CN109705354A - A kind of preparation method of vinyl trifluoro propyl silica gel - Google Patents
A kind of preparation method of vinyl trifluoro propyl silica gel Download PDFInfo
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- CN109705354A CN109705354A CN201910058043.8A CN201910058043A CN109705354A CN 109705354 A CN109705354 A CN 109705354A CN 201910058043 A CN201910058043 A CN 201910058043A CN 109705354 A CN109705354 A CN 109705354A
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Abstract
The present invention provides a kind of preparation methods of vinyl trifluoro propyl silica gel, and the preparation method comprises the following steps: trifluoro propyl methyl cyclotrisiloxane, vinyl ring body, vinyl fluoride silicone oil and base catalyst being mixed in reaction unit, telomerisation；Then be added the acid esters neutralization reaction of fluorine silicon substrate, heat up negative pressure state under take off it is low, by condensation collect low molecule reuse, then cool to room temperature discharging, obtain the vinyl trifluoro propyl silica gel；Preparation method provided by the invention is without adding solvent and promotor, pass through the synergistic effect of vinyl fluoride silicone oil, vinyl fluoride silicon alkoxide and fluorine silicon substrate acid esters, under the premise of guaranteeing raw rubber quality, product yield with higher, the vinyl trifluoro propyl silica gel molecular weight being prepared reach as high as 1,300,000, and molecular weight distribution is relatively narrow, contents of ethylene is up to 0.5%, significant effect is blocked, can be used as fluorine silicon mixing collagen material, is applied to the fields such as turbocharger tube, O-ring seal.
Description
Technical field
The invention belongs to fluorine silicon materials fields, are related to a kind of preparation method of vinyl trifluoro propyl silica gel.
Background technique
Fluorine silicon materials with the characteristic of silicon materials and fluorine material, wherein organosilicon material have excellent thermal stability,
The advantages that hydrophobicity, resistance to oxidation, weatherability, electrical insulating property, low temperature flexibility, UV resistant.The electronegativity of fluorine is heretofore known
Maximum, the bond energy of the carbon-fluorine bond of formation is larger, sufficiently stable, and fluorine atom is very close in the arrangement of carbon skeleton outer layer, can be with
Main chain and interior molecules are protected, so that fluorine material has excellent heat resistance, chemical stability, weatherability, inoxidizability etc.
Advantage.Therefore fluorine silicon materials national defence, weaving, medical medicine, building, machinery, electric, communications and transportation, food, chemical industry,
The fields such as agricultural and household chemicals are widely used.
Trifluoro propyl silica gel is using-Si-O- to have methyl on main chain, silicon atom and containing fluoroalkyl and to add convenient for vulcanization
Work and the heavy polymer of a small amount of methyl, vinylsiloxane segment introduced.The Si-O-Si structure of main chain maintains silicon
The flexibility and thermal stability of rubber backbone, and the Polyfluoroalkyl on side-chain structure then assigns fluorine silicone rubber fabulous solvent resistance
Energy.Trifluoro propyl silica gel is the basic material of fluorine-silicon compounded rubber stock.Fluorine silicone rubber be it is currently the only can -70 DEG C to 230 DEG C use
Resistance to oil product, be a kind of collection silicon rubber heat-resisting, cold resistance, weatherability, compression recovery, resilience, release property and fluorine rubber
The excellent performances such as glue oil resistant and solvent resistance are in the novel elastomer of one.Fluorine silicone rubber be mainly used in aerospace field,
In the fields such as superior automobile, it can be used as diaphragm, washer and the sealing element in engine and fuel tank.
China starts late to the research in fluorine silicone rubber field, and the Chinese Academy of Sciences completes the system of fluoropolymer emulsion at the initial stage sixties
It is standby, and synthesized trifluoro propyl silica gel sample；Then under the joint efforts of the Chinese Academy of Sciences and Shanghai organic fluorine material research institute, close
At the trifluoro propyl silica gel for being equivalent to U.S. product LS-420；The seventies SF series trifluoro propyl silica gel pilot scale obtain at
Function.But domestic fluorine silicone rubber is there are many defects, as initiator is remaining, small molecule ring body content is higher, molecular weight distribution compared with
Width etc., product properties and external product have certain gap, are mainly manifested in heat-resistant stability, tearing toughness, shore hardness etc.
In performance indicator, this is restricted it in the application of the high leading-edge field such as aerospace.
CN101245146A discloses a kind of preparation method of high molecular weight fluorine silicon raw rubber, is prepared using alkyl lithium catalyst
The fluorine silicon raw rubber of molecular weight height and narrowly distributing out, solvent is not had in polymerization reaction, is reduced environmental pollution, but still use
The promotor (methyl ethyl ketone, tetrahydrofuran, dimethylformamide) of 10-100 times of catalyst quality.CN100469818C is disclosed
A kind of method for preparing fluoro-silicone elastomer prepares fluorosilicone using self-control chlorofluorosilane, then from fluorosilicone be raw material system
Standby trifluoro propyl silica gel solves the production of trifluoro propyl silica gel from source, wherein fluorine silicon polysiloxanes tetramethylammonium hydroxide/
Fluorine silicon raw rubber is aggregated under the catalysis of silanol lithium.CN102225997A discloses a kind of preparation side of raw fluorinated silicone rubber with high molecular weight
Method prepares novel fluorine vinyl ring body, can solve vinyl and be unevenly distributed problem on main polymer chain, obtains a kind of high
The fluorine silicon raw rubber of molecular weight, high-temperature stable.CN103739844A discloses a kind of preparation method of heat cure crude rubber of fluorinated silicone rubber,
Potassium hydroxide and tetramethyl divinyl disiloxane are prepared into catalyst prepolymerization body, the performed polymer catalytic activity is high, and nothing
Promotor, end-capping reagent need to be added.EP0563902A1 causes polymerization using anion active, and Dimethylsilanediol is dissolved in first
Benzene and n-BuLi are prepared into butyl lithium base catalyst, and methyl ring body, vinyl ring body is first added, and are prepared into after prepolymer and add again
Enter trifluoro propyl methyl cyclotrisiloxane, obtain the silicon-fluorine polymer object of methyl block, the available molecular weight distribution of this method is equal
Even product, but use more dangerous n-BuLi.In method disclosed in US4287353, by KOH or NaOH and water, three
Glycol dimethyl ether is prepared into catalyst, reacts the fluorine for preparing 400-19000cps with trifluoro propyl methyl cyclotrisiloxane afterwards
Silicon polymer does not refer to the synthesis of higher molecular weight polymer.Trifluoro propyl methyl cyclotrisiloxane is dissolved in by US5079291
Acetone, acetonitrile, react with hexamethyldisilazane, remove solvent afterwards, and nitrogen jet obtains fluorine-silicon-oxygen polymer, and this method uses
A large amount of solvent.US5041586A discloses a kind of preparation method of novel silicon base phosphate, using phosphoric acid in cyclohexane solution
In reacted with hydroxy silicon oil, prepare silicon substrate phosphate, which has very high catalysis for the synthesis of organosilicon polymer
Efficiency.
But there are still trifluoro propyl silica gel to be still difficult to by ethenyl blocking and Miscibility for current preparation method
The problem of, how to develop the new method of one kind has important value for the performance for promoting trifluoro propyl silica gel.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of preparation sides of vinyl trifluoro propyl silica gel
Method, with solve trifluoro propyl silica gel be difficult to by ethenyl blocking and with trifluoro propyl methyl cyclotrisiloxane (D3F) compatibility
The problems such as, achieve the effect that preparation process simply while having both that environmentally protective, yield is high.
To achieve this purpose, the present invention adopts the following technical scheme:
The present invention provides a kind of preparation method of vinyl trifluoro propyl silica gel, the preparation method includes following step
It is rapid: trifluoro propyl methyl cyclotrisiloxane, vinyl ring body, vinyl fluoride silicone oil and base catalyst are mixed in reaction unit
It closes, telomerisation；Then be added the acid esters neutralization reaction of fluorine silicon substrate, heat up negative pressure state under take off it is low, pass through condensation collect low molecule
Reuse then cools to room temperature discharging, obtains the vinyl trifluoro propyl silica gel.
Preparation method provided by the invention, preparation process is simple, easy to operate, without adding solvent and promotor, passes through
The synergistic effect of vinyl fluoride silicone oil, vinyl fluoride silicon alkoxide and fluorine silicon substrate acid esters has under the premise of guaranteeing raw rubber quality
Higher product yield, the vinyl trifluoro propyl silica gel molecular weight being prepared reach as high as 1,300,000, molecular weight distribution compared with
Narrow, compatibility is good, and contents of ethylene is up to 0.5%, blocks significant effect.
The present invention is using cooperation addition vinyl fluoride silicone oil solves second after the heat preservation telomerization of vinyl silicon alkoxide and in raw material
Alkenyl capping problem.The preferential attack D link of vinyl silicon alkoxide base catalyst, the reactivity of base catalyst, in the following order
Fall progressively: D3 (hexamethyl cyclotrisiloxane) > D4 (octamethylcy-clotetrasiloxane) > MD2M > MDM > MM (hexamethyldisiloxane), because
This, common vinyl double seal head can not carry out ethenyl blocking.Wherein M represents simple function group chain link, such as-SiO (CH3)3；D
Two functional group's chain links are represented, such as
In the present invention, due to fluorine silicon product have good release property, it is very poor with organosilicon product compatibility, thus need by
Base catalyst and acid neutralizing agent are prepared into the oligomer containing trifluoropropyl group, promote compatibility.
Preparation method provided by the invention, fluorine silicon substrate acid esters are added after other compositions telomerisation as neutralizer.And
Vinyl fluoride silicone oil is indispensable raw material, and the molecular weight of product is adjusted.
Preferably, the base catalyst is vinyl fluoride silicon alkoxide.
Preferably, the vinyl fluoride silicon alkoxide, which is reacted by vinyl fluoride silicone oil with alkali, is prepared.Specific reaction equation is such as
Shown in lower:
WhereinFor vinyl fluoride silicon alkoxide, MOH is alkali.M represents the original of the metal in alkali
Son, the value of n are 0~10000.
It is of the present invention to take off low meaning are as follows: small molecule oligomer is removed under high-temperature vacuum.
Preferably, the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide, tetrabutyl phosphorus or
In phosphonitrilic chloride any one or at least two combination；Appointing preferably in sodium hydroxide, potassium hydroxide or lithium hydroxide
It anticipates a kind of or at least two combinations.
Preferably, the vinyl fluoride silicone oil is reacted under stirring with alkali, is carried out under protective gas protection.
Preferably, the protective gas include in nitrogen, argon gas or helium any one or at least two combination.
Preferably, the speed of the stirring be 50~600rpm, such as can be 50rpm, 100rpm, 150rpm,
250rpm, 300rpm, 400rpm, 555rpm or 600rpm etc., preferably 100~400rpm.
Preferably, the mass ratio of the vinyl fluoride silicone oil and alkali is 10~30:1, such as can be 10:1,12:1,15:
1,18:1,22:1,25:1,28:1 or 30:1 etc..
Preferably, the temperature that the vinyl fluoride silicone oil is reacted with alkali be 60~150 DEG C, such as can be 60 DEG C, 80 DEG C,
90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C or 150 DEG C etc., preferably 80~150 DEG C, more preferable 110~130 DEG C.
Preferably, the time that the vinyl fluoride silicone oil is reacted with alkali is 2~5h, such as can be 2h, 3h, 4h or 5h
Deng.
Preferably, the vinyl fluoride silicone oil carries out taking off after reaction low with alkali, and taking off low temperature is 110~160 DEG C,
Such as it can be 110 DEG C, 120 DEG C, 130 DEG C, 150 DEG C or 160 DEG C etc., preferably 130~150 DEG C.
Preferably, the vinyl fluoride silicone oil carries out taking off after reaction low with alkali, and taking off the low time is 2~5h, such as
It can be 2h, 3h, 4h or 5h etc., preferably 3~4h.
Preferably, the pressure of negative pressure is to be adjusted to negative pressure, the pressure of negative pressure after reaction for the vinyl fluoride silicone oil and alkali
Power -0.1~-0.08MPa, such as can be -0.1MPa, -0.085MPa or -0.08MPa etc., preferably -0.1MPa.
Preferably, the fluorine silicon substrate acid esters is reacted with acid by hydroxy terminated fluorosilicone oil and is prepared；Specific reaction equation is as follows:
Wherein RH is acid, and wherein the value of n is 0~10000.
Preferably, it is described acid include phosphoric acid, trifluoromethanesulfonic acid, sulfuric acid or acetic acid in any one or at least two group
It closes；Preferably phosphoric acid and/or acetic acid.
Preferably, the hydroxy terminated fluorosilicone oil is reacted under stirring with acid, is carried out under protective gas protection.
Preferably, the protective gas include in nitrogen, argon gas or helium any one or at least two combination；
Preferably, the speed of the stirring be 50~600rpm, such as can be 50rpm, 100rpm, 200rpm,
300rpm, 400rpm, 500rpm or 600rpm etc., preferably 100~400rpm.
Preferably, the hydroxy terminated fluorosilicone oil and acid mass ratio be 10~30:1, such as can be 10:1,15:1,18:1,
20:1,23:1,25:1,27:1 or 30:1 etc..
Preferably, the hydroxy terminated fluorosilicone oil is 80~120 DEG C with temperature react of acid, for example, can be 80 DEG C, 90 DEG C,
100 DEG C, 110 DEG C or 120 DEG C etc..
Preferably, the hydroxy terminated fluorosilicone oil and time for react of acid are 2~10h, for example, can be 2h, 3h, 4h, 5h, 6h,
7h, 8h, 9h or 10h etc..
Preferably, the hydroxy terminated fluorosilicone oil carries out taking off after reaction low with acid, and taking off low temperature is 110~160 DEG C, example
It such as can be 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C or 160 DEG C, preferably 130~150 DEG C.
Preferably, the hydroxy terminated fluorosilicone oil carries out taking off after reaction low with acid, and taking off the low time is 5~10h, such as can
To be 5h, 6h, 7h, 8h, 9h or 10h etc., preferably 6-8h.
Preferably, the hydroxy terminated fluorosilicone oil and acid are adjusted to negative pressure after reaction, and the pressure -0.1 of negative pressure~-
0.08MPa, such as can be -0.1MPa, -0.085MPa or -0.08MPa etc., preferably -0.1MPa.
Preferably, the purity of the trifluoro propyl methyl cyclotrisiloxane is 95%~99.9%, such as can be 95%,
96%, 97%, 98%, 99% or 99.9% etc., preferably 97%~99.5%.
Preferably, the vinyl ring body includes dimethyl siloxane mixed methylcyclosiloxane, three silicon oxygen of trimethyl triethylene basic ring
It is arbitrary a kind of in alkane, t etram-ethyltetravinylcyclotetrasiloxane；It is preferred that trimethyl trivinyl cyclotrisiloxane.
Preferably, the structural formula of vinyl fluoride silicone oil of the present invention is
Wherein the value of n is 0~10000, such as can be 0,100,1000,5000,8000 or 10000 etc., preferably 1~1000；
Further preferably 2~800.
Preferably, the structural formula of the hydroxy terminated fluorosilicone oil isWherein the value of n is 0
~10000, such as can be 0,100,1000,5000,8000 or 10000 etc., preferably 1~1000；Further preferably 2~
800。
Preferably, the trifluoro propyl methyl cyclotrisiloxane further includes individually carrying out heat preservation dehydration before reactions
Step.
Moisture influences reaction very big in reaction system of the present invention, and the moisture in raw material is to influence catalyst activity and raw rubber
One of principal element of molecular weight stability, therefore, the step of heat preservation is dehydrated is carried out before reaction can promote catalyst activity,
Promotion prepares the molecular weight stability of product.
