CN114044787A - Diphenyl silicon compound and preparation method and application thereof - Google Patents
Diphenyl silicon compound and preparation method and application thereof Download PDFInfo
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- BPYFPNZHLXDIGA-UHFFFAOYSA-N diphenylsilicon Chemical compound C=1C=CC=CC=1[Si]C1=CC=CC=C1 BPYFPNZHLXDIGA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 51
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 22
- 239000004970 Chain extender Substances 0.000 claims abstract description 20
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- 239000004945 silicone rubber Substances 0.000 claims description 39
- -1 hydroxylamine compound Chemical class 0.000 claims description 30
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000005060 rubber Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 7
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 claims description 3
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 7
- 238000013040 rubber vulcanization Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ORRNVHHOEJMPDQ-UHFFFAOYSA-N ethoxy-hydroxy-dimethoxysilane Chemical compound CCO[Si](O)(OC)OC ORRNVHHOEJMPDQ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000007541 indentation hardness test Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0892—Compounds with a Si-O-N linkage
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
Abstract
The invention relates to a diphenyl silicon compound and a preparation method and application thereof, wherein the diphenyl silicon compound has the following structural formula; wherein R is1And R3Each independently selected from hydrogen, methyl and ethyl, R2And R4Each independently selected from methyl, ethyl, propyl and phenyl. The diphenyl silicon compound can be used as a chain extender in a silicon rubber vulcanization process, and can greatly improve the high temperature resistance of room temperature vulcanized silicon rubber.
Description
Technical Field
The invention relates to the technical field of organic compounds, in particular to a diphenyl silicon compound which can be used as a chain extender for greatly improving the high-temperature resistance of room-temperature vulcanized silicone rubber, and a preparation method and application thereof.
Background
With the rapid development of aerospace technology, the performance requirements of the ultra-high-speed aircraft on the adhesive and the coating for the outer surface thermal insulation layer are higher and higher. The main chain of the organic silicon resin is an inorganic-Si-O-Si-structure, the side group is an organic alkane chain structure, and the bond energy (443.7KJ/mol) of Si-O bond is very high and is far higher than the bond energy (351KJ/mol) of C-O bond and C-C bond (347KJ/mol), so that the organic silicon resin is not easy to be damaged at high temperature, has excellent high temperature resistance compared with other polymers, and is also often used in the field of aerospace.
Conventional silicone rubber-based adhesives and coatings are typically used at temperatures below 250 ℃ due to side group oxidation and backbone cyclization degradation of the silicone resin at elevated temperatures. In order to inhibit main chain cyclization degradation and side group oxidation degradation, a great deal of related research is carried out by the predecessors, and the discovery shows that the introduction of phenyl in the main chain or the side group of the silicone rubber can greatly inhibit the cyclization degradation rate of the silicone rubber through the steric hindrance effect of the phenyl and improve the high temperature resistance of the silicone rubber.
107 glue (hydroxyl-terminated polydimethylsiloxane) is a common room temperature vulcanized silicone rubber in the market, has the advantages of low viscosity, easy processing, low volatile content, wide marketization range, easy purchase, low price and the like, but has poor high temperature resistance because the hydroxyl-terminated glue is easy to cause main chain tripping cyclization degradation at high temperature. Therefore, the utilization of phenyl silane assistant to improve the high temperature resistance of 107 glue has become a hot research.
Disclosure of Invention
In view of the above analysis, an embodiment of the present invention aims to provide a diphenyl silicon compound, which can be used for vulcanization of silicone rubber to solve the problem of poor high temperature resistance of silicone rubber (e.g., 107 rubber), and a preparation method and application thereof.
In one aspect, an embodiment of the present invention provides a diphenyl silicon compound, which has the following structural formula:
wherein R is1And R3Each independently selected from hydrogen, methyl and ethyl, R2And R4Each independently selected from methyl, ethyl, propyl and phenyl.
According to one embodiment of the invention, R1、R2Each independently selected from methyl and ethyl; and/or, R3、R4Each independently selected from methyl and ethyl.
According to one embodiment of the invention, R1Is hydrogen, R2Is isopropyl or phenyl; and/or, R3Is hydrogen, R4Is isopropyl or phenyl.
In another aspect, an embodiment of the present invention provides a method for preparing the diphenyl silicon compound, which comprises reacting tetramethyldiphenyldihydrotrisiloxane and a hydroxylamine compound.
According to one embodiment of the invention, the hydroxylamine compound comprises one or more of N, N-diethylhydroxylamine, N-dimethylhydroxylamine, N-isopropylhydroxylamine, phenylhydroxylamine; and/or the presence of a gas in the gas,
the reaction temperature of the reaction is 20-70 ℃.
According to an embodiment of the present invention, 70 to 100 parts by mass of tetramethyldiphenyldihydrotrisiloxane is added to a container containing 38 to 59 parts by mass of the hydroxylamine compound in a batch manner during the charging time to perform a reaction.
According to an embodiment of the present invention, the feeding time is 1 to 4 hours, and the reaction time is 12 to 18 hours.
An embodiment of the present invention further provides a chain extender for a vulcanization process of silicone rubber, which comprises the above diphenyl silicon compound.
The invention further provides a preparation method of the vulcanized silicone rubber, which comprises the steps of reacting raw materials to prepare the vulcanized silicone rubber; the raw materials comprise crude rubber, a curing agent and a chain extender, wherein the chain extender comprises the diphenyl silicon compound.
The invention further provides that the mass ratio of the raw rubber to the chain extender is 100 (1-3); and/or the raw rubber is a hydroxyl-terminated siloxane polymer.
The diphenyl silicon compound provided by the embodiment of the invention can be used as a chain extender in a silicon rubber vulcanization process, and can improve the high temperature resistance of the obtained room temperature vulcanized silicon rubber.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention. Wherein:
FIG. 1 is an infrared spectrum of terminal diethylaminooxy tetramethyldiphenyltrisiloxane (DPHN) and tetramethyldiphenyldihydrotrisiloxane (DPHH) of example 1 of the present invention.
Detailed Description
The following detailed description of the preferred embodiments of the invention is provided to illustrate the principles of the invention and not to limit the scope of the invention.
One embodiment of the present invention provides a diphenyl silicon compound having the following structural formula:
wherein R is1And R3Each independently selected from hydrogen, methyl and ethyl, R2And R4Each independently selected from methyl, ethyl, propyl and phenyl.
The diphenyl silicon compound provided by the embodiment of the invention can be used as a chain extender in a silicon rubber vulcanization process, and both ends of the diphenyl silicon compound are aminoxy groups (-N-O), so that the diphenyl silicon compound can be subjected to condensation crosslinking reaction with silicon hydroxyl in raw rubber without a catalyst due to higher reactivity of the aminoxy groups; meanwhile, hydroxylamine is removed through condensation reaction, a small amount of hydroxylamine remained in the system can play an antioxidation role in the silicon rubber, and the side group oxidation reaction of the silicon rubber at high temperature can be inhibited. And the steric hindrance effect of the phenyl structure in the diphenyl silicon compound can greatly improve the high temperature resistance of the room temperature vulcanized silicone rubber.
In one embodiment, R1、R2Each independently selected from methyl and ethyl.
In one embodiment, R1Is methyl, R2Is methyl.
In one embodiment, R1Is ethyl, R2Is ethyl.
In one embodiment, R1Is methyl, R2Is ethyl.
In one embodiment, R3、R4Each independently selected from methyl and ethyl.
In one embodiment, R3Is methyl, R4Is methyl.
In one embodiment, R3Is ethyl, R4Is ethyl.
In one embodiment, R3Is a firstRadical, R4Is ethyl.
In one embodiment, R2And R4Each independently selected from methyl, ethyl, n-propyl, isopropyl and phenyl.
In one embodiment, R1Is hydrogen, R2Is isopropyl or phenyl.
In one embodiment, R3Is hydrogen, R4Is isopropyl or phenyl.
An embodiment of the present invention provides a method for preparing the diphenyl silicon compound, which comprises reacting tetramethyldiphenyldihydrotrisiloxane and a hydroxylamine compound.
In one embodiment, the hydroxylamine compound comprises R1R2N-OH and/or R3R4N-OH，R1R2N-OH and R3R4N-OH is a different compound, and R1、R2、R3、R4The foregoing definitions apply.
In one embodiment, the hydroxylamine compound comprises one or more of N, N-diethylhydroxylamine, N-dimethylhydroxylamine, N-isopropylhydroxylamine, and phenylhydroxylamine, preferably N, N-diethylhydroxylamine, which has high reactivity, good oxidation resistance, and is readily available and available, resulting in low production cost.
In one embodiment, the reaction of tetramethyldiphenyldihydrotrisiloxane and hydroxylamine compound may be carried out without a solvent, or a solvent such as benzene, toluene, cyclohexane, n-hexane, etc. may be added to the reaction system.
In one embodiment, the reaction temperature of the tetramethyldiphenyldihydrotrisiloxane and the hydroxylamine compound is 20 to 70 ℃, such as 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 66 ℃, 68 ℃, 69 ℃.
