CN105885052A - Preparation method of vinyl-terminated polymethyl ethyl siloxane - Google Patents
Preparation method of vinyl-terminated polymethyl ethyl siloxane Download PDFInfo
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- CN105885052A CN105885052A CN201610308939.3A CN201610308939A CN105885052A CN 105885052 A CN105885052 A CN 105885052A CN 201610308939 A CN201610308939 A CN 201610308939A CN 105885052 A CN105885052 A CN 105885052A
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- ethenyl blocking
- weight portion
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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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Abstract
The invention relates to a preparation method of vinyl-terminated polymethyl ethyl siloxane. The polymethyl ethyl siloxane and tetramethyl tetravinyl cyclotetrasiloxane are taken as reaction monomers, divinyl-tetramethyl-disiloxanc is taken as a capping agent, different catalysts and dosages are selected, through ring opening polymerization reaction, the reaction temperature, the time, the dosage of the capping agent, the neutralizer and the dosage of the neutralizer are controlled during the reaction, and the vinyl-terminated polymethyl ethyl siloxane is prepared. The vinyl-terminated polymethyl ethyl siloxane prepared by the preparation method has the advantages of low glass transition temperature, no crystallization, simple preparation technologyand easiness in reaction control, and scale production can be realized.
Description
Technical field
The invention belongs to the preparing technical field of organosilicon macromolecule compound, be specifically related to a kind of poly-Methylethyl of ethenyl blocking
The preparation method of siloxanes.
Background technology
At low temperatures, owing to molecular thermalmotion weakens, molecule segment and strand are frozen for rubber, and rubber will gradually lose bullet
Property, lose using value.The resistance to low temperature of rubber is mainly the most relevant with the two of its high polymer conversion processes: glass transition and
Crystallization.Having pusher side base can rotate freely around Si-O main chain in polysiloxane molecule, intramolecular and intermolecular force are little, point
Sub-compliance is good, and making polysiloxanes is the polymer that in known polymer science field, glass transition temperature is minimum.But, with
As a example by polydiethylsiloxane, its glass transition temperature is-145 DEG C, is minimum in institute's polysiloxane, but due to poly-two
Ethylsiloxane molecular structure is regular, causes it 0 DEG C and about-70 DEG C crystallizations.Therefore, although the glass of polydiethylsiloxane
Glass transition temperature is the lowest, but owing to it exists crystallinity, the minimum use temperature making polydiethylsiloxane is its crystallization temperature,
Rather than glass transition temperature.Therefore, its cryogenic property can not meet far away requirement.
Preparing copolymer, the regularity destroying polydiethylsiloxane strand by introducing other link is to reduce its degree of crystallinity
Effective ways.Chinese patent document CN 103342897A (application number: 201310322504.0) discloses low temperature resistant add-on type
The preparation method of room temperature vulcanized silicone rubber, the method step is: by octamethylcy-clotetrasiloxane, hexaetcycletrisiloxane, 1,3,5,7
Tetramethyl 1,3,5,7 tetravinyl cyclotetrasiloxanes and ethenyl blocking agent mix homogeneously, be heated to 80～170 DEG C, adds catalysis
Agent polyreaction；After reaction terminates, being warming up to 180～200 DEG C, evacuation removes little molecule low-boiling-point substance, prepares sulphurated siliastic
Rubber；In sulfuration silicon rubber raw rubber, add white carbon, mix homogeneously, process 20～120min in 70～180 DEG C, be cooled to
Room temperature, adds cross-linking agent and catalyst, mix homogeneously, cured at room temperature 1～7 days, prepares low temperature resistant addition type room temperature vulcanized silicon
Rubber.Brewer has synthesized poly-diethyl-diphenyl siloxane, poly-diethyl-two trifluoro propyl methylsiloxane, works as diphenyl
Content of siloxane more than 10% or trifluoro propyl methylsiloxane content more than 20% time, the copolymer obtained does not crystallizes.(see:
J.R.Brewer,et al.,Polymer,1994,vol 35,5109-5117.)
