CN105778100A - Organosilicon tackifier and preparation method thereof and addition type silicone rubber composition - Google Patents
Organosilicon tackifier and preparation method thereof and addition type silicone rubber composition Download PDFInfo
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- CN105778100A CN105778100A CN201410819596.8A CN201410819596A CN105778100A CN 105778100 A CN105778100 A CN 105778100A CN 201410819596 A CN201410819596 A CN 201410819596A CN 105778100 A CN105778100 A CN 105778100A
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Abstract
The invention provides an organosilicon tackifier and its preparation method. The structure of the organosilicon tackifier is as shown in the formula I or in the formula II. The invention also provides an addition type silicone rubber composition containing the organosilicon tackifier. The addition type silicone rubber composition with the application of the organosilicon tackifier has good bonding performance with a base material.
Description
Technical field
The invention belongs to silicone rubber technical field, particularly relate to a kind of organic silicon rigidity-increasing stick and preparation method thereof and the addition-type silicon rubber compositions containing this organic silicon rigidity-increasing stick.
Background technology
Addition-type silicon rubber have no coupling product in sulfidation, shrinkage factor low and can the advantage such as profound solidification, be rapