CN105384936B - A kind of preparation method of multi-vinyl silicone oil - Google Patents
A kind of preparation method of multi-vinyl silicone oil Download PDFInfo
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- CN105384936B CN105384936B CN201510969515.7A CN201510969515A CN105384936B CN 105384936 B CN105384936 B CN 105384936B CN 201510969515 A CN201510969515 A CN 201510969515A CN 105384936 B CN105384936 B CN 105384936B
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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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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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
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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
- C08G77/08—Preparatory processes characterised by the catalysts used
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Abstract
The present invention relates to a kind of preparation methods of multi-vinyl silicone oil, include the following steps: that linear body, t etram-ethyltetravinylcyclotetrasiloxane and closure agent are added in reaction kettle, are heated to 130 DEG C~150 DEG C, potassium hydroxide is added to be stirred to react, temperature is kept, is vacuumized, dehydration is carried out, restore normal pressure, phosphoric acid is added or silicon substrate phosphate neutralizes, neutralization finishes, and heating negative pressure removing low molecule obtains product.The present invention prepares multi-vinyl silicone oil by primary raw material of linear body, has cost of material low, and the simple advantage of method meets current development trend, has good development prospect.
Description
Technical field
The present invention relates to a kind of preparation methods of multi-vinyl silicone oil, belong to polysiloxanes synthesis field.
Background technique
Multi-vinyl silicone oil is also known as high-vinyl silicone oil, is vinyl or methyl blocking and middle shot contains vinyl
Dimethyl silicone polymer, for the raw material of add-on type liquid silicon rubber and organic silicon potting adhesive, the modifying agent of rubber compound plays and changes
Kind crosslink density can also be used as plastic additive to improve tearing toughness, hardness and resilience.
Multi-vinyl silicone oil main preparation methods are using dimethicone, and vinyl ring body and closure agent are original
Material, with potassium hydroxide or tetramethylammonium hydroxide etc. for catalyst, then heating reaction makes catalyst failure, removes low molecule
It is made.Chinese patent document CN103467744A (application number: 201310390993.3) discloses a kind of system of vinyl silicone oil
Preparation Method, comprising: 800 parts of octamethylcy-clotetrasiloxanes are added and are stirred in reaction kettle, 1~20 part of basic catalyst is added in anti-
Answer in kettle and stir, and be warming up to 60~70 DEG C of constant-temperature vacuums and kept for 0.5~1 hour, be added 0.5~20 part of vinyl closure agent in
In reaction kettle, 60~70 DEG C of constant temperature are stirred 5~10 minutes, are added in 1~50 part of vinyl ring body reaction kettle and are stirred, are warming up to
90~100 DEG C of constant temperature are kept for 4~6 hours, then are warming up to heat up again after 150~160 DEG C of constant temperature are kept for 0.5~1 hour and be carried out very
Sky removing low-boiling-point substance to no low molecule flows out to arrive vinyl silicone oil.Chinese patent document CN104231276A (application number:
201410423864.4) a kind of preparation method of vinyl-terminated silicone fluid is disclosed, it is in parts by mass, hydroxy-end capped by 500 parts
Linear polydimethysiloxane, 1-10 parts of vinyl list end sockets, 0.007-0.015 parts of trifluoromethane sulfonic acids are first at 55 DEG C -80 DEG C
Lower reaction 1-2h, then 2-4h is reacted at 80-100 DEG C, vacuum degree 0.01-0.1MPa, leading to NH3 after reaction will be in reaction solution
Be neutrality to PH, filtering obtains vinyl-terminated silicone fluid product.But patent document CN103467744A uses prestox ring
Tetrasiloxane is raw material, and joined a large amount of basic catalyst, can learn that its catalyst is temporary urges by its process
Agent, heat resolve inevitably generate harmful or gas with foreign flavor, also have certain influence for the quality of oil.Patent document
CN104231276A hydroxyl endblocked polydimethylsiloxane and vinyl list end socket are primary raw material, use wire body for raw material trifluoro
Methanesulfonic acid is catalyst, and vinyl list end socket is expensive, and trifluoromethanesulfonic acid corrosivity is extremely strong, very for equipment requirement
Height, and neutralized using ammonia, will cause product has certain irritation ammonia taste.
