CN111234233B - Phenyl silicone resin and preparation method thereof - Google Patents
Phenyl silicone resin and preparation method thereof Download PDFInfo
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- CN111234233B CN111234233B CN202010225711.4A CN202010225711A CN111234233B CN 111234233 B CN111234233 B CN 111234233B CN 202010225711 A CN202010225711 A CN 202010225711A CN 111234233 B CN111234233 B CN 111234233B
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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
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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
- C08G77/06—Preparatory processes
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- 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
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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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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Abstract
The invention provides phenyl silicone resin and a preparation method thereof. The preparation raw materials of the phenyl silicone resin comprise: the modified siloxane prepolymer comprises a chlorine-containing siloxane monomer, an organic solvent, organic amine, hydroxyl-terminated methyl trifluoropropyl siloxane, phenyl silicone resin prepolymer and water. The phenyl silicone machine has excellent mechanical properties and flexibility, and also has the functions of toughening, oil resistance and low surface energy, and meanwhile, has a good modification space.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to phenyl silicone resin and a preparation method thereof.
Background
The phenyl silicone resin is one of organic silicon resin series, is an organic-inorganic hybrid polymer, has a molecular main chain of an inorganic structure with Si-O bonds, has organic groups as side chains, has the properties of heat resistance, electric insulation and the like of common organic silicon materials, also has higher refractive index and good high and low temperature resistance, can be widely used as high-temperature resistant paint, and can also be used for packaging high-power light-emitting diodes. The organic silicon resin is used as a necessary raw material of some high-end organic silicon products, although the dosage is small, the organic silicon resin is indispensable, at present, domestic silicon resin is produced less, and common silicon resin has a highly cross-linked network structure, high hardness and strength and poor toughness; the silicone rubber has a spiral long-chain structure and good elasticity, but is low in crosslinking degree and hardness and easy to scratch.
CN107459652A provides a heat-resistant silicone resin curable at room temperature and a preparation method thereof. The invention firstly synthesizes an alkoxy silane compound containing a hexafluoro butyl aryl ether structure, and then prepares alkoxy-terminated organic silicon resin by copolymerizing with a trifunctional silicon resin prepolymer and hydroxyl silicone oil. The organic silicon resin can be cured at room temperature to reach 450 ℃ after being mixed with trialkoxysilane and a curing catalyst, and has an elastic-plastic silicon resin material. However, the silicone resin material obtained by the method has the defects of low hardness, scratch resistance and the like, so that the application condition of the material is narrow
CN108707231A discloses a preparation method of methyl phenyl silicone resin and a coating. The preparation method comprises the following steps of taking all or part of methyl trichlorosilane, dimethyl dichlorosilane, phenyl trichlorosilane and diphenyl dichlorosilane as monomer raw materials, carrying out cohydrolysis in the presence of an organic solvent which is not soluble in water to generate organic siloxanol, adding 8% tetramethyl ammonium hydroxide butanol solution serving as a nucleophilic reaction catalyst, and carrying out catalytic condensation to finally prepare the organic silicon resin polymer with a specific structure and high reaction activity. However, the heat resistance of the silicone resin material obtained by the method still needs to be further improved.
Therefore, the development of a phenyl silicone resin with high activity and good toughness is currently studied in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide phenyl silicone resin and a preparation method thereof, wherein the phenyl silicone resin has excellent mechanical properties and flexibility, also has the functions of toughening, oil resistance and low surface energy, and also has a good modification space.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a phenyl silicone resin, wherein the preparation raw materials of the phenyl silicone resin comprise: the modified siloxane prepolymer comprises a chlorine-containing siloxane monomer, an organic solvent, organic amine, hydroxyl-terminated methyl trifluoropropyl siloxane, phenyl silicone resin prepolymer and water.
The basic chemical reaction of the phenyl silicone resin is that silicon hydroxyl and silicon chloride bonds are dehydrochlorinated to form silicon-oxygen-silicon bonds. According to the invention, hydroxyl-terminated methyl trifluoropropyl siloxane is added into the phenyl silicone resin, so that the phenyl silicone resin product has both a nano phenyl molecular group and a methyl trifluoropropyl siloxane chain link, and other positions of silicon on the active group silicon hydroxyl are methyl, so that the activity is better. Therefore, the phenyl silicone resin product has the functions of toughening, oil resistance and low surface energy, and simultaneously has good modification space. Meanwhile, fluorine groups are introduced into hydroxyl-terminated methyl trifluoropropyl siloxane, so that the phenyl silicone resin has lower surface energy, oil resistance, antifouling property and excellent anti-sticking property. The dihydroxy polytrifluoropropylmethylsiloxane has terminal hydroxyl groups, so that branched silicone resin and linear silicone are combined, the silicone resin has better flexibility, and application materials needing certain toughness in high-temperature occasions provide possibility.