Preferably, the temperature of the heat preservation dehydration is 50~80 DEG C, such as can be 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C etc.,
Preferably 55~70 DEG C.
Preferably, the time of the heat preservation dehydration is 1~3h, such as can be 1h, 2h or 3h etc., preferably 2h.
Preferably, the trifluoro propyl methyl cyclotrisiloxane, vinyl ring body, vinyl fluoride silicone oil, vinyl fluoride silicon
The mass ratio of alkoxide and fluorine silicon substrate acid esters is (5500~12000): (17~258): (2~13): (1~4).
In the present invention, reaction time and reaction temperature influence the molecular weight of final product and molecular weight distribution huge,
If the condition of reaction cannot be controlled, D3F is easily returned and is stung into D4F, so that required high molecular weight and molecular weight can not be obtained
The fluorine silicon raw rubber of narrowly distributing.
Preferably, the telomerisation carries out under protective gas protection.
Preferably, the protective gas include in nitrogen, argon gas or helium any one or at least two combination.
Preferably, the temperature of the telomerisation be 80~150 DEG C, such as can be 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C,
120 DEG C, 130 DEG C, 140 DEG C or 150 DEG C etc., preferably 110~130 DEG C.
Preferably, the time of the telomerisation is 1~3h, such as can be 1h, 2h or 3h etc., preferably 2h.
Preferably, the telomerisation is carried out in the case where revolving speed is the stirring of 50~500rpm, such as can be
50rpm, 100rpm, 200rpm, 300rpm, 400rpm or 500rpm etc.；It is preferred that 100~300rpm.
Preferably, the time of the neutralization reaction is 2~5h, such as can be 2h, 3h, 4h or 5h etc., preferably 3~
4h。
Preferably, after the neutralization reaction, include thing steps that heating up, it is low to take off under negative pressure state.
In the present invention, the substance of low molecular weight is sloughed, can further collect to recycle by condensing.
Preferably, heating is to be warming up to 130~170 DEG C, such as can be 130 DEG C, 140 after the neutralization reaction
DEG C, 150 DEG C or 160 DEG C etc., preferably 140~160 DEG C.
Preferably, the pressure of negative pressure is -0.1~-0.08MPa after the neutralization reaction；Preferably -0.1MPa.
Preferably, it is 2~6h that the low time is taken off after the neutralization reaction, such as can be 2h, 3h, 4h, 5h or 6h
Deng preferably 3~4h.
Preferably, the preparation method of the vinyl trifluoro propyl silica gel is the following steps are included: by trifluoro propyl methyl ring
Trisiloxanes is in reaction unit, 1~3h of heat preservation dehydration at a temperature of 50~80 DEG C, successively by second under protective gas protection
Alkenyl ring body, vinyl fluoride silicone oil and vinyl fluoride silicon alkoxide are added in reaction unit and mix, three silicon of trifluoro propyl methyl ring
Oxygen alkane, vinyl ring body, vinyl fluoride silicone oil, vinyl fluoride silicon alkoxide and fluorine silicon substrate acid esters mass ratio be (5500~
12000): (17~258): (2~13): (1~4), the telomerisation 1 in the case where revolving speed is 50~500rpm, temperature is 80~150 DEG C
~3h；Fluorine silicon substrate acid esters 2~5h of neutralization reaction is then added, is warming up to 130~170 DEG C, is -0.1~-0.08MPa in pressure；
Under take off low 2~6h, by condensation collect low molecular weight substance reuse, then cool to room temperature discharging, obtain the vinyl three
Fluoropropyl silica gel.Such as the specific reaction equation of above-mentioned reaction can be as follows:
The value that the value that wherein value of n is 0~10000, s is 6000~9000, m is 40~300.
Reaction unit of the present invention can be reaction kettle, flask etc..
Compared with the existing technology, the invention has the following advantages:
Preparation method provided by the invention, simple process, environmentally protective solvent-free and promotor pass through vinyl fluoride silicon
The synergistic effect of oil, vinyl fluoride silicon alkoxide and fluorine silicon substrate acid esters, under the premise of guaranteeing raw rubber quality, product with higher
Yield, the vinyl trifluoro propyl silica gel molecular weight being prepared reach as high as 1,300,000, and molecular weight distribution is relatively narrow, and compatibility is good
It is good, and contents of ethylene can reach 0.5%, blocks significant effect, can be used as fluorine silicon mixing collagen material, be applied to turbine
The fields such as pressure inlet, O-ring seal, application value is high, has a extensive future.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment is prepared by the following method vinyl fluoride silicon alkoxide
Vinyl fluoride silicon alkoxide: it in the four-hole boiling flask of the 250mL equipped with stirring, thermometer and reflux condensing tube, is added
90g vinyl fluoride silicone oil, 10g sodium hydroxide are warming up to 150 DEG C, -0.1MPa shape at 120 DEG C, insulation reaction 3h under nitrogen protection
Heat preservation takes off low 3h under state, collects low molecule reuse by condensation, stirs evenly, obtain vinyl silicon alkoxide.
Embodiment 2
The present embodiment is prepared by the following method fluorine silicon substrate acid esters
In the four-hole boiling flask of the 250mL equipped with stirring, thermometer and reflux condensing tube, addition 100g hydroxy terminated fluorosilicone oil,
5g phosphoric acid is warming up to 150 DEG C at 100 DEG C, insulation reaction 7h under nitrogen protection, and heat preservation takes off low 3h under -0.1MPa state, by cold
It is solidifying to collect low molecule reuse, obtain fluorine silicon substrate phosphate.
