CN116102733A - Solid pure organic silicon resin, preparation method thereof and organic silicon resin composition - Google Patents
Solid pure organic silicon resin, preparation method thereof and organic silicon resin composition Download PDFInfo
- Publication number
- CN116102733A CN116102733A CN202310055293.2A CN202310055293A CN116102733A CN 116102733 A CN116102733 A CN 116102733A CN 202310055293 A CN202310055293 A CN 202310055293A CN 116102733 A CN116102733 A CN 116102733A
- Authority
- CN
- China
- Prior art keywords
- organic silicon
- silicon resin
- solid
- silicone resin
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007787 solid Substances 0.000 title claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 30
- 239000010703 silicon Substances 0.000 title claims abstract description 30
- 239000011342 resin composition Substances 0.000 title claims abstract description 25
- 229920005989 resin Polymers 0.000 title claims abstract description 23
- 239000011347 resin Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006482 condensation reaction Methods 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000012074 organic phase Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000000413 hydrolysate Substances 0.000 claims abstract 4
- 239000012071 phase Substances 0.000 claims abstract 2
- 229920002050 silicone resin Polymers 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 5
- 239000012803 melt mixture Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical group C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012463 white pigment Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012943 hotmelt Substances 0.000 description 4
- -1 oxy silane Chemical compound 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZAADUWCLWTWDSZ-UHFFFAOYSA-N dichloro-dodecyl-methylsilane Chemical compound CCCCCCCCCCCC[Si](C)(Cl)Cl ZAADUWCLWTWDSZ-UHFFFAOYSA-N 0.000 description 2
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 235000014692 zinc oxide Nutrition 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
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a solid pure organic silicon resin, a preparation method thereof and an organic silicon resin composition. The preparation method of the solid pure organic silicon resin comprises the following steps: r is R 4 MeSiCl 2 Deionized water, hydrochloric acid and toluene to form a first mixed solution; and R is taken as 5 MeSiCl 2 And PhR 6 SiCl 2 Forming a second mixed solution; the second mixture is dripped into the first mixture to carry out hydrolysis reaction, thus obtaining the second mixtureA hydrolysate; adding disilane monomers into the first hydrolysate to continue hydrolysis reaction, and separating an organic phase and a water phase from the obtained product; and (3) regulating the pH value of the organic phase separated in the step (S3) to 7.8-8.2, performing condensation reaction to obtain a condensation reaction product, and removing the solvent and low-boiling substances from the condensation reaction product to obtain the solid organic silicon resin. The solid pure organic silicon resin has better softening point and melt viscosity.
Description
The patent application of the invention is a divisional application. The invention of the original application is named as follows: a solid pure organic silicon resin and a preparation method thereof; the application date is as follows: 2021. 11 months and 30 days; application number 202111461162.1.
Technical Field
The invention relates to the field of high polymer materials, in particular to solid pure organic silicon resin, a preparation method thereof and an organic silicon resin composition.
Technical Field
The silicone resin is thermosetting polyorganosiloxane with a highly cross-linked structure, and has excellent heat resistance, cold resistance, weather resistance, electrical insulation, hydrophobicity, anti-sticking and demolding properties and the like compared with other organic resins due to the special structure; therefore, it is widely used as a high and low temperature resistant insulating paint, a heat resistant paint, a weather resistant paint, an ablation resistant paint, a high and low temperature resistant electrically insulating molding compound, and the like.
If the silicone resin has a melting point lower than 40 ℃, the silicone resin is not solid or is a solid having a viscous surface, and it is difficult to mold. While the softening point of the solid silicone resin is high, the silicone resin is difficult to be uniformly mixed with other components at the conventional batching temperature (usually below 100 ℃) when the molding compound is batched; in addition, in molding of a molding compound, it is generally necessary to control the molding temperature to a high temperature of 150 to 190℃in order to improve the mold filling property of the molding compound, and these defects result in poor low-temperature processability of the silicone molding compound, and it is difficult to achieve compounding and molding at a relatively low temperature.
