CN107189442A - A kind of modifying methylphenyl silicone resin based on nano concave earth and preparation method thereof - Google Patents
A kind of modifying methylphenyl silicone resin based on nano concave earth and preparation method thereof Download PDFInfo
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- CN107189442A CN107189442A CN201710500839.5A CN201710500839A CN107189442A CN 107189442 A CN107189442 A CN 107189442A CN 201710500839 A CN201710500839 A CN 201710500839A CN 107189442 A CN107189442 A CN 107189442A
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- silicone resin
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- concave earth
- methyl phenyl
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 74
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002689 soil Substances 0.000 claims abstract description 24
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 16
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 abstract description 9
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000005054 phenyltrichlorosilane Substances 0.000 claims abstract description 7
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005055 methyl trichlorosilane Substances 0.000 claims abstract description 6
- 239000008096 xylene Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000005046 Chlorosilane Substances 0.000 claims description 16
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 16
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- YCIVSJFIXXVSRH-UHFFFAOYSA-N amino-methyl-phenylsilicon Chemical compound C[Si](N)C1=CC=CC=C1 YCIVSJFIXXVSRH-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 36
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- -1 Methylphenylsiloxane Chemical class 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 241000549556 Nanos Species 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- QMMBZOSZCYBCDC-UHFFFAOYSA-N NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC QMMBZOSZCYBCDC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 150000005172 methylbenzenes Chemical class 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- HICCMIMHFYBSJX-UHFFFAOYSA-N [SiH4].[Cl] Chemical compound [SiH4].[Cl] HICCMIMHFYBSJX-UHFFFAOYSA-N 0.000 description 1
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical compound [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a kind of modifying methylphenyl silicone resin based on nano concave earth and preparation method thereof, the modifying methylphenyl silicone resin is main as made by dimethylbenzene, the recessed soil of modified Nano and methyl phenyl silicone resin prepolymer；The recessed soil of modified Nano is made by cetyl trimethylammonium bromide concentrated hydrochloric acid solution and nano concave earth；The methyl phenyl silicone resin prepolymer is dissolved in dimethylbenzene and adds aqueous acetone solution after methyl trichlorosilane, dimethyldichlorosilane, diphenyl dichlorosilane, phenyl trichlorosilane mixing to be made.The present invention adds the recessed soil of modified Nano to improve the heat resistance of methyl phenyl silicone resin in methyl phenyl silicone resin preparation process, so as to change the structure of methyl phenyl silicone resin, improves the heat resistance of methyl phenyl silicone resin；Preparation method of the present invention is simple, uses nano concave earth easily to be obtained for raw material, cost is low, is adapted in large-scale production, modifying process, remaining reagent portion can be applied mechanically with circulation and stress, free from environmental pollution.
Description
Technical field
The present invention relates to a kind of organic siliconresin, and in particular to a kind of modifying methylphenyl silicone resin based on nano concave earth
And preparation method thereof.
Background technology
Current developing rapidly with science and technology, nowadays in many electronics applications, to sensitive circuit and electricity
Sub- component reliability requires more and more higher.Silicone resin material is a variety of due to being widely used in good performance
Acted in electronic component with playing insulation, moistureproof, shockproof etc..
Methyl phenyl silicone resin has excellent heat resistance and dielectric properties, is a kind of very attractive thermally protective materials
Use resin matrix.Methyl phenyl silicone resin is that, using Si-O-Si as skeleton, the bond energy of Si-O keys is 450kJ/mol in silicones,
So the heat endurance of methyl phenyl silicone resin is high, the chemical bond of (or radiation exposure) molecule is not broken, not decomposed under high temperature.
Sun Jutao etc. is prepared for a kind of high temperature resistant phenyl methyl silicones, and synthetic method is as follows：In there-necked flask, add and steam
Distilled water and toluene, are added dropwise the phenyl trichlorosilane, diphenyl dichlorosilane, methyl trichlorosilane and two of metering under fast stirring
Dimethyl dichlorosilane (DMCS), keeps constant temperature.After completion of dropping, branch vibration layer is stood, solvent layer is washed with water, then titrated with NaOH solution
To neutral, depressurized at 60~80 DEG C and steam toluene, then be warming up to 130~140 DEG C of decompression condensations, obtain a kind of hard resin production
Thing, initial decomposition temperature of the product in air atmosphere is at 220 DEG C or so.Maximum thermal weight loss is 29%, maximum thermal weight loss temperature
Spend for 600 DEG C of (synthesis and its research of heat-resisting and curing performance of high-temperature resistant organic silicon resin, aeronautical material journal, 2005,25
(1)：25-29), silicones is prepared using the method, is also easy to produce gel, and the control of methyl phenyl silicone resin molecular weight is not easy, point
Son amount distributing inhomogeneity.