Preferably, the phenyl silicone resin is prepared from the following raw materials in parts by weight: 10-20 parts of a chlorine-containing siloxane monomer, 600-700 parts of an organic solvent, 30-50 parts of organic amine, 250-350 parts of hydroxyl-terminated methyl trifluoropropyl siloxane, 350-450 parts of a phenyl silicone resin prepolymer and 50-150 parts of water.
In the present invention, the weight parts of the chlorine-containing siloxane monomer are 10 to 20 parts, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, and the like.
In the present invention, the organic solvent may be, for example, 600 to 700 parts by weight, for example, 600 parts, 610 parts, 620 parts, 630 parts, 640 parts, 650 parts, 660 parts, 670 parts, 680 parts, 690 parts, 700 parts, or the like.
In the present invention, the organic amine is 30 to 50 parts by weight, for example, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, and the like.
In the present invention, the hydroxyl-terminated methyltrifluoropropylsiloxane may be 250 to 350 parts by weight, for example, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts, 300 parts, 310 parts, 320 parts, 330 parts, 340 parts, 350 parts, and the like.
In the present invention, the phenyl silicone prepolymer is 350 to 450 parts by weight, for example, 350 parts, 360 parts, 370 parts, 380 parts, 390 parts, 400 parts, 410 parts, 420 parts, 430 parts, 440 parts, 450 parts, etc.
In the present invention, the water is 50 to 150 parts by weight, for example, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, etc.
Preferably, the chlorine-containing siloxane monomer comprises any one of or a combination of at least two of methyldichlorosilane, methyltrichlorosilane, dimethyldichlorosilane or diethyldichlorosilane, preferably dimethyldichlorosilane.
Preferably, the organic solvent comprises any one or a combination of at least two of toluene, xylene and/or methyl isobutyl ketone.
Preferably, the organic amine includes any one of dimethylamine, ethylenediamine, diethylamine, triethylamine or propylenediamine or a combination of at least two thereof.
The polymerization degree of the hydroxyl-terminated methyltrifluoropropylsiloxane is preferably 40 to 150dp, and may be, for example, 40dp, 50dp, 60dp, 70dp, 80dp, 90dp, 100dp, 110dp, 120dp, 130dp, 140dp, 150 dp. The polymerization degree of the hydroxyl-terminated methyl trifluoropropyl siloxane is controlled within the range, so that the mechanical properties and flexibility of the hydroxyl-terminated methyl trifluoropropyl siloxane can be further improved. If the polymerization degree of the hydroxyl-terminated methyl trifluoropropyl siloxane is too high, the phenyl silicone resin has poor fluidity and is easily degraded by heating; if the polymerization degree of the hydroxyl-terminated methyltrifluoropropylsiloxane is too low, the mechanical strength of the phenyl silicone resin is impaired.
Preferably, the end-capping agent of the hydroxy-terminated methyltrifluoropropylsiloxane is a hydroxy-terminated polysiloxane.
Preferably, the hydroxyl-terminated methyltrifluoropropylsiloxane has a fluorine content of 10 to 35%, and may be, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 22%, 24%, 26%, 28%, 30%, 31%, 33%, 35%, or the like. Fluorine groups are introduced into hydroxyl-terminated methyl trifluoropropyl siloxane, so that phenyl silicone resin has lower surface energy, oil resistance, antifouling property and excellent anti-sticking property.
Preferably, the phenyl silicone prepolymer has a solid content of 20 to 40 wt%, and may be, for example, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%, or the like.
Preferably, the weight average molecular weight of the phenyl silicone resin prepolymer is 1000-1500 daltons, such as 1000 daltons, 1100 daltons, 1200 daltons, 1300 daltons, 1400 daltons, 1500 daltons, and the like.
Preferably, the phenyl silicone resin prepolymer is prepared from the following raw materials: chlorosilane mixtures, toluene and water. The preparation method of the phenyl silicone resin comprises the following steps: the chlorosilane mixture and the toluene are added into distilled water in a dropwise manner, wherein the purpose of adding the water is to convert all silicon-chlorine bonds into silicon-hydroxyl bonds, dissolve and absorb hydrogen chloride, and remove tail gas.
