure with octahydroxybutyl POSS, and uses gas phase white carbon black to modify to form a polyhydroxy active structure, thereby improving the stability of the white carbon black in methyl phenyl silicone resin.
3. The invention uses diethyl ether and benzene as solvents, and uses the solubility of the mixture of chlorosilane and the slight solubility of the mixture of chlorosilane and water to effectively control a hydrolysis reaction system, thereby achieving the effect of controlling the hydrolysis reaction of the mixture of chlorosilane.
Detailed Description
The invention is described in detail with reference to examples, but without any limitation to the claims of the invention.
Example 1
A preparation method of methyl phenyl silicone resin comprises the following steps:
step 1, mixing methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane at a low temperature by stirring to form a chlorosilane mixed solution, wherein the volume ratio of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane is 1:1:5:3, and the stirring speed of low-temperature stirring and mixing is 100r/min, and the temperature is 5 ℃;
step 2, adding the octahydroxybutyl POSS into the diethyl ether-benzene mixed solution, stirring uniformly, performing ultrasonic dispersion for 20min to obtain a suspension, adding the chlorosilane mixed solution, and performing low-temperature ultrasonic treatment for 20min to obtain the suspension; the concentration of the octahydroxybutyl POSS in the diethyl ether-benzene mixed solution is 1g/L, the volume ratio of diethyl ether to benzene in the diethyl ether-benzene mixed solution is 4:1, and the stirring speed of uniform stirring is 200r/min; the ultrasonic frequency of the ultrasonic dispersion is 60kHz, and the temperature is 5 ℃; the concentration of the chlorosilane mixed solution in the suspension mixed solution is 400g/L, the temperature of the low-temperature ultrasonic treatment is 5 ℃, and the ultrasonic frequency is 50kHz;
step 3, adding the mixed suspension into a reaction kettle, introducing mixed gas, standing for 2 hours, then performing reduced pressure distillation, and performing ultrasonic dispersion to obtain a silane prepolymer mixture, wherein the mixed gas is formed by mixing water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 8:1, the introducing speed is 4mL/min, and the standing temperature is 5 ℃; the pressure of the reduced pressure distillation is 80% of the atmospheric pressure, and the temperature is 20 ℃; the ultrasonic frequency of the ultrasonic dispersion is 70kHz, and the temperature is 10 ℃;
step 4, adding modified filler into the prepolymer, dispersing at low temperature to form a homogeneous dispersion liquid, and then reacting the catalyst at constant temperature for 2 hours to obtain the prefabricated methyl phenyl silicone resin; the modified filler adopts silane modified gas-phase white carbon black, the addition amount of the modified filler is 10% of the mass of the chlorosilane mixed solution, the low-temperature dispersion adopts low-temperature ultrasonic treatment, the ultrasonic frequency is 60kHz, and the temperature is 5 ℃; the addition amount of the catalyst is 1% of the mass of the chlorosilane mixed solution, the catalyst adopts triethylene diamine, the catalyst is rapidly stirred before the constant-temperature reaction, the stirring speed is 1000r/min, the temperature of the constant-temperature reaction is 60 ℃, and the vacuum degree is 0.06MPa;
and 5, adding a stabilizer into the prefabricated methyl phenyl silicone resin, and uniformly stirring to obtain the methyl phenyl silicone resin, wherein acetic acid is adopted as the stabilizer, the adding amount of the stabilizer is 0.2% of the mass of the prefabricated methyl phenyl silicone resin, and the stirring speed is 100r/min.
