CN110128461B - Radiation-resistant additive, synthesis thereof and method for preparing radiation-resistant silicon rubber material - Google Patents
Radiation-resistant additive, synthesis thereof and method for preparing radiation-resistant silicon rubber material Download PDFInfo
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- CN110128461B CN110128461B CN201910283521.5A CN201910283521A CN110128461B CN 110128461 B CN110128461 B CN 110128461B CN 201910283521 A CN201910283521 A CN 201910283521A CN 110128461 B CN110128461 B CN 110128461B
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 47
- 230000005855 radiation Effects 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000654 additive Substances 0.000 title claims abstract description 19
- 230000000996 additive effect Effects 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 title claims description 14
- 230000015572 biosynthetic process Effects 0.000 title claims description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 37
- 239000004945 silicone rubber Substances 0.000 claims description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 239000002808 molecular sieve Substances 0.000 claims description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005915 ammonolysis reaction Methods 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000010074 rubber mixing Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 2
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical group CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical group C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 238000007789 sealing Methods 0.000 abstract description 3
- 238000004891 communication Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000013016 damping Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- JJZFJUJKZUIFKN-UHFFFAOYSA-N 1,2-ditert-butyl-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C(C)(C)C)=C1C(C)(C)C JJZFJUJKZUIFKN-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
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- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides an irradiation-resistant additive and a synthesis method thereof and a method for preparing an irradiation-resistant silicon rubber material. The radiation-resistant silicon rubber material prepared by the invention has good radiation resistance, can be used for producing various rubber products such as wires, cable sheaths, rubber gaskets, sealing parts, membranes and the like in various radiation occasions, and can be widely applied to the fields of aerospace, nuclear industry, electronic communication, chemical industry, medicine, ships and the like which need high-energy radiation resistance.
Description
Technical Field
The invention belongs to the technical field of special rubber functional materials and production thereof, and relates to an irradiation-resistant additive containing a polyphenyl silazane structure, a synthesis method thereof and a preparation method for preparing an irradiation-resistant silicon rubber material.
Background
Since the oil crisis has occurred, countries around the world generally pay attention to the development and utilization of energy, and people are always dedicated to searching for energy capable of replacing oil. Therefore, nuclear power is regarded as a safe, clean and reliable energy source, and development and utilization of the nuclear power are more and more emphasized. In order to ensure the safety of nuclear power equipment, electrical instruments, wire and cable insulation materials, gasket sealing members and the like in the equipment, a large amount of high polymer elastomer sealing materials are used. Such sealing materials are required not only to have sufficient radiation resistance but also to withstand harsh environmental conditions such as high temperature, vacuum, high voltage, steam, various chemical media, and the like. However, some polymers with good resistance to high temperatures and chemicals do not necessarily have the ability to withstand irradiation, such as conventional dimethylsilicone rubber. Although the dimethyl silicone rubber has wide applicable temperature range and good medium resistance and electrical property, the dimethyl silicone rubber has radiation resistanceThe performance is not as good as that of the common hydrocarbon rubber. The dimethyl silicone rubber is subjected to 12.9-15.48 multiplied by 103C/kg (5-6 multiplied by 10)7Lomb) lose elasticity after irradiation, and the irradiation resistance of the specially-matched methyl vinyl silicone rubber can only reach about 2.58X 104C/kg (1X 10)8Lun), for which it is necessary to try to improve the radiation resistance of the silicone rubber.
It is known that polymer materials containing aromatic rings have high radiation resistance because bulky aromatic rings contain conjugated double bonds and can absorb radiation energy, which stabilizes the polymer materials. Therefore, the proper introduction of phenyl groups into the silicone rubber molecule is expected to improve the radiation resistance of the silicone rubber material. The Chinese patent CN100480333C and the U.S. patents US3032531, US3876605, US5196228A and the like all adopt phenyl silicone rubber as raw rubber to prepare rubber with radiation resistance, the radiation resistance of the silicone rubber is really improved, and the radiation resistance can reach 5 multiplied by 108Around, they are still inadequate in the face of today's higher radiation resistance requirements. Therefore, it is necessary to further improve the irradiation resistance of the phenyl silicone rubber.
Disclosure of Invention
The invention provides an irradiation-resistant additive containing a polyphenyl silazane structure, a synthesis process thereof and a preparation method for manufacturing an irradiation-resistant silicon rubber material, aiming at the conditions of the prior art. The prepared radiation-resistant silicon rubber material can be used for a protective layer of a radiation-resistant and high-temperature-resistant outgoing line of a nuclear power station, and can be independently used or compounded with fabrics to prepare rubber hooping pieces, rubber gaskets, rubber sleeves and various radiation-resistant sectional materials.
The invention aims to provide an irradiation-resistant additive, which is of a structure containing polyphenyl silazane and has a structural formula as follows:
the preparation method of the irradiation-resistant additive comprises the following steps:
(1) preparation for Synthesis
Drying the molecular sieve in a box type resistance furnace at 400-450 ℃ for 3.0-5.0 h, cooling the molecular sieve in a dryer, putting the dried molecular sieve in a container containing toluene, and standing for more than 2 days for later use; the used glass instrument and the stirring rod are put into an oven after being cleaned, the temperature of the oven is set to be 120-125 ℃, the oven is dried for 1.5-2 h, and the glass instrument is cooled for standby application, wherein the glass instrument comprises a four-opening reaction bottle, an air guide pipe, a reflux condenser pipe and a constant-pressure liquid dropping device;
(2) intermediate synthesis reaction
Installing a stirring device at the middle opening of a four-opening reaction bottle, respectively installing an air guide pipe, a reflux condenser pipe and a constant-pressure liquid dropping device at the side opening, introducing nitrogen passing through a drying tower with a molecular sieve from the air guide pipe, exhausting air in the four-opening reaction bottle, weighing 50-90 parts by mass of methyl phenyl dichlorosilane and 80-120 parts by mass of toluene, and pouring into the four-opening reaction bottle; starting stirring, opening condensed water, and continuously introducing nitrogen;
weighing 80-120 parts by mass of triphenyl silanol and 40-60 parts by mass of pyridine and 60-100 parts by mass of toluene to prepare a solution, slowly dripping the solution into a four-mouth reaction bottle through a constant-pressure dropping funnel to react, cooling the solution by adopting an ice water bath to control the temperature below 10 ℃, and finishing dripping within 3-6 hours; heating by using an oil bath, heating to 25 +/-5 ℃, reacting for 1-3 h, then heating to 80 +/-5 ℃, and reacting for 3-6 h; stopping heating, continuously introducing nitrogen, and cooling to below 40 ℃;
weighing 0.8-1.2 parts by mass of methanol, weighing 5-10 parts by mass of toluene to prepare a solution, slowly dropwise adding the solution into a four-mouth reaction bottle through a constant-pressure funnel to react at 40 +/-5 ℃, continuously keeping the temperature at 40 +/-5 ℃ after dropwise adding for 1-3 h, and reacting for 0.5-3 h to obtain an intermediate filtrate;
(3) product synthesis
Under the protection of nitrogen, starting to stir the filtrate, cooling by adopting an ice water bath, controlling the temperature below 15 ℃, and quickly introducing ammonia gas to carry out ammonolysis reaction for 5-6 hours to obtain an ammonolysis product; then heating to 60 +/-5 ℃ by using an oil bath, controlling the temperature to be 60 +/-5 ℃, and decompressing until no solvent is evaporated to obtain the white solid triphenyl siloxy methyl phenyl silazane.
The method for preparing the irradiation-resistant silicone rubber by adopting the irradiation-resistant additive comprises the following steps:
(1) preparing a rubber compound slice: placing 100 parts by mass of phenyl silicone rubber raw rubber on a double-roll rubber mixing mill, simultaneously adding 5-25 parts of poly-phenyl silazane irradiation-resistant additive, 30-70 parts of white carbon black and 5-15 parts of structure control agent after roll coating, uniformly mixing, and then thinly discharging the mixture out of a sheet;
(2) heat treatment of rubber compound slices: placing the rubber compound in a kneading machine, setting the temperature of the kneading machine to be 120-180 ℃, continuing to mix for 1-10 h, and cooling for later use;
(3) adding a vulcanizing agent: placing the rubber compound slice after high-temperature treatment on a double-roller rubber mixing mill, wrapping rollers, adding 0.5-1.2 parts by mass of a vulcanizing agent, uniformly mixing, and then discharging the rubber compound slice for later use;
(4) and (3) vulcanization molding of the rubber material: the rubber material is vulcanized for one section on a pressure forming machine under the following conditions: multiplying by 10min at 90-170 ℃; then carrying out secondary vulcanization in an oven: molding the rubber material product at 200 ℃ for 4h to form various shapes according to requirements.