Preferably, the mass ratio of the chlorosilane to the toluene is 1 (1-3); wherein "1 to 3" may be, for example, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3.
Preferably, the chlorosilane mixture includes methyltrichlorosilane, dimethyldichlorosilane, methylphenyldichlorosilane, and phenyltrichlorosilane;
preferably, the mass ratio of the methyltrichlorosilane, the dimethyldichlorosilane, the methylphenyldichlorosilane and the phenyltrichlorosilane in the chlorosilane mixture is 1:1:3: 3.
In a second aspect, the present invention provides a method for preparing the phenyl silicone resin according to the first aspect, the method comprising the steps of: mixing and stirring a chlorine-containing siloxane monomer, an organic solvent, organic amine and hydroxyl-terminated methyl trifluoropropyl siloxane, adding a phenyl silicone resin prepolymer, organic amine and water, mixing, hydrolyzing and drying to obtain the phenyl silicone resin.
Preferably, the preparation method specifically comprises the following steps:
(1) dissolving hydroxyl-terminated methyl trifluoropropyl siloxane in an organic solvent, dropwise adding the obtained solution into a mixed solution containing a chlorosilane monomer, the organic solvent and organic amine, and mixing and stirring the obtained solution to obtain a product I;
(2) and (2) adding the product obtained in the step (1) into a mixed solution of a phenyl silicone prepolymer and organic amine one drop by one drop, stirring, filtering, adding water for hydrolysis, and drying to obtain the phenyl silicone.
Preferably, the mixing and stirring of step (1) is carried out under a protective gas, which is nitrogen.
Preferably, the mixing and stirring temperature in the step (1) is 10 to 30 ℃, for example, 10 ℃, 12 ℃, 14 ℃, 16 ℃, 18 ℃, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃ and the like.
Preferably, the mixing and stirring time in the step (1) is 0.5-2 h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, etc., preferably 1 h.
Preferably, the mass ratio of the methyl trifluoropropyl siloxane to the organic solvent in the step (1) is (0.4-0.6): 1; the "0.4 to 0.6" may be, for example, 0.4, 0.42, 0.44, 0.46, 0.48, 0.5, 0.52, 0.54, 0.56, 0.58, 0.6, etc.
Preferably, the mass ratio of the chlorine-containing siloxane monomer, the organic solvent and the organic amine in the step (1) is (1-2): (6-7): 3-5);
wherein, 1-2 can be 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, etc.;
wherein, the '6-7' can be 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, etc.;
wherein, 3 to 5 can be 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, etc.
Preferably, the stirring temperature in step (2) is-10 to 20 ℃, for example, -10 ℃, -5 ℃, 0 ℃, 10 ℃, 15 ℃, 20 ℃ and the like.
Preferably, the stirring time in step (2) is 0.5 to 2 hours, for example, 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1 hour, 1.2 hour, 1.4 hour, 1.6 hour, 1.8 hour and 2 hours, preferably 1 hour.
Preferably, the mass ratio of the phenyl silicone prepolymer to the organic amine in the step (2) is (15-25): 1; wherein, 15 to 25 can be 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, etc.
Preferably, the hydrolysis temperature in the step (2) is-10 to 20 ℃, for example, -10 ℃, -5 ℃, 0 ℃, 10 ℃, 15 ℃, 20 ℃ and the like.
Preferably, the hydrolysis in the step (2) is performed for 20-40 min, such as 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min, and preferably 30 min.
Preferably, the preparation method specifically comprises the following steps:
(1) dissolving hydroxyl-terminated methyl trifluoropropyl siloxane in an organic solvent, wherein the mass ratio of the methyl trifluoropropyl siloxane to the organic solvent is (0.4-0.6): 1, then dropwise adding the mixture into a mixed solution of a chloro siloxane monomer, the organic solvent and organic amine, wherein the mixed solution comprises the chloro siloxane monomer, the organic solvent and the organic amine, and mixing and stirring the mixture for 0.5-2 hours at 10-30 ℃ under the protection of nitrogen to obtain a first product;
(2) and (2) adding the product obtained in the step (1) into a mixed solution of a phenyl silicone prepolymer and organic amine dropwise, stirring for 0.5-2 h at the temperature of-10-20 ℃, filtering, adding water at the temperature of-10-20 ℃, stirring for 20-40 min, and drying to obtain the phenyl silicone resin.
