CN112898574B - Preparation method of organic silicon resin - Google Patents
Preparation method of organic silicon resin Download PDFInfo
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- CN112898574B CN112898574B CN202110357633.8A CN202110357633A CN112898574B CN 112898574 B CN112898574 B CN 112898574B CN 202110357633 A CN202110357633 A CN 202110357633A CN 112898574 B CN112898574 B CN 112898574B
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- ether
- reaction
- organic silicon
- cyclosiloxane
- perfluoro
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000010703 silicon Substances 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 title claims abstract description 37
- 239000011347 resin Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- -1 polysiloxane Polymers 0.000 claims abstract description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- 229920002050 silicone resin Polymers 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 12
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002981 blocking agent Substances 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 10
- 125000005394 methallyl group Chemical group 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 claims description 8
- HAURRGANAANPSQ-UHFFFAOYSA-N cis-2,4,6-Trimethyl-2,4,6-triphenylcyclotrisiloxane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 HAURRGANAANPSQ-UHFFFAOYSA-N 0.000 claims description 8
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- XOCOMEGNVMCRMP-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octaethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CC[Si]1(CC)O[Si](CC)(CC)O[Si](CC)(CC)O[Si](CC)(CC)O1 XOCOMEGNVMCRMP-UHFFFAOYSA-N 0.000 claims description 2
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 claims description 2
- BPMGYFSWCJZSBA-UHFFFAOYSA-N C[SiH](C)O[SiH3] Chemical compound C[SiH](C)O[SiH3] BPMGYFSWCJZSBA-UHFFFAOYSA-N 0.000 claims description 2
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- MRRXLWNSVYPSRB-UHFFFAOYSA-N ethenyl-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)C=C MRRXLWNSVYPSRB-UHFFFAOYSA-N 0.000 claims description 2
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 claims description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- PBPJPEGDEUOZHC-UHFFFAOYSA-N 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentakis-phenyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 PBPJPEGDEUOZHC-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 239000002952 polymeric resin Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- DCAADTQUFYNVHS-UHFFFAOYSA-N [SiH3]O.[Na] Chemical compound [SiH3]O.[Na] DCAADTQUFYNVHS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NTSNXSJENBZFSF-UHFFFAOYSA-N [Na+].[SiH3][O-] Chemical compound [Na+].[SiH3][O-] NTSNXSJENBZFSF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to the technical field of preparation of silicone resin, and discloses a preparation method of organic silicone resin, which comprises the following steps: s1, adding cyclosiloxane and phenyl cyclosiloxane into a reactor, and heating to remove water; s2, adding an initiator, an accelerator, a blocking agent and an anhydrous solvent into the reactor in the S1 for reaction, and removing the anhydrous solvent after the reaction is finished to obtain a prepolymer containing vinyl; and S3, adding the prepolymer in the S2, a platinum catalyst, hydrogen-containing polysiloxane and fluorine-containing allyl ether into an anhydrous solvent for reaction, and removing the solvent after the reaction is finished to obtain the organic silicon resin. According to the preparation method, the prepared organic silicon resin is good in compatibility with a resin matrix and good in dispersibility by adopting a step polymerization mode.
Description
Technical Field
The invention belongs to the technical field of silicone resin, and particularly relates to a preparation method of organic silicone resin.
Background
Organosilicon, i.e., organosilicon compounds, are compounds which contain Si-C bonds and in which at least one organic group is directly bonded to a silicon atom, and those compounds in which an organic group is bonded to a silicon atom by oxygen, sulfur, nitrogen or the like are also conventionally known as organosilicon compounds. The polysiloxane with a silicon-oxygen bond (-Si-O-Si-) as a framework is the most abundant type of organosilicon compounds, has the deepest research and the widest application, and accounts for more than 90% of the total consumption.