In one embodiment, the reaction temperature of the tetramethyldiphenyl dihydrotrisiloxane and the hydroxylamine compound is 65-70 ℃.
In one embodiment, the reaction pressure of the tetramethyldiphenyldihydrotrisiloxane and the hydroxylamine compound is atmospheric pressure.
In one embodiment, the reaction time of the tetramethyldiphenyldihydrotrisiloxane and the hydroxylamine compound is 12 to 18 hours, and further 16 to 18 hours, such as 13 hours, 14 hours, 15 hours, and 17 hours.
In one embodiment, under the conditions of no water, no oxygen and inert gas protection, 70-100 parts by mass of tetramethyldiphenyl dihydrotrisiloxane is added into a container containing 38-59 parts by mass of hydroxylamine compound in batches for reaction, and the product diphenyl silicon compound is obtained by rotary evaporation and purification after the reaction is finished.
In one embodiment, the charging time of the tetramethyldiphenyldihydrotrisiloxane may be 1 to 4 hours, such as 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, etc., wherein 2 hours is preferred.
In one embodiment, the inert gas comprises nitrogen and/or argon, preferably nitrogen.
In one embodiment, the pressure of the rotary evaporation is negative pressure ranging from-0.095 MPa to-0.1 MPa.
In one embodiment, the temperature of rotary evaporation is 95 ℃ to 115 ℃, e.g., 100 ℃, 105 ℃, 110 ℃.
In one embodiment, the time for spin-steaming is 1 to 4 hours, such as 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours.
An embodiment of the invention provides a chain extender for a vulcanization process of silicone rubber, which comprises the diphenyl silicon compound.
The diphenyl silicon compound provided by the embodiment of the invention is used as a chain extender in a silicon rubber vulcanization process, can improve the high temperature resistance of the obtained room temperature vulcanized silicon rubber, and enables the room temperature vulcanized silicon rubber to have certain oxidation resistance.
The invention provides a preparation method of silicon sulfide rubber, which comprises the steps of reacting raw materials to prepare the silicon sulfide rubber; the raw materials comprise crude rubber, a curing agent and a chain extender, wherein the chain extender comprises the diphenyl silicon compound.
In one embodiment, the prepared vulcanized silicone rubber is room temperature vulcanized silicone rubber.
In one embodiment, the prepared vulcanized silicone rubber is a room temperature vulcanized silicone rubber containing phenyl groups.
In one embodiment, the content of phenyl groups in the prepared vulcanized silicone rubber is 0.35 to 1.03%, such as 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%.
In one embodiment, the raw rubber may be a hydroxyl terminated siloxane polymer, such as 107 silicone rubber.
In one embodiment, the mass ratio of the raw rubber to the diphenyl silicon compound as the chain extender is 100 (1-3), for example, 100:1, 100:1.5, 100:2, 100:2.5, and 100: 3.
In one embodiment, the curing agent may be ethyl orthosilicate, methyl orthosilicate, methyltrimethoxysiloxane, polysilazane, or the like.
In one embodiment, the feedstock further comprises a filler, such as a reinforcing agent; the reinforcing agent can be calcium carbonate, carbon black, silicon micropowder, aerogel powder and the like.
The vulcanized silicone rubber containing phenyl prepared by the preparation method provided by the embodiment of the invention has excellent high-temperature resistance.
An embodiment of the invention provides an application of the diphenyl silicon compound as a chain extender in preparation of a high-temperature-resistant adhesive, a high-temperature-resistant sealant, a high-temperature-resistant coating, low-temperature-resistant silicone rubber and phenyl silicone rubber.
The diphenyl silicon compound, the preparation method and the application thereof according to an embodiment of the present invention will be further described with reference to the following specific examples. The percentages in the examples and comparative examples are by mass unless otherwise specified. The N, N-diethylhydroxylamine used in the examples and comparative examples was obtained from Shanghai Ron reagent company; tetramethyldiphenyldihydrotrisiloxane is available from Hubei Jinleda chemical Co., Ltd; hydroxyl terminated polydimethylsiloxane (107 silicone rubber) was purchased from Chen chemical research design institute, GmbH; the fumed silica is purchased from Hubei Huifu nanometer materials GmbH; the XH-A300C-2 curing agent was purchased from Beijing Star aircraft electro-mechanical Equipment, Inc.
The performance test conditions of the vulcanized silicone rubber in the examples and the comparative examples are as follows:
and (3) testing tensile property: type 1 dumbbell-shaped sample bars are prepared according to the requirements of GB/T528-2009 vulcanized rubber or thermoplastic rubber tensile stress strain performance measurement, and are tested by a CMT4204 electronic universal tester, and the moving speed of a clamp holder is 500 mm/min.