Along etc. be prepared for a kind of new methyl phenyl silicone resin containing amino, with phenyltrimethoxysila,e (PTMS) and
N- (β-aminoethyl)-γ-aminopropyltriethoxy-dimethoxysilane (Si-602) is raw material, under conditions of salt acid as catalyst,
Methylphenylsiloxane containing amino is prepared for by hydrolytie polycondensation.Thermogravimetric (TG) analysis result shows, when PTMS with
The mol ratio of Si-602 raw material proportionings is 9: 1, and methyl phenyl silicone resin is thermally-stabilised general, and weightless at 800 DEG C is 43.41%.(contain
The synthesis of the methyl phenyl silicone resin of amino and sign, polymer material science and engineering, 2010,26 (12)：27-30), the party
Methyl phenyl silicone resin heat endurance prepared by method is general, and its application is very restricted.
The method of modifying cost of methyl phenyl silicone resin is high in the prior art, while the modifying methylphenyl silicone resin prepared
Heat endurance is general, and is not suitable for extensive modernization industry production problem.
The content of the invention
Goal of the invention：The problem of existing for prior art, the present invention provides a kind of modified methyl based on nano concave earth
Phenyl polysiloxane；The modifying methylphenyl silicone resin based on nano concave earth improves the heat resistance of methyl phenyl silicone resin, solution
The method of modifying cost of certainly existing methyl phenyl silicone resin is high, and is not suitable for extensive modernization industry production problem.
The present invention also provides the preparation method of the modifying methylphenyl silicone resin based on nano concave earth.
Technical scheme：To achieve these goals, a kind of modified methyl phenyl based on nano concave earth as described herein
Silicones, is mainly 100-110 in mass ratio by dimethylbenzene, the recessed soil of modified Nano and methyl phenyl silicone resin prepolymer:1:50-
Made by 60；The recessed soil of the modified Nano is in mass ratio with nano concave earth by cetyl trimethylammonium bromide concentrated hydrochloric acid solution
12-13：5-6 is made；The methyl phenyl silicone resin prepolymer is by methyl trichlorosilane, dimethyldichlorosilane, diphenyl two
Chlorosilane, phenyl trichlorosilane in mass ratio 10:10:25-28:Dimethylbenzene, which is dissolved in, after 15-18 mixing adds aqueous acetone solution
It is made.
Wherein, catalyst TMAH is also included in the modifying methylphenyl silicone resin, consumption is methylbenzene
The 0.5-0.8% of base silicone prepolymer quality；Preferable amount is the 0.5 of methyl phenyl silicone resin pre-polymerization amount of substance.
Wherein, the cetyl trimethylammonium bromide concentrated hydrochloric acid solution is by cetyl trimethylammonium bromide and quality point
Number 35-37% concentrated hydrochloric acid solutions are 1 in mass ratio：(3-4) is mixed；It is preferred that six alkyl trimethyl ammonium bromides and mass fraction 35%
Concentrated hydrochloric acid solution is 1 in mass ratio：3 mixing.
Preferably, the modifying methylphenyl silicone resin based on nano concave earth, mainly recessed by dimethylbenzene, modified Nano
Soil and methyl phenyl silicone resin prepolymer are 100 in mass ratio:1:Made by 50；The recessed soil of modified Nano is by cetyl three
Methyl bromide ammonium concentrated hydrochloric acid solution is 12 in mass ratio with nano concave earth：5 are made；The methyl phenyl silicone resin prepolymer is by first
Base trichlorosilane, dimethyldichlorosilane, diphenyl dichlorosilane, phenyl trichlorosilane in mass ratio 10:10:25:15 mixing
After be dissolved in dimethylbenzene add aqueous acetone solution be made.
