CN114854020A - Synthetic method of methoxy-terminated structured control agent silicone oil - Google Patents
Synthetic method of methoxy-terminated structured control agent silicone oil Download PDFInfo
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- 229920002545 silicone oil Polymers 0.000 title claims abstract description 37
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 25
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 25
- 239000002585 base Substances 0.000 claims abstract description 25
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 dimethyl siloxane Chemical class 0.000 claims abstract description 17
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 150000007524 organic acids Chemical class 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 16
- 239000010452 phosphate Substances 0.000 claims description 16
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 16
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 8
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 8
- 229940043256 calcium pyrophosphate Drugs 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 8
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 8
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims description 8
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 8
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 8
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 8
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 229920002379 silicone rubber Polymers 0.000 abstract description 16
- 239000004945 silicone rubber Substances 0.000 abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000006229 carbon black Substances 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 229910008051 Si-OH Inorganic materials 0.000 abstract description 7
- 229910006358 Si—OH Inorganic materials 0.000 abstract description 7
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 15
- 239000005060 rubber Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000010292 electrical insulation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a synthetic method of a methoxy-terminated structured control agent silicone oil, and particularly relates to the field of fine chemical engineering, which comprises the following synthetic steps: step S1: fully mixing dimethyl dimethoxysilane and dimethyl siloxane mixed ring (DMC) in a reaction kettle; step S2: adding an alkali metal catalyst or a quaternary ammonium base catalyst, heating to 80-135 ℃, reacting for 3-8 hours at constant temperature, and opening the ring of DMC at the reaction temperature; step S3: stopping the reaction by adding a terminator or breaking the catalyst at high temperature after the DMC is completely opened in step S2; step S4: and (4) cooling the reaction product terminated in the step S3 to obtain the low-molecular methoxy silicone oil. Compared with the traditional hydroxyl silicone oil, the low-molecular methoxy silicone oil can improve the quality of the organic silicone rubber, reacts with the white carbon black Si-OH to generate the methanol, is easier to post-process, improves the product quality, has simple and environment-friendly process, almost does not produce three wastes, and has low energy consumption.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a synthetic method of a methoxy-terminated structured control agent silicone oil.
Background
In the organic silicon rubber processing technology, white carbon black is commonly used for reinforcing the heat vulcanized silicone rubber, and because active Si-OH contained on the surface of the white carbon black can react with Si-O bonds or terminal Si-OH in raw silicone rubber molecules to generate hydrogen bonds or undergo condensation, the white carbon black is difficult to uniformly disperse in the silicone rubber material, and the mixed material can be slowly hardened in the storage process, the plasticity is reduced, the back refining cannot be performed, the processing performance is reduced, and the structurization phenomenon is generated. In order to improve the affinity between the silicone rubber particles and the filler particles, reduce the generation of hydrogen bonds, improve the dispersibility of the filler in the rubber compound, improve the mixing process and the storage stability, and prevent and weaken the continuous structuring phenomenon, a structure control agent is required to be added into the rubber compound. The structure control agent acts with Si-OH groups on the surface of the white carbon black, so that the formation of hydrogen bonds among particles is inhibited.
Low viscosity hydroxy silicone oils (viscosity of 20-30 cSt) are one of the commonly used structural control agents. Hydroxyl of low-viscosity hydroxyl silicone oil reacts with Si-OH of white carbon black to remove H in the mixing process of raw rubber and white carbon black 2 O, so as to improve the affinity between the rubber particles and the filler particles, reduce the generation of hydrogen bonds, improve the dispersibility of the filler in the rubber compound, improve the mixing process and the storage stability, and prevent and weaken the continuous structuring phenomenon. However, the water molecules thus generated are difficult to completely discharge, and remain in the rubber as moisture, which affects the quality of the rubber product, such as transparency, stickiness, electrical insulation performance, and the like.
The methoxy silicone oil reacts with Si-OH of the white carbon black in the mixing process of the raw rubber and the white carbon black to remove methanol, so that the affinity between rubber particles and filler particles is improved, the generation of hydrogen bonds is reduced, the dispersity of the filler in the rubber material is improved, the mixing process and the storage stability are improved, and the continuous structuring phenomenon is prevented and weakened. The removed methanol is easily discharged to the outside of the rubber, does not influence the transparency of the rubber, makes the rubber dry and comfortable, does not influence the electrical insulation performance and the like, and can be used for electronic products and the like; therefore, how to produce the low-viscosity hydroxyl silicone oil more suitable for the processing technology of the organic silicon rubber becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a synthetic method of a methoxy-terminated structured control silicone oil, and the technical problems to be solved by the invention are as follows: how to solve the problem of H generation by reaction with white carbon black in the existing mechanical silicone rubber processing 2 O, which is difficult to completely eliminate and affects the product quality; such as high water vapor, fogging of the product, influence on transparency, stickiness of the product, difficulty in post-processing and influence on electrical insulation performance.
In order to achieve the purpose, the invention provides the following technical scheme: a synthetic method of methoxy-terminated structured control agent silicone oil comprises the following synthetic steps:
step S1: fully mixing dimethyl dimethoxysilane and dimethyl siloxane mixed ring (DMC) in a reaction kettle;
step S2: adding an alkali metal catalyst or a quaternary ammonium base catalyst, heating to 80-135 ℃, reacting for 3-8 hours at constant temperature, and opening the ring of DMC at the reaction temperature;
step S3: stopping the reaction by adding a terminator or breaking the catalyst at high temperature after the DMC is completely opened in step S2;
step S4: and (4) cooling the reaction product terminated in the step S3 to obtain the low-molecular methoxy silicone oil.
In a preferred embodiment, the weight ratio of the dimethyldimethoxysilane to the dimethylsiloxane mixed ring body (DMC) in the step S1 is 1: 1-1.5.
In a preferred embodiment, the alkali metal catalyst is set to KOH and the quaternary ammonium base catalyst is set to tetramethylammonium hydroxide or tetrabutylammonium hydroxide in step S2, wherein the dosage of the alkali metal catalyst or the quaternary ammonium base catalyst is 50-500 ppm.
In a preferred embodiment, the terminator used in step S3 is provided as a phosphate or an organic acid.
In a preferred embodiment, the phosphate is any one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate, or potassium dihydrogen phosphate, and the organic acid is any one of sulfinic acid, acetic acid, formic acid, or sulfonic acid.
In a preferred embodiment, the molar ratio of the amount of the terminator to the catalyst is set to 1: 1-1.5, and quantifying the proportion of the terminating agent amount and the catalyst, thereby effectively avoiding the increase of excessive impurities on the premise of ensuring the termination of the reaction.
In a preferred embodiment, the temperature for the high temperature destruction of the catalyst to stop the reaction in the step S3 is set to 180 ℃ to 220 ℃, and the crystalline surface of the catalyst is destroyed by the high temperature to inactivate the catalyst, thereby terminating the reaction.
The invention has the technical effects and advantages that:
compared with the traditional hydroxyl silicone oil, the low-molecular methoxy silicone oil can improve the quality of the organic silicone rubber, reacts with the white carbon black Si-OH to generate the methanol, is easier to post-process, improves the product quality, has simple and environment-friendly process, almost does not produce three wastes, and has low energy consumption.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a synthetic method of a methoxy-terminated structured control agent silicone oil, which comprises the following synthetic steps:
step S1: fully mixing dimethyl dimethoxy silane and dimethyl siloxane mixed ring body (DMC) in a reaction kettle, wherein the weight ratio of the dimethyl dimethoxy silane to the dimethyl siloxane mixed ring body (DMC) is 1: 1-1.5;
step S2: adding an alkali metal catalyst or a quaternary ammonium base catalyst, heating to 80-135 ℃, reacting for 3-8 hours at constant temperature, setting the alkali metal catalyst as KOH and the quaternary ammonium base catalyst as tetramethylammonium hydroxide or tetrabutylammonium hydroxide, wherein the dosage of the alkali metal catalyst or the quaternary ammonium base catalyst is 50-500ppm, and the DMC is opened by the reaction temperature;