Dimethyldichlorosilane obtains hydrolysate through hydrolysis, and hydrolysate is by linear body and dimethyl ring body (abbreviation ring body) group
At hydrolysate obtains ring body by cracking rectifying.Present some monomer producers use wire loop separating technology, by hydrolysate by steaming
Fraction goes out ring body, obtains linear body, linear body is since without cracking rectifying, relative to ring body, cost is relatively low, technologically advanced
Organic silicon monomer producer uses wire loop separating technology one after another.Moreover, linear body is hydroxy-end capped low viscosity linear silicone oils, viscosity
Range is in 50~120mPa.s, and non-volatile, property is stablized, safer than dimethyl ring body in terms of storing transport, linear body
Application it is also increasingly extensive.
It is rarely reported with linear regime for the research of multi-vinyl silicone oil, therefore develops and prepare more second by raw material of linear body
The technique of alkenyl silicone oil has great importance.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of multi-vinyl silicone oil.
Term explanation:
Linear body: dimethyldichlorosilane is hydrolyzed, and obtains hydrolysate, and hydrolysate is made of linear body and ring body, linearly
Body be it is isolated from Dimethyldichlorosilane hydrolysate, can be isolated by the prior art, it is also commercially available to obtain.
Technical scheme is as follows:
A kind of preparation method of multi-vinyl silicone oil, includes the following steps:
(1) linear body, t etram-ethyltetravinylcyclotetrasiloxane and closure agent are mixed, is stirred evenly；
(2) 130 DEG C~150 DEG C are heated to, potassium hydroxide is added, is stirred to react 3~5h；
(3) reaction temperature is kept, is vacuumized, 2~4h of dehydration is carried out；
(4) restore normal pressure, be added in phosphoric acid or silicon substrate phosphate and 0.5~1h；
(5) it neutralizes and finishes, be warming up to 160~180 DEG C, negative pressure removes 2~4h of low molecule to get multi-vinyl silicone oil.
, according to the invention it is preferred to, t etram-ethyltetravinylcyclotetrasiloxane, linear body and end socket described in step (1)
The mass ratio of agent is (3~15): 100:(0.45~4)；
Preferably, the closure agent is the methyl-silicone oil or vinyl-terminated silicone fluid that the degree of polymerization is 2~5, and molecular formula is as follows
It is shown:
Wherein n=2~5, R=CH3Or CH=CH2。
, according to the invention it is preferred to, the additional amount of potassium hydroxide described in step (2) is linear body, four ethylene of tetramethyl
0.00001~0.000025 times of basic ring tetrasiloxane and closure agent gross mass.
, according to the invention it is preferred to, be evacuated in step (3) gauge pressure be -10~-5KPa, the retention time 0.5~
Then 1.5h makes gauge pressure -25~-15KPa, 1.5~2.5h of retention time.Strict control pressure is wanted in reaction process, to prevent
Dehydration is too fast, and slug phenomenon occurs.
, according to the invention it is preferred to, phosphoric acid described in step (4) or silicon substrate phosphate additional amount are that matter is added in potassium hydroxide
1.2~1.7 times of amount, wherein the additional amount of silicon substrate phosphate is in terms of phosphoric acid.
Beneficial effects of the present invention are as follows:
1, the present invention uses linear body for primary raw material, has better cost advantage compared with prior art, linear body
Compared to dimethicone energy conservation and environmental protection, storage and transport are also safer for production, meet current development trend, the present invention
With good prospect.
2, preparation process of the invention is simple, the equipment for preparing multi-vinyl silicone oil for the of less demanding of equipment, tradition
This technique can be used to prepare multi-vinyl silicone oil, and high compared to dimethyl ring body technique conversion per pass is used, adopts
It is catalyst than using product appearance prepared by temporary catalyst tetramethylammonium hydroxide good with potassium hydroxide.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and however, it is not limited to this.
Linear body used in following embodiment is Shandong Eastern Mountain organosilicon material organosilicon material Products, and viscosity is
73mPa.s, remaining raw material are commercial products, are the known raw material of personnel of technical field.