The preparation method of modifying methylphenyl silicone resin of the present invention based on nano concave earth, comprises the following steps：
(1) nano concave earth is placed in distilled water at room temperature and stirred, nano concave earth suspension is obtained, by cetyl trimethyl
Ammonium bromide mixes to obtain cetyl trimethylammonium bromide concentrated hydrochloric acid solution with concentrated hydrochloric acid, by the dense salt of cetyl trimethylammonium bromide
Acid solution is added drop-wise in nano concave earth suspension, continues to stir, and heating heating, filtering, deionized water cyclic washing, vacuum is done
It is dry, grinding, sieve to obtain the recessed soil of modified Nano；
(2) methyl trichlorosilane, dimethyldichlorosilane, diphenyl dichlorosilane, phenyl trichlorosilane are mixed, obtains chlorine
Silane mixture；Chlorosilane mixture is dissolved in dimethylbenzene, is made under chlorosilane xylene solution, stirring and acetone is slowly added dropwise
The aqueous solution is hydrolyzed in chlorosilane xylene solution, obtains silanol xylene solution, neutrality is washed to distillation, obtain first
Base phenyl polysiloxane prepolymer；
(3) the recessed soil of dimethylbenzene, modified Nano, the mixing of methyl phenyl silicone resin prepolymer are weighed in proportion, add catalyst
TMAH, carries out polycondensation reaction, and reaction is dried in vacuo after terminating, and obtains modifying methylphenyl silicone resin.
Wherein, step (1) nano concave earth and distilled water mass volume ratio are 1:20-22g/ml.
Step (1) heating is heated to 90-100 DEG C, reacts 18-20h.
Wherein, the mass volume ratio of step (2) chlorosilane mixture and dimethylbenzene is 1:2-3g/ml.It is preferred that chlorine silicon
The mass volume ratio of alkane mixture and dimethylbenzene is 1:2g/ml.
Step (2) dimethylbenzene is 4 with aqueous acetone solution volume ratio:Acetone and water press body in 3-3.5, aqueous acetone solution
Product compares 2:3 mixing.It is preferred that dimethylbenzene is 4 with aqueous acetone solution volume ratio:3.
The temperature of step (2) described hydrolysis is 20-25 DEG C, reacts 3-4h.
The temperature of step (2) described polycondensation reaction is 90-100 DEG C, reacts 15-16h.
All reagents of the present invention and raw material are by commercially available.
Beneficial effect：Compared with prior art, the invention has the advantages that：
The present invention adds to improve the heat resistance of methyl phenyl silicone resin in methyl phenyl silicone resin preparation process
Recessed native the modifying methylphenyl silicone resin composite of modified Nano, so as to change the structure of methyl phenyl silicone resin, improves first
The heat resistance of base phenyl polysiloxane, modifying methylphenyl silicone resin has good high-temperature stability, various available for preparing
The isolation protective material of electronic circuit board and component.
Preparation method of the present invention is simple, uses nano concave earth easily to be obtained for raw material, cost is low, is adapted to large-scale production,
In modifying process, remaining reagent portion can be applied mechanically with circulation and stress, free from environmental pollution.And the recessed soil of China relatively enriches, profit
With attapulgite, as raw material, not only cost is low, and expands the application of attapulgite.
Brief description of the drawings
Fig. 1 is the thermogravimetric analysis figure of modifying methylphenyl silicone resin prepared by the embodiment of the present invention 1；
Fig. 2 is the thermogravimetric analysis figure of modifying methylphenyl silicone resin prepared by the embodiment of the present invention 2；
Fig. 3 is the thermogravimetric analysis figure of modifying methylphenyl silicone resin prepared by the embodiment of the present invention 3.
