CN115160789A - Radiation-resistant phenylene ether foamed silicone rubber and preparation method thereof - Google Patents
Radiation-resistant phenylene ether foamed silicone rubber and preparation method thereof Download PDFInfo
- Publication number
- CN115160789A CN115160789A CN202210962319.7A CN202210962319A CN115160789A CN 115160789 A CN115160789 A CN 115160789A CN 202210962319 A CN202210962319 A CN 202210962319A CN 115160789 A CN115160789 A CN 115160789A
- Authority
- CN
- China
- Prior art keywords
- phenylene ether
- silicone rubber
- parts
- terminated
- resistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 83
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 79
- 230000005855 radiation Effects 0.000 title claims description 21
- 238000002360 preparation method Methods 0.000 title description 9
- -1 siloxane backbone Chemical group 0.000 claims abstract description 31
- 229920002545 silicone oil Polymers 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
- 238000005187 foaming Methods 0.000 claims abstract description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 9
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 20
- VZSUUFCWNGDTIE-UHFFFAOYSA-N hydroxy-[4-[4-[hydroxy(dimethyl)silyl]phenoxy]phenyl]-dimethylsilane Chemical compound C1=CC([Si](C)(O)C)=CC=C1OC1=CC=C([Si](C)(C)O)C=C1 VZSUUFCWNGDTIE-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- YBNBOGKRCOCJHH-UHFFFAOYSA-N hydroxy-[4-[hydroxy(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound C[Si](C)(O)C1=CC=C([Si](C)(C)O)C=C1 YBNBOGKRCOCJHH-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229920001955 polyphenylene ether Polymers 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000002285 radioactive effect Effects 0.000 abstract description 3
- 239000004088 foaming agent Substances 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 239000000565 sealant Substances 0.000 abstract description 2
- 239000003566 sealing material Substances 0.000 abstract description 2
- 239000004636 vulcanized rubber Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000012535 impurity Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 239000006261 foam material Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 231100000987 absorbed dose Toxicity 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Abstract
The invention provides an irradiation-resistant phenylene ether expanded silicone rubber which comprises the following components in parts by weight: 50-60 parts of vinyl-terminated phenylene ether silicone rubber; 1-2 parts of hydroxy-terminated phenylene ether silicone rubber; 8-15 parts of fumed silica; 10-20 parts of ferric oxide; 2-10 parts of light calcium carbonate; 1-2 parts of hydrogen-containing silicone oil; 0.01-0.1 part of catalyst. The vinyl-terminated phenylene ether silicone rubber can be used as a base rubber of an external heat-proof material of addition type room temperature vulcanized rubber and reacts with hydrogen-containing silicone oil to be used as a crosslinking component; the hydroxyl-terminated phenylene ether silicone rubber reacts with hydrogen-containing silicone oil to form hydrogen gas which is discharged as a foaming agent component. The siloxane backbone containing phenylene ether groups has superior irradiation resistance to polysiloxanes of methyl, phenyl, etc. groups. The material can be used as foaming sealant for cable wells of equipment such as nuclear reactors, neutron accelerators and the like and heat-insulating sealing material for radioactive pipelines.
Description
Technical Field
The invention relates to the technical field of organic chemical synthesis, in particular to irradiation-resistant phenylene ether foamed silicone rubber and a preparation method thereof.
Background
The silicon rubber foam material is a porous high polymer elastomer prepared by foaming silicon rubber, and can be divided into room temperature vulcanization type and high temperature vulcanization type, wherein the room temperature vulcanization type can be formed in situ, has the effects of filling, sealing, damping and the like, has process convenience, and is widely applied. In severe irradiation environments such as nuclear power plants, neutron accelerators and X-ray inspection equipment, irradiation-resistant materials are generally required to be used for sealing, but the existing common silicone rubber foam materials cannot be directly used in the harsh environment.
Phenylene silicone rubber is a type of silicone rubber in which phenylene groups are introduced on a polysiloxane main chain. The introduction of phenylene group can raise the radiation resistance of silicone rubber greatly, and the existence of aromatic ring can raise the rigidity of molecular chain, reduce flexibility, raise glass transition temperature, lower cold resistance and raise tensile strength. The phenylene silicon rubber has excellent high temperature resistance and radiation resistance, the high temperature resistance can reach 250-300 ℃, and the phenylene silicon rubber has the characteristics of good dielectric property, moisture resistance, mildew resistance, water vapor resistance and the like.