Embodiment 1
1000g linear body, end-vinyl silicon that 30g t etram-ethyltetravinylcyclotetrasiloxane and the 4.5g degree of polymerization are 2
Oil is added in reaction kettle, and stirring is heated to 130 DEG C, and 0.01035g potassium hydroxide is added, and is stirred to react 3h, keeps temperature, is taken out
Vacuum carries out dehydration, and controlling gauge pressure in reaction kettle is -10KPa, then retention time 0.5h makes gauge pressure-in reaction kettle
15KPa, retention time 2.5h restore normal pressure, are added in phosphoric acid 0.0124g and finish with 0.5h, neutralization, are warming up to 180 DEG C, negative pressure
Low molecule 2h is removed to get multi-vinyl silicone oil.
Embodiment 2
1000g linear body, 150g t etram-ethyltetravinylcyclotetrasiloxane and the 40g degree of polymerization add for 5 methyl-silicone oil
Enter into reaction kettle, stir, be heated to 150 DEG C, is added 0.25g polysiloxanes potassium alcoholate (potassium hydroxide quality content 12.3%),
It is stirred to react 5h, keeps temperature, vacuumize, carry out dehydration, controlling gauge pressure in reaction kettle is -5KPa, retention time 1.5h,
Then make gauge pressure -25KPa in reaction kettle, retention time 1.5h, restore normal pressure, be added in phosphoric acid 0.0523g and 1h, neutralized
Finish, is warming up to 160 DEG C, negative pressure removes low molecule 4h to get multi-vinyl silicone oil.
Embodiment 3
1000g linear body, end-vinyl silicon that 100g t etram-ethyltetravinylcyclotetrasiloxane and the 13g degree of polymerization are 3
Oil is added in reaction kettle, and stirring is heated to 140 DEG C, and 0.01695g potassium hydroxide is added, and is stirred to react 4h, keeps temperature, is taken out
Vacuum carries out dehydration, and controlling gauge pressure in reaction kettle is -8KPa, then retention time 1h makes gauge pressure-in reaction kettle
20KPa, retention time 2h restore normal pressure, and silicon substrate phosphate (phosphoric acid quality content 17%) 0.15g is added, and neutralize 0.8h, neutralize
It finishes, is warming up to 170 DEG C, negative pressure removes low molecule 3h to get multi-vinyl silicone oil.
Comparative example 1
1000g octamethylcy-clotetrasiloxane, 30g t etram-ethyltetravinylcyclotetrasiloxane and the 4.5g degree of polymerization are 2
Vinyl-terminated silicone fluid is added in reaction kettle, and stirring is heated to 145 DEG C, and 0.01035g potassium hydroxide is added, is stirred to react 3h,
It is added in phosphoric acid 0.0124g and is finished with 0.5h, neutralization, be warming up to 180 DEG C, negative pressure removes low molecule 2h to get more vinyl silicon
Oil.
Comparative example 2
1000g octamethylcy-clotetrasiloxane, 150g t etram-ethyltetravinylcyclotetrasiloxane and the 40g degree of polymerization are 5
Methyl-silicone oil is added in reaction kettle, and stirring is heated to 100 DEG C, and 0.05g tetramethylammonium hydroxide is added, is stirred to react 5h, is risen
Temperature keeps temperature 1h to 160 DEG C, and then negative pressure removes low molecule 4h to get multi-vinyl silicone oil.