End break elongation test: testing by adopting a CMT4204 electronic universal testing machine;
and (3) hardness testing: according to the GB/T531-2008 vulcanized rubber or thermoplastic rubber indentation hardness test method part 1: shore Durometer (Shore hardness) hardness test of vulcanized rubber was performed using a durometer (SLX-a, Lelotte test instruments, Inc., Rich, L.C.).
And (3) testing high-temperature resistance: the thermal weight loss test of the vulcanized rubber is carried out by adopting an SDT Q600 thermogravimetric analyzer of TA Instruments company, the temperature is increased from room temperature to 800 ℃ at the temperature rise rate of 10 ℃/min under the nitrogen atmosphere, the temperature with the thermal weight loss rate of 5 percent is recorded and is recorded as T5％。
Example 1
Preparation of terminal diethylaminooxy tetramethyl diphenyl trisiloxane
Under the protection of nitrogen, 80g of tetramethyl diphenyl Dihydrotrisiloxane (DPHH) is added into a reaction vessel containing 49.31g N, N-diethylhydroxylamine within 2h, the feeding temperature is kept at about 65 ℃, the reaction temperature is kept at 65 ℃ after the feeding is finished, the reaction is carried out for 16h, and the whole reaction process is protected by nitrogen. The reacted material is distilled under the conditions of 100 ℃ and-0.1 MPa for 2h under reduced pressure to remove redundant N, N-diethylhydroxylamine, and the terminal diethylaminooxy tetramethyl diphenyl trisiloxane (DPHN) with the yield of 93 percent is obtained.
Of terminal diethylaminooxy tetramethyldiphenyltrisiloxane (DPHN) and tetramethyldiphenyldihydrotrisiloxane (DPHH)The infrared spectrum is shown in FIG. 1. As can be seen from the figure, methylene (-CH) is present in DPHN2- (peak position: 2850. 2930cm-1) And N-O bond (peak position: 1377cm-1) (ii) a In addition, when the infrared spectrum of DPHN was compared with that of DPHH, a peak corresponding to Si-H bond in DPHN (peak position: 2167 cm)-1) Completely disappeared, and no hydroxyl peak (peak position: 3600cm-1Left and right). The infrared data show that Si-H has been completely substituted with aminooxy groups and that no hydroxylamine remains in the terminal diethylaminooxytetramethyldiphenyltrisiloxane.
Preparation of vulcanized Silicone rubber
Dispersing 107 silicon rubber and fumed silica at a high speed according to the mass ratio of 100:25, and mixing to obtain the base rubber. Then, uniformly mixing the three substances according to the proportion of the base rubber XH-A300C-2 curing agent and terminal diethylaminooxy tetramethyl diphenyl trisiloxane as 100:4:1, pouring the mixture into a polytetrafluoroethylene mold, curing the mixture into a sheet with the thickness of 2mm, and curing the sheet at room temperature for 7 days to obtain the room temperature vulcanized silicone rubber containing phenyl, wherein the phenyl content of the room temperature vulcanized silicone rubber is 0.35%.
Example 2
The base adhesive and terminal diethylaminooxy tetramethyl diphenyl trisiloxane prepared in example 1 were mixed uniformly according to the proportion of the base adhesive XH-A300C-2 curing agent and terminal diethylaminooxy tetramethyl diphenyl trisiloxane 100:4:3, poured into a polytetrafluoroethylene mold, cured into a sheet with a thickness of 2mm, and cured at room temperature for 7 days to obtain phenyl-containing room temperature vulcanized silicone rubber with a phenyl content of 1.03%.
Comparative example 1
Uniformly mixing the base rubber prepared in the example 1 and an XH-A300C-2 curing agent according to the mass ratio of 100:4, pouring the mixture into a polytetrafluoroethylene mold, curing the mixture into a sheet with the thickness of 2mm, and curing the sheet at room temperature for 7 days to obtain the room temperature vulcanized silicone rubber.
Comparative example 2
The base rubber prepared in example 1, an XH-A300C-2 curing agent and dimethyl diethoxy siloxane were uniformly mixed in a mass ratio of (100: 4: 3), poured into a polytetrafluoroethylene mold, cured into a sheet with a thickness of 2mm, and cured at room temperature for 7 days to obtain room temperature vulcanized silicone rubber.
The vulcanized silicone rubbers of the above examples and comparative examples were subjected to a chipping test in accordance with the foregoing method, and the specific results are shown in table 1 below.
TABLE 1
| Tensile Strength (MPa) | Elongation at break | Shore A hardness | T5％(℃) | |
| Example 1 | 2.51 | 191％ | 56 | 396 |
| Example 2 | 2.75 | 224％ | 55 | 441 |
| Comparative example 1 | 2.41 | 180％ | 58 | 379 |
| Comparative example 2 | 2.56 | 210％ | 50 | 360 |
The test results in Table 1 show that the temperature (396 ℃, 441 ℃) at which the thermal weight loss rate of the vulcanized silicone rubber prepared in the examples 1 and 2 is 5% is obviously higher than the temperature (379 ℃, 360 ℃) of the comparative example 1 and the comparative example 2, and the high temperature resistance of the vulcanized silicone rubber prepared in the examples 1 and 2 is obviously improved. Meanwhile, compared with the vulcanized silicone rubber of comparative example 1, the tensile strength and the elongation at break of the vulcanized silicone rubber of examples 1 and 2 are also obviously improved.
The results show that the vulcanized silicone rubber prepared in the embodiment of the invention has higher high-temperature resistance and stronger mechanical property compared with the vulcanized silicone rubber of comparative example 1 without adding the chain extender of the invention. In addition, compared with the vulcanized silicone rubber of comparative example 2 added with the conventional chain extender, the vulcanized silicone rubber prepared by the embodiment of the invention has higher high-temperature resistance (the weight loss is 5 percent, and the temperature difference is 81 ℃).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A diphenyl silicon compound having the formula:
wherein R is1And R3Each independently selected from hydrogen, methyl and ethylRadical, R2And R4Each independently selected from methyl, ethyl, propyl and phenyl.
2. The diphenyl silicon compound of claim 1, wherein R is1、R2Each independently selected from methyl and ethyl; and/or the presence of a gas in the gas,
R3、R4each independently selected from methyl and ethyl.
3. The diphenyl silicon compound of claim 1, wherein R is1Is hydrogen, R2Is isopropyl or phenyl; and/or the presence of a gas in the gas,
R3is hydrogen, R4Is isopropyl or phenyl.
4. A method for preparing the diphenyl silicon compound as described in any one of claims 1 to 3, comprising reacting tetramethyldiphenyldihydrotrisiloxane with a hydroxylamine compound.
5. The method of claim 4 wherein the hydroxylamine compound comprises one or more of N, N-diethylhydroxylamine, N-dimethylhydroxylamine, N-isopropylhydroxylamine, phenylhydroxylamine; and/or the presence of a gas in the gas,
the reaction temperature of the reaction is 20-70 ℃.
6. The method according to claim 4 or 5, wherein 70 to 100 parts by mass of tetramethyldiphenyldihydrotrisiloxane is added in portions to a container containing 38 to 59 parts by mass of the hydroxylamine compound for the reaction during the addition time.
7. The process according to any one of claims 4 to 6, wherein the feeding time is 1 to 4 hours and the reaction time is 12 to 18 hours.
8. A chain extender for vulcanization process of silicone rubber comprising the diphenylsilicon compound of any one of claims 1 to 3.
9. A preparation method of silicon sulfide rubber comprises the steps of reacting raw materials to prepare silicon sulfide rubber; the raw materials comprise raw rubber, a curing agent and a chain extender, wherein the chain extender comprises the diphenyl silicon compound of any one of claims 1 to 3.
10. The preparation method of claim 9, wherein the mass ratio of the raw rubber to the chain extender is 100 (1-3); and/or the presence of a gas in the gas,
the raw rubber is a hydroxyl-terminated siloxane polymer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5490349A (en) * | 1977-12-28 | 1979-07-18 | Toshiba Silicone | Cold cure polyorganosiloxane composition |
| JPH07149907A (en) * | 1993-08-23 | 1995-06-13 | Hercules Inc | Sih-terminated chain extender for organosilicone polymer |
| JPH08127657A (en) * | 1994-10-31 | 1996-05-21 | Dow Corning Asia Ltd | Production of cured diphenylsiloxane and cured product |
-
2021
- 2021-12-17 CN CN202111555795.9A patent/CN114044787A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5490349A (en) * | 1977-12-28 | 1979-07-18 | Toshiba Silicone | Cold cure polyorganosiloxane composition |
| JPH07149907A (en) * | 1993-08-23 | 1995-06-13 | Hercules Inc | Sih-terminated chain extender for organosilicone polymer |
| JPH08127657A (en) * | 1994-10-31 | 1996-05-21 | Dow Corning Asia Ltd | Production of cured diphenylsiloxane and cured product |
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