Although above-mentioned copolymer does not exist crystallinity, but the open loop condition of two kinds of reaction monomers and open-loop rate are different, make copolymer
Preparation technology more complicated, relatively costly.
Summary of the invention
For the deficiencies in the prior art, the present invention provides the system of a kind of simple, practical ethenyl blocking polymethy ethylsiloxane
Preparation Method.
Technical scheme is as follows:
The preparation method of a kind of ethenyl blocking polymethy ethylsiloxane, comprises the following steps that
(1) by 100 weight portion methyl ethyl cyclosiloxane, 0～10 weight portion t etram-ethyltetravinylcyclotetrasiloxane and 0.1～15
Weight portion divinyl tetramethyl disiloxane mix homogeneously, is warming up to 40～60 DEG C, under 1～10Pa pressure, and stirring dehydration
10～60min；
(2) logical nitrogen, is warming up to 60～80 DEG C, adds the catalyst of 0.1～5 weight portions, and makes catalyst dissolution；
(3) it is warming up to 100～170 DEG C, polyreaction occurs, react 1～2h；Add the nertralizer of 0.001～2 weight portions,
Reaction 0.5～1h；
(4) last, it is warming up to 180～200 DEG C, under 1～10Pa pressure, removes low-molecular material, the removing time is 0.5～3h,
Obtain ethenyl blocking polymethy ethylsiloxane.
According to the present invention, when t etram-ethyltetravinylcyclotetrasiloxane is 0 weight portion, described ethenyl blocking poly-methyl second
The structural formula of radical siloxane is as follows:
Wherein, a is natural number, a=80～1200；
When t etram-ethyltetravinylcyclotetrasiloxane is more than 0 weight portion, described ethenyl blocking polymethy ethylsiloxane
Structural formula is as follows:
Wherein, a, b are natural number, a=80～1200, and b/ (a+b)=0.001～0.05.
According to the invention it is preferred to, the methyl ethyl cyclosiloxane described in step (1) is 1,3,5-trimethyl-1,3,5-tri-second
Basic ring trisiloxanes, 1,3,5,7-tetramethyl-1, one or both the mixture in 3,5,7-tetraethyl cyclotetrasiloxanes；
Preferably, the weight portion of t etram-ethyltetravinylcyclotetrasiloxane is 0～5 part, the weight of divinyl tetramethyl disiloxane
Amount part is 0.15～10.In the present invention, divinyl tetramethyl disiloxane uses as end-capping reagent.
According to the invention it is preferred to, the catalyst described in step (2) be Tetramethylammonium hydroxide, tetrabutylammonium hydroxide phosphorus,
Lithium hydrate, sodium hydroxide, potassium hydroxide, Cesium hydrate., or the silicon alkoxide of these materials；It is furthermore preferred that catalyst is
The silicon alkoxide of Tetramethylammonium hydroxide, the silicon alkoxide of tetrabutylammonium hydroxide phosphorus, the silicon alkoxide of potassium hydroxide or the silanol of Cesium hydrate.
Salt；
Preferably, the weight portion of catalyst is 0.5～3.
According to the invention it is preferred to, the nertralizer described in step (3) is ethylene chlorhydrin, phosphoric acid or silica-based phosphate ester.Add
Reaction system is neutralized to neutrality by nertralizer.
Beneficial effects of the present invention:
1, preparation method of the present invention is simple, mild condition, and easy control of reaction system is produced on a large scale.
2, cheaper starting materials of the present invention is easy to get, low production cost.
3, the ethenyl blocking polymethy ethylsiloxane that prepared by the present invention does not crystallizes, and resistance to low temperature is excellent, glass transition temperature
Degree is less than-125 DEG C.