Compared with the prior art, the invention has the following beneficial effects:
(1) the phenyl silicone resin disclosed by the invention has a nano phenyl molecular group and also contains methyl trifluoropropyl siloxane chain links, the activity is better, fluorine groups and terminal hydroxyl groups are introduced into hydroxyl-terminated methyl trifluoropropyl siloxane, so that the phenyl silicone resin has lower surface energy, and is excellent in oil resistance, antifouling property and anti-sticking property, and the branched silicone resin is combined with linear silicone to ensure that the silicone resin has better flexibility.
(2) The phenyl silicone resin has the hardness of 60-80 Shore A, the tensile strength of 2.5-4 MPa, the elongation at break of 50-160% and the surface tension of 15-20 mN/m.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The phenyl silicone prepolymers provided in the following examples were obtained by the following preparation method:
100 parts of chlorosilane mixture (mixture of methyl trichlorosilane, dimethyl dichlorosilane, methyl phenyl dichlorosilane and phenyl trichlorosilane in a mass ratio of 1:1:3: 3) and 200 parts of toluene are added into a three-neck flask and uniformly mixed, 700 parts of distilled water is dropwise added into the mixed solution at room temperature, the dropwise adding time is 30min, the mixed solution reacts at room temperature for 1h after the dropwise adding is finished, the hydrolysis is finished, and then the pre-polymerization is carried out at 50 ℃ for 3h, so that 30 wt% of phenyl silicone resin prepolymer is obtained, and the weight-average molecular weight is 1200.
Example 1
The embodiment provides a phenyl silicone resin, and a preparation method thereof specifically includes the following steps:
(1) dissolving 300 parts of hydroxyl-terminated methyl trifluoropropyl siloxane in 580 parts of toluene, then dropwise adding the solution into a flask filled with a mixed solution of 16 parts of dimethyldichlorosilane, 64 parts of toluene and 20 parts of diethylamine, mixing and stirring the solution for 1 hour at 25 ℃ under the protection of nitrogen, and absorbing tail gas HCl by using 1mol/L sodium hydroxide aqueous solution after the reaction is finished to obtain a product I;
(2) and (2) dropwise adding all the product obtained in the step (1) into a mixed solution containing 400 parts of phenyl silicone resin prepolymer and 20 parts of diethylamine, stirring for 1h at 10 ℃, filtering, adding 100 parts of distilled water at 10 ℃, stirring for 30min, and drying to obtain the phenyl silicone resin.
The polymerization degree of the hydroxyl-terminated methyl trifluoropropyl siloxane is 100dp, the end-capping agent of the hydroxyl-terminated methyl trifluoropropyl siloxane is hydroxyl-terminated polysiloxane, and the fluorine content in the hydroxyl-terminated methyl trifluoropropyl siloxane is 20%.
Example 2
The embodiment provides a phenyl silicone resin, and a preparation method thereof specifically includes the following steps:
(1) dissolving 350 parts of hydroxyl-terminated methyl trifluoropropyl siloxane in 470 parts of toluene, then dropwise adding the dissolved methyl trifluoropropyl siloxane into a flask filled with a mixed solution of 20 parts of diethyldichlorosilane, 60 parts of toluene and 20 parts of triethylamine, mixing and stirring for 1h at 25 ℃ under the protection of nitrogen, and absorbing tail gas HCl by using 1mol/L sodium hydroxide aqueous solution after the reaction is finished to obtain a product I;
(2) and (2) dropwise adding all the product obtained in the step (1) into a mixed solution containing 400 parts of phenyl silicone resin prepolymer and 20 parts of triethylamine, stirring for 1h at 20 ℃, filtering, adding 100 parts of distilled water at 10 ℃, stirring for 30min, and drying to obtain the phenyl silicone resin.
The polymerization degree of the hydroxyl-terminated methyl trifluoropropyl siloxane is 40, the end-capping agent of the hydroxyl-terminated methyl trifluoropropyl siloxane is hydroxyl-terminated polysiloxane, and the fluorine content of the hydroxyl-terminated methyl trifluoropropyl siloxane is 10%.
Example 3
The embodiment provides a phenyl silicone resin, and a preparation method thereof specifically includes the following steps:
(1) dissolving 250 parts of hydroxyl-terminated methyl trifluoropropyl siloxane in 570 parts of toluene, then dropwise adding the dissolved methyl trifluoropropyl siloxane into a flask filled with a mixed solution of 20 parts of diethyldichlorosilane, 60 parts of toluene and 20 parts of triethylamine, mixing and stirring for 1h at 25 ℃ under the protection of nitrogen, and absorbing tail gas HCl by using 1mol/L sodium hydroxide aqueous solution after the reaction is finished to obtain a product I;
(2) and (2) dropwise adding all the product obtained in the step (1) into a mixed solution containing 400 parts of phenyl silicone resin prepolymer and 20 parts of triethylamine, stirring for 1h at 5 ℃, filtering, adding 100 parts of distilled water at 5 ℃, stirring for 30min, and drying to obtain the phenyl silicone resin.
The polymerization degree of the hydroxyl-terminated methyl trifluoropropyl siloxane is 150, the end-capping agent of the hydroxyl-terminated methyl trifluoropropyl siloxane is hydroxyl-terminated polysiloxane, and the fluorine content of the hydroxyl-terminated methyl trifluoropropyl siloxane is 15%.
Example 4
This example provides a phenyl silicone resin, which is different from example 1 only in that the amount of the hydroxyl-terminated methyltrifluoropropylsiloxane added is 200 parts, and the contents of other components and the preparation method are unchanged.
Example 5
This example provides a phenyl silicone resin, which is different from example 1 only in that the amount of the hydroxyl-terminated methyltrifluoropropylsiloxane added is 400 parts, and the contents of other components and the preparation method are unchanged.
Example 6
This example provides a phenyl silicone resin, which is different from example 1 only in that the polymerization degree of the hydroxyl-terminated methyltrifluoropropylsiloxane is 20, and the contents of other components and the preparation method are not changed.
Example 7
This example provides a phenyl silicone resin, which is different from example 1 only in that the polymerization degree of the hydroxyl-terminated methyltrifluoropropylsiloxane is 200, and the contents of other components and the preparation method are unchanged.
Example 8
This example provides a phenyl silicone resin, which is different from example 1 only in that the addition amount of the phenyl silicone resin prepolymer is 300 parts, and the contents of other components and the preparation method are not changed.
Example 9
This example provides a phenyl silicone resin, which is different from example 1 only in that the addition amount of the phenyl silicone resin prepolymer is 500 parts, and the contents of other components and the preparation method are not changed.
Comparative example 1
This comparative example provides a phenyl silicone resin, which differs from example 1 only in that no hydroxy-terminated methyltrifluoropropylsiloxane is added, and the contents of the other components and the preparation method are unchanged.
Comparative example 2
This comparative example provides a phenyl silicone resin, which differs from example 1 only in that the hydroxy-terminated methyltrifluoropropylsiloxane is replaced by a polysiloxane-terminated methyltrifluoropropylsiloxane, and the contents of the other components and the preparation method are unchanged.
Performance testing
After 1% of titanate chelate is added to the phenyl silicone resins prepared in examples 1 to 9 and the phenyl silicone resins prepared in comparative examples 1 to 2, the phenyl silicone resins were cured in a fume hood at room temperature for 7 days, and then various performance tests were performed. Wherein, Shore hardness is tested according to GB/T531.1-2008, tensile strength and elongation are tested according to GB/T528-2009, flexibility: the testing method is that a sheet with the thickness of 1mm and the length of 5cm is folded for 5 times and does not crack to be qualified; surface tension GB/T9286-88. The specific test results are shown in table 1 (wherein "-" represents no test):
TABLE 1
From the above test data, the phenyl silicone resin prepared in embodiments 1 to 9 has a hardness of 60 to 80shore a, a tensile strength of 2.5 to 4MPa, an elongation at break of 50 to 160%, and a surface tension of 15 to 20mN/m, which indicates that the phenyl silicone resin prepared in the present invention has both a nano phenyl molecular group and a methyl trifluoropropyl siloxane chain link, and has a good activity, and the hydroxyl-terminated methyl trifluoropropyl siloxane introduces a fluoro group and a terminal hydroxyl group, so that the phenyl silicone resin has a lower surface energy, is oil-resistant, antifouling, and has an excellent anti-sticking property, and the branched silicone resin is combined with the linear silicone resin, so that the silicone resin has a better flexibility.
In contrast, in comparative example 1, hydroxyl-terminated methyl trifluoropropyl siloxane is not added, the prepared silicone resin has hardness of over 90Shore A, is very brittle, cannot test tensile strength and elongation at break, has no flexibility, and has no fluorine group and terminal hydroxyl group, and the prepared phenyl silicone resin has high surface tension, and has poor oil resistance, antifouling property and anti-sticking property. Comparative example 2 the hydroxyl terminated methyl trifluoropropyl siloxane was replaced with polysiloxane terminated methyl trifluoropropyl siloxane without hydroxyl grafted chlorosilane, the resin was milky white paste that delaminated after long time, did not cure at ambient temperature and could not be tested because the phenyl silicone intermediate was not compatible with methyl trifluoropropyl polysiloxane without grafting and had to be compatible with the aid of solvent.
The applicant states that the present invention is illustrated by the above examples to describe the phenyl silicone resin and the preparation method thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must rely on the above examples to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. The preparation method of the phenyl silicone resin is characterized by specifically comprising the following steps of:
(1) dissolving hydroxyl-terminated methyl trifluoropropyl siloxane in an organic solvent, wherein the mass ratio of the hydroxyl-terminated methyl trifluoropropyl siloxane to the organic solvent is (0.4-0.6): 1, then dropwise adding the hydroxyl-terminated methyl trifluoropropyl siloxane to a mixed solution of a chloro siloxane monomer, the organic solvent and organic amine, wherein the mixed solution has the mass ratio of (1-2): 6-7): 3-5, and mixing and stirring the mixture at the temperature of 10-30 ℃ for 0.5-2 h to obtain a product I;
(2) dropwise adding the product obtained in the step (1) into a mixed solution of a phenyl silicone prepolymer and organic amine in a mass ratio of (15-25): 1, stirring for 0.5-2 h at-10-20 ℃, filtering, adding water, hydrolyzing for 20-40 min at-10-20 ℃, and drying to obtain the phenyl silicone;
the preparation raw materials of the phenyl silicone resin comprise the following components in parts by weight: 10-20 parts of a chlorine-containing siloxane monomer, 600-700 parts of an organic solvent, 30-50 parts of organic amine, 250-350 parts of hydroxyl-terminated methyl trifluoropropyl siloxane, 350-450 parts of a phenyl silicone resin prepolymer and 50-150 parts of water;
the polymerization degree of the hydroxyl-terminated methyl trifluoropropyl siloxane is 40-150 dp, the end-capping agent of the hydroxyl-terminated methyl trifluoropropyl siloxane is hydroxyl-terminated polysiloxane, and the fluorine content in the hydroxyl-terminated methyl trifluoropropyl siloxane is 10-35%;
the solid content of the phenyl silicone resin prepolymer is 20-40 wt%, and the weight average molecular weight of the phenyl silicone resin prepolymer is 1000-1500 daltons;
the preparation raw materials of the phenyl silicone resin prepolymer comprise: chlorosilane mixtures, toluene and water; the mass ratio of the chlorosilane mixture to toluene is 1 (1-3), and the chlorosilane mixture is a mixture of methyltrichlorosilane, dimethyldichlorosilane, methylphenyldichlorosilane and phenyltrichlorosilane in a mass ratio of 1:1:3: 3.
2. The method for preparing phenylsilicone resin according to claim 1, wherein the chlorine-containing siloxane monomer comprises any one or a combination of at least two of methyldichlorosilane, methyltrichlorosilane, dimethyldichlorosilane or diethyldichlorosilane.
3. The method for preparing phenyl silicone resin according to claim 2, wherein the chlorine-containing siloxane monomer is dimethyldichlorosilane.
4. The method of claim 1, wherein the organic solvent comprises any one or a combination of at least two of toluene, xylene, and/or methyl isobutyl ketone.
5. The method of claim 1, wherein the organic amine comprises one or a combination of at least two of dimethylamine, ethylenediamine, diethylamine, triethylamine or propylenediamine.
6. The method for preparing phenyl silicone resin according to claim 1, wherein the mixing and stirring in step (1) are performed under a protective gas, wherein the protective gas is nitrogen.
7. The method for preparing phenyl silicone resin according to claim 1, wherein the mixing and stirring time in step (1) is 1 h.
8. The method for preparing phenyl silicone resin according to claim 1, wherein the stirring time in step (2) is 1 h.
9. The method for preparing phenyl silicone resin according to claim 1, wherein the hydrolysis of step (2) is performed for 30 min.
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| CN103204994B (en) * | 2013-04-16 | 2015-06-10 | 江苏大学 | Preparation method of phenyl silicon resin |
| CN110408034B (en) * | 2019-08-16 | 2021-07-13 | 湖北兴瑞硅材料有限公司 | Synthetic method of phenyl block silicone resin |
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