Wherein, the modified filler adopts silane modified gas-phase white carbon black, and particularly adopts trihydroxy phenyl silicone resin modified gas-phase white carbon black; the preparation method of the modified filler comprises the following steps: a1, adding gas-phase white carbon black into diethyl ether, uniformly stirring to form slurry, and then performing ball milling treatment on the slurry for 10min to obtain white carbon black slurry, wherein the mass ratio of the gas-phase white carbon black to the diethyl ether is 10:1, the uniform stirring speed is 200r/min, the ball milling treatment pressure is 0.2MPa, and the temperature is 5 ℃; a2, adding diethyl ether into the white carbon black slurry, and performing ultrasonic treatment for 20min to obtain white carbon black suspension, wherein the white carbon black concentration in the white carbon black suspension is 100g/L, the ultrasonic frequency of ultrasonic treatment is 40kHz, and the temperature is 5 ℃; a3, adding phenyl trichlorosilane into the white carbon black suspension, performing ultrasonic treatment for 20min, and then performing reduced pressure distillation to form a concentrated solution; the addition amount of the phenyl trichlorosilane is 1% of the mass of the gas-phase white carbon black, the ultrasonic frequency of ultrasonic treatment is 60kHz, and the temperature is 5 ℃; the pressure of the reduced pressure distillation is 80% of the atmospheric pressure, and the temperature is 30 ℃; a4, carrying out suction filtration on the concentrated solution to obtain filter residues, then spraying the filter residues into a reaction kettle for sedimentation to obtain the trihydroxyphenyl modified fumed silica, wherein the spraying speed is 5g/min, and the spraying area is 200cm 2 The atmosphere of the reaction kettle is the mixed atmosphere of nitrogen and water vapor, the volume ratio of the nitrogen to the water vapor is 10:1, and the temperature is 35 ℃.
Example 2
A preparation method of methyl phenyl silicone resin comprises the following steps:
step 1, mixing methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane at a low temperature by stirring to form a chlorosilane mixed solution, wherein the volume ratio of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane is 1:1:7:5, and the stirring speed of low-temperature stirring and mixing is 200r/min, and the temperature is 10 ℃;
step 2, adding the octahydroxybutyl POSS into the diethyl ether-benzene mixed solution, stirring uniformly, performing ultrasonic dispersion for 30min to obtain a suspension, adding the chlorosilane mixed solution, and performing low-temperature ultrasonic treatment for 30min to obtain the suspension; the concentration of the octahydroxybutyl POSS in the diethyl ether-benzene mixed solution is 3g/L, the volume ratio of diethyl ether to benzene in the diethyl ether-benzene mixed solution is 4:2, and the stirring speed of uniform stirring is 400r/min; the ultrasonic frequency of the ultrasonic dispersion is 80kHz, and the temperature is 10 ℃; the concentration of the chlorosilane mixed solution in the suspension mixed solution is 600g/L, the temperature of the low-temperature ultrasonic treatment is 10 ℃, and the ultrasonic frequency is 80kHz;
step 3, adding the mixed suspension into a reaction kettle, introducing mixed gas, standing for 3 hours, then performing reduced pressure distillation, and performing ultrasonic dispersion to obtain a silane prepolymer mixture, wherein the mixed gas is formed by mixing water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 10:1, the introducing speed is 7mL/min, and the standing temperature is 10 ℃; the pressure of the reduced pressure distillation is 90% of the atmospheric pressure, and the temperature is 30 ℃; the ultrasonic frequency of the ultrasonic dispersion is 80kHz, and the temperature is 15 ℃;
step 4, adding modified filler into the prepolymer, dispersing at low temperature to form a homogeneous dispersion liquid, and then reacting the catalyst at constant temperature for 5 hours to obtain the prefabricated methyl phenyl silicone resin; the modified filler adopts silane modified gas-phase white carbon black, the addition amount of the modified filler is 20% of the mass of the chlorosilane mixed solution, the low-temperature dispersion adopts low-temperature ultrasonic treatment, the ultrasonic frequency is 80kHz, and the temperature is 10 ℃; the addition amount of the catalyst is 2% of the mass of the chlorosilane mixed solution, the catalyst adopts triethylene diamine, the catalyst is rapidly stirred before the constant-temperature reaction, the stirring speed is 2000r/min, the temperature of the constant-temperature reaction is 65 ℃, and the vacuum degree is 0.06MPa;
and 5, adding a stabilizer into the prefabricated methyl phenyl silicone resin, and uniformly stirring to obtain the methyl phenyl silicone resin, wherein acetic acid is adopted as the stabilizer, the adding amount of the stabilizer is 0.5% of the mass of the prefabricated methyl phenyl silicone resin, and the stirring speed is-300 r/min.