Because of the unique structure of the organic silicon, the organic silicon has the properties of inorganic materials and organic materials, has the basic properties of low surface tension, small viscosity-temperature coefficient, high compressibility, high gas permeability and the like, has the excellent characteristics of high and low temperature resistance, electric insulation, oxidation resistance stability, weather resistance, flame resistance, hydrophobicity, corrosion resistance, innocuity, smell resistance, physiological inertia and the like, and is widely applied to industries of aerospace, electronics, architecture, transportation, chemical industry, textile, food, light industry, medical treatment and the like, wherein the organic silicon is mainly applied to sealing, bonding, lubrication, coating, surface activity, demolding, defoaming, foam inhibition, water resistance, moisture resistance, inert filling and the like. Along with the continuous increase of the quantity and variety of the organic silicon, the application field is widened continuously, a unique important product system in the new chemical industry material is formed, and many varieties are indisputable and indispensable for other chemicals.
The organic silicon can be divided into silicone oil, silicone resin and silicone rubber according to chemical structure and performance. The silicone resin can be added into a polymer material matrix as an elastomer or a functional auxiliary agent, so that the toughness, the surface smoothness, the wear resistance, the scratch resistance and other performances of the material are improved, but the surface energy of the organosilicon is low, the compatibility with most resins is poor, and the dispersibility in the resins is poor, so that the application of the silicone resin is limited.
Therefore, it is important to develop a silicone resin having good compatibility with a polymer resin.
Disclosure of Invention
< technical problem to be solved by the invention >
The existing organic silicon resin has poor compatibility with high polymer resin and poor dispersing effect, so that the application of the organic silicon resin is limited.
< technical scheme adopted by the invention >
The invention aims to provide a preparation method of organic silicon resin.
The specific contents are as follows:
the invention provides a preparation method of organic silicon resin, which comprises the following steps:
s1, adding cyclosiloxane and phenyl cyclosiloxane into a reactor, and heating to remove water;
s2, adding an initiator, an accelerator and a blocking agent into the reactor in the S1 for reaction, and removing the solvent after the reaction is finished to obtain a prepolymer containing vinyl;
and S3, adding the prepolymer in the S2, a platinum catalyst, hydrogen-containing polysiloxane and fluorine-containing allyl ether into an anhydrous solvent for reaction, and removing the solvent after the reaction is finished to obtain the organic silicon resin.
< beneficial effects achieved by the invention >
(1) The invention adopts a sectional polymerization mode to prepare polysiloxane macromolecular prepolymer firstly, and then prepares the ultra-high molecular weight polysiloxane with a core-shell structure through hydrosilylation reaction, no special equipment is needed in the preparation process, the energy consumption is low, the reaction control is simple, and the industrialization is easy to realize.
(2) According to the invention, the polysiloxane prepolymer containing vinyl, the hydrogen-containing siloxane and the platinum catalyst are subjected to hydrosilylation reaction to form the polysiloxane with the core-shell structure, so that the compatibility of the organic silicon resin and the high polymer resin is improved, and the dispersibility of the organic silicon resin in the resin matrix is improved.
(3) After phenyl cyclosiloxane and cyclosiloxane are adopted for ring opening, copolymerization reaction occurs, and as the phenyl cyclosiloxane has the function of stabilizing free radicals, the residual free radicals under the conditions of high temperature and irradiation can be promoted, so that the stability of the phenyl cyclosiloxane is improved; meanwhile, the introduction of phenyl can also improve the low temperature resistance of the organic silicon resin.
(4) According to the invention, the linear polysiloxane is prepared through a cyclosiloxane ring-opening reaction, and the side chain of the organic silicon resin is substituted with a heteroatom through the fluorination of the linear polysiloxane and fluorine-containing allyl ether, so that the solvent resistance and compressibility of the organic silicon resin are improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a preparation method of organic silicon resin, which comprises the following steps:
s1, adding cyclosiloxane and phenyl cyclosiloxane into a reactor, and heating to remove water;
s2, adding an initiator, an accelerator and a blocking agent into the reactor in the S1 for reaction, and removing the solvent after the reaction is finished to obtain a prepolymer containing vinyl;
and S3, adding the prepolymer in the S2, a platinum catalyst, hydrogen-containing polysiloxane and fluorine-containing allyl ether into an anhydrous solvent for reaction, and removing the solvent after the reaction is finished to obtain the organic silicon resin.