The method for preparing the radiation-resistant silicone rubber is characterized in that the raw phenyl silicone rubber is raw methyl phenyl silicone rubber with the content of methyl phenyl chain links of 10-30 percent or raw diphenyl silicone rubber with the content of diphenyl chain links of 5-20 percent.
The method for preparing the radiation-resistant silicone rubber is characterized in that the white carbon black refers to any one of fumed silica A380, A200, HL300, HL380 or precipitated silica T383.
The method for preparing the radiation-resistant silicone rubber is characterized in that the structure control agent is diphenyl dimethoxysilane or diphenyl diethoxysilane.
The method for preparing the radiation-resistant silicone rubber is characterized in that the vulcanizing agent is 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide or dicumyl peroxide or di-tert-butyl cumene peroxide or benzoyl peroxide or 2, 4-dichlorobenzoyl peroxide.
The invention has the advantages that: the siloxane radiation-resistant additive containing polyphenyl has more aromatic rings, conjugated double bonds are contained in the aromatic rings, the siloxane radiation-resistant additive can absorb radiation energy and can further improve the radiation resistance of the phenyl silicone rubber, and meanwhile, amino groups exist in the molecular structure of the radiation-resistant additive and can react with silicon hydroxyl groups on the surface of white carbon black in the silicone rubber, so that the surface of the modified white carbon black is grafted, the polyphenyl group structure is stable and cannot be separated out in a silicone rubber component system, and the radiation-resistant additive has good compatibility with the phenyl silicone rubber system and does not influence the physical and mechanical properties of the phenyl silicone rubber material.
The radiation-resistant silicone rubber material prepared by the invention can be used for producing various rubber products such as wires, cable sheaths, rubber gaskets, sealing parts, membranes and the like in various radiation occasions, and can be widely applied to the fields of aerospace, nuclear industry, electronic communication, chemical industry, medicine, ships and the like which need high-energy radiation resistance.
Detailed description of the invention
The technical scheme of the invention is further detailed by combining the following embodiments:
the preparation method of the silazane damping agent containing the triphenylsiloxane structure comprises the following steps:
(1) preparation for Synthesis
Drying the molecular sieve in a box type resistance furnace at 400 ℃ for 3.0h, cooling the molecular sieve in a dryer, putting the dried molecular sieve in a container containing toluene, and standing for more than 2 days for later use; the used glass instrument and the stirring rod are put into an oven after being cleaned, the temperature of the oven is set to be 120 ℃, the glass instrument is dried for 2 hours and is used after being cooled, and the glass instrument comprises a four-opening reaction bottle, an air duct, a reflux condenser tube and a constant-pressure liquid dropping device.
(2) Intermediate synthesis reaction
A stirring device is arranged at the middle opening of a four-opening reaction bottle, a gas guide pipe, a reflux condenser pipe and a constant-pressure dropping device are respectively arranged at the side openings of the four-opening reaction bottle, nitrogen passing through a molecular sieve drying tower is introduced from the gas guide pipe, air in the four-opening reaction bottle is exhausted, and 70 parts of methyl phenyl dichlorosilane and 100 parts of methylbenzene are weighed and poured into the four-opening reaction bottle. Starting stirring, opening condensed water and continuously introducing nitrogen.
Weighing 100 parts of triphenyl silanol and 50 parts of pyridine and 80 parts of toluene to prepare a solution, slowly dripping the solution into a four-mouth reaction bottle through a constant-pressure dropping funnel to react, cooling the solution by adopting an ice water bath to control the temperature below 10 ℃, and finishing dripping for 6 hours; heating the mixture by using an oil bath, heating the mixture to 25 +/-2 ℃, reacting for 3 hours, then heating the mixture to 80 +/-2 ℃, and reacting for 6 hours. Stopping heating, continuously introducing nitrogen, and cooling to below 40 deg.C.