Embodiment 1-3 product and comparative example 1-2 product index
| Index | Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 | Embodiment 3 |
| Appearance | It is colorless and transparent | It is colorless and transparent | It is colorless and transparent | Clear pale yellow color | It is colorless and transparent |
| 25 DEG C of viscosity (mPa.s) | 17643 | 18130 | 657 | 692 | 4820 |
| Contents of ethylene (wt%) | 1.88 | 1.82 | 4.05 | 3.98 | 2.95 |
| Conversion per pass (%) | 91.5 | 87.3 | 93.2 | 86.7 | 92.4 |
Claims (4)
1. a kind of preparation method of multi-vinyl silicone oil, includes the following steps:
(1) linear body, t etram-ethyltetravinylcyclotetrasiloxane and closure agent are mixed, is stirred evenly；
The linear body is isolated from Dimethyldichlorosilane hydrolysate；
The mass ratio of the t etram-ethyltetravinylcyclotetrasiloxane, linear body and closure agent is (3 ~ 15): 100:(0.45 ~
4)；
(2) 130 DEG C ~ 150 DEG C are heated to, potassium hydroxide is added, is stirred to react 3 ~ 5h；
(3) reaction temperature is kept, is vacuumized, 2 ~ 4h of dehydration is carried out；
Being evacuated to gauge pressure is -10 ~ -5KPa, then 0.5 ~ 1.5h of retention time makes gauge pressure -25 ~ -15KPa, is kept
1.5 ~ 2.5h of time；
(4) restore normal pressure, be added in phosphoric acid or silicon substrate phosphate and 0.5 ~ 1h；
(5) it neutralizes and finishes, be warming up to 160 ~ 180 DEG C, negative pressure removes 2 ~ 4 h of low molecule to get multi-vinyl silicone oil.
2. the preparation method of multi-vinyl silicone oil according to claim 1, which is characterized in that end socket described in step (1)
Agent is the methyl-silicone oil or vinyl-terminated silicone fluid that the degree of polymerization is 2 ~ 5, and molecular formula is as follows:
。
3. the preparation method of multi-vinyl silicone oil according to claim 1, which is characterized in that hydrogen-oxygen described in step (2)
The additional amount for changing potassium is the 0.00001 ~ 0.000025 of linear body, t etram-ethyltetravinylcyclotetrasiloxane and closure agent gross mass
Times.
4. the preparation method of multi-vinyl silicone oil according to claim 1, which is characterized in that phosphoric acid described in step (4)
Or silicon substrate phosphate additional amount is quality is added in potassium hydroxide 1.2 ~ 1.7 times, wherein the additional amount of silicon substrate phosphate is with phosphoric acid
Meter.
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| CN201510969515.7A CN105384936B (en) | 2015-12-21 | 2015-12-21 | A kind of preparation method of multi-vinyl silicone oil |
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| CN105384936B true CN105384936B (en) | 2019-03-05 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108034051A (en) * | 2017-12-28 | 2018-05-15 | 中科院广州化学有限公司 | A kind of vinyl polysiloxane and preparation method and application |
| CN108359098A (en) * | 2018-02-26 | 2018-08-03 | 广州盛泰诺新材料科技有限公司 | A kind of vinyl silicone oil and preparation method thereof |
| CN112646188B (en) * | 2020-12-17 | 2022-08-30 | 山东东岳高分子材料有限公司 | Linear organic fluorine-containing polysiloxane and preparation method and application thereof |
| CN113698606B (en) * | 2021-08-10 | 2023-03-24 | 湖北兴瑞硅材料有限公司 | Preparation method of vinyl silicone oil with low content of cyclic bodies |
| CN116063681A (en) * | 2023-02-07 | 2023-05-05 | 山东大学 | Double-layer structure vinyl end capping Process for the preparation of polysiloxanes |
| CN115772265B (en) * | 2023-02-10 | 2023-05-12 | 山东东岳有机硅材料股份有限公司 | Vinyl fluorine-containing polysiloxane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3853933A (en) * | 1974-01-14 | 1974-12-10 | Gen Electric | Continuous process for producing polysiloxane oils utilizing a carbon black catalyst |
| CN101885845A (en) * | 2010-07-16 | 2010-11-17 | 东莞市贝特利新材料有限公司 | Method for synthesizing vinyl phenyl silicone oil |
-
2015
- 2015-12-21 CN CN201510969515.7A patent/CN105384936B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3853933A (en) * | 1974-01-14 | 1974-12-10 | Gen Electric | Continuous process for producing polysiloxane oils utilizing a carbon black catalyst |
| CN101885845A (en) * | 2010-07-16 | 2010-11-17 | 东莞市贝特利新材料有限公司 | Method for synthesizing vinyl phenyl silicone oil |
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Address after: 256401 Tangshan, Shandong, Huantai Town, Zibo Applicant after: Shandong Dongyue organosilicon material Limited by Share Ltd Address before: 256401 Tangshan, Shandong, Huantai Town, Zibo Applicant before: Shandong Dongyue Silicon Material co., Ltd. |
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