Disclosure of Invention
On the basis of taking up previous research experience, the invention aims to provide the solid pure organic silicon resin which has better softening point and melt viscosity, is suitable for preparing organic silicon resin composition with better processability and solidifiability, and the other aims to provide the preparation method for the organic silicon resin composition, so that the industrial production is facilitated.
A solid pure silicone resin having a structure according to formula 1, formula 1:
the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 2 ＝-CH 3， -CH=CH 2， -Ph，-C 8 H 16， -C 12 H 25， />
，-C 3 H 6 SH；R 3 =
，-Ph ；
n, m and q are any integer and satisfy n.gtoreq.1, m.gtoreq.1, q.gtoreq.gtoreq.0.
The molecular weight of the solid pure organic silicon resin is 2000-50000 units.
The solid pure organic silicon resin is prepared by mixing a monomer R 2 MeSiCl and PhR 3 SiCl 2 Is prepared by hydrolytic copolymerization, wherein R 2 ＝-CH 3， -CH=CH 2 ，-Ph，-C 8 H 16， -C 12 H 25 ,
，-C 3 H 6 SH；R 3 =/>
， -Ph。
The solid pure organic silicon resin is blocked by trimethylchlorosilane or triphenylchlorosilane.
Method for preparing the solid pure organic silicon resin, R is selected from the following components 2 The MeSiCl is polymerized into a linear high molecular polymer, namely an A chain link according to a certain proportion; and then put PhR 3 SiCl 2 The various monomers are mixed, hydrolyzed and copolymerized according to a certain proportion to obtainA silicone resin with a three-dimensional structure or a T-shaped structure, and the molecular formula is a B chain link; the a-mer and the B-mer are then physically blended or chemically copolymerized into a macromolecular polymer having blocks.
The softening point of the solid pure organic silicon resin is 40-70 ℃.
A silicone resin composition comprising a solid pure silicone resin of the structure of formula 1.
The organic silicon resin composition also comprises a cross-linking agent and an inorganic filler.
The cross-linking agent is one of tetrahydroxy silane, vinyl tripropoxy silane, tetramethoxy silane, tetraacetyl oxy silane, phenyl tributyl ketoxime silane and tetraisopropyl oxy silane.
The inorganic filler comprises one or more of silicon dioxide, pyrogenic titanium dioxide, calcium carbonate, diatomite, aluminum oxide, aluminum hydroxide, zinc oxide, zinc carbonate and white pigment.
The object of the present invention is to provide a novel solid pure silicone resin, and a composition made of the silicone resin prepared by the present invention has hot melt property and excellent processability and curability.
Description of the embodiments
The present invention will be further described in detail with reference to the following embodiments, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Softening point of hot-melt silicone: the hot-melt silicones were placed on a hot plate set to 25 ℃ to 100 ℃, doctor blades were used to confirm their state, and the liquefaction temperature was adopted as the softening point.
Melt viscosity: the melt viscosity of the hot melt silicone and curable particulate silicone resin compositions at 100 ℃ was measured using a rheometer AR 2000EX (manufactured by TA Instruments Japan inc.) at a shear rate of 5 (1/s).
Example 1
In a reactor equipped with a stirrer, a thermometer and a condensing reflux element, starting the stirrer, adding 5mol of methyl vinyl dichlorosilane, 30mol of deionized water, 6mol of hydrochloric acid with the concentration of 0.05N and 1500ml of toluene to form a first mixed solution;
slowly heating the reactor while slowly dropping a second mixed solution consisting of 2mol of methylvinyldichlorosilane, 7mol of diphenyldichlorosilane and 1500ml of toluene into the reactor;
after the second mixed liquid is added dropwise, keeping the internal temperature of the reactor at 180 ℃, carrying out hydrolysis reaction for 3 hours in a reflux state to obtain a hydrolysis reaction product, and adding 5mol of dimethyl dichlorosilane for reaction for 1 hour; cooling and standing the obtained hydrolysis reaction product for layering, and separating an organic phase and an aqueous phase;
the separated organic phase is added into a reactor with the same setting as the reactor after the pH value is adjusted to 8 by potassium hydroxide, a stirrer is started, the internal temperature of the reactor is kept at 175 ℃, and condensation reaction is carried out for 5 hours under the reflux state, thus obtaining a condensation reaction product; and removing the solvent and low-boiling-point substances in the condensation reaction product through reduced pressure distillation to obtain colorless transparent solid, namely the solid pure organic silicon resin.
Example 2
In a reactor equipped with a stirrer, a thermometer and a condensing reflux element, 5mol of methyldodecyl dichlorosilane, 40mol of deionized water, 4.5mol of hydrochloric acid with the concentration of 0.05N and 2000ml of toluene are added into the reactor to form a first mixed solution by starting the stirrer;
slowly heating the reactor while slowly dropwise adding a second mixed solution consisting of 5mol of diphenyldichlorosilane, 2mol of methyldodecyldichlorosilane and 1600ml of toluene into the reactor;
after the second mixed liquid is added dropwise, keeping the internal temperature of the reactor at 140 ℃, and carrying out hydrolysis reaction for 15 hours under a reflux state to obtain a hydrolysis reaction product, wherein if 3mol of diphenyl dichlorosilane is used, the reaction is carried out for 1.5 hours; cooling and standing the obtained hydrolysis reaction product for layering, and separating an organic phase and an aqueous phase;
the separated organic phase is added into a reactor with the same setting as the reactor after the pH value is regulated to 8.2 by potassium hydroxide, a stirrer is started, the internal temperature of the reactor is kept at 180 ℃, and condensation reaction is carried out for 5 hours under the reflux state, thus obtaining a condensation reaction product; and removing the solvent and low-boiling-point substances in the condensation reaction product through reduced pressure distillation to obtain colorless transparent solid, namely the solid pure organic silicon resin.
Example 3
In a reactor equipped with a stirrer, a thermometer and a condensing reflux element, starting the stirrer, adding 3mol of methyl mercapto propyl dichlorosilane, 40ml of deionized water, 4.5mol of hydrochloric acid with the concentration of 0.05N and 2000ml of toluene to form a first mixed solution;
slowly heating the reactor while slowly dropwise adding a second mixed solution consisting of 7mol of diphenyl dichlorosilane, 2mol of methyl mercapto propyl dichlorosilane and 1600ml of toluene into the reactor;
after the second mixed liquid is added dropwise, keeping the internal temperature of the reactor at 120 ℃, carrying out hydrolysis reaction for 10 hours under a reflux state to obtain a hydrolysis reaction product, adding 3mol of dimethyl dichlorosilane, and reacting for 0.5 hour; cooling and standing the obtained hydrolysis reaction product for layering, and separating an organic phase and an aqueous phase;
the separated organic phase is added into a reactor with the same setting as the reactor after the pH value is regulated to 7.8 by potassium hydroxide, a stirrer is started, the internal temperature of the reactor is kept at 130 ℃, and condensation reaction is carried out for 3 hours under the reflux state, thus obtaining a condensation reaction product; and removing the solvent and low-boiling-point substances in the condensation reaction product through reduced pressure distillation to obtain colorless transparent solid, namely the solid pure organic silicon resin.
Properties of the silicone resins described in Table 1
As can be seen from Table 1, the silicone resin prepared by the invention has better softening point and melt viscosity.
Examples 4 to 6 preparation of Silicone resin compositions
The preparation method comprises the following steps: 100 parts by weight of the silicone resin prepared in examples 1 to 3, 7 parts by weight of a crosslinking agent (tetraethoxysilane), 400 parts by weight of an inorganic filler (silica), 1 part by weight of a condensation catalyst (dibutyltin dilaurate), and 40 parts by weight of a white pigment (rutile type titanium dioxide) were uniformly mixed and then added to a kneader, melt mixing treatment was performed at 40 ℃, and the obtained melt mixture was cooled and solidified and pulverized into particles, whereby silicone resin compositions were obtained, the properties of which are shown in table 2.