Accompanying drawing explanation
Fig. 1 is the nmr spectrum (H NMR) of the ethenyl blocking polymethy ethylsiloxane of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Below by specific embodiment and combine accompanying drawing technical scheme is further elaborated, but the protected model of the present invention
Enclose and be not limited to this.
The raw materials used convenient source that is, commercial products in embodiment.
Embodiment 1
Take 500g 1,3,5-trimethyl-1,3,5-triethyl group cyclotrisiloxane, 4.9g tetramethyl tetravinyl ring silicon four oxygen alkane and 3.1g
Divinyl tetramethyl disiloxane joins in the reactor equipped with thermometer, mechanical agitation, condenser and nitrogen conduit, opens
Open stirring, be warming up to 40 DEG C, under 10Pa pressure, be dehydrated 30min；Logical nitrogen, is warming up to 60 DEG C, adds 7.5g's
Tetramethylammonium hydroxide silicon alkoxide, and make it dissolve；It is warming up to 110 DEG C, polyreaction occurs, react 1h；Add 0.13
G ethylene chlorhydrin, reacts 0.5h；Finally, being warming up to 180 DEG C, under 10Pa pressure, remove low-molecular material, the time is 1h,
To ethenyl blocking polymethy ethylsiloxane.The nmr spectrum (H NMR) of ethenyl blocking polymethy ethylsiloxane
It is listed in Fig. 1.
Embodiment 2
Take 500g 1,3,5-trimethyl-1,3,5-triethyl group cyclotrisiloxane, 11.5g tetramethyl tetravinyl ring silicon four oxygen alkane and 1g
Divinyl tetramethyl disiloxane joins in the reactor equipped with thermometer, mechanical agitation, condenser and nitrogen conduit, opens
Open stirring, be warming up to 40 DEG C, under 8Pa pressure, be dehydrated 35min；Logical nitrogen, is warming up to 60 DEG C, adds the tetramethyl of 5g
Base ammonium hydroxide silicon alkoxide, and make it dissolve；It is warming up to 110 DEG C, polyreaction occurs, react 1h；Add 0.13g 2-
2-chloroethyl alcohol, reacts 0.5h；Finally, being warming up to 180 DEG C, under 10Pa pressure, remove low-molecular material, the time is 1h, obtains
Ethenyl blocking polymethy ethylsiloxane.
Embodiment 3
Take 500g 1,3,5,7-tetramethyl-1,3,5,7-tetraethyl cyclotetrasiloxane and 1g divinyl tetramethyl disiloxane join
In reactor equipped with thermometer, mechanical agitation, condenser and nitrogen conduit, open stirring, be warming up to 40 DEG C, press at 8Pa
Under power, it is dehydrated 35min；Logical nitrogen, is warming up to 120 DEG C, adds the potassium hydroxide silicon alkoxide of 7.5g, and makes it dissolve；Rise
To 140 DEG C, there is polyreaction in temperature, reacts 1.5h；Add 0.13g phosphoric acid, react 1h；Finally, it is warming up to 180 DEG C,
Under 10Pa pressure, removing low-molecular material, the time is 1.5h, obtains ethenyl blocking polymethy ethylsiloxane.
Embodiment 4
Take 500g 1,3,5,7-tetramethyl-1,3,5,7-tetraethyl cyclotetrasiloxanes, 4.9g tetramethyl tetravinyl ring silicon four oxygen alkane and
48g divinyl tetramethyl disiloxane joins in the reactor equipped with thermometer, mechanical agitation, condenser and nitrogen conduit,
Open stirring, be warming up to 40 DEG C, under 10Pa pressure, be dehydrated 30min；Logical nitrogen, is warming up to 120 DEG C, adds 10g
Potassium hydroxide silicon alkoxide, and make it dissolve；It is warming up to 140 DEG C, polyreaction occurs, react 1.5h；Add 3.25g
Silica-based phosphate ester, reacts 1h；Finally, being warming up to 180 DEG C, under 10Pa pressure, remove low-molecular material, the time is 1.5h,
Obtain ethenyl blocking polymethy ethylsiloxane.