Wherein the modified filler adopts silane modified gas-phase white carbon black, and particularly adopts trihydroxy phenyl silicone resin modified gas-phase white carbonBlack; the preparation method of the modified filler comprises the following steps: a1, adding gas-phase white carbon black into diethyl ether, uniformly stirring to form slurry, and then performing ball milling treatment on the slurry for 20min to obtain white carbon black slurry, wherein the mass ratio of the gas-phase white carbon black to the diethyl ether is 12:1, the uniform stirring speed is 400r/min, the ball milling treatment pressure is 0.3MPa, and the temperature is 10 ℃; a2, adding diethyl ether into the white carbon black slurry, and performing ultrasonic treatment for 30min to obtain white carbon black suspension, wherein the white carbon black concentration in the white carbon black suspension is 500g/L, the ultrasonic frequency of ultrasonic treatment is 60kHz, and the temperature is 10 ℃; a3, adding phenyl trichlorosilane into the white carbon black suspension, performing ultrasonic treatment for 30min, and then performing reduced pressure distillation to form a concentrated solution; the addition amount of the phenyl trichlorosilane is 2% of the mass of the gas-phase white carbon black, the ultrasonic frequency of ultrasonic treatment is 80kHz, and the temperature is 10 ℃; the pressure of the reduced pressure distillation is 90% of the atmospheric pressure, and the temperature is 35 ℃; a4, carrying out suction filtration on the concentrated solution to obtain filter residues, then spraying the filter residues into a reaction kettle for sedimentation to obtain the trihydroxyphenyl modified fumed silica, wherein the spraying speed is 10g/min, and the spraying area is 400cm 2 The atmosphere of the reaction kettle is a mixed atmosphere of nitrogen and water vapor, the volume ratio of the nitrogen to the water vapor is 12:1, and the temperature is 40 ℃.
Example 3
A preparation method of methyl phenyl silicone resin comprises the following steps:
step 1, mixing methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane at a low temperature by stirring to form a chlorosilane mixed solution, wherein the volume ratio of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane is 1:1:6:4, and the stirring speed of low-temperature stirring and mixing is 150r/min, and the temperature is 8 ℃;
step 2, adding the octahydroxybutyl POSS into the diethyl ether-benzene mixed solution, stirring uniformly, performing ultrasonic dispersion for 25min to obtain a suspension, adding the chlorosilane mixed solution, and performing low-temperature ultrasonic treatment for 25min to obtain the suspension; the concentration of the octahydroxybutyl POSS in the diethyl ether-benzene mixed solution is 2g/L, the volume ratio of diethyl ether to benzene in the diethyl ether-benzene mixed solution is 4:1, and the stirring speed of uniform stirring is 300r/min; the ultrasonic frequency of the ultrasonic dispersion is 70kHz, and the temperature is 8 ℃; the concentration of the chlorosilane mixed solution in the suspension mixed solution is 500g/L, the temperature of the low-temperature ultrasonic treatment is 8 ℃, and the ultrasonic frequency is 70kHz;
step 3, adding the mixed suspension into a reaction kettle, introducing mixed gas, standing for 2 hours, then performing reduced pressure distillation, and performing ultrasonic dispersion to obtain a silane prepolymer mixture, wherein the mixed gas is formed by mixing water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 9:1, the introducing speed is 6mL/min, and the standing temperature is 8 ℃; the pressure of the reduced pressure distillation is 85% of the atmospheric pressure, and the temperature is 25 ℃; the ultrasonic frequency of the ultrasonic dispersion is 75kHz, and the temperature is 12 ℃;
step 4, adding modified filler into the prepolymer, dispersing at low temperature to form a homogeneous dispersion liquid, and then reacting the catalyst at constant temperature for 4 hours to obtain the prefabricated methyl phenyl silicone resin; the modified filler adopts silane modified gas-phase white carbon black, the addition amount of the modified filler is 15% of the mass of the chlorosilane mixed solution, the low-temperature dispersion adopts low-temperature ultrasonic treatment, the ultrasonic frequency is 70kHz, and the temperature is 8 ℃; the addition amount of the catalyst is 2% of the mass of the chlorosilane mixed solution, the catalyst adopts triethylene diamine, the catalyst is rapidly stirred before the constant-temperature reaction, the stirring speed is 1500r/min, the temperature of the constant-temperature reaction is 63 ℃, and the vacuum degree is 0.06MPa;
and 5, adding a stabilizer into the prefabricated methyl phenyl silicone resin, and uniformly stirring to obtain the methyl phenyl silicone resin, wherein acetic acid is adopted as the stabilizer, the adding amount of the stabilizer is 0.4% of the mass of the prefabricated methyl phenyl silicone resin, and the stirring speed is 200r/min.