Characterization of low temperature processability: the components of the silicone resin composition were mixed uniformly and then fed into a kneader, and melt-mixing treatment was performed at 40 ℃, and the obtained melt mixture was cooled and solidified and pulverized into particles. The obtained pellets were fed into a transfer molding machine, and the pellets were pushed into a metal mold having a cavity size of 50cm×50cm×5mm at 80 ℃ under a pressure of 7MPa, and held for 200 seconds for molding. After the mold was cooled to room temperature, the molded article was taken out as a test sample by opening the mold. The appearance of the test sample was evaluated by naked eyes. If less than 5 cracks or pores appear on the surface of the test sample, the test sample is marked as O; if more than 5 cracks or voids appear on the surface of the test sample, it is marked as "X".
Curability: curability was evaluated using a rheometer MDR 2000 (manufactured by Alpha Technologies, ltd.). In examples 1 to 4, the curing temperature was 150 ℃. For the measurement, when the torque value is 100% after three minutes of measurement, the time (seconds) taken to obtain a 1% torque value is indicated by T1, and the time (seconds) taken to obtain a 90% torque value is indicated by T90.
Moldability: the silicone resin composition was cast with a copper lead frame using a transfer molding machine to prepare a molded product having a length of 35mm, a width of 25mm and a height of 1 mm. In examples 4 to 6, the molding conditions were a molding temperature of 150℃and a press-bonding time of 120 seconds. The molded product was removed from the metal mold, cooled to 25 ℃, and then visually inspected for molding defects such as the presence or absence of breakage, peeling from the lead frame, and the like.
Hardness of the cured product: the silicone resin composition was heated at 150 ℃ for two hours to prepare a cured product. The hardness of the cured product was measured by a type D durometer specified in JIS K7215-1986, "durometer hardness test method for Plastic (Durometer hardness testing method for plastics)".
Flexural strength of cured product: the silicone resin composition was heated at 150 ℃ for two hours to prepare a cured product. The flexural strength of the cured product was measured by a method specified in JIS K6911-1955, "general test method for thermosetting plastics (General testing method for thermosetting plastics)".
Characterization of weather resistance: the silicone resin composition was compression molded into test specimens having dimensions of 10mm by 2 mm. The test sample is placed in an ultraviolet-visible spectrophotometer, the light reflectivity at 350nm-400nm is measured and is recorded as initial reflectivity r 0 . Then, after taking out the test sample and placing it in an environment at a temperature of 85℃and a relative humidity of 85% for 1000 hours, the light reflectance at 350nm to 400nm was measured again and recorded as the final reflectance r 1 . By the formula: Δr= ((r) 0 -r 1 )/r 0 ) 100% and the amount of attenuation Δr (%) of the reflectance was calculated, thereby characterizing the weather resistance of the silicone resin composition.
TABLE 2 Performance index of Silicone resin compositions
As can be seen from Table 2, the test results show that the silicone resin compositions of examples 4 to 6 of the present invention all have low-temperature processability, and good moldability and weather resistance.
Claims (10)
1. The preparation method of the solid pure organic silicon resin is characterized by comprising the following steps of:
s1, monomer R 4 MeSiCl 2 Deionized water, hydrochloric acid and toluene to form a first mixed solution; and the monomers R 5 MeSiCl 2 And monomer PhR 6 SiCl 2 Forming a second mixed solution;
s2, dropwise adding the second mixture into the first mixture to carry out hydrolysis reaction to obtain a first hydrolysate;
s3, adding disilane monomers into the first hydrolysate to continue hydrolysis reaction, and separating an organic phase and a water phase from the obtained product;
s4, carrying out condensation reaction on the organic phase separated in the step S3 to obtain a condensation reaction product, and removing a solvent and low-boiling-point substances from the condensation reaction product to obtain the solid organic silicon resin;
wherein R is 4 And R is 5 Are all selected from-ch=ch 2 、-C 8 H 16 、-C 12 H 25 、
、-C 3 H 6 Any one of SH;
R 6 selected from the group consisting of
or-Ph; q is more than or equal to 0;
preferably, the disilane monomer is dimethyldichlorosilane or diphenyldichlorosilane.