Embodiment 3
The present embodiment prepares vinyl trifluoro propyl silica gel by following steps
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F is at 50 DEG C for addition ,-
Nitrogen is replaced under heat preservation dehydration 1h, -0.1MPa under 0.1MPa, 15g vinyl ring body, 0.53g second are successively added into reaction kettle
Alkenyl fluorosilicon oil, 0.5g vinyl fluoride silicon alkoxide are stirred evenly in the case where revolving speed is 300rpm, in 110 DEG C of heat preservation telomerisation 2h,
1.2g fluorine silicon substrate phosphate is added to neutralize, reaction 3h is sufficiently stirred, is warming up to 150 DEG C, heat preservation takes off low 4h under -0.1MPa state,
Low molecule reuse is collected by condensation, discharging is then cooled to room temperature, obtains 880g vinyl trifluoro propyl silica gel.
Embodiment 4
The present embodiment prepares vinyl trifluoro propyl silica gel by following steps
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F is at 50 DEG C for addition ,-
Nitrogen is replaced under heat preservation dehydration 3h, -0.1MPa under 0.1MPa, 12g vinyl ring body, 0.53g second are successively added into reaction kettle
Alkenyl fluorosilicon oil, 0.5g vinyl fluoride silicon alkoxide are stirred evenly in the case where revolving speed is 50rpm, in 150 DEG C of heat preservation telomerisation 1h, are added
Enter the neutralization of 1.2g fluorine silicon substrate phosphate, reaction 1h is sufficiently stirred, be warming up to 170 DEG C, heat preservation takes off low 2h under -0.1MPa state, leads to
It crosses condensation and collects low molecule reuse, then cool to room temperature discharging, obtain 880g vinyl trifluoro propyl silica gel.
Embodiment 5
The present embodiment prepares vinyl trifluoro propyl silica gel by following steps
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F is at 80 DEG C for addition ,-
Nitrogen is replaced under heat preservation dehydration 1h, -0.08MPa under 0.08MPa, 9g vinyl ring body, 0.53 second are successively added into reaction kettle
Alkenyl fluorosilicon oil, 0.5g vinyl fluoride silicon alkoxide are stirred evenly in the case where revolving speed is 500rpm, in 80 DEG C of heat preservation telomerisation 5h, are added
Enter the neutralization of 1.2g fluorine silicon substrate phosphate, reaction 5h is sufficiently stirred, be warming up to 130 DEG C, heat preservation takes off low 6h under -0.08MPa state, leads to
It crosses condensation and collects low molecule reuse, then cool to room temperature discharging, obtain 880g vinyl trifluoro propyl silica gel.
Embodiment 6
The present embodiment and the difference of embodiment 4 are only that the present embodiment does not include the steps that heat preservation dehydration after D3F is added,
But directly reacted, it is specific as follows:
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F, 12g vinyl is added
Ring body, 0.53g vinyl fluoride silicone oil, 0.5g vinyl fluoride silicon alkoxide are stirred evenly in the case where revolving speed is 50rpm, are kept the temperature at 110 DEG C
Telomerisation 1.5h is added 1.2g fluorine silicon substrate phosphate and neutralizes, and reaction 1.5h is sufficiently stirred, is warming up to 160 DEG C, -0.08MPa shape
Heat preservation takes off low 3h under state, collects low molecule reuse by condensation, then cools to room temperature discharging, obtain 880g vinyl trifluoropropyl
Base silica gel.
Comparative example 1
The difference of this comparative example and embodiment 4 is only that, vinyl fluoride silicone oil is substituted for vinyl double seal head, specifically such as
Under:
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F is at 60 DEG C for addition ,-
Nitrogen is replaced under heat preservation dehydration 1.5h, -0.1MPa under 0.1MPa, 12g vinyl ring body, 0.2g second are successively added into reaction kettle
Alkenyl double-seal head, 0.5g vinyl fluoride silicon alkoxide are stirred evenly in the case where revolving speed is 40rpm, in 110 DEG C of heat preservation telomerisation 1h, are added
Enter the neutralization of 1.2g fluorine silicon substrate phosphate, reaction 3h is sufficiently stirred, be warming up to 150 DEG C, heat preservation takes off low 2h under -0.1MPa state, leads to
It crosses condensation and collects low molecule reuse, then cool to room temperature discharging, obtain 880g vinyl trifluoro propyl silica gel.
Comparative example 2
The difference of this comparative example and embodiment 4 is only that, vinyl fluoride silicon alkoxide is replaced silicon alkoxide, fluorine in this comparative example
Silicon substrate phosphate is substituted for silicon substrate phosphate, specific as follows:
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F is at 60 DEG C for addition ,-
Nitrogen is replaced under heat preservation dehydration 1.5h, -0.1MPa under 0.1MPa, 12g vinyl ring body, 0.53 second are successively added into reaction kettle
Alkenyl fluorosilicon oil, 0.5g silicon alkoxide are stirred evenly in the case where revolving speed is 40rpm, and in 110 DEG C of heat preservation telomerisation 1h, 1.5g silicon is added
Base phosphate neutralizes, and reaction 3h is sufficiently stirred, and is warming up to 150 DEG C, and heat preservation takes off low 2h under -0.1MPa state, is collected by condensation
Low molecule reuse then cools to room temperature discharging, obtains 880g vinyl trifluoro propyl silica gel.