step S3: after the DMC is completely opened in step S2, the reaction is stopped by adding a terminating agent or breaking the catalyst at high temperature, the terminating agent is set to be phosphate or organic acid, the phosphate is set to be any one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate, or potassium dihydrogen phosphate, the organic acid is set to be any one of sulfinic acid, acetic acid, formic acid, or sulfonic acid, and the molar ratio of the terminating agent to the catalyst is set to be 1: 1-1.5, quantifying the proportion of the terminating agent amount and the catalyst, and effectively avoiding the increase of excessive impurities on the premise of ensuring the termination reaction; the temperature for stopping the reaction of the high-temperature catalyst is set to be 180-220 ℃, and the crystallization surface of the catalyst is damaged by using high temperature, so that the catalyst loses activity, and the reaction is stopped;
step S4: cooling the reaction product obtained in the step S3 to obtain low-molecular methoxy silicone oil;
specifically, the present embodiment includes the following steps:
step S1: fully mixing dimethyl dimethoxy silane and dimethyl siloxane mixed ring body (DMC) in a reaction kettle, wherein the weight ratio of the dimethyl dimethoxy silane to the dimethyl siloxane mixed ring body (DMC) is 1: 1;
step S2: adding an alkali metal catalyst or a quaternary ammonium base catalyst, heating to 80 ℃, reacting for 8 hours at constant temperature, setting the alkali metal catalyst as KOH, and setting the quaternary ammonium base catalyst as tetramethylammonium hydroxide or tetrabutylammonium hydroxide, wherein the dosage of the alkali metal catalyst or the quaternary ammonium base catalyst is 50ppm, and the reaction temperature enables the DMC to open the ring;
step S3: after the DMC is completely opened in step S2, the reaction is stopped by adding a terminating agent or breaking the catalyst at high temperature, the terminating agent is set to be phosphate or organic acid, the phosphate is set to be any one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate, or potassium dihydrogen phosphate, the organic acid is set to be any one of sulfinic acid, acetic acid, formic acid, or sulfonic acid, and the molar ratio of the terminating agent to the catalyst is set to be 1: 1, quantifying the proportion of the terminating agent and the catalyst, and effectively avoiding the increase of excessive impurities on the premise of ensuring the termination reaction; the temperature for stopping the reaction of the high-temperature catalyst is set to be 180 ℃, and the crystallization surface of the catalyst is damaged by utilizing the high temperature, so that the catalyst loses activity, and the reaction is stopped;
step S4: and (4) cooling the reaction product terminated in the step S3 to obtain the low-molecular methoxy silicone oil.
Example 2:
the invention provides a synthetic method of a methoxy-terminated structured control agent silicone oil, which comprises the following synthetic steps:
step S1: fully mixing dimethyl dimethoxy silane and dimethyl siloxane mixed cyclic compound (DMC) in a reaction kettle, wherein the weight ratio of the dimethyl dimethoxy silane to the dimethyl siloxane mixed cyclic compound (DMC) is 1: 1-1.5;
step S2: adding an alkali metal catalyst or a quaternary ammonium base catalyst, heating to 80-135 ℃, reacting for 3-8 hours at constant temperature, setting the alkali metal catalyst as KOH and the quaternary ammonium base catalyst as tetramethylammonium hydroxide or tetrabutylammonium hydroxide, wherein the dosage of the alkali metal catalyst or the quaternary ammonium base catalyst is 50-500ppm, and the DMC is opened by the reaction temperature;
step S3: after the DMC is completely opened in step S2, the reaction is stopped by adding a terminating agent or breaking the catalyst at high temperature, the terminating agent is set to be phosphate or organic acid, the phosphate is set to be any one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate, or potassium dihydrogen phosphate, the organic acid is set to be any one of sulfinic acid, acetic acid, formic acid, or sulfonic acid, and the molar ratio of the terminating agent to the catalyst is set to be 1: 1-1.5, quantifying the proportion of the terminating agent amount and the catalyst, and effectively avoiding the increase of excessive impurities on the premise of ensuring the termination reaction; the temperature for stopping the reaction of the high-temperature catalyst is set to be 180-220 ℃, and the crystallization surface of the catalyst is damaged by using high temperature, so that the catalyst loses activity, and the reaction is stopped;
step S4: cooling the reaction product obtained in the step S3 to obtain low-molecular methoxy silicone oil;
specifically, the present embodiment includes the following steps:
step S1: fully mixing dimethyl dimethoxy silane and dimethyl siloxane mixed ring body (DMC) in a reaction kettle, wherein the weight ratio of the dimethyl dimethoxy silane to the dimethyl siloxane mixed ring body (DMC) is 1: 1.25;