The components of the raw materials of the organic silicon resin comprise, by weight, 51-99 parts of cyclosiloxane, 1-49 parts of phenyl cyclosiloxane, 0.01-1 part of an initiator, 0-1 part of an accelerator, 0.05-5 parts of a blocking agent, 0.5-20 ppm (calculated by metal platinum) of a platinum catalyst, 1-15 parts of hydrogen-containing polysiloxane and 5-10 parts of fluorine-containing allyl ether.
In the invention, in S1, the cyclosiloxane comprises hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane or octaethyl cyclotetrasiloxane, the phenyl cyclosiloxane is methylphenyl cyclosiloxane, and the methylphenyl cyclosiloxane comprises one or more of trimethyl triphenylcyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane and pentamethyl pentacyclopentasiloxane.
In the invention, in S2, the end-capping agent comprises at least one of vinyl pentamethyl disiloxane, divinyl tetramethyl disiloxane, tetravinyl dimethyl disiloxane or dimethyl vinyl ethoxy silane.
In the present invention, in S3, the molecular weight of the hydrogen-containing polysiloxane is 500 to 10000.
In the present invention, in S3, the fluorine-containing allyl ether includes perfluoro (methallyl) ether, perfluoro (ethylallyl) ether, perfluoro (n-propylallyl) ether, perfluoro-2-propoxypropylallyl ether, perfluoro-3-methoxy-n-propylallyl ether, perfluoro-2-methoxy-ethylallyl ether, or perfluoro-methoxy-methallyl ether.
In the invention, in S2, the initiator is alkali metal silicon alkoxide, and the accelerator comprises tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoric triamide or N-methylpyrrolidone.
In the present invention, S1 is heated at 50 to 90 ℃.
In the invention, in S2, N 2 The reaction temperature is 90-130 ℃ and the reaction time is 25-40 h under the atmosphere.
In the invention, in S3, N 2 The reaction temperature is 90-110 ℃ and the reaction time is 15-24 h under the atmosphere.
In the present invention, the anhydrous solvent is at least one of benzene, toluene, tetrahydrofuran, methylene chloride, dioxane, n-hexane, cyclohexane, petroleum ether, n-heptane and n-pentane.
< example >
Example 1
The organic silicon resin comprises the following raw materials:
75 parts of octamethyl cyclotetrasiloxane, 25 parts of trimethyl triphenyl cyclotrisiloxane, 0.5 part of silanol sodium salt, 0.2 part of N-methyl pyrrolidone, 2 parts of divinyl tetramethyl disiloxane, 15ppm of platinum catalyst, 10 parts of hydrogen-containing polysiloxane with molecular weight of 1000 and 8 parts of perfluoro (methallyl) ether.
The preparation method of the organic silicon resin comprises the following steps:
s1, adding octamethyl cyclotetrasiloxane and trimethyl triphenyl cyclotrisiloxane into a reactor, and heating to remove water at a temperature of 60 ℃;
s2, dissolving sodium siliconate, N-methylpyrrolidone and divinyl tetramethyl disiloxane in toluene, adding the mixture into a reactor in S1 for reaction, and removing toluene after the reaction is finished to obtain a prepolymer containing vinyl; n (N) 2 The reaction temperature was 110℃and the reaction time was 40h under an atmosphere.
And S3, adding the prepolymer in S2, a platinum catalyst, hydrogen-containing polysiloxane and perfluoro (methallyl) ether into toluene for reaction, and removing the toluene after the reaction is finished to obtain the organic silicon resin. N (N) 2 The reaction temperature is 100 ℃ and the reaction time is 15h under the atmosphere.
Example 2
The organic silicon resin comprises the following raw materials:
55 parts of octamethyl cyclotetrasiloxane, 45 parts of trimethyl triphenyl cyclotrisiloxane, 0.02 part of sodium silanol, 0.08 part of N-methyl pyrrolidone, 0.1 part of divinyl tetramethyl disiloxane, 5ppm of platinum catalyst, 5 parts of hydrogen-containing polysiloxane with molecular weight of 1000 and 5 parts of perfluoro (methallyl) ether.