In order to meet the high requirements of high temperature resistance and radiation resistance of materials in places with serious radiation resistance, the development and innovation of the phenylene silicone rubber are urgently needed, so that the foamed sealant and the heat-insulating sealing material of radioactive pipelines, which can be applied to cable wells of equipment such as nuclear reactors, neutron accelerators and the like, are obtained.
Disclosure of Invention
The invention provides an irradiation-resistant phenylene ether foamed silicone rubber and a preparation method thereof in order to meet the requirements of an irradiation-resistant position power transmission line.
In order to achieve the technical purpose, the invention specifically adopts the following technical scheme: the radiation-resistant phenylene ether expanded foaming silicone rubber is characterized by comprising the following components in parts by weight:
50-60 parts of vinyl-terminated phenylene ether silicone rubber; 1-2 parts of hydroxy-terminated phenylene ether silicone rubber; 8-15 parts of fumed silica; 10-20 parts of ferric oxide; 2-10 parts of light calcium carbonate; 1-2 parts of hydrogen-containing silicone oil; 0.01-0.1 part of catalyst.
Further, the hydrogen-containing silicone oil includes any one of methyl hydrogen-containing silicone oil and methylphenyl hydrogen-containing silicone oil.
Further, the catalyst includes any one of an isopropyl alcohol chloroplatinate solution or a vinyl siloxane chloroplatinic acid complex.
Further, the vinyl-terminated phenylene ether silicone rubber has a structure represented by formula 1:
wherein x, y and z are the degree of polymerization.
Further, the vinyl-terminated phenylene ether silicone rubber is prepared as follows:
adding 50-60 parts by weight of octamethylcyclotetrasiloxane, 10-30 parts by weight of 4,4 '-bis (dimethylhydroxysilyl) diphenyl ether or a mixture of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 1, 4-bis (dimethylhydroxysilyl) benzene and 10-20 parts by weight of divinyltetramethyldisiloxane into a reactor, and vacuumizing and drying;
adding a catalyst, heating and stirring in an inert atmosphere to react to obtain a siloxane copolymer;
heating to destroy the catalyst, heating again, and removing low molecular weight substances in vacuum to obtain the vinyl-terminated phenylene ether silicone rubber.
Further, the hydroxy-terminated phenylene ether silicone rubber has a structure represented by formula 2:
wherein k, m and n are the degree of polymerization.
Further, the preparation method of the hydroxyl-terminated phenylene ether silicone rubber comprises the following steps:
adding 50-60 parts by weight of octamethylcyclotetrasiloxane siloxane, 10-30 parts by weight of 4,4 '-bis (dimethylhydroxysilyl) diphenyl ether or a mixture of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 1, 4-bis (dimethylhydroxysilyl) benzene and 10-20 parts by weight of hydroxyl silicone oil into a reactor, and vacuumizing and drying;
adding a catalyst, heating and stirring in an inert atmosphere to react to obtain a siloxane copolymer;
heating to destroy the catalyst, heating again, and removing low molecular weight substances in vacuum to obtain the hydroxy-terminated phenylene ether silicone rubber.
The invention also provides a preparation method of the radiation-resistant phenylene ether expanded foamed silicone rubber, which comprises the following steps: fully mixing the vinyl-terminated phenylene ether silicone rubber, the hydroxyl-terminated phenylene ether silicone rubber and the fumed silica on a three-roll mill, adding iron oxide, light calcium carbonate and hydrogen-containing silicone oil, continuously mixing and thinly introducing to obtain foamed base rubber, adding a catalyst, uniformly stirring, and standing and foaming the material to obtain the irradiation-resistant phenylene ether foamed silicone rubber.
Compared with the prior art, the invention has the following beneficial effects:
(1) The vinyl-terminated phenylene ether silicone rubber can be used as a base rubber of an external heat-proof material of addition type room temperature vulcanized rubber and reacts with hydrogen-containing silicone oil to be used as a crosslinking component; the hydroxyl-terminated phenylene ether silicone rubber reacts with hydrogen-containing silicone oil to form hydrogen gas which is discharged as a foaming agent component. The siloxane backbone containing phenylene ether groups has superior irradiation resistance to polysiloxanes of methyl, phenyl, etc. groups.
(2) According to the invention, the vinyl-terminated phenylene ether silicone rubber is added on the basis of the hydroxyl-terminated phenylene ether silicone rubber, both the vinyl-terminated phenylene ether silicone rubber and the hydrogen-containing silicone rubber can react, a cross-linked structure formed by the vinyl-terminated phenylene ether silicone rubber participating in cross-linking mainly plays a supporting role, and a closed-cell small-bubble structure is formed, so that the foaming material has certain strength and hardness, and the problem that the foaming material formed by the reaction of the hydroxyl-terminated phenylene ether silicone rubber and the hydrogen-containing silicone oil is low in strength and hardness is solved.
(3) According to the invention, both vinyl-terminated and hydroxyl-terminated phenyl ether phenylene phenyl polysiloxane are introduced with methyl phenyl side chains, and the methyl phenyl hydrogen-containing silicone oil is used as a cross-linking agent, so that the micro-phase separation of the general methyl hydrogen-containing silicone oil and the two phenyl ether phenylene polysiloxanes is reduced, and the phenomenon of incomplete cross-linking reaction caused by phase separation is avoided.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Reagents, equipment and methods employed in the present invention are reagents, equipment and methods conventionally commercially available in the art and conventionally used methods, unless otherwise specified.
The terms "comprises," "comprising," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
Preparing vinyl-terminated phenylene ether silicone rubber with the molar ratio of phenylene ether chain links of 9.8 percent, and compiling into a base rubber A1:
(1) 50 parts of octamethylcyclotetrasiloxane (D4), 30g of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 10g of divinyltetramethyldisiloxane are charged into a 500ml three-necked reaction flask equipped with a stirrer, reflux condenser and thermometer, and the mixture is kept at a constant temperature of 60 ℃ for 30min under vacuum to remove moisture and CO 2 Impurities;
(2) Adding 0.5g of tetramethylammonium hydroxide silicon alkoxide, stirring and reacting in a nitrogen atmosphere under the normal pressure condition, heating to 100 ℃, and carrying out equilibrium reaction for 3 hours to obtain a siloxane copolymer;
(3) Heating to 170 ℃ to destroy the catalyst, and maintaining for 1h;
(4) The temperature is raised, the vacuum pump is started, and the temperature is kept at 180 ℃/5mmHg for 2h.
Preparing hydroxyl-terminated phenylene ether silicone rubber with the molar ratio of phenylene ether chain links of 9.8 percent, and compiling into a base rubber B1:
(1) 50 parts of octamethylcyclotetrasiloxane (D4), 30g of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 10g of hydroxysilicone oil were added to a 500ml three-neck reaction flask equipped with a stirrer, reflux condenser and thermometer, and the mixture was kept at 60 ℃ for 30min under vacuum to remove moisture and CO 2 Impurities;
(2) Adding 0.5g of tetramethylammonium hydroxide silicon alkoxide, stirring and reacting in a nitrogen atmosphere under the normal pressure condition, heating to 100 ℃, and carrying out equilibrium reaction for 3 hours to obtain a siloxane copolymer;
(3) Heating to 170 ℃ to destroy the catalyst, and maintaining for 1h;
(4) The temperature is raised, the vacuum pump is started, and the temperature is kept at 180 ℃/5mmHg for 2h.
Fully mixing 50g of vinyl-terminated phenylene ether silicone rubber A1, 1g of hydroxyl-terminated phenylene ether silicone rubber B1 and 8g of fumed silica on a three-roll machine, adding 15g of iron oxide, 8g of light calcium carbonate and 1g of hydrogen-containing silicone oil, continuously mixing and thinly passing to obtain foamed base rubber, adding 0.05g of chloroplatinic acid isopropanol solution, uniformly stirring, and standing and foaming the material to obtain the irradiation-resistant phenylene ether foamed silicone rubber.
Example 2
Preparing vinyl-terminated phenylene ether silicone rubber with 10.9 percent of molar ratio of phenylene ether chain links, and compiling into a base rubber A2:
(1) 60 parts of octamethylcyclotetrasiloxane siloxane (D4), 30g of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 10g of divinyltetramethyldisiloxane are placed in a 500ml three-neck reaction flask equipped with a stirrer, reflux condenser and thermometer, and the mixture is kept at a constant temperature of 60 ℃ for 30min under vacuum to remove moisture and CO 2 Impurities;
(2) Adding 0.5g of tetramethylammonium hydroxide silicon alkoxide, stirring and reacting in a nitrogen atmosphere under the normal pressure condition, heating to 100 ℃, and carrying out equilibrium reaction for 3 hours to obtain a siloxane copolymer;
(3) Heating to 170 ℃ to destroy the catalyst, and maintaining for 1h;
(4) The temperature is raised, the vacuum pump is started and the temperature is kept at 180 ℃/55mmHg for 2h.
Preparing the hydroxyl-terminated phenylene ether silicone rubber with the molar ratio of phenylene ether chain links of 10.9 percent, and compiling as a base rubber B2:
(1) 60 parts of octamethylcyclotetrasiloxane (D4), 30g of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 10g of hydroxysilicone oil were added to a 500ml three-neck reaction flask equipped with a stirrer, reflux condenser and thermometer, and the mixture was kept at 60 ℃ for 30min under vacuum to remove moisture and CO 2 Impurities;
(2) Adding 0.5g of tetramethylammonium hydroxide silicon alkoxide, stirring and reacting in a nitrogen atmosphere under the normal pressure condition, heating to 100 ℃, and carrying out equilibrium reaction for 3 hours to obtain a siloxane copolymer;
(3) Heating to 170 ℃ to destroy the catalyst, and maintaining for 1h;
(4) The temperature is raised, the vacuum pump is started and the temperature is kept at 180 ℃/55mmHg for 2h.
The preparation method comprises the following steps of fully mixing 60g of vinyl-terminated phenylene ether silicone rubber A2, 2g of hydroxyl-terminated phenylene ether silicone rubber B2 and 12g of fumed silica on a three-roll machine, then adding 10g of ferric oxide, 2g of light calcium carbonate and 2g of hydrogen-containing silicone oil, continuously mixing and thinly passing to obtain foaming base rubber, then adding 0.1g of chloroplatinic acid isopropanol solution, uniformly stirring, standing and foaming the material to obtain the irradiation-resistant phenylene ether foaming silicone rubber.
Example 3
Preparing vinyl-terminated phenylene ether silicone rubber with the molar ratio of phenylene ether chain units of 16.8 percent, and compiling into a base rubber A3:
(1) 50 parts of octamethylcyclotetrasiloxane siloxane (D4), 20g of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 10g of divinyltetramethyldisiloxane are added into a 500ml three-port reaction flask provided with a stirring and reflux condenser and a thermometer, and the mixture is kept at a constant temperature of 60 ℃ for 30min under a vacuum condition to remove moisture and CO 2 Impurities;
(2) Adding 0.5g of tetramethylammonium hydroxide silicon alkoxide, stirring and reacting in a nitrogen atmosphere under the normal pressure condition, heating to 100 ℃, and carrying out equilibrium reaction for 3 hours to obtain a siloxane copolymer;
(3) Heating to 170 ℃ to destroy the catalyst, and maintaining for 1h;
(4) The temperature is raised, the vacuum pump is started, and the temperature is kept at 180 ℃/5mmHg for 2h.
Preparing hydroxyl-terminated phenylene ether silicone rubber with the molar ratio of phenylene ether chain links of 16.8 percent, and compiling into a base rubber B3:
(1) 50 parts of octamethylcyclotetrasiloxane (D4), 20g of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 10g of hydroxysilicone oil were added to a 500ml three-neck reaction flask equipped with a stirrer, a reflux condenser and a thermometer, and the mixture was kept at a constant temperature of 60 ℃ for 30min under vacuum to remove moisture and CO 2 Impurities;
(2) Adding 0.5g of tetramethylammonium hydroxide silicon alkoxide, stirring and reacting in a nitrogen atmosphere under the normal pressure condition, heating to 100 ℃, and carrying out equilibrium reaction for 3 hours to obtain a siloxane copolymer;
(3) Heating to 170 ℃ to destroy the catalyst, and maintaining for 1h;
(4) The temperature is raised, the vacuum pump is started, and the operation lasts for 2h at 180 ℃/5 mmHg.
The preparation method comprises the following steps of fully mixing 60g of vinyl-terminated phenylene ether silicone rubber A3, 1g of hydroxyl-terminated phenylene ether silicone rubber B3 and 15g of fumed silica on a three-roll machine, adding 18g of iron oxide, 10g of light calcium carbonate and 1.5g of hydrogen-containing silicone oil, continuously mixing and thinly passing to obtain foaming base rubber, adding 0.02g of vinyl siloxane chloroplatinic acid complex, uniformly stirring, and standing and foaming the material to obtain the irradiation-resistant phenylene ether expanded foamed silicone rubber.