Embodiment
Embodiment 1
(1) 10g nano concave earths are placed in 600rpm in 200ml distilled water at room temperature and stir 30min, obtained nano concave earth and hang
Supernatant liquid, 6g cetyl trimethylammonium bromides are mixed with the concentrated hydrochloric acid of 18g mass fractions 37%, cetyl trimethyl bromination is obtained
Ammonium concentrated hydrochloric acid solution, is 12 in mass ratio by cetyl trimethylammonium bromide concentrated hydrochloric acid solution and nano concave earth:5 are slowly added dropwise
Into nano concave earth suspension, continue to stir, and be warming up to 100 DEG C, react 18h, filtering, deionized water cyclic washing is to without bromine
Ion, is dried under vacuum to constant weight at 50 DEG C, grinds, and crosses 400 mesh sieves, obtains the recessed soil of modified Nano；
(2) by 20g methyl trichlorosilanes, 20g dimethyldichlorosilanes, 50g diphenyl dichlorosilanes, 30g phenyl trichlorines
Silane is dissolved in 240ml xylene solvents, and chlorosilane xylene solution is made；72ml acetone and 108ml water are mixed into obtain acetone
The aqueous solution, aqueous acetone solution is slowly added under stirring into chlorosilane xylene solution, and control hydrolysis rate is slowly added dropwise, control
Hydrolysising reacting temperature is 20 DEG C；Reaction 4h is hydrolyzed, obtains silanol xylene solution, is then washed to neutrality with 30 DEG C of distillations,
That is methyl phenyl silicone resin prepolymer；
(3) the recessed soil of 100ml dimethylbenzene, 1g modified Nanos, 50g methyl phenyl silicone resins prepolymer and 0.25g tetramethyls are taken
Ammonium hydroxide is added in three-neck flask, stirring, and it is 90 DEG C to control polycondensation reaction temperature, is reacted 16 hours, and reaction is shifted after terminating
To vacuum drying chamber, it is dried in vacuo at 60 DEG C, obtains modifying methylphenyl silicone resin；Its thermogravimetric analysis figure is shown in Fig. 1, modified methyl benzene
The starting thermal weight loss temperature of base silicones is 370 DEG C；Thermal weight loss is 6% at 600 DEG C；Temperature is that the weightlessness at 800 DEG C is 16%；
Modifying methylphenyl silicone resin weight after 870 DEG C has tended to balance.As can be seen here, the modified methyl that prepared by the present embodiment 1
Phenyl polysiloxane heat resistance is good.
Embodiment 2
(1) 30g nano concave earths are placed in 600rpm in 600ml distilled water at room temperature and stir 30min, obtained nano concave earth and hang
Supernatant liquid, 18g cetyl trimethylammonium bromides are mixed with the concentrated hydrochloric acid of 54g mass fractions 37%, cetyl trimethyl bromine is obtained
Change ammonium concentrated hydrochloric acid solution, be 12 in mass ratio by cetyl trimethylammonium bromide concentrated hydrochloric acid solution and nano concave earth:5 slow drops
Be added in nano concave earth suspension, continue to stir, and be warming up at 100 DEG C and react 18h, filter, obtain the recessed soil of modified Nano, go from
Sub- water cyclic washing is dried under vacuum to constant weight to without bromide ion at 50 DEG C, grinds, and crosses the sieve of 400 mesh, obtains modified Nano recessed
Soil；
(2) by 40g methyl trichlorosilanes, 40g dimethyldichlorosilanes, 100g diphenyl dichlorosilanes, 60g phenyl trichlorines
Silane is dissolved in 480ml xylene solvents, and chlorosilane xylene solution is made；144ml acetone and 216ml water are mixed into obtain acetone
The aqueous solution, is slowly added to aqueous acetone solution into chlorosilane xylene solution under stirring, control hydrolysis rate, controls hydrolysis
Temperature is 20 DEG C；Reaction 4h is hydrolyzed, obtains silanol xylene solution, is then washed to neutrality, i.e. methylbenzene with 30 DEG C of distillations
Base silicone prepolymer；
(2) the recessed soil of 200ml dimethylbenzene, 2g modified Nanos, 100g methyl phenyl silicone resins prepolymer and 0.5g tetramethyls are taken
Ammonium hydroxide is added in three-neck flask, stirring, and it is 90 DEG C to control polycondensation reaction temperature, is reacted 16 hours, and reaction is shifted after terminating
To vacuum drying chamber, it is dried in vacuo at 60 DEG C, obtains modifying methylphenyl silicone resin；Its thermogravimetric analysis figure is shown in Fig. 2, modified methyl benzene
The starting thermal weight loss temperature of base silicones is 370 DEG C；Thermal weight loss is 8% at 600 DEG C；Temperature is that the weightlessness at 800 DEG C is 17%；
Modifying methylphenyl silicone resin weight after 870 DEG C has tended to balance.As can be seen here, the modified methyl that prepared by the present embodiment 2
Phenyl polysiloxane heat resistance is good.