Comparative example 3
The difference of this comparative example and embodiment 4 is only that, vinyl fluoride silicon alkoxide is replaced silicon alkoxide, second in this comparative example
Alkenyl fluorosilicon oil is substituted for vinyl double seal head, fluorine silicon substrate phosphate is substituted for silicon substrate phosphate, specific as follows:
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F is at 60 DEG C for addition ,-
Nitrogen is replaced under heat preservation dehydration 1.5h, -0.1MPa under 0.1MPa, 12g vinyl ring body, 0.2g second are successively added into reaction kettle
Alkenyl double-seal head, 0.5g silicon alkoxide are stirred evenly in the case where revolving speed is 40rpm, and in 110 DEG C of heat preservation telomerisation 1h, 1.5g silicon is added
Base phosphate neutralizes, and reaction 3h is sufficiently stirred, and is warming up to 150 DEG C, and heat preservation takes off low 4h under -0.1MPa state, is collected by condensation
Low molecule reuse then cools to room temperature discharging, obtains 880g vinyl trifluoro propyl silica gel.
Comparative example 4
The difference of this comparative example and embodiment 4 is only that the temperature of this comparative example telomerisation is 50 DEG C, specific as follows:
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F is at 50 DEG C for addition ,-
Nitrogen is replaced under heat preservation dehydration 1h, -0.1MPa under 0.1MPa, 12g vinyl ring body, 0.53g second are successively added into reaction kettle
Alkenyl fluorosilicon oil, 0.5g vinyl fluoride silicon alkoxide are stirred evenly in the case where revolving speed is 50rpm, in 50 DEG C of heat preservation telomerisation 2h, are added
Enter the neutralization of 1.2g fluorine silicon substrate phosphate, reaction 1h is sufficiently stirred, be warming up to 150 DEG C, heat preservation takes off low 4h under -0.1MPa state, leads to
It crosses condensation and collects low molecule reuse, then cool to room temperature discharging, obtain 600g vinyl trifluoro propyl silica gel.
Comparative example 5
The difference of this comparative example and embodiment 4 is only that the temperature of this comparative example telomerisation is 200 DEG C, specific as follows:
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F is at 50 DEG C for addition ,-
Nitrogen is replaced under heat preservation dehydration 2h, -0.1MPa under 0.1MPa, 12g vinyl ring body, 0.53g second are successively added into reaction kettle
Alkenyl fluorosilicon oil, 0.5g vinyl fluoride silicon alkoxide are stirred evenly in the case where revolving speed is 100rpm, in 200 DEG C of heat preservation telomerisation 1h,
1.2g fluorine silicon substrate phosphate is added to neutralize, reaction 1h is sufficiently stirred, is warming up to 160 DEG C, heat preservation takes off low 2h under -0.09MPa state,
Low molecule reuse is collected by condensation, discharging is then cooled to room temperature, obtains 780g vinyl trifluoro propyl silica gel.
Comparative example 6
The difference of this comparative example and embodiment 4 is only that the time of this comparative example telomerisation is 20min, specific as follows:
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F, 12g vinyl is added
Ring body, 0.53g vinyl fluoride silicone oil, 0.5g vinyl fluoride silicon alkoxide are stirred evenly in the case where revolving speed is 30rpm, are kept the temperature at 110 DEG C
Telomerisation 20min is added 1.2g fluorine silicon substrate phosphate and neutralizes, and reaction 1.5h is sufficiently stirred, is warming up to 160 DEG C, -0.08MPa
Heat preservation takes off low 3h under state, collects low molecule reuse by condensation, then cools to room temperature discharging, obtain 500g vinyl trifluoro
Propyl silica gel.
Comparative example 7
The difference of this comparative example and embodiment 4 is only that the time of this comparative example telomerisation is 4h, specific as follows:
In the 1L opening reaction kettle equipped with stirring, thermometer and reflux condensing tube, 936g D3F, 12g vinyl is added
Ring body, 0.53g vinyl fluoride silicone oil, 0.5g vinyl fluoride silicon alkoxide are stirred evenly in the case where revolving speed is 60rpm, are kept the temperature at 100 DEG C
Telomerisation 4h is added 1.2g fluorine silicon substrate phosphate and neutralizes, and reaction 1.5h is sufficiently stirred, is warming up to 170 DEG C, -0.08MPa state
Lower heat preservation takes off low 2h, collects low molecule reuse by condensation, then cools to room temperature discharging, obtain 800g vinyl trifluoro propyl
Silica gel.