The preparation method of the organic silicon resin comprises the following steps:
s1, adding octamethyl cyclotetrasiloxane and trimethyl triphenyl cyclotrisiloxane into a reactor, and heating to remove water at a temperature of 60 ℃;
s2, dissolving sodium siliconate, N-methylpyrrolidone and divinyl tetramethyl disiloxane in tetrahydrofuran, adding the mixture into a reactor in S1 for reaction, and removing the tetrahydrofuran after the reaction is finished to obtain a prepolymer containing vinyl; n (N) 2 The reaction temperature was 110℃and the reaction time was 40h under an atmosphere.
And S3, adding the prepolymer in S2, a platinum catalyst, hydrogen-containing polysiloxane and perfluoro (methallyl) ether into toluene for reaction, and removing tetrahydrofuran after the reaction is finished to obtain the organic silicon resin. N (N) 2 The reaction temperature was 130℃and the reaction time was 40h under an atmosphere.
Example 3
The organic silicon resin comprises the following raw materials:
95 parts of octamethyl cyclotetrasiloxane, 5 parts of trimethyl triphenyl cyclotrisiloxane, 0.1 part of sodium silanol, 0.8 part of N-methyl pyrrolidone, 5 parts of divinyl tetramethyl disiloxane, 20ppm of platinum catalyst, 15 parts of hydrogen-containing polysiloxane with molecular weight of 1000 and 10 parts of perfluoro (methallyl) ether.
The preparation method of the organic silicon resin comprises the following steps:
s1, adding octamethyl cyclotetrasiloxane and trimethyl triphenyl cyclotrisiloxane into a reactor, and heating to remove water at a temperature of 60 ℃;
s2, dissolving sodium siliconate, N-methylpyrrolidone and divinyl tetramethyl disiloxane in tetrahydrofuran, adding the mixture into a reactor in S1 for reaction, and removing the mixture after the reaction is finishedRemoving tetrahydrofuran to obtain a prepolymer containing vinyl; n (N) 2 The reaction temperature was 110℃and the reaction time was 40h under an atmosphere.
And S3, adding the prepolymer in S2, a platinum catalyst, hydrogen-containing polysiloxane and perfluoro (methallyl) ether into toluene for reaction, and removing tetrahydrofuran after the reaction is finished to obtain the organic silicon resin. N (N) 2 The reaction temperature was 90℃and the reaction time was 24h under an atmosphere.
Example 4
This example differs from example 1 in that the sodium silanolate is replaced by a barium silanolate salt.
Comparative example
Comparative example 1
This comparative example differs from example 1 in that perfluoro (methallyl) ether was not added.
< test example >
The effect of the core-shell structure silicone resins prepared in examples 1 to 3 and comparative example 1 on the performance of the LED (light emitting element) silicone encapsulating material was tested as follows, and the test results are shown in table 1.
TABLE 1 Effect of core-shell mechanism Silicone resin on LED packaging Material Performance
| Silicone resin | Tensile Strength (MPa) | Elongation at break (%) | Hardness (A) |
| Comparative example 1 | 4.2 | 98 | 65 |
| Example 1 | 5.9 | 117 | 87 |
| Example 2 | 5.2 | 110 | 78 |
| Example 3 | 4.9 | 105 | 73 |
From the experimental results in table 1, it is known that the use of the silicone resin prepared in the examples can improve the compatibility with the resin matrix, and improve the hardness and tensile properties.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the organic silicon resin is characterized by comprising the following steps of:
s1, adding cyclosiloxane and phenyl cyclosiloxane into a reactor, and heating to remove water;
s2, adding an initiator, an accelerator, a blocking agent and an anhydrous solvent into the reactor in the S1 for reaction, and removing the anhydrous solvent after the reaction is finished to obtain a prepolymer containing vinyl;
s3, adding the prepolymer in the S2, a platinum catalyst, hydrogen-containing polysiloxane and fluorine-containing allyl ether into an anhydrous solvent for reaction, and removing the solvent after the reaction is finished to obtain organic silicon resin;
in S1, the cyclosiloxane comprises hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane or octaethyl cyclotetrasiloxane, the phenyl cyclosiloxane is methylphenyl cyclosiloxane, and the methylphenyl cyclosiloxane comprises at least one of trimethyl triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane or pentamethyl pentaphenyl cyclopentasiloxane;
in S2, the end-capping agent comprises at least one of vinyl pentamethyl disiloxane, divinyl tetramethyl disiloxane, tetravinyl dimethyl disiloxane or dimethyl vinyl ethoxy silane.