Embodiment 3
(1) 10g nano concave earths are placed in 600rpm in 220ml distilled water at room temperature and stir 30min, obtained nano concave earth and hang
Supernatant liquid, 4g cetyl trimethylammonium bromides are mixed with the concentrated hydrochloric acid of 24g mass fractions 35%, cetyl trimethyl bromination is obtained
Ammonium concentrated hydrochloric acid solution, is 13 in mass ratio by cetyl trimethylammonium bromide concentrated hydrochloric acid solution and nano concave earth:6 are slowly added dropwise
Into nano concave earth suspension, continue to stir, and be warming up to 90 DEG C, react 20h, filtering, deionized water cyclic washing is to without bromine
Ion, is dried under vacuum to constant weight at 50 DEG C, grinds, and crosses 400 mesh sieves, obtains the recessed soil of modified Nano；
(2) by 20g methyl trichlorosilanes, 20g dimethyldichlorosilanes, 56g diphenyl dichlorosilanes, 36g phenyl trichlorines
Silane is dissolved in 264ml xylene solvents, and chlorosilane xylene solution is made；92.4ml acetone and 138.6ml water are mixed
Aqueous acetone solution, aqueous acetone solution is slowly added under stirring into chlorosilane xylene solution, and control hydrolysis rate is slowly added dropwise,
It is 25 DEG C to control hydrolysising reacting temperature；Reaction 3h is hydrolyzed, silanol xylene solution is obtained, in being then washed to 30 DEG C of distillations
Property, i.e. methyl phenyl silicone resin prepolymer；
(3) the recessed soil of 110ml dimethylbenzene, 1g modified Nanos, 60g methyl phenyl silicone resins prepolymer and 0.48g tetramethyls are taken
Ammonium hydroxide is added in three-neck flask, stirring, and it is 100 DEG C to control polycondensation reaction temperature, is reacted 15 hours, and reaction is shifted after terminating
To vacuum drying chamber, it is dried in vacuo at 60 DEG C, obtains modifying methylphenyl silicone resin；Its thermogravimetric analysis figure is shown in Fig. 3, the modified methyl
The starting thermal weight loss temperature of phenyl polysiloxane is 370 DEG C；Thermal weight loss is 7% at 600 DEG C；Temperature is that the weightlessness at 800 DEG C is
17%；Modifying methylphenyl silicone resin weight after 870 DEG C has tended to balance.As can be seen here, the modification that prepared by the present embodiment 3
Methyl phenyl silicone resin heat resistance is good.
Test example 1
Every heat resistance index of modifying methylphenyl silicone resin prepared by the test present invention, as a result as shown in table 1.
Comparative example 1 is prepared for a kind of high temperature resistant phenyl methyl silicones for grandson's act great waves etc. in background technology, and (high temperature resistant is organic
The synthesis of silicones and its research of heat-resisting and curing performance, aeronautical material journal, 2005,25 (1)：25-29).
Comparative example 2 be background technology in along etc. be prepared for a kind of new methyl phenyl silicone resin containing amino, (contain amino
Methyl phenyl silicone resin synthesis and sign, polymer material science and engineering, 2010,26 (12)：27-30).
Comparative example 3 is identical with the component and preparation method of the embodiment of the present invention 1, and difference is not containing step (1)
The recessed soil of modified Nano of preparation；
Comparative example 4 is identical with the component and preparation method of the embodiment of the present invention 1, and difference is not containing step
(1) the recessed soil of modified Nano prepared, but the common nano concave earth of the quality such as step (3) addition.
Every heat resistance index of the modifying methylphenyl silicone resin of table 1
As shown in Table 1, the modifying methylphenyl silicone resin that prepared by the present invention, excellent heat resistance has compared with comparative example
Obvious advantage, while without the modifying methylphenyl silicone resin that modified Nano is recessed native or only adds common nano concave earth
Heat resistance illustrates to add the obtained modifying methylphenyl silicone resin composite wood of the recessed soil of modified Nano also significantly lower than the present invention
Material, changes the structure of methyl phenyl silicone resin, the heat resistance of methyl phenyl silicone resin is improved, with good high temperature resistance super
Property.