2. The process according to claim 1, wherein the monomers R 4 MeSiCl 2 Monomer R 5 MeSiCl 2 Monomers PhR 6 SiCl 2 And a disilane monomer in a molar ratio of (3-5): 2: (5-7): (3-5).
3. The preparation method according to claim 1, wherein in the step S2, the temperature of the hydrolysis reaction is 120-180 ℃, and the time of the hydrolysis reaction is 3-15 hours;
preferably, in the step S3, the time of the hydrolysis reaction is 0.5-1.5 h;
preferably, in the step S4, the temperature of the condensation reaction is 130-180 ℃, and the time of the condensation reaction is 3-5 hours.
4. The preparation method of claim 1, wherein the molecular weight of the solid pure organic silicon resin is 2000-50000;
preferably, the softening point of the solid pure organic silicon resin is 40-70 ℃.
5. A solid, pure silicone resin, characterized in that it is prepared by the preparation method according to any one of claims 1 to 4.
6. The solid, pure silicone resin of claim 5, wherein the solid, pure silicone resin has a structure according to formula (i):
R 2 selected from-CH 3, -ch=ch 2 、-Ph、-C 8 H 16 、-C 12 H 25 、
、-C 3 H 6 Any one of SH;
R 3 selected from the group consisting of
or-Ph; />
n, m and q are any integer and satisfy n.gtoreq.1, m.gtoreq.1, q.gtoreq.gtoreq.0.
7. A silicone resin composition comprising the solid pure silicone resin of claim 5 or 6 and a cross-linking agent.
8. The silicone resin composition of claim 7, wherein the cross-linking agent is one of tetrahydroxysilane, vinyltripropoxysilane, tetramethoxysilane, tetraacetoxysilane, phenyltributylketoxime silane, tetraisopropoxysilane.
9. The silicone resin composition according to claim 7 or 8, wherein the silicone resin composition further comprises an inorganic filler and a condensation catalyst;
preferably, the inorganic filler comprises one or more of silica, fumed titania, calcium carbonate, diatomaceous earth, alumina, aluminum hydroxide, zinc oxide, zinc carbonate, white pigment;
preferably, the condensation catalyst is dibutyl tin dilaurate.
10. A method of preparing a silicone resin composition as set forth in any one of claims 7 to 9, comprising the steps of: and (3) uniformly mixing the solid organic silicon resin, the cross-linking agent, the inorganic filler and the catalyst, adding the mixture into a kneader, carrying out melt mixing treatment to obtain a melt mixture, and then cooling and solidifying the melt mixture and then crushing the melt mixture to obtain the organic silicon resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310055293.2A CN116102733A (en) | 2021-11-30 | 2021-11-30 | Solid pure organic silicon resin, preparation method thereof and organic silicon resin composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310055293.2A CN116102733A (en) | 2021-11-30 | 2021-11-30 | Solid pure organic silicon resin, preparation method thereof and organic silicon resin composition |
| CN202111461162.1A CN113968972A (en) | 2021-11-30 | 2021-11-30 | Solid pure organic silicon resin and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111461162.1A Division CN113968972A (en) | 2021-11-30 | 2021-11-30 | Solid pure organic silicon resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116102733A true CN116102733A (en) | 2023-05-12 |
Family
ID=79590538
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111461162.1A Pending CN113968972A (en) | 2021-11-30 | 2021-11-30 | Solid pure organic silicon resin and preparation method thereof |
| CN202310055293.2A Pending CN116102733A (en) | 2021-11-30 | 2021-11-30 | Solid pure organic silicon resin, preparation method thereof and organic silicon resin composition |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111461162.1A Pending CN113968972A (en) | 2021-11-30 | 2021-11-30 | Solid pure organic silicon resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN113968972A (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012797B (en) * | 2012-11-23 | 2015-03-11 | 广东聚合有机硅材料有限公司 | Preparation method of methyl phenyl vinyl silicone oil |