Embodiment 5
Take 300g 1,3,5-trimethyl-1,3,5-triethyl group cyclotrisiloxane, 200g 1,3,5,7-tetramethyl-1,3,5,7-tetrem basic ring four
Siloxanes, 4.9g tetramethyl tetravinyl ring silicon four oxygen alkane and 3.1g divinyl tetramethyl disiloxane join equipped with temperature
In the reactor of meter, mechanical agitation, condenser and nitrogen conduit, open stirring, be warming up to 40 DEG C, under 10Pa pressure,
Dehydration 30min；Logical nitrogen, is warming up to 120 DEG C, adds the Cesium hydrate. silicon alkoxide of 5g, and makes it dissolve；It is warming up to 140 DEG C,
There is polyreaction, react 1.5h；Add the silica-based phosphate ester of 0.85g, react 1h；Finally, it is warming up to 180 DEG C, 10Pa
Under pressure, removing low-molecular material, the time is 1.5h, obtains ethenyl blocking polymethy ethylsiloxane.
Test example 1
The physicochemical property of ethenyl blocking polymethy ethylsiloxane embodiment 1～5 prepared detects, result such as table 1 institute
Show.
Table 1
| Embodiment | Contents of ethylene (wt%) | Viscosity (mPa s) | Productivity (%) |
| 1 | 0.48 | 8.10×103 | 86 |
| 2 | 0.76 | 3.95×104 | 89 |
| 3 | 0.06 | 4.36×104 | 90 |
| 4 | 2.79 | 3.20×10 | 83 |
| 5 | 0.47 | 7.74×103 | 86 |
Claims (9)
1. a preparation method for ethenyl blocking polymethy ethylsiloxane, comprises the following steps that
(1) by 100 weight portion methyl ethyl cyclosiloxane, 0～10 weight portion t etram-ethyltetravinylcyclotetrasiloxane and 0.1～15
Weight portion divinyl tetramethyl disiloxane mix homogeneously, is warming up to 40～60 DEG C, under 1～10Pa pressure, and stirring dehydration
10～60min；
(2) logical nitrogen, is warming up to 60～80 DEG C, adds the catalyst of 0.1～5 weight portions, and makes catalyst dissolution；
(3) it is warming up to 100～170 DEG C, polyreaction occurs, react 1～2h；Add the nertralizer of 0.001～2 weight portions,
Reaction 0.5～1h；
(4) last, it is warming up to 180～200 DEG C, under 1～10Pa pressure, removes low-molecular material, the removing time is 0.5～3h,
Obtain ethenyl blocking polymethy ethylsiloxane.
The preparation method of ethenyl blocking polymethy ethylsiloxane the most according to claim 1, it is characterised in that when four
When methyl tetravinyl cyclotetrasiloxane is 0 weight portion, the structural formula of described ethenyl blocking polymethy ethylsiloxane is as follows:
Wherein, a is natural number, a=80～1200；
When t etram-ethyltetravinylcyclotetrasiloxane is more than 0 weight portion, described ethenyl blocking polymethy ethylsiloxane
Structural formula is as follows:
Wherein, a, b are natural number, a=80～1200, and b/ (a+b)=0.001～0.05.
The preparation method of ethenyl blocking polymethy ethylsiloxane the most according to claim 1, it is characterised in that step
(1) methyl ethyl cyclosiloxane described in is 1,3,5-trimethyl-1,3,5-triethyl group cyclotrisiloxane, 1,3,5,7-tetramethyl
One or both mixture in-1,3,5,7-tetraethyl cyclotetrasiloxane.
The preparation method of ethenyl blocking polymethy ethylsiloxane the most according to claim 1, it is characterised in that step
(1) in, the weight portion of t etram-ethyltetravinylcyclotetrasiloxane is 0～5 part.