step S2: adding an alkali metal catalyst or a quaternary ammonium base catalyst, heating to 100 ℃, reacting for 5.5 hours at constant temperature, setting the alkali metal catalyst as KOH and the quaternary ammonium base catalyst as tetramethylammonium hydroxide or tetrabutylammonium hydroxide, wherein the dosage of the alkali metal catalyst or the quaternary ammonium base catalyst is 275ppm, and the reaction temperature enables DMC to open loop;
step S3: after the DMC is completely opened in step S2, the reaction is stopped by adding a terminating agent or breaking the catalyst at high temperature, the terminating agent is set to be phosphate or organic acid, the phosphate is set to be any one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate, or potassium dihydrogen phosphate, the organic acid is set to be any one of sulfinic acid, acetic acid, formic acid, or sulfonic acid, and the molar ratio of the terminating agent to the catalyst is set to be 1: 1.25, quantifying the proportion of the terminating agent amount to the catalyst, and effectively avoiding the increase of excessive impurities on the premise of ensuring the termination reaction; the temperature for stopping the reaction of the high-temperature catalyst is set to be 200 ℃, and the crystallization surface of the catalyst is damaged by utilizing the high temperature, so that the catalyst loses activity, and the reaction is stopped;
step S4: and (4) cooling the reaction product terminated in the step S3 to obtain the low-molecular methoxy silicone oil.
Example 3:
the invention provides a synthetic method of a methoxy-terminated structured control agent silicone oil, which comprises the following synthetic steps:
step S1: fully mixing dimethyl dimethoxy silane and dimethyl siloxane mixed ring body (DMC) in a reaction kettle, wherein the weight ratio of the dimethyl dimethoxy silane to the dimethyl siloxane mixed ring body (DMC) is 1: 1-1.5;
step S2: adding an alkali metal catalyst or a quaternary ammonium base catalyst, heating to 80-135 ℃, reacting for 3-8 hours at constant temperature, setting the alkali metal catalyst as KOH and the quaternary ammonium base catalyst as tetramethylammonium hydroxide or tetrabutylammonium hydroxide, wherein the dosage of the alkali metal catalyst or the quaternary ammonium base catalyst is 50-500ppm, and the DMC is opened by the reaction temperature;
step S3: after the DMC is completely opened in step S2, the reaction is stopped by adding a terminating agent or breaking the catalyst at high temperature, the terminating agent is set to be phosphate or organic acid, the phosphate is set to be any one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate, or potassium dihydrogen phosphate, the organic acid is set to be any one of sulfinic acid, acetic acid, formic acid, or sulfonic acid, and the molar ratio of the terminating agent to the catalyst is set to be 1: 1-1.5, quantifying the proportion of the terminating agent amount and the catalyst, and effectively avoiding the increase of excessive impurities on the premise of ensuring the termination reaction; the temperature for stopping the reaction of the high-temperature catalyst is set to be 180-220 ℃, and the crystallization surface of the catalyst is damaged by using high temperature, so that the catalyst loses activity, and the reaction is stopped;
step S4: cooling the reaction product obtained in the step S3 to obtain low-molecular methoxy silicone oil;
specifically, the present embodiment includes the following steps:
step S1: fully mixing dimethyl dimethoxy silane and dimethyl siloxane mixed ring body (DMC) in a reaction kettle, wherein the weight ratio of the dimethyl dimethoxy silane to the dimethyl siloxane mixed ring body (DMC) is 1: 1.5;
step S2: adding an alkali metal catalyst or a quaternary ammonium base catalyst, heating to 135 ℃, reacting at constant temperature for 3 hours, wherein the alkali metal catalyst is KOH, the quaternary ammonium base catalyst is tetramethylammonium hydroxide or tetrabutylammonium hydroxide, the dosage of the alkali metal catalyst or the quaternary ammonium base catalyst is 500ppm, and the reaction temperature enables DMC to open loop;
step S3: after the DMC is completely opened in step S2, the reaction is stopped by adding a terminating agent or breaking the catalyst at high temperature, the terminating agent is set to be phosphate or organic acid, the phosphate is set to be any one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate, or potassium dihydrogen phosphate, the organic acid is set to be any one of sulfinic acid, acetic acid, formic acid, or sulfonic acid, and the molar ratio of the terminating agent to the catalyst is set to be 1: 1.5, quantifying the proportion of the terminating agent amount to the catalyst, and effectively avoiding the increase of excessive impurities on the premise of ensuring the termination reaction; the temperature for stopping the reaction of the high-temperature catalyst is set to be 220 ℃, and the crystallization surface of the catalyst is damaged by utilizing the high temperature, so that the catalyst loses activity, and the reaction is stopped;
step S4: and (4) cooling the reaction product terminated in the step S3 to obtain the low-molecular methoxy silicone oil.