| JP6348446B2 (en) * | 2015-04-15 | 2018-06-27 | 信越化学工業株式会社 | Branched organopolysiloxane and method for producing the same |
| CN107501942B (en) * | 2017-08-29 | 2020-10-02 | 北京康美特科技股份有限公司 | Moldable silicone resin, composition and semiconductor light-emitting element thereof |
| CN111454456B (en) * | 2020-05-20 | 2022-04-22 | 湖北兴瑞硅材料有限公司 | Synthesis method of high-performance phenyl block silicone resin |
| CN113087912A (en) * | 2021-03-01 | 2021-07-09 | 陈亚荣 | Processing technology of heat-resistant high-viscosity benzyl silicone oil |
-
2021
- 2021-11-30 CN CN202111461162.1A patent/CN113968972A/en active Pending
- 2021-11-30 CN CN202310055293.2A patent/CN116102733A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN113968972A (en) | 2022-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101505626B1 (en) | White heat-curable silicone resin composition, optoelectronic part case, and molding method | |
| TWI465519B (en) | Polysiloxane resin composition for optical semiconductor devices | |
| JP4801320B2 (en) | Addition reaction curable organopolysiloxane resin composition | |
| TWI393747B (en) | Silicone resin composition and pre-mold package | |
| KR101569533B1 (en) | Composition for silicone resin | |
| US8658755B2 (en) | Silicon-containing curable composition and cured product thereof | |
| EP2295499B1 (en) | Underfill composition and an optical semiconductor device | |
| JP5793824B2 (en) | Organosilicon compound, thermosetting composition containing the organosilicon compound, and sealing material for optical semiconductor | |
| KR20070085392A (en) | Silicone composition and cured silicone resin | |
| EP3037457A1 (en) | Curable silicone resin composition | |
| KR20130073894A (en) | Novel organosilicon compound and thermosetting resin composition, cured resin, and semiconductor sealing material containing said organosilicon compound | |
| JP2010031269A (en) | Thermosetting silicone resin-epoxy resin composition, and pre-mold package formed with the same | |
| KR101141110B1 (en) | Polymer obtained with silsesquioxane derivative | |
| KR20110132533A (en) | Composition for thermosetting silicone resin | |
| JP2014177570A (en) | Thermosetting silicone resin composition | |
| JP2003012767A (en) | Curable epoxy resin composition | |
| JPH06298897A (en) | Curable resin composition | |
| TWI665236B (en) | Moldable organic silicon resin, composition and semiconductor light emitting element thereof | |
| JP6627705B2 (en) | Thermosetting silicone resin composition, optical semiconductor device and semiconductor package using the molded product | |
| US9403983B2 (en) | White thermosetting silicone resin composition for a light-emitting semiconductor device and a case for installing a light-emitting semiconductor element | |
| JPH03275726A (en) | Silicone-based block polymer and production thereof | |
| CN116102733A (en) | Solid pure organic silicon resin, preparation method thereof and organic silicon resin composition | |
| US20070142573A1 (en) | Epoxy/silicone hybrid resin composition and cured part | |
| JP2011132299A (en) | Silicone resin composition | |
| JPH01299827A (en) | Mtq/polysiloxane mixed resin, its production and coating/injection sealing composition containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Country or region after: China Address after: Unit 405, Building C1, Innovation Building, No. 182 Science Avenue, Science City, Guangzhou High tech Industrial Development Zone, Guangzhou City, Guangdong Province Applicant after: Guangzhou Sloco New Materials Co.,Ltd. Address before: No. 182, Science Avenue, Innovation Building, Science City, Guangzhou Development Zone, Guangdong Province, China Applicant before: GUANGZHOU SILOK POLYMER Co.,Ltd. Country or region before: China |