The preparation method of ethenyl blocking polymethy ethylsiloxane the most according to claim 1, it is characterised in that step
(1) in, the weight portion of divinyl tetramethyl disiloxane is 0.15～10.
The preparation method of ethenyl blocking polymethy ethylsiloxane the most according to claim 1, it is characterised in that step
(2) catalyst described in be Tetramethylammonium hydroxide, tetrabutylammonium hydroxide phosphorus, Lithium hydrate, sodium hydroxide, potassium hydroxide,
Cesium hydrate., or the silicon alkoxide of these materials.
The preparation method of ethenyl blocking polymethy ethylsiloxane the most according to claim 6, it is characterised in that step
(2) catalyst described in is the silicon alkoxide of Tetramethylammonium hydroxide, the silicon alkoxide of tetrabutylammonium hydroxide phosphorus, the silicon of potassium hydroxide
Alkoxide or the silicon alkoxide of Cesium hydrate..
The preparation method of ethenyl blocking polymethy ethylsiloxane the most according to claim 1, it is characterised in that step
(2) weight portion of the catalyst described in is 0.5～3.
The preparation method of ethenyl blocking polymethy ethylsiloxane the most according to claim 1, it is characterised in that step
(3) nertralizer described in is ethylene chlorhydrin, phosphoric acid or silica-based phosphate ester.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286799A (en) * | 2022-10-08 | 2022-11-04 | 常熟市斯泰普新材料有限公司 | Triblock polysiloxane quaternary ammonium salt and preparation method thereof |
| CN115678012A (en) * | 2022-11-01 | 2023-02-03 | 中科院广州化学有限公司 | Multi-terminal alkylene branched polysiloxane and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827371A (en) * | 2011-06-17 | 2012-12-19 | 中国科学院大连化学物理研究所 | Functional polysiloxane, preparation method of functional polysiloxane and application of functional polysiloxane in gas separation membrane |
| CN103333338A (en) * | 2013-07-11 | 2013-10-02 | 江苏天辰硅材料有限公司 | Vinyl silicone oil and synthetic method thereof |
| CN103342897A (en) * | 2013-07-29 | 2013-10-09 | 山东大学 | Method for preparing low-temperature resisting addition type room-temperature vulcanized silicone rubber |
-
2016
- 2016-05-10 CN CN201610308939.3A patent/CN105885052A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827371A (en) * | 2011-06-17 | 2012-12-19 | 中国科学院大连化学物理研究所 | Functional polysiloxane, preparation method of functional polysiloxane and application of functional polysiloxane in gas separation membrane |
| CN103333338A (en) * | 2013-07-11 | 2013-10-02 | 江苏天辰硅材料有限公司 | Vinyl silicone oil and synthetic method thereof |
| CN103342897A (en) * | 2013-07-29 | 2013-10-09 | 山东大学 | Method for preparing low-temperature resisting addition type room-temperature vulcanized silicone rubber |
Non-Patent Citations (1)
| Title |
|---|
| 岳岩: "甲基乙基环硅氧烷的制备与应用研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ期》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286799A (en) * | 2022-10-08 | 2022-11-04 | 常熟市斯泰普新材料有限公司 | Triblock polysiloxane quaternary ammonium salt and preparation method thereof |
| CN115286799B (en) * | 2022-10-08 | 2023-02-24 | 常熟市斯泰普新材料有限公司 | Triblock polysiloxane quaternary ammonium salt and preparation method thereof |
| CN115678012A (en) * | 2022-11-01 | 2023-02-03 | 中科院广州化学有限公司 | Multi-terminal alkylene branched polysiloxane and preparation method and application thereof |
| CN115678012B (en) * | 2022-11-01 | 2023-07-14 | 中科院广州化学有限公司 | Multi-terminal olefin-based branched polysiloxane, and preparation method and application thereof |
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