CN108034051A - A kind of vinyl polysiloxane and preparation method and application - Google Patents
A kind of vinyl polysiloxane and preparation method and application Download PDFInfo
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- CN108034051A CN108034051A CN201711463158.2A CN201711463158A CN108034051A CN 108034051 A CN108034051 A CN 108034051A CN 201711463158 A CN201711463158 A CN 201711463158A CN 108034051 A CN108034051 A CN 108034051A
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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
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- 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
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- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
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Abstract
The invention belongs to the technical field of polysiloxanes, discloses a kind of vinyl polysiloxane and preparation method and application.Method is：(1) 100~200 parts of DMC are mixed with 20~60 parts of methylvinylcyclosiloxanes, vacuum dehydration processing, obtains dehydration mix monomer；(2) dehydration mix monomer is mixed with 1~20 part of end-capping reagent, is warming up to 100~110 DEG C；0.1~5 part of temporary catalyst is added, is warming up to 110~115 DEG C, 1~3h of insulation reaction；120~125 DEG C are warming up to, 3~5h of insulation reaction；130~135 DEG C are continuously heating to, reacts 1~3h, obtains reaction product；(3) reaction product is subjected to subsequent treatment, obtains vinyl polysiloxane；The number is parts by weight.The method of the present invention is simple, and cost is low, and monomer conversion is high；Synthesis and modified and mould release preparation applied to silicon rubber, silicones.
Description
Technical field
The invention belongs to the technical field of polysiloxanes, is related to a kind of method for efficiently preparing polysiloxanes, and in particular to
The vinyl polysiloxane that the high-efficiency synthesis method and this method of a kind of vinyl polysiloxane are prepared, the vinyl gather
Siloxanes is used to prepare mould release product and silicon rubber.
Technical background
Polysiloxanes is the side chain connection organic group (methyl, phenyl, ethyl, vinyl etc.) using Si-O-Si as main chain.
This organic-inorganic structure assigns its excellent chemical stability, higher compliance, and resistant of high or low temperature function admirable is resistance to
Hou Xing, lubricity, and the performance such as relatively low surface tension, are widely applied waterproof material, self-cleaning material, building materials, electricity
The every field such as sub- device, are the basic materials of the organosilicon products such as common silicone oil, silicon rubber, silicones, have extensively and
The application on basis.
Vinyl polysiloxane (also known as vinyl) refers mainly to the linear polysiloxane that end group or side chain contain vinyl, and one
As be water white transparency liquid.Vinyl polysiloxane not only remains polysiloxane excellent properties, while imparts again
Its other special nature, active vinyl-functional can be reacted with other compounds；Or new crosslinking curing body can be passed through
System is cured；Some has bioactivity etc., has excellent resistant of high or low temperature, lubricity, radioresistance and compatibility, is
The wide product of development prospect.Vinyl polysiloxane is mainly used as the additive of addition-type silicon rubber, to strengthen silicon rubber
Intensity and hardness；With available for making liquid silastic；It is organic material reaction a variety of with polyurethane, acrylic acid etc., can be made into
Performance more preferably new material；The important synthesis material of silicone release agent, the content of the vinyl of vinyl polysiloxane and
Purity has the performance of product important influence.
With the development of society, release liners play the effect to become more and more important in our social life, plus people
To the pay attention to day by day of environment, the mould release of release liners is also gradually to emulsion-type and solvent-free sexual development.Vinyl polysiloxane is made
Its important raw material, plays irreplaceable effect, vinyl polysiloxane preparation process, the height of yield, vinyl
Content and molecular weight seriously restrict the performance of product.
At present, the method for synthesizing ethylene based polysiloxane is mainly hydrolysis and the ring monomer of siloxanes or chlorosilane
The ring-opening polymerisation of (DMC or D4 and vinyl monomer).Hydrolytic process general procedure is cumbersome, seriously corroded, while to the pure of monomer
Degree requirement is higher, and due to the presence of water, hydroxyl polysiloxane may be produced in preparation process, influences the purity of product.
The common method of vinyl polysiloxane is by the ring-opening polymerisation under the action of acid or base catalyst of ring monomer, then uses ethene
Radical siloxane is blocked.Ring-opening polymerisation generally comprises polymerisation in bulk, polymerisation in solution and emulsion polymerization.Polymerisation in bulk is solvent-free,
Emulsifying agent, additive etc., post processing is fairly simple, therefore the present invention uses bulk-anion polymerization.
DMC (dimethicone mixture) is generally using dimethyldichlorosilane as primary raw material, by hydrolysis
It is prepared, due to the influence of hydrolysis degree or catalyst, in addition to containing octamethylcy-clotetrasiloxane, also has other ring lists
Body (D3D5D6) generation, the content of its middle ring monomer is also different.Because the Open loop temperature and open-loop rate of different ring monomers
Different, if allowing different ring monomer ring-opening polymerisations at that same temperature, the conversion ratio of monomer is affected certainly.Certain is public
Department is using DMC as raw material, and at a certain temperature, base catalyst ring-opening polymerisation prepares vinyl polysiloxane.Other monomers turn
Rate is less than ring D4Conversion ratio under the same conditions.[prepared by Li En, Chen Haiping, Miao Gang, U.S. duckweed, analogy dawn base catalyst
Low-viscosity methyl-silicone oil and vinyl silicone oil [J] organosilicon materials, 2013, (6):441~443]；Check experiment was done, will
For DMC at 110 DEG C, 120 DEG C, 130 DEG C of isothermal reactions, the conversion ratio of product only has 60% or so, seriously affects the poly- silica of vinyl
The yield of alkane.
Therefore development goal yield high income, cost is low, small investment, post-processes the synthesis of simple vinyl polysiloxane
Technique is increasingly important.
The content of the invention
The present invention is directed to shortcoming and defect existing in the prior art, there is provided a kind of preparation side of vinyl polysiloxane
Method.The present invention makes the abundant open loop of monomer of dimethicone mixture, carries and produced monomer by way of progressively heating up
Conversion ratio, adds yield.DMC is under conditions of tetramethylammonium hydroxide makees catalyst, by the way of progressively heating up, passes through
Speed and the time of heating are controlled, improves the conversion ratio of each ring body；The atomic radius of nitrogen is smaller in tetramethylammonium hydroxide at the same time,
Do not allow destructible silicon oxygen bond, can break ring body and the balance of linear product yet, be conducive to the raising of yield；In addition, pass through control
The ratio of monomer and end-capping reagent processed, can effectively control the molecular weight and viscosity of vinyl polysiloxane, therefore can high efficiency
Synthesis high yield vinyl polysiloxane.
Another object of the present invention is to provide the vinyl polysiloxane obtained by above-mentioned preparation method.
Another object of the present invention is the application of above-mentioned vinyl polysiloxane.The vinyl polysiloxane is used to make
Standby and/or modified silicon rubber, silicones and/or mould release.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
(1) 100~200 parts by weight DMC are mixed with 20~60 parts by weight methylvinylcyclosiloxanes, at vacuum dehydration
Reason, obtains dehydration mix monomer；
(2) the dehydration mix monomer of step (1) is mixed with 1~20 parts by weight end-capping reagent, is warming up to 100~110 DEG C；Add
Enter the temporary catalyst of 0.1~5 parts by weight, be warming up to 110~115 DEG C, 1~3h of insulation reaction；120~125 DEG C are warming up to, is protected
3~5h of temperature reaction；130~135 DEG C are continuously heating to, reacts 1~3h, obtains reaction product；
(3) reaction product is subjected to subsequent treatment, obtains vinyl polysiloxane；The number is parts by weight.
The subsequent treatment refers to the reaction product of step (3) at 180~210 DEG C, vacuum for -0.08~-
Under conditions of 0.09Mpa processing until flowing out without cut go out, obtain vinyl polysiloxane；Or the reaction product by step (3)
Rotated, unreacted monomer is screwed out, is cooled to room temperature, obtains vinyl polysiloxane.