Weighing 1 part of methanol, weighing 8 parts of toluene to prepare a solution, slowly dripping the solution into a four-mouth reaction bottle through a constant pressure funnel to react at 40 +/-2 ℃, continuously keeping the temperature at 40 +/-2 ℃ after dripping for 1.5h, and reacting for 3h to obtain an intermediate filtrate.
(3) Product synthesis
And (3) under the protection of nitrogen, starting to stir the filtrate, cooling by adopting an ice water bath, controlling the temperature to be below 10 ℃, and quickly introducing ammonia gas to carry out ammonolysis reaction for 6 hours to obtain an ammonolysis product. Heating to 65 ℃ was then started with an oil bath and the temperature was controlled at 65 ℃ under reduced pressure until no solvent evaporated to give a white solid triphenylsiloxymethylphenylsilazane.
The method for preparing the damping silicone rubber by adopting the components of the formula in the table 1 comprises the following steps:
(1) rubber compound sheet preparation
Placing 100 parts by mass of phenyl silicone rubber raw rubber on a double-roller rubber mixing mill, simultaneously adding 5-25 parts of polyphenyl silazane irradiation-resistant additive, 30-70 parts of white carbon black and 5-15 parts of structure control agent after roller coating, uniformly mixing, and thinly discharging the mixture out of a sheet;
(2) heat treatment of rubber mixtures
Placing the rubber compound in a kneading machine, setting the temperature of the kneading machine to be 120-180 ℃, continuing to mix for 1-10 h, and cooling for later use;
(3) adding a vulcanizing agent
Placing the heat-treated rubber compound slice on a double-roller rubber mixing mill, wrapping rollers, adding 0.5-1.2 parts of vulcanizing agent, mixing uniformly, and then discharging the slice for later use;
(4) vulcanization molding of rubber compounds
Carrying out first-stage vulcanization on a pressure forming machine under the conditions: multiplying by 10min at 90-170 ℃; then carrying out secondary vulcanization in an oven: conditions are as follows: and (4) forming the radiation-resistant silicon rubber product with the required shape at 200 ℃ for 4 h.
The physical and mechanical properties of the radiation-resistant silicone rubber samples prepared from the formulation components listed in table 1. Wherein, 1) mechanical property test: testing the tensile strength and the elongation at break according to GB/T528; testing the hardness according to GB/T531; 2) the irradiation source is 60 Co-gamma ray, and the total irradiation dose is 5 multiplied by 105Gy, dose rate 50Gy/min, air atmosphere. The test results are shown in Table 1.
Claims (10)
1. The irradiation-resistant additive is characterized by being of a structure containing polyphenyl silazane and having a structural formula as follows:
2. the method of claim 1, wherein the method comprises the steps of:
(1) preparation for Synthesis
Drying the molecular sieve in a box type resistance furnace at 400-450 ℃ for 3.0-5.0 h, cooling the molecular sieve in a dryer, and putting the dried molecular sieve in a container containing toluene; cleaning the glass instrument and the stirring rod, drying in an oven, and cooling for later use;
(2) intermediate synthesis reaction
Installing a stirring device at the middle opening of a four-opening reaction bottle, respectively installing an air guide pipe, a reflux condenser pipe and a constant-pressure liquid dropping device at the side opening, introducing nitrogen passing through a drying tower with a molecular sieve from the air guide pipe, exhausting air in the four-opening reaction bottle, weighing 50-90 parts by mass of methyl phenyl dichlorosilane and 80-120 parts by mass of toluene, and pouring into the four-opening reaction bottle; starting stirring, opening condensed water, and continuously introducing nitrogen;
weighing 80-120 parts by mass of triphenyl silanol and 40-60 parts by mass of pyridine and 60-100 parts by mass of toluene to prepare a solution, slowly dripping the solution into a four-mouth reaction bottle through a constant-pressure dropping funnel to react, cooling the solution by adopting an ice water bath to control the temperature below 10 ℃, and finishing dripping within 3-6 hours; heating by using an oil bath, heating to 25 +/-5 ℃, reacting for 1-3 h, then heating to 80 +/-5 ℃, and reacting for 3-6 h; stopping heating, continuously introducing nitrogen, and cooling to below 40 ℃;
weighing 0.8-1.2 parts by mass of methanol, weighing 5-10 parts by mass of toluene to prepare a solution, slowly dripping the solution into a four-mouth reaction bottle through a constant-pressure funnel to react, heating to 40 +/-5 ℃, finishing dripping for 1-3 h, continuously keeping the temperature at 40 +/-5 ℃, and reacting for 0.5-3 h to obtain an intermediate filtrate;
(3) product synthesis
Stirring the filtrate under the protection of nitrogen, cooling the filtrate by adopting an ice water bath, controlling the temperature below 15 ℃, and quickly introducing ammonia gas to carry out ammonolysis reaction for 5-6 hours to obtain an ammonolysis product; then heating to 60 +/-5 ℃ by using an oil bath, controlling the temperature to be 60 +/-5 ℃, and decompressing until no solvent is evaporated to obtain the white solid triphenyl siloxy methyl phenyl silazane.