Wherein, the modified filler adopts silane modified gas-phase white carbon black, and particularly adopts trihydroxy phenyl silicone resin modified gas-phase white carbon black; the preparation method of the modified filler comprises the following steps: a1, adding gas-phase white carbon black into diethyl ether, uniformly stirring to form slurry, and then performing ball milling treatment on the slurry for 15min to obtain white carbon black slurry, wherein the mass ratio of the gas-phase white carbon black to the diethyl ether is 11:1, the uniform stirring speed is 300r/min, and the ball milling treatment pressure is adopted0.3MPa and 8 ℃; a2, adding diethyl ether into the white carbon black slurry, and performing ultrasonic treatment for 25min to obtain white carbon black suspension, wherein the white carbon black concentration in the white carbon black suspension is 300g/L, the ultrasonic frequency of ultrasonic treatment is 50kHz, and the temperature is 8 ℃; a3, adding phenyl trichlorosilane into the white carbon black suspension, performing ultrasonic treatment for 25min, and then performing reduced pressure distillation to form a concentrated solution; the addition amount of the phenyl trichlorosilane is 2% of the mass of the gas-phase white carbon black, the ultrasonic frequency of ultrasonic treatment is 70kHz, and the temperature is 8 ℃; the pressure of the reduced pressure distillation is 85% of the atmospheric pressure, and the temperature is 33 ℃; a4, carrying out suction filtration on the concentrated solution to obtain filter residues, then spraying the filter residues into a reaction kettle for sedimentation to obtain the trihydroxyphenyl modified fumed silica, wherein the spraying speed is 8g/min, and the spraying area is 300cm 2 The atmosphere of the reaction kettle is the mixed atmosphere of nitrogen and water vapor, the volume ratio of the nitrogen to the water vapor is 11:1, and the temperature is 38 ℃.
Comparative example 1
A preparation method of methyl phenyl silicone resin comprises the following steps:
step 1, mixing methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane at a low temperature by stirring to form a chlorosilane mixed solution, wherein the volume ratio of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane is 1:1:6:4, and the stirring speed of low-temperature stirring and mixing is 150r/min, and the temperature is 8 ℃;
step 2, adding the octahydroxybutyl POSS into the diethyl ether-benzene mixed solution, stirring uniformly, performing ultrasonic dispersion for 25min to obtain a suspension, adding the chlorosilane mixed solution, and performing low-temperature ultrasonic treatment for 25min to obtain the suspension; the concentration of the octahydroxybutyl POSS in the diethyl ether-benzene mixed solution is 2g/L, the volume ratio of diethyl ether to benzene in the diethyl ether-benzene mixed solution is 4:1, and the stirring speed of uniform stirring is 300r/min; the ultrasonic frequency of the ultrasonic dispersion is 70kHz, and the temperature is 8 ℃; the concentration of the chlorosilane mixed solution in the suspension mixed solution is 500g/L, the temperature of the low-temperature ultrasonic treatment is 8 ℃, and the ultrasonic frequency is 70kHz;
step 3, adding the mixed suspension into a reaction kettle, introducing mixed gas, standing for 2 hours, then performing reduced pressure distillation, and performing ultrasonic dispersion to obtain a silane prepolymer mixture, wherein the mixed gas is formed by mixing water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 9:1, the introducing speed is 6mL/min, and the standing temperature is 8 ℃; the pressure of the reduced pressure distillation is 85% of the atmospheric pressure, and the temperature is 25 ℃; the ultrasonic frequency of the ultrasonic dispersion is 75kHz, and the temperature is 12 ℃;