The vinyl polysiloxane is Vi-PMS-Vi, more than one in Me-PViMS-Me, Vi-PViMS-Vi；Vi-
The structural formula of PMS-Vi, Me-PViMS-Me, Vi-PViMS-Vi：
Wherein Vi:Vinyl, 4<x<200,4<y<50, x, y are integer.
The dimethicone mixture (DMC) is hexamethyl cyclotrisiloxane (D3), octamethylcy-clotetrasiloxane
(D4), decamethylcyclopentaandoxane (D5), and the mixture such as ten dimethyl circulation siloxanes (D6)；Different manufacturers are chosen to carry
The percentage composition of the DMC of confession, wherein octamethylcy-clotetrasiloxane (D4) are 70%；75%；80%；85% etc.；
The methylvinylcyclosiloxane is t etram-ethyltetravinylcyclotetrasiloxane, six vinyl pregnancy basic rings, six silicon
Eight siloxanes of oxygen alkane or eight alkenyl ring of prestox more than one；
The end-capping reagent is two silicon of divinyl tetramethyl disiloxane, Vinyldimethylethoxysilane or hexamethyl
Any one in oxygen alkane；
The temporary catalyst is tetramethylammonium hydroxide, tetramethyl phosphonium hydroxide, tetramethylammonium hydroxide silicon alkoxide
Or more than one in tetramethyl phosphonium hydroxide silicon alkoxide；Or the silicon alkoxide of tetramethylammonium hydroxide, tetramethyl phosphonium hydroxide
Its structure of silicon alkoxide (R4N(Me2SiO) OH, R4P(Me2SiO)OH)；Because temporary catalyst, being heated to certain temperature can
To resolve into small-molecule substance, it is easier to remove；
The temperature of the processing of vacuum dehydration described in step (1) is 80~90 DEG C, and vacuum is -0.07~-0.09MPa, is taken off
The water time is 0.5~2h, is preferably 1~2h；
In step (2), the Open loop temperature of D3 is 105~115 DEG C, and the reaction time is 1~3h；The Open loop temperature of D4 is 115
~125 DEG C, 3~5h of reaction time；120~135 DEG C of the Open loop temperature of more than D5,1~3h of reaction time；
Heating rate is 5 DEG C/min~10 DEG C/min in step (2)；
Subsequent treatment in step (3)：The decomposition temperature of temporary catalyst be 139 DEG C, by system temperature be adjusted to 140 DEG C~
180 DEG C, temporary catalyst is decomposed, temperature is then adjusted to 180~210 DEG C, deviate from low-boiling-point substance, until flowing out without cut goes out.
The present invention is originally by way of progressively heating up, and the speed and efficiency of control ring monomer open loop, technical process is simple, into
This is low, because DMC raw materials are easy to get, and cost is low, and product yield is high, molecular weight and easily controllable, reactivity height, stable storing
Property it is good, can be widely applied to synthesis and modified and silicone release agent the important source material of silicon rubber, silicones.
The present invention has the following advantages that compared with prior art and effect：
(1) raw material is easy to get, and production cost is relatively low；
(2) by way of progressively heating up, by increasing capacitance it is possible to increase the open loop efficiency of cyclosiloxane, improves yield；
(3) molecular weight of vinyl polysiloxane can be accurately controlled, while molecular weight distribution relative narrower.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Monomer conversion：Monomer conversion measures：It is (W1) that cuvette, which is made, to weigh quality with masking foil, reacts small every half
When sample, it is (W2) to weigh quality, is put into baking oven and volatilizees by unreacted reactant, until weighing apparatus in, it is (W3) to weigh quality.Based on formula
Calculate：
Conversion ratio=[(W3-W1)/(W2-W1)] * 100%.