Claims (10)
1. a kind of modifying methylphenyl silicone resin based on nano concave earth, it is characterised in that main recessed by dimethylbenzene, modified Nano
Soil and methyl phenyl silicone resin prepolymer are 100-110 in mass ratio:1:Made by 50-60；The recessed soil of modified Nano is by ten
Six alkyl trimethyl ammonium bromide concentrated hydrochloric acid solutions are 12-13 in mass ratio with nano concave earth：5-6 is made；The aminomethyl phenyl silicon
Resin prepolymer by methyl trichlorosilane, dimethyldichlorosilane, diphenyl dichlorosilane, phenyl trichlorosilane in mass ratio
10:10:25-28:15-18 mixing after be dissolved in dimethylbenzene add aqueous acetone solution be made.
2. the modifying methylphenyl silicone resin according to claim 1 based on nano concave earth, it is characterised in that the modification
Also include catalyst TMAH in methyl phenyl silicone resin, consumption is methyl phenyl silicone resin pre-polymerization amount of substance
0.5-0.8%.
3. the modifying methylphenyl silicone resin according to claim 1 based on nano concave earth, it is characterised in that described 16
Alkyl trimethyl ammonium bromide concentrated hydrochloric acid solution is pressed by cetyl trimethylammonium bromide with mass fraction 35-37% concentrated hydrochloric acid solutions
Mass ratio is 1：3-4 is mixed.
4. a kind of preparation method of the modifying methylphenyl silicone resin based on nano concave earth described in claim 1, its feature exists
In comprising the following steps：
(1) nano concave earth is placed in distilled water at room temperature and stirred, nano concave earth suspension is obtained, by cetyl trimethyl bromination
Ammonium mixes to obtain cetyl trimethylammonium bromide concentrated hydrochloric acid solution with concentrated hydrochloric acid, and cetyl trimethylammonium bromide concentrated hydrochloric acid is molten
Drop is added in nano concave earth suspension, continues to stir, and heating heating, filtering, deionized water cyclic washing, vacuum drying is ground
Mill, sieve to obtain the recessed soil of modified Nano；
(2) methyl trichlorosilane, dimethyldichlorosilane, diphenyl dichlorosilane, phenyl trichlorosilane are mixed, obtains chlorosilane
Mixture；Chlorosilane mixture is dissolved in dimethylbenzene, is made under chlorosilane xylene solution, stirring that acetone is slowly added dropwise is water-soluble
Liquid is hydrolyzed in chlorosilane xylene solution, obtains silanol xylene solution, neutrality is washed to distillation, obtain methylbenzene
Base silicone prepolymer；
(3) the recessed soil of dimethylbenzene, modified Nano, the mixing of methyl phenyl silicone resin prepolymer are weighed in proportion, add catalyst tetramethyl
Base ammonium hydroxide, carries out polycondensation reaction, and reaction is dried in vacuo after terminating, and obtains modifying methylphenyl silicone resin.
5. preparation method according to claim 4, it is characterised in that step (1) nano concave earth and distillation water quality
Volume ratio is 1:20-22.
6. preparation method according to claim 4, it is characterised in that step (1) heating is heated to 90-100 DEG C, instead
Answer 18-20h.
7. preparation method according to claim 4, it is characterised in that step (2) chlorosilane mixture and dimethylbenzene
Mass volume ratio be 1:2-3g/ml.
8. preparation method according to claim 4, it is characterised in that step (2) dimethylbenzene and aqueous acetone solution body
Product is than being 4:3-3.5.
9. preparation method according to claim 4, it is characterised in that the temperature of step (2) described hydrolysis is 20-25 DEG C,
React 3-4h.
10. preparation method according to claim 4, it is characterised in that the temperature of step (2) described polycondensation reaction is 90-
100 DEG C, react 15-16h.
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| CN112143452A (en) * | 2020-10-21 | 2020-12-29 | 南京信息工程大学 | Organic high-temperature-resistant packaging adhesive and preparation method thereof |
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| CN112143452B (en) * | 2020-10-21 | 2022-05-17 | 南京信息工程大学 | Organic high-temperature-resistant packaging adhesive and preparation method thereof |
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