step 4, adding the gas-phase white carbon black into the prepolymer, dispersing at low temperature to form a homogeneous dispersion liquid, and then reacting the catalyst at constant temperature for 4 hours to obtain the prefabricated methyl phenyl silicone resin; the addition amount of the gas-phase white carbon black is 15% of the mass of the chlorosilane mixed solution, the low-temperature dispersion is carried out by adopting low-temperature ultrasonic treatment, the ultrasonic frequency is 70kHz, and the temperature is 8 ℃; the addition amount of the catalyst is 2% of the mass of the chlorosilane mixed solution, the catalyst adopts triethylene diamine, the catalyst is rapidly stirred before the constant-temperature reaction, the stirring speed is 1500r/min, the temperature of the constant-temperature reaction is 63 ℃, and the vacuum degree is 0.06MPa;
and 5, adding a stabilizer into the prefabricated methyl phenyl silicone resin, and uniformly stirring to obtain the methyl phenyl silicone resin, wherein acetic acid is adopted as the stabilizer, the adding amount of the stabilizer is 0.4% of the mass of the prefabricated methyl phenyl silicone resin, and the stirring speed is 200r/min.
Comparative example 2
A preparation method of methyl phenyl silicone resin comprises the following steps:
step 1, mixing methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane at a low temperature by stirring to form a chlorosilane mixed solution, wherein the volume ratio of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane is 1:1:6:4, and the stirring speed of low-temperature stirring and mixing is 150r/min, and the temperature is 8 ℃;
step 2, adding the chlorosilane mixed solution into the diethyl ether-benzene mixed solution, uniformly stirring, and carrying out low-temperature ultrasonic treatment for 25min to obtain a suspension mixed solution; the volume ratio of diethyl ether to benzene in the diethyl ether-benzene mixed solution is 4:1, the concentration of the chlorosilane mixed solution in the suspension mixed solution is 500g/L, the temperature of low-temperature ultrasonic treatment is 8 ℃, and the ultrasonic frequency is 70kHz;
step 3, adding the mixed suspension into a reaction kettle, introducing mixed gas, standing for 2 hours, then performing reduced pressure distillation, and performing ultrasonic dispersion to obtain a silane prepolymer mixture, wherein the mixed gas is formed by mixing water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 9:1, the introducing speed is 6mL/min, and the standing temperature is 8 ℃; the pressure of the reduced pressure distillation is 85% of the atmospheric pressure, and the temperature is 25 ℃; the ultrasonic frequency of the ultrasonic dispersion is 75kHz, and the temperature is 12 ℃;
step 4, adding modified filler into the prepolymer, dispersing at low temperature to form a homogeneous dispersion liquid, and then reacting the catalyst at constant temperature for 4 hours to obtain the prefabricated methyl phenyl silicone resin; the modified filler adopts silane modified gas-phase white carbon black, the addition amount of the modified filler is 15% of the mass of the chlorosilane mixed solution, the low-temperature dispersion adopts low-temperature ultrasonic treatment, the ultrasonic frequency is 70kHz, and the temperature is 8 ℃; the addition amount of the catalyst is 2% of the mass of the chlorosilane mixed solution, the catalyst adopts triethylene diamine, the catalyst is rapidly stirred before the constant-temperature reaction, the stirring speed is 1500r/min, the temperature of the constant-temperature reaction is 63 ℃, and the vacuum degree is 0.06MPa;
and 5, adding a stabilizer into the prefabricated methyl phenyl silicone resin, and uniformly stirring to obtain the methyl phenyl silicone resin, wherein acetic acid is adopted as the stabilizer, the adding amount of the stabilizer is 0.4% of the mass of the prefabricated methyl phenyl silicone resin, and the stirring speed is 200r/min.