Embodiment 1
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
By 19.6g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5.2g t etram-ethyltetravinylcyclotetrasiloxanes (hundred
Clever prestige) it is placed in reaction vessel, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixing
Thing；1.82g divinyl tetramethyl disiloxanes are added into dehydration monomer mixture, are warming up to 100 DEG C；It is temporary to add 0.49g
When property catalyst tetramethylammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 3h；It is warming up to
130 DEG C, insulation reaction 1h, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, vacuumize-
0.09MPa leads to nitrogen, is distillated to no cut, obtains water white transparency product vinyl polysiloxane.The conversion of monomer in the present embodiment
Rate is 89.6%.
Embodiment 2
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
27g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 6.2g t etram-ethyltetravinylcyclotetrasiloxanes are placed in three
In mouth flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；To dehydration monomer
3.6g divinyl tetramethyl disiloxanes are added in mixture, are warming up to 100 DEG C；Add the temporary catalyst tetramethyls of 0.56g
Base ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 3h；130 DEG C are warming up to, insulation reaction
1h, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, -0.09MPa is vacuumized and leads to nitrogen and take off as low as
No cut distillates, and obtains water white transparency product vinyl polysiloxane.The conversion ratio of monomer is 91.2% in the present embodiment.
Embodiment 3
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
19.6g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5.2g t etram-ethyltetravinylcyclotetrasiloxanes are placed in
In three-necked flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；It is single to dehydration
1.82g divinyl tetramethyl disiloxanes are added in body mixture, are warming up to 90 DEG C；Add the temporary catalyst four of 0.49g
Ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 3h；130 DEG C are warming up to, insulation is anti-
1h is answered, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, vacuumize -0.09MPa lead to nitrogen take off it is low
Distillated to no cut, obtain water white transparency product vinyl polysiloxane.The conversion ratio of monomer is 88% in the present embodiment.
Embodiment 4
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
19.6g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5.2g t etram-ethyltetravinylcyclotetrasiloxanes are placed in
In three-necked flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；It is single to dehydration
1.82g divinyl tetramethyl disiloxanes are added in body mixture, are warming up to 90 DEG C；Add the temporary catalyst four of 0.49g
Ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 3h；130 DEG C are warming up to, insulation is anti-
1h is answered, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, vacuumize -0.09MPa lead to nitrogen take off it is low
Distillated to no cut, obtain water white transparency product vinyl polysiloxane.The conversion ratio of monomer is 89% in the present embodiment.
Embodiment 5
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
19.6g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5.2g t etram-ethyltetravinylcyclotetrasiloxanes are placed in
In three-necked flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；It is single to dehydration
1.82g divinyl tetramethyl disiloxanes are added in body mixture, are warming up to 100 DEG C；Add the temporary catalyst four of 0.49g
Ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 3h；130 DEG C are warming up to, insulation is anti-
1h is answered, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, vacuumize -0.09MPa lead to nitrogen take off it is low
Distillated to no cut, obtain water white transparency product vinyl polysiloxane.The conversion ratio of monomer is 89.6% in the present embodiment.
Embodiment 6
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
24g DMC (Jinan Gu Ruite Chemical Co., Ltd.s) and 6.8g t etram-ethyltetravinylcyclotetrasiloxanes are placed in three
In mouth flask, 90 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；To dehydration monomer
1.82g divinyl tetramethyl disiloxanes are added in mixture, are warming up to 100 DEG C；Add the temporary catalyst tetramethyls of 0.53g
Base ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 3h；130 DEG C are warming up to, insulation reaction
1h, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, -0.09MPa is vacuumized and leads to nitrogen and take off as low as
No cut distillates, and obtains water white transparency product vinyl polysiloxane.The conversion ratio of monomer is 90.5% in the present embodiment.