2. The preparation method of the organic silicon resin according to claim 1, wherein the organic silicon resin comprises, by weight, 51-99 parts of cyclosiloxane, 1-49 parts of phenyl cyclosiloxane, 0.01-1 part of an initiator, 0-1 part of an accelerator, 0.05-5 parts of a blocking agent, 1-15 parts of hydrogen-containing polysiloxane, 5-10 parts of fluorine-containing allyl ether, and 0.5-20 ppm of a platinum catalyst based on the total weight of the organic silicon resin raw material.
3. The method for producing a silicone resin according to claim 1, wherein in S3, the molecular weight of the hydrogen-containing polysiloxane is 500 to 10000.
4. The method for producing a silicone resin according to claim 1 or 2, wherein in S3, the fluorine-containing allyl ether includes perfluoro (methallyl) ether, perfluoro (ethylallyl) ether, perfluoro (n-propylallyl) ether, perfluoro-2-propoxypropylallyl ether, perfluoro-3-methoxy-n-propylallyl ether, perfluoro-2-methoxy-ethylallyl ether, or perfluoro-methoxy-methallyl ether.
5. The method for preparing the organic silicon resin according to claim 1 or 2, wherein in S2, the initiator is an alkali metal silicon alkoxide, and the accelerator comprises tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoric triamide or N-methylpyrrolidone.
6. The method for producing a silicone resin according to claim 1, wherein in S1, heating is performed at 50 to 90 ℃.
7. The method for producing a silicone resin according to claim 1 or 2, wherein in S2, N 2 The reaction temperature is 90-130 ℃ and the reaction time is 25-40 h under the atmosphere.
8. The method for producing a silicone resin according to claim 1 or 2, wherein in S3, N 2 The reaction temperature is 90-110 ℃ and the reaction time is 15-24 h under the atmosphere.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5892086A (en) * | 1998-05-29 | 1999-04-06 | Pcr, Inc. | Perfluorinated ether organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes |
| WO2007043788A1 (en) * | 2005-10-13 | 2007-04-19 | Lg Chem, Ltd. | Composition of acryl-silicone complex, preparing method and use thereof |
| EP2639258A1 (en) * | 2012-03-13 | 2013-09-18 | Shin-Etsu Chemical Co., Ltd. | Curable Silicone Resin Composition and Optoelectronic Device |
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| CN104098905B (en) * | 2013-04-08 | 2016-09-28 | 上海华硅化工新材料有限公司 | A kind of LED lens strong elasticity phenyl organic siliconresin and preparation method thereof |
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| CN107216459B (en) * | 2017-05-16 | 2021-02-26 | 太仓中化环保化工有限公司 | Preparation method of perfluoropolyether fluorine-based fluorosilane with multiple hydrolysis active end groups |
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-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5892086A (en) * | 1998-05-29 | 1999-04-06 | Pcr, Inc. | Perfluorinated ether organo substituted cyclosiloxanes and copolymers prepared from these cyclosiloxanes |
| WO2007043788A1 (en) * | 2005-10-13 | 2007-04-19 | Lg Chem, Ltd. | Composition of acryl-silicone complex, preparing method and use thereof |
| EP2639258A1 (en) * | 2012-03-13 | 2013-09-18 | Shin-Etsu Chemical Co., Ltd. | Curable Silicone Resin Composition and Optoelectronic Device |
Non-Patent Citations (1)
| Title |
|---|
| 疏水性聚硅氧烷的合成及其构建的超分子研究;潘家炎;《中国博士学位论文全文数据库 工程科技Ⅰ辑》(第第2019（08）期期);第B014-132页 * |
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