Example 4
Preparing vinyl-terminated phenylene ether silicone rubber with the molar ratio of phenylene ether chain links of 22.7 percent, and compiling into a base rubber A4:
(1) 70g of octamethylcyclotetrasiloxane siloxane (D4), 2g of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 15g of divinyltetramethyldisiloxane were put in a 500ml three-necked reaction flask equipped with a stirrer, reflux condenser and thermometer, and the mixture was kept at a constant temperature of 60 ℃ for 30min under vacuum to remove moisture and CO 2 Impurities;
(2) Adding 0.5g of tetramethylammonium hydroxide silicon alkoxide, stirring and reacting in a nitrogen atmosphere under the normal pressure condition, heating to 100 ℃, and carrying out equilibrium reaction for 3 hours to obtain a siloxane copolymer;
(3) Heating to 170 ℃ to destroy the catalyst, and maintaining for 1h;
(4) The temperature is raised, the vacuum pump is started, and the temperature is kept at 180 ℃/5mmHg for 2h.
Preparing hydroxyl-terminated phenylene ether silicone rubber with the molar ratio of phenylene ether chain links of 22.7 percent, and compiling into base rubber B4:
(1) 70g of octamethylcyclotetrasiloxane (D4), 20g of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 15g of hydroxysilicone oil are added into a 500ml three-port reaction bottle provided with a stirring reflux condenser and a thermometer, the temperature is kept at 60 ℃ for 30min under a vacuum condition, and moisture and CO are removed 2 Impurities;
(2) Adding 0.5g of tetramethylammonium hydroxide silicon alkoxide, stirring and reacting in a nitrogen atmosphere under normal pressure, heating to 100 ℃, and carrying out equilibrium reaction for 3 hours to obtain a siloxane copolymer;
(3) Heating to 170 ℃ to destroy the catalyst, and maintaining for 1h;
(4) The temperature is raised, the vacuum pump is started, and the operation lasts for 2h at 180 ℃/5 mmHg.
The preparation method comprises the following steps of fully mixing 55g of vinyl-terminated phenylene ether silicone rubber A3, 1g of hydroxyl-terminated phenylene ether silicone rubber B3 and 10g of fumed silica on a three-roll machine, adding 12g of iron oxide, 5g of light calcium carbonate and 1g of hydrogen-containing silicone oil, continuously mixing and thinly passing to obtain foamed base rubber, adding 0.08g of vinyl siloxane chloroplatinic acid complex, uniformly stirring, standing and foaming the material to obtain the irradiation-resistant phenylene ether foamed silicone rubber.
The above example is taken as a sample, and then the sample to be detected is subjected to gamma rays (1X 10) in the air 6 Gy absorbed dose) and the stress relaxation rate after irradiation changes along with the change of the molar content of phenylene ether chain links, and specific indexes are shown in Table 1.
And (3) stress relaxation rate test: the stress relaxation rate of the sample was measured using an electronic creep relaxation tester at a test temperature of 25 ℃ and a relative humidity of 55%.
TABLE 1
As can be seen from the detection data of the stress relaxation rate after radiation resistance, the stress relaxation rate of the room-temperature foaming phenylene ether silicone rubber is gradually increased after gamma ray irradiation in the air along with the increase of the molar content of the phenylene ether chain links, namely the rebound resilience is increased, which indicates that the radiation resistance of the organosilicon polymer can be effectively improved by the phenylene ether chain links.
Carrying out a compression performance test: testing with universal material testing machine at room temperature according to standard GB/T7757-93, continuously loading and unloading for 3 times, taking the average value of 3 times as test result, loading rate 0.5mm/min, deformation value measured by balanced extensometer, all data automatically collected by microcomputer, the concrete indexes are shown in Table 2, the change of deformation rate of foamed silicone rubber with the increase of phenylene ether chain link
As is well known, foam materials have good resilience before irradiation; after irradiation, the hardness is increased, the resilience force is reduced, and the deformation rate can be greatly changed. The data in table 2 show the change in the deformation rate of the sample after gamma irradiation in air. The deformation rate of the material decreased with the increase in the phenylene ether linkages, indicating that the radiation resistance of the foam increased and the resilience increased with the increase in the phenylene ether linkages.