Embodiment 7
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
19.6g DMC (Jinan Gu Ruite Chemical Co., Ltd.s) and 5.2g t etram-ethyltetravinylcyclotetrasiloxanes are placed in
In three-necked flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；It is single to dehydration
1.82g divinyl tetramethyl disiloxanes are added in body mixture, are warming up to 100 DEG C；Add the temporary catalyst four of 0.49g
Ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 3h；130 DEG C are warming up to, insulation is anti-
1h is answered, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, vacuumize -0.09MPa lead to nitrogen take off it is low
Distillated to no cut, obtain water white transparency product vinyl polysiloxane.The conversion ratio of monomer is 86% in the present embodiment.
Embodiment 8
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
207g DMC (Jinan Gu Ruite Chemical Co., Ltd.s) and 40g t etram-ethyltetravinylcyclotetrasiloxanes are placed in three
In mouth flask, 90 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；To dehydration monomer
25g divinyl tetramethyl disiloxanes are added in mixture, are warming up to 100 DEG C；Add the temporary catalyst tetramethyl hydrogen of 6g
Amine-oxides, are warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 3h；130 DEG C, insulation reaction 1h are warming up to,
Obtain reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, vacuumize -0.09MPa lead to nitrogen take off as low as without
Cut distillates, and obtains water white transparency product vinyl polysiloxane.The conversion ratio of monomer is 87% in the present embodiment.
Embodiment 9
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
19.6g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5.2g t etram-ethyltetravinylcyclotetrasiloxanes are placed in
In three-necked flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；It is single to dehydration
1.82g divinyl tetramethyl disiloxanes are added in body mixture, are warming up to 100 DEG C；Add the temporary catalyst four of 0.49g
Ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 4h；130 DEG C are warming up to, insulation is anti-
1h is answered, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, vacuumize -0.09MPa lead to nitrogen take off it is low
Distillated to no cut, obtain water white transparency product vinyl polysiloxane.The conversion ratio of monomer is 88.9% in the present embodiment.
Embodiment 10
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
15g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 3g t etram-ethyltetravinylcyclotetrasiloxanes are placed in three mouthfuls
In flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；Mixed to dehydration monomer
0.12g divinyl tetramethyl disiloxanes are added in compound, are warming up to 100 DEG C；Add the temporary catalyst tetramethyls of 0.49g
Ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 4h；130 DEG C are warming up to, insulation reaction
1h, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, -0.09MPa is vacuumized and leads to nitrogen and take off as low as
No cut distillates, and obtains water white transparency product vinyl polysiloxane.Its number-average molecular weight Mn is 2.35*104, molecular weight distribution is
1.34.The conversion ratio of monomer is 89.2% in the present embodiment.
Embodiment 11
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
15g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5g t etram-ethyltetravinylcyclotetrasiloxanes are placed in three mouthfuls
In flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；Mixed to dehydration monomer
0.24g divinyl tetramethyl disiloxanes are added in compound, are warming up to 100 DEG C；Add the temporary catalyst tetramethyls of 0.49g
Ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 4h；130 DEG C are warming up to, insulation reaction
1h, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, -0.09MPa is vacuumized and leads to nitrogen and take off as low as
No cut distillates, and obtains water white transparency product vinyl polysiloxane.Its number-average molecular weight Mn is 1.89*104, molecular weight distribution is
1.56.The conversion ratio of monomer is 90.2% in the present embodiment.
Embodiment 12
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
30g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5g t etram-ethyltetravinylcyclotetrasiloxanes are placed in three mouthfuls
In flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；Mixed to dehydration monomer
1.5g divinyl tetramethyl disiloxanes are added in compound, are warming up to 100 DEG C；Add the temporary catalyst tetramethyls of 0.49g
Ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 4h；130 DEG C are warming up to, insulation reaction
1h, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, -0.09MPa is vacuumized and leads to nitrogen and take off as low as
No cut distillates, and obtains water white transparency product vinyl polysiloxane.Its number-average molecular weight Mn is 1.58*104, molecular weight and its point
Cloth is 1.12.The conversion ratio of monomer is 86% in the present embodiment.