Example 4:
the low-molecular methoxy silicone oils prepared in the above examples 1 to 3 were used for the processing of silicone rubber, and the comparative examples of silicone rubber prepared by using hydroxy silicone oil were attached, and the obtained rubbers were subjected to the performance tests to obtain the following data:
as can be seen from the above table, the methoxy silicone oil prepared by the method of examples 1 to 3 replaces hydroxy silicone oil for processing of silicone rubber, so that no water mist remains in the processed silicone rubber, thereby ensuring the product quality of the silicone rubber, ensuring high transparency of the silicone rubber, preventing the occurrence of the stickiness phenomenon of rubber products, ensuring that the dielectric strength is above 30MV/m, and ensuring the electrical insulation performance of the silicone rubber.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (7)
1. A synthetic method of methoxy end capping structured control agent silicone oil is characterized in that: the method comprises the following synthetic steps:
step S1: fully mixing dimethyl dimethoxysilane and dimethyl siloxane mixed ring (DMC) in a reaction kettle;
step S2: adding an alkali metal catalyst or a quaternary ammonium base catalyst, heating to 80-135 ℃, reacting for 3-8 hours at constant temperature, and opening the ring of DMC at the reaction temperature;
step S3: stopping the reaction by adding a terminator or breaking the catalyst at high temperature after the DMC is completely opened in step S2;
step S4: and (4) cooling the reaction product terminated in the step S3 to obtain the low-molecular methoxy silicone oil.
2. The method for synthesizing the methoxy-terminated structured control silicone oil as claimed in claim 1, wherein the method comprises the following steps: the weight ratio of the dimethyl dimethoxy silane to the dimethyl siloxane mixed ring body (DMC) in the step S1 is 1: 1-1.5.
3. The method for synthesizing the methoxy-terminated structured control silicone oil as claimed in claim 1, wherein the method comprises the following steps: in the step S2, the alkali metal catalyst is set to KOH, and the quaternary ammonium base catalyst is set to tetramethylammonium hydroxide or tetrabutylammonium hydroxide, wherein the dosage of the alkali metal catalyst or the quaternary ammonium base catalyst is 50-500 ppm.
4. The method for synthesizing the methoxy-terminated structured control silicone oil as claimed in claim 3, wherein the method comprises the following steps: the terminator used in step S3 is set to be a phosphate or an organic acid.
5. The method for synthesizing the methoxy-terminated structured control silicone oil as claimed in claim 4, wherein the method comprises the following steps: the phosphate is any one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, calcium pyrophosphate or potassium dihydrogen phosphate, and the organic acid is any one of sulfinic acid, acetic acid, formic acid or sulfonic acid.
6. The method for synthesizing the methoxy-terminated structured control silicone oil as claimed in claim 4, wherein the method comprises the following steps: the molar ratio of the terminating agent amount to the catalyst is set to be 1: 1-1.5.
7. The method for synthesizing the methoxy-terminated structured control silicone oil as claimed in claim 1, wherein the method comprises the following steps: the temperature at which the high temperature catalyst is broken to stop the reaction in the step S3 is set to 180 to 220 ℃.
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| CN202210533078.4A CN114854020A (en) | 2022-05-16 | 2022-05-16 | Synthetic method of methoxy-terminated structured control agent silicone oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116253881A (en) * | 2022-09-09 | 2023-06-13 | 云南众合硅基新材料有限公司 | Synthesis method of methoxy-terminated vinyl silicone oil structuring control agent |
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| CN105524280A (en) * | 2016-01-15 | 2016-04-27 | 浙江润禾有机硅新材料有限公司 | Branched chain silicone oil and preparation method thereof |
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| CN116253881A (en) * | 2022-09-09 | 2023-06-13 | 云南众合硅基新材料有限公司 | Synthesis method of methoxy-terminated vinyl silicone oil structuring control agent |
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