Wherein, the modified filler adopts silane modified gas-phase white carbon black, and particularly adopts trihydroxy phenyl silicone resin modified gas-phase white carbon black; the preparation method of the modified filler comprises the following steps: a1, adding gas-phase white carbon black into diethyl ether, uniformly stirring to form slurry, and then performing ball milling treatment on the slurry for 15min to obtain white carbon black slurry, wherein the mass ratio of the gas-phase white carbon black to the diethyl ether is 11:1, the uniform stirring speed is 300r/min, the ball milling treatment pressure is 0.3MPa, and the temperature is 8 ℃; a2, adding diethyl ether into the white carbon black slurry, and performing ultrasonic treatment for 25min to obtain a white carbon black suspension, wherein the concentration of the white carbon black in the white carbon black suspension is as follows300g/L, the ultrasonic frequency of ultrasonic treatment is 50kHz, and the temperature is 8 ℃; a3, adding phenyl trichlorosilane into the white carbon black suspension, performing ultrasonic treatment for 25min, and then performing reduced pressure distillation to form a concentrated solution; the addition amount of the phenyl trichlorosilane is 2% of the mass of the gas-phase white carbon black, the ultrasonic frequency of ultrasonic treatment is 70kHz, and the temperature is 8 ℃; the pressure of the reduced pressure distillation is 85% of the atmospheric pressure, and the temperature is 33 ℃; a4, carrying out suction filtration on the concentrated solution to obtain filter residues, then spraying the filter residues into a reaction kettle for sedimentation to obtain the trihydroxyphenyl modified fumed silica, wherein the spraying speed is 8g/min, and the spraying area is 300cm 2 The atmosphere of the reaction kettle is the mixed atmosphere of nitrogen and water vapor, the volume ratio of the nitrogen to the water vapor is 11:1, and the temperature is 38 ℃.
Comparative example 3
A preparation method of methyl phenyl silicone resin comprises the following steps:
step 1, mixing methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane at a low temperature by stirring to form a chlorosilane mixed solution, wherein the volume ratio of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluylene phenyldichlorosilane is 1:1:6:4, and the stirring speed of low-temperature stirring and mixing is 150r/min, and the temperature is 8 ℃;
step 2, adding the chlorosilane mixed solution into the diethyl ether-benzene mixed solution, uniformly stirring, and carrying out low-temperature ultrasonic treatment for 25min to obtain a suspension mixed solution; the volume ratio of diethyl ether to benzene in the diethyl ether-benzene mixed solution is 4:1, the concentration of the chlorosilane mixed solution in the suspension mixed solution is 500g/L, the temperature of low-temperature ultrasonic treatment is 8 ℃, and the ultrasonic frequency is 70kHz;
step 3, adding the mixed suspension into a reaction kettle, introducing mixed gas, standing for 2 hours, then performing reduced pressure distillation, and performing ultrasonic dispersion to obtain a silane prepolymer mixture, wherein the mixed gas is formed by mixing water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 9:1, the introducing speed is 6mL/min, and the standing temperature is 8 ℃; the pressure of the reduced pressure distillation is 85% of the atmospheric pressure, and the temperature is 25 ℃; the ultrasonic frequency of the ultrasonic dispersion is 75kHz, and the temperature is 12 ℃;
step 4, adding the gas-phase white carbon black into the prepolymer, dispersing at low temperature to form a homogeneous dispersion liquid, and then reacting the catalyst at constant temperature for 4 hours to obtain the prefabricated methyl phenyl silicone resin; the addition amount of the gas-phase white carbon black is 15% of the mass of the chlorosilane mixed solution, the low-temperature dispersion is carried out by adopting low-temperature ultrasonic treatment, the ultrasonic frequency is 70kHz, and the temperature is 8 ℃; the addition amount of the catalyst is 2% of the mass of the chlorosilane mixed solution, the catalyst adopts triethylene diamine, the catalyst is rapidly stirred before the constant-temperature reaction, the stirring speed is 1500r/min, the temperature of the constant-temperature reaction is 63 ℃, and the vacuum degree is 0.06MPa;
and 5, adding a stabilizer into the prefabricated methyl phenyl silicone resin, and uniformly stirring to obtain the methyl phenyl silicone resin, wherein acetic acid is adopted as the stabilizer, the adding amount of the stabilizer is 0.4% of the mass of the prefabricated methyl phenyl silicone resin, and the stirring speed is 200r/min.