3. The method for preparing a radiation-resistant additive as claimed in claim 2, wherein the glass apparatus in the synthesis preparation step includes a four-port reaction vessel, a gas-guide tube, a reflux condenser tube and a constant pressure dropping device.
4. The method for preparing the radiation-resistant additive according to claim 2, wherein the preparation steps for synthesis are as follows: drying the molecular sieve in a box type resistance furnace at 400-450 ℃ for 3.0-5.0 h, cooling the molecular sieve in a dryer, putting the dried molecular sieve in a container containing toluene, and standing for more than 2 days for later use; the used glass instrument and the stirring rod are put into an oven after being cleaned, the temperature of the oven is set to be 120-125 ℃, the oven is baked for 1.5-2 h, and the glass instrument and the stirring rod are cooled for standby.
5. The method for preparing the radiation-resistant silicone rubber by using the radiation-resistant additive as claimed in claim 1, characterized in that the preparation method comprises the steps of:
(1) preparing a rubber compound slice: placing 100 parts by mass of phenyl silicone rubber raw rubber on a double-roll rubber mixing mill, simultaneously adding 5-25 parts of poly-phenyl silazane irradiation-resistant additive, 30-70 parts of white carbon black and 5-15 parts of structure control agent after roll coating, uniformly mixing, and then thinly discharging the mixture out of a sheet;
(2) heat treatment of rubber compound slices: placing the rubber compound slice in a kneading machine, setting the temperature of the kneading machine to be 120-180 ℃, continuing to mix for 1-10 h, and cooling for later use;
(3) adding a vulcanizing agent: placing the rubber compound slice after high-temperature treatment on a double-roller rubber mixing mill, wrapping rollers, adding 0.5-1.2 parts by mass of a vulcanizing agent, uniformly mixing, and then discharging the rubber compound slice for later use;
(4) and (3) vulcanization molding of the rubber material: the rubber material is vulcanized for one section on a pressure forming machine under the following conditions: 90-170 ℃ for 10 min; then carrying out secondary vulcanization in an oven: molding the rubber material product into various shapes at 200 ℃ for 4 hours according to requirements.
6. The method for preparing radiation-resistant silicone rubber according to claim 5, wherein the raw phenyl silicone rubber is raw methyl phenyl silicone rubber having a methyl phenyl chain unit content of 10% to 30%.
7. The method for preparing radiation-resistant silicone rubber according to claim 5, wherein the raw phenyl silicone rubber is raw diphenyl silicone rubber having a diphenyl chain unit content of 5% to 20%.
8. The method for preparing the radiation-resistant silicone rubber according to claim 5, wherein the silica is any one of fumed silica A380, A200, HL300, HL380 or precipitated silica T383.
9. The method for preparing the radiation-resistant silicone rubber according to claim 5, wherein the structure control agent is diphenyldimethoxysilane or diphenyldiethoxysilane.
10. The method for preparing radiation-resistant silicone rubber according to claim 5, wherein the vulcanizing agent is 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, dicumyl peroxide, di-tert-butyl cumene peroxide, benzoyl peroxide or 2, 4-dichlorobenzoyl peroxide.
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| CN106751863A (en) * | 2016-12-26 | 2017-05-31 | 沈阳化工大学 | A kind of silicon rubber radiation hardness auxiliary agent and preparation method thereof |
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| CN106751863A (en) * | 2016-12-26 | 2017-05-31 | 沈阳化工大学 | A kind of silicon rubber radiation hardness auxiliary agent and preparation method thereof |
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