The vinyl trifluoro propyl silica gel of embodiment 3-6 and comparative example 1-7 preparation is subjected to molecular weight and contents of ethylene
Measurement, concrete outcome is as shown in table 1 below:
Table 1
| Sample | Theoretical molecular weight | Theoretical contents of ethylene | Actual molecular weight | Practical contents of ethylene | Molecular weight distribution |
| Embodiment 3 | 60w | 0.5% | 58.9w | 0.510% | 1.46 |
| Embodiment 4 | 90w | 0.4% | 91.4w | 0.397% | 1.39 |
| Embodiment 5 | 120w | 0.3% | 128w | 0.298% | 1.43 |
| Embodiment 6 | 90w | 0.4% | 45.7w | 0.391% | 4.25 |
| Comparative example 1 | 90w | 0.4% | 115.1w | 0.265% | 3.19 |
| Comparative example 2 | 90w | 0.4% | 53.6w | 0.196% | 3.31 |
| Comparative example 3 | 90w | 0.4% | 68.4w | 0.118% | 4.87 |
| Comparative example 4 | 90w | 0.4% | 51.6w | 0.311% | 4.27 |
| Comparative example 5 | 90w | 0.4% | 58.1w | 0.382% | 6.20 |
| Comparative example 6 | 90w | 0.4% | 25.6w | 0.123% | 6.54 |
| Comparative example 7 | 90w | 0.4% | 52.1w | 0.382% | 5.38 |
By the comparison of embodiment 3-6 and comparative example 1-7 it is found that catalytic activity and compatibility divide molecular weight, molecular weight
Cloth and contents of ethylene are affected, and to obtain the raw rubber of high molecular weight and narrow molecular weight distribution, the reaction time with react
Temperature is equally critically important.The wherein meaning of the letter in table " w " representative " ten thousand ".
The Applicant declares that the preparation of the present invention is explained by the above embodiments vinyl trifluoro propyl silica gel of the invention
Method, but the invention is not limited to above-mentioned method detaileds, that is, do not mean that the present invention must rely on above-mentioned method detailed ability
Implement.It should be clear to those skilled in the art, any improvement in the present invention, to each raw material of product of the present invention etc.
Effect replacement and addition, the selection of concrete mode of auxiliary element etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of preparation method of vinyl trifluoro propyl silica gel, which is characterized in that the preparation method comprises the following steps: will
Trifluoro propyl methyl cyclotrisiloxane, vinyl ring body, vinyl fluoride silicone oil and base catalyst mix in reaction unit, telomerization
Reaction；Then be added the acid esters neutralization reaction of fluorine silicon substrate, heat up negative pressure state under take off it is low, by condensation collect low molecule reuse, so
After be cooled to room temperature discharging, obtain the vinyl trifluoro propyl silica gel.
2. preparation method according to claim 1, which is characterized in that the base catalyst is vinyl fluoride silicon alkoxide；
Preferably, the vinyl fluoride silicon alkoxide, which is reacted by vinyl fluoride silicone oil with alkali, is prepared；
Preferably, the alkali includes sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide, tetrabutyl phosphorus or chlorination
In phosphonitrile any one or at least two combination；It is preferably any one in sodium hydroxide, potassium hydroxide or lithium hydroxide
Kind or at least two combination；
Preferably, the vinyl fluoride silicone oil is reacted under stirring with alkali, is carried out under protective gas protection；
Preferably, the protective gas include in nitrogen, argon gas or helium any one or at least two combination；
Preferably, the speed of the stirring is 50~600rpm；Preferably 100~400rpm.
3. preparation method according to claim 2, which is characterized in that the mass ratio of the vinyl fluoride silicone oil and alkali is 10
~30:1；
Preferably, the temperature that the vinyl fluoride silicone oil is reacted with alkali be 60~150 DEG C, preferably 80~150 DEG C, more preferable 110
~130 DEG C；
Preferably, the time that the vinyl fluoride silicone oil is reacted with alkali is 2~5h；
Preferably, the vinyl fluoride silicone oil carries out taking off after reaction low with alkali, and taking off low temperature is 110~160 DEG C, preferably
130~150 DEG C；
Preferably, the vinyl fluoride silicone oil carries out taking off after reaction low with alkali, and taking off the low time is 2~5h；Preferably 3~
4h；
Preferably, the vinyl fluoride silicone oil and alkali are adjusted to negative pressure, pressure -0.1~-0.08MPa of negative pressure after reaction；
Preferably -0.1MPa.
4. preparation method according to claim 1, which is characterized in that the fluorine silicon substrate acid esters is anti-with acid by hydroxy terminated fluorosilicone oil
It should be prepared；
Preferably, it is described acid include phosphoric acid, trifluoromethanesulfonic acid, sulfuric acid or acetic acid in any one or at least two combination；
Preferably phosphoric acid and/or acetic acid；
Preferably, the hydroxy terminated fluorosilicone oil is reacted under stirring with acid, is carried out under protective gas protection；
Preferably, the protective gas include in nitrogen, argon gas or helium any one or at least two combination；
Preferably, the speed of the stirring is 50~600rpm；Preferably 100~400rpm.
5. the preparation method according to claim 4, which is characterized in that the hydroxy terminated fluorosilicone oil and acid mass ratio be 10~
30:1；
Preferably, the temperature that the hydroxy terminated fluorosilicone oil is reacted with acid is 80~120 DEG C；
Preferably, the time that the hydroxy terminated fluorosilicone oil is reacted with acid is 2~10h；
Preferably, the hydroxy terminated fluorosilicone oil carries out taking off after reaction low with acid, and taking off low temperature is 110~160 DEG C, preferably
130~150 DEG C；
Preferably, the hydroxy terminated fluorosilicone oil carries out taking off after reaction low with acid, and taking off the low time is 5~10h；Preferably 6~
8h；
Preferably, the hydroxy terminated fluorosilicone oil and acid are adjusted to negative pressure after reaction, and the pressure of negative pressure is -0.1~-0.08MPa；
Preferably -0.1MPa.
6. preparation method according to any one of claims 1-5, which is characterized in that three silicon of trifluoro propyl methyl ring
The purity of oxygen alkane is 95%~99.9%；Preferably 97%~99.5%；
Preferably, the vinyl ring body includes dimethyl siloxane mixed methylcyclosiloxane, trimethyl trivinyl cyclotrisiloxane, four
It is arbitrary a kind of in methyl tetravinyl cyclotetrasiloxane；It is preferred that trimethyl trivinyl cyclotrisiloxane；
Preferably, the structural formula of the vinyl fluoride silicone oil isThe wherein value of n
It is 0~10000；Preferably 1~1000；Further preferably 2~800；
Preferably, the structural formula of the hydroxy terminated fluorosilicone oil isWherein the value of n be 0~
10000；Preferably 1~1000；Further preferably 2~800.
7. preparation method according to claim 1 to 6, which is characterized in that three silicon of trifluoro propyl methyl ring
Oxygen alkane before reactions, further includes the steps that individually carrying out heat preservation dehydration；
Preferably, the temperature of the heat preservation dehydration is 50~80 DEG C；Preferably 55~70 DEG C；
Preferably, the time of the heat preservation dehydration is 1~3h；Preferably 2h.
8. preparation method described in any one of -7 according to claim 1, which is characterized in that three silicon of trifluoro propyl methyl ring
Oxygen alkane, vinyl ring body, vinyl fluoride silicone oil, vinyl fluoride silicon alkoxide and fluorine silicon substrate acid esters mass ratio be (5500~
12000): (17~258): (2~13): (1~4)；
Preferably, the telomerisation carries out under protective gas protection；
Preferably, the protective gas include in nitrogen, argon gas or helium any one or at least two combination；
Preferably, the temperature of the telomerisation is 80~150 DEG C；Preferably 110~130 DEG C；
Preferably, the time of the telomerisation is 1~3h；Preferably 2h；
Preferably, the telomerisation is carried out in the case where revolving speed is the stirring of 50~500rpm；It is preferred that 100~300rpm；
Preferably, the time of the neutralization reaction is 2~5h；Preferably 3~4h.
9. preparation method according to claim 1 to 8, which is characterized in that after the neutralization reaction, also
Including the steps that heating up, it is low to take off under negative pressure state；
Preferably, heating is to be warming up to 130~170 DEG C after the neutralization reaction；Preferably 140~160 DEG C；
Preferably, the pressure of negative pressure is -0.1~-0.08MPa after the neutralization reaction；Preferably -0.1MPa；
Preferably, it is 2~6h that the low time is taken off after the neutralization reaction；Preferably 3~4h.
10. preparation method according to claim 1 to 9, which is characterized in that the preparation method includes following
Step: by trifluoro propyl methyl cyclotrisiloxane in reaction unit, 1~3h of heat preservation dehydration, is being protected at a temperature of 50~80 DEG C
Successively vinyl ring body, vinyl fluoride silicone oil and vinyl fluoride silicon alkoxide are added in reaction unit under the gas shield of shield property and mixed
It closes, trifluoro propyl methyl cyclotrisiloxane, vinyl ring body, vinyl fluoride silicone oil, vinyl fluoride silicon alkoxide and fluorine silicon substrate acid esters
Mass ratio be (5500~12000): (17~258): (2~13): (1~4), revolving speed be 50~500rpm, temperature 80
1~3h of telomerisation at~150 DEG C；Fluorine silicon substrate acid esters 2~5h of neutralization reaction is then added, is warming up to 130~170 DEG C, is pressing
Power is -0.1~-0.08MPa；Under take off low 2~6h, by condensation collect low molecular weight substance reuse, then cool to room temperature out
Material, obtains the vinyl trifluoro propyl silica gel.
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| CN110183852A (en) * | 2019-05-20 | 2019-08-30 | 黄广展 | A kind of tear-proof silicon compounded rubber stock and preparation method thereof |
| CN111621017A (en) * | 2020-06-16 | 2020-09-04 | 湖北兴瑞硅材料有限公司 | Ternary polymerization fluorosilicone rubber and preparation method thereof |
| CN114230796A (en) * | 2021-12-17 | 2022-03-25 | 江西蓝星星火有机硅有限公司 | Raw rubber production method |
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| CN110183852A (en) * | 2019-05-20 | 2019-08-30 | 黄广展 | A kind of tear-proof silicon compounded rubber stock and preparation method thereof |
| CN111621017A (en) * | 2020-06-16 | 2020-09-04 | 湖北兴瑞硅材料有限公司 | Ternary polymerization fluorosilicone rubber and preparation method thereof |
| WO2022177332A1 (en) * | 2021-02-18 | 2022-08-25 | (주)휴넷플러스 | Photosensitive composition comprising organic metal compound and polysiloxane copolymer, and preparation method therefor |
| CN114230796A (en) * | 2021-12-17 | 2022-03-25 | 江西蓝星星火有机硅有限公司 | Raw rubber production method |
| CN115572390A (en) * | 2022-09-09 | 2023-01-06 | 新纳奇材料科技江苏有限公司 | Preparation method of phosphonitrile chloride catalyst and application of phosphonitrile chloride catalyst in preparation of vinyl-terminated polydimethylsiloxane |
| CN115430408A (en) * | 2022-09-23 | 2022-12-06 | 全椒科利德电子材料有限公司 | Preparation method and preparation system of high-purity ammonia |
| CN115772265A (en) * | 2023-02-10 | 2023-03-10 | 山东东岳有机硅材料股份有限公司 | Vinyl fluorine-containing polysiloxane and preparation method thereof |
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