Performance detection
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (9)
1. A preparation method of methyl phenyl silicone resin is characterized in that: the method comprises the following steps:
step 1, mixing methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and toluenephenyldichlorosilane at a low temperature under stirring to form a chlorosilane mixed solution;
step 2, adding the octahydroxybutyl POSS into the diethyl ether-benzene mixed solution, uniformly stirring, performing ultrasonic dispersion for 20-30min to obtain a suspension, adding the chlorosilane mixed solution, and performing low-temperature ultrasonic treatment for 20-30min to obtain the suspension mixed solution;
step 3, adding the mixed suspension into a reaction kettle, introducing mixed gas, standing for 2-3h, then performing reduced pressure distillation, and performing ultrasonic dispersion to obtain a silane prepolymer mixture;
step 4, adding modified filler into the prepolymer, dispersing at low temperature to form a homogeneous dispersion liquid, and then reacting the catalyst at constant temperature for 2-5h to obtain the prefabricated methyl phenyl silicone resin;
and 5, adding the stabilizer into the prefabricated methyl phenyl silicone resin, and uniformly stirring to obtain the methyl phenyl silicone resin.
2. The method for preparing methylphenyl silicone resin according to claim 1, characterized in that: the volume ratio of the methyltrichlorosilane to the dimethyldichlorosilane to the phenyltrichlorosilane to the tolylene phenyldichlorosilane in the step 1 is 1:1:5-7:3-5, the stirring speed of low-temperature stirring and mixing is 100-200r/min, and the temperature is 5-10 ℃.
3. The method for preparing methylphenyl silicone resin according to claim 1, characterized in that: the concentration of the octahydroxybutyl POSS in the step 2 in the diethyl ether-benzene mixed solution is 1-3g/L, the volume ratio of diethyl ether to benzene in the diethyl ether-benzene mixed solution is 4:1-2, and the stirring speed of uniform stirring is 200-400r/min; the ultrasonic frequency of the ultrasonic dispersion is 60-80kHz, and the temperature is 5-10 ℃. .
4. The method for preparing methylphenyl silicone resin according to claim 1, characterized in that: the concentration of the chlorosilane mixed solution in the step 2 in the suspension mixed solution is 400-600g/L, the temperature of the low-temperature ultrasonic treatment is 5-10 ℃, and the ultrasonic frequency is 50-80kHz.
5. The method for preparing methylphenyl silicone resin according to claim 1, characterized in that: the mixed gas in the step 3 is formed by mixing water vapor and nitrogen, the volume ratio of the water vapor to the nitrogen is 8-10:1, the introducing speed is 4-7mL/min, and the standing temperature is 5-10 ℃. .
6. The method for preparing methylphenyl silicone resin according to claim 1, characterized in that: the pressure of reduced pressure distillation in the step 3 is 80-90% of atmospheric pressure, and the temperature is 20-30 ℃; the ultrasonic frequency of the ultrasonic dispersion is 70-80kHz, and the temperature is 10-15 ℃.
7. The method for preparing methylphenyl silicone resin according to claim 1, characterized in that: the modified filler in the step 4 adopts silane modified gas-phase white carbon black, the addition amount of the modified filler is 10-20% of the mass of the chlorosilane mixed solution, the low-temperature dispersion adopts low-temperature ultrasonic treatment, the ultrasonic frequency is 60-80kHz, and the temperature is 5-10 ℃.
8. The method for preparing methylphenyl silicone resin according to claim 1, characterized in that: the addition amount of the catalyst in the step 4 is 1-2% of the mass of the chlorosilane mixed solution, the catalyst adopts triethylene diamine, the catalyst is rapidly stirred before the constant-temperature reaction, the stirring speed is 1000-2000r/min, the constant-temperature reaction temperature is 60-65 ℃, and the vacuum degree is 0.06MPa.
9. The method for preparing methylphenyl silicone resin according to claim 1, characterized in that: the stabilizer in the step 5 adopts acetic acid, the adding amount of the stabilizer is 0.2-0.5% of the mass of the prefabricated methyl phenyl silicone resin, and the stirring speed is 100-300r/min.
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