Embodiment 13
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
15g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5g t etram-ethyltetravinylcyclotetrasiloxanes are placed in three mouthfuls
In flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；Mixed to dehydration monomer
0.24g divinyl tetramethyl disiloxanes are added in compound, are warming up to 100 DEG C；Add the temporary catalyst tetramethyls of 0.49g
Hydroxide phosphine, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 4h；130 DEG C are warming up to, insulation reaction
1h, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, -0.09MPa is vacuumized and leads to nitrogen and take off as low as
No cut distillates, and obtains water white transparency product vinyl polysiloxane.Its number-average molecular weight Mn is 1.35*104, molecular weight distribution is
1.59.The conversion ratio of monomer is 89.6% in the present embodiment.
Embodiment 14
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
19.6g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5.2g t etram-ethyltetravinylcyclotetrasiloxanes are placed in
In three-necked flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；It is single to dehydration
1.82g divinyl tetramethyl disiloxanes are added in body mixture, are warming up to 100 DEG C；Add the temporary catalyst four of 0.49g
Methyl hydrogen phosphine oxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 4h；130 DEG C are warming up to, insulation is anti-
1h is answered, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, vacuumize -0.09MPa lead to nitrogen take off it is low
Distillated to no cut, obtain water white transparency product vinyl polysiloxane.Its number-average molecular weight Mn is 1.85*104, molecular weight and its
It is distributed as 1.44.The conversion ratio of monomer is 92% in the present embodiment.
Embodiment 15
A kind of preparation method of vinyl polysiloxane, comprises the following steps：
19.6g DMC (the new four seas Chemical Co., Ltd. in Hubei) and 5.2g t etram-ethyltetravinylcyclotetrasiloxanes are placed in
In three-necked flask, 80 DEG C are warming up to, stirring is evacuated to -0.09MPa, is dehydrated 1h, obtains dehydration monomer mixture；It is single to dehydration
1.82g divinyl tetramethyl disiloxanes are added in body mixture, are warming up to 100 DEG C；Add the temporary catalyst four of 0.49g
Ammonium hydroxide, is warming up to 110 DEG C, insulation reaction 1h；120 DEG C are warming up to, insulation reaction 4h；130 DEG C are warming up to, insulation is anti-
1h is answered, obtains reaction product；Reaction product is warming up to 180 DEG C, decomposes catalyst, vacuumize -0.09MPa lead to nitrogen take off it is low
Distillated to no cut, obtain water white transparency product vinyl polysiloxane.Its number-average molecular weight Mn is 1.45*104, molecular weight and its
It is distributed as 1.87.The conversion ratio of monomer is 89.3% in the present embodiment.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
- A kind of 1. preparation method of vinyl polysiloxane, it is characterised in that：Comprise the following steps：(1) 100~200 parts of DMC are mixed with 20~60 parts of methylvinylcyclosiloxanes, vacuum dehydration processing, is dehydrated Mix monomer；(2) the dehydration mix monomer of step (1) is mixed with 1~20 part of end-capping reagent, is warming up to 100~110 DEG C；Add 0.1~5 The temporary catalyst of part, is warming up to 110~115 DEG C, 1~3h of insulation reaction；120~125 DEG C are warming up to, 3~5h of insulation reaction； 130~135 DEG C are continuously heating to, reacts 1~3h, obtains reaction product；(3) reaction product is subjected to subsequent treatment, obtains vinyl polysiloxane；The number is parts by weight.
- 2. the preparation method of vinyl polysiloxane according to claim 1, it is characterised in that：The vinyl polysiloxane is Vi-PMS-Vi, more than one in Me-PViMS-Me, Vi-PViMS-Vi；Vi-PMS- The structural formula of Vi, Me-PViMS-Me, Vi-PViMS-Vi：Wherein Vi:Vinyl, 4<x<200,4<y<50, x, y are integer.
- 3. the preparation method of vinyl polysiloxane according to claim 1, it is characterised in that：The methylvinylcyclosiloxane is t etram-ethyltetravinylcyclotetrasiloxane, six vinyl pregnancy basic rings, six siloxanes Or eight alkenyl ring of prestox, eight siloxanes more than one；The end-capping reagent is divinyl tetramethyl disiloxane, Vinyldimethylethoxysilane or hexamethyldisiloxane In any one.
- 4. the preparation method of vinyl polysiloxane according to claim 1, it is characterised in that：The temporary catalyst is One in tetramethylammonium hydroxide, tetramethyl phosphonium hydroxide, tetramethylammonium hydroxide silicon alkoxide or tetramethyl phosphonium hydroxide silicon alkoxide More than kind.
- 5. the preparation method of vinyl polysiloxane according to claim 1, it is characterised in that：Vacuum described in step (1) The temperature of dehydration is 80~90 DEG C, and vacuum is -0.07~-0.09MPa, and dewatering time is 0.5~2h.
- 6. the preparation method of vinyl polysiloxane according to claim 1, it is characterised in that：The subsequent treatment refer to by The reaction product of step (3) is at 180~210 DEG C, and processing is until flowing out without cut under conditions of vacuum is -0.08~-0.09Mpa Go out, obtain vinyl polysiloxane；Or rotated the reaction product of step (3), unreacted monomer is screwed out, is cooled down To room temperature, vinyl polysiloxane is obtained.
- A kind of 7. vinyl polysiloxane obtained by any one of claim 1~6 preparation method.
- 8. the application of vinyl polysiloxane according to claim 7, it is characterised in that：The vinyl polysiloxane is used for Preparation and/or modified silicon rubber, silicones and/or mould release.
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| CN109776803A (en) * | 2018-12-21 | 2019-05-21 | 中科院广州化学有限公司南雄材料生产基地 | A kind of poly- (dimethyl siloxane-co- methyl vinyl silicone) molecular weight of regulation and its preparation method of distribution |
| CN111234230A (en) * | 2020-03-23 | 2020-06-05 | 新纳奇材料科技江苏有限公司 | Preparation method of single-terminal vinyl polydimethylsiloxane |
| CN112646488A (en) * | 2020-12-23 | 2021-04-13 | 捷凌特电子(深圳)有限公司 | Solvent type ultra-light release agent |
| CN113563725A (en) * | 2021-08-18 | 2021-10-29 | 佛山市天宝利硅工程科技有限公司 | Addition type liquid silicone rubber and preparation method and application thereof |
| CN114644835A (en) * | 2022-04-19 | 2022-06-21 | 中油路之星新材料有限公司 | Low-temperature SBS (styrene butadiene styrene) modified asphalt and preparation method thereof |
| CN115386086A (en) * | 2022-08-02 | 2022-11-25 | 长缆电工科技股份有限公司 | Preparation method of dimethyl silicone oil |
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| CN109776803A (en) * | 2018-12-21 | 2019-05-21 | 中科院广州化学有限公司南雄材料生产基地 | A kind of poly- (dimethyl siloxane-co- methyl vinyl silicone) molecular weight of regulation and its preparation method of distribution |
| CN109776803B (en) * | 2018-12-21 | 2021-07-23 | 中科院广州化学有限公司南雄材料生产基地 | Preparation method for regulating and controlling molecular weight and distribution of poly (dimethylsiloxane-co-methylvinylsiloxane) |
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| CN112646488A (en) * | 2020-12-23 | 2021-04-13 | 捷凌特电子(深圳)有限公司 | Solvent type ultra-light release agent |
| CN113563725A (en) * | 2021-08-18 | 2021-10-29 | 佛山市天宝利硅工程科技有限公司 | Addition type liquid silicone rubber and preparation method and application thereof |
| CN114644835A (en) * | 2022-04-19 | 2022-06-21 | 中油路之星新材料有限公司 | Low-temperature SBS (styrene butadiene styrene) modified asphalt and preparation method thereof |
| CN115386086A (en) * | 2022-08-02 | 2022-11-25 | 长缆电工科技股份有限公司 | Preparation method of dimethyl silicone oil |
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