From the data of stress relaxation rate and deformation rate, the larger the proportion of the phenylene ether chain links in the foamed silicone rubber is, the better the elasticity is, the higher the rebound resilience is, and the deformation is small. Therefore, the phenylene ether expanded foamed silicone rubber is a novel silicone rubber foam material with excellent radiation resistance, can be applied to foamed sealing of cable wells of equipment such as nuclear reactors, neutron accelerators and the like and heat-insulating sealing of high-energy radioactive pipelines, and has the advantages of radiation aging resistance, long service life, simplicity in maintenance and the like.
Finally, it should also be noted that the above-mentioned list is only a specific embodiment of the invention. It is obvious that the invention is not limited to the above-described embodiments, but many operational combinations are possible. All matters hithertofore set forth or suggested by those skilled in the art, including the description herein, are to be understood as being within the scope of the invention.
Claims (8)
1. The radiation-resistant phenylene ether expanded silicone rubber is characterized by comprising the following components in parts by weight: 50-60 parts of vinyl-terminated phenylene ether silicone rubber; 1-2 parts of hydroxy-terminated phenylene ether silicone rubber; 8-15 parts of fumed silica; 10-20 parts of ferric oxide; 2-10 parts of light calcium carbonate; 1-2 parts of hydrogen-containing silicone oil; 0.01-0.1 part of catalyst.
2. The radiation-resistant phenylene ether foamed silicone rubber according to claim 1, wherein the hydrogen-containing silicone oil comprises any one of methyl hydrogen-containing silicone oil and methyl phenyl hydrogen-containing silicone oil.
3. The radiation-resistant phenylene ether foamed silicone rubber according to claim 1, wherein the catalyst comprises any one of a chloroplatinic acid isopropanol solution or a vinyl siloxane chloroplatinic acid complex.
4. The radiation-resistant phenylene ether foamed silicone rubber according to claim 1, wherein the vinyl-terminated phenylene ether silicone rubber has a structure represented by formula 1:
wherein x, y and z are the degree of polymerization.
5. The radiation-resistant phenylene ether foamed silicone rubber according to claim 4, wherein the vinyl-terminated phenylene ether silicone rubber is prepared by the following method:
adding 50-60 parts by weight of octamethylcyclotetrasiloxane siloxane, 10-30 parts by weight of 4,4 '-bis (dimethylhydroxysilyl) diphenyl ether or a mixture of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 1, 4-bis (dimethylhydroxysilyl) benzene and 10-20 parts by weight of divinyltetramethyldisiloxane into a reactor, and vacuumizing and drying; adding a catalyst, heating and stirring in an inert atmosphere to react to obtain a siloxane copolymer;
heating to destroy the catalyst, heating again, and removing low molecular weight substances in vacuum to obtain the vinyl-terminated phenylene ether silicone rubber.
6. The radiation-resistant phenylene ether foamed silicone rubber according to claim 1, wherein the hydroxyl-terminated phenylene ether silicone rubber has a structure represented by formula 2:
wherein k, m and n are the degree of polymerization.
7. The radiation-resistant phenylene ether foamed silicone rubber according to claim 6, wherein the hydroxyl-terminated phenylene ether silicone rubber is prepared by the following method:
adding 50-60 parts by weight of octamethylcyclotetrasiloxane siloxane, 10-30 parts by weight of 4,4 '-bis (dimethylhydroxysilyl) diphenyl ether or a mixture of 4,4' -bis (dimethylhydroxysilyl) diphenyl ether and 1, 4-bis (dimethylhydroxysilyl) benzene and 10-20 parts by weight of hydroxyl silicone oil into a reactor, and vacuumizing and drying;
adding a catalyst, heating and stirring in an inert atmosphere to react to obtain a siloxane copolymer;
heating to destroy the catalyst, heating again, and removing low molecular weight substances in vacuum to obtain the hydroxy-terminated phenylene ether silicone rubber.
8. The process for producing a radiation-resistant polyphenylene ether foamed silicone rubber as claimed in any one of claims 1 to 7, comprising the steps of: fully mixing vinyl-terminated phenylene ether silicone rubber, hydroxyl-terminated phenylene ether silicone rubber and fumed silica on a three-roll mill, adding iron oxide, light calcium carbonate and hydrogen-containing silicone oil, continuously mixing and thinly passing to obtain foamed base rubber, adding a catalyst, uniformly stirring, and standing and foaming the material to obtain the irradiation-resistant phenylene ether foamed silicone rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210962319.7A CN115160789A (en) | 2022-08-11 | 2022-08-11 | Radiation-resistant phenylene ether foamed silicone rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210962319.7A CN115160789A (en) | 2022-08-11 | 2022-08-11 | Radiation-resistant phenylene ether foamed silicone rubber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115160789A true CN115160789A (en) | 2022-10-11 |
Family
ID=83480186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210962319.7A Withdrawn CN115160789A (en) | 2022-08-11 | 2022-08-11 | Radiation-resistant phenylene ether foamed silicone rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115160789A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004362A (en) * | 2014-04-14 | 2014-08-27 | 茂名市信龙科技有限公司 | Phenylene-phenylene ether organosilicon material for power type LED packaging and preparation method thereof |
| CN105086458A (en) * | 2015-08-31 | 2015-11-25 | 无锡市嘉邦电力管道厂 | Semi-conducting silicon rubber shielding material for cables |
| CN112126231A (en) * | 2020-10-12 | 2020-12-25 | 东莞市润银实业有限公司 | Radiation-resistant and high-temperature-resistant phenylene ether silicone rubber and preparation method thereof |
-
2022
- 2022-08-11 CN CN202210962319.7A patent/CN115160789A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004362A (en) * | 2014-04-14 | 2014-08-27 | 茂名市信龙科技有限公司 | Phenylene-phenylene ether organosilicon material for power type LED packaging and preparation method thereof |
| CN105086458A (en) * | 2015-08-31 | 2015-11-25 | 无锡市嘉邦电力管道厂 | Semi-conducting silicon rubber shielding material for cables |
| CN112126231A (en) * | 2020-10-12 | 2020-12-25 | 东莞市润银实业有限公司 | Radiation-resistant and high-temperature-resistant phenylene ether silicone rubber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 韩淑玉 等: ""国产苯醚撑硅橡胶应用研究"", 《特种橡胶制品》, pages 132 - 133 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107216845B (en) | Siloxane-terminated polyurethane sealant and preparation method thereof | |
| CN109851835B (en) | Organosilicon surfactant for hard polyurethane foam and preparation method thereof | |
| CN107522864B (en) | Silane modified polymer and preparation method thereof | |
| CN110862797A (en) | Silane-terminated polyether sealant and preparation method thereof | |
| EP3431552A1 (en) | Addition-curable silicone rubber composition and cured product | |
| US9228086B2 (en) | Siloxane based hollow fibers | |
| Labouriau et al. | Aging mechanisms in RTV polysiloxane foams | |
| CN112225872A (en) | Waterborne polyurethane and preparation method thereof | |
| CN113004484A (en) | Low-temperature-resistant oil-resistant thermoplastic silicone rubber-polyurethane elastomer and preparation method thereof | |
| CN115160789A (en) | Radiation-resistant phenylene ether foamed silicone rubber and preparation method thereof | |
| CN112920423B (en) | Preparation method of core-shell structure organic silicon resin | |
| CN112961302A (en) | High-temperature and high-humidity resistant polyurethane foam material | |
| Lei et al. | Oxime–Urethane Structure‐Based Dynamically Crosslinked Polyurethane with Robust Reprocessing Properties | |
| US3061556A (en) | Preparation of cellular polyurethane plastics | |
| CN111138864B (en) | Fluorine-containing oil-resistant anti-swelling silicone rubber foam material and preparation method thereof | |
| CN115124718A (en) | Vinyl-terminated phenylene ether silicone rubber and preparation method thereof | |
| CN113604034B (en) | Flame-retardant environment-friendly foamed plastic and preparation method thereof | |
| CN113913022B (en) | Addition type silicone rubber composition with prolonged vulcanization operation time and preparation method thereof | |
| JP3914372B2 (en) | Polyurethane resin composition and polyurethane resin | |
| EP4365239A1 (en) | Addition-curable silicone rubber composition and cured silicone rubber product | |
| CN115160574A (en) | Hydroxy-terminated phenylene ether silicone rubber and preparation method thereof | |
| CN114907809A (en) | Moisture-curing single-component polyurethane adhesive with good weather resistance and preparation method and application thereof | |
| JP5271548B2 (en) | Hardly discolorable soft polyurethane foam | |
| CN111234164A (en) | Air-tight blocking polyurethane foam and preparation method thereof | |
| CN109553775B (en) | Anti-tear auxiliary agent for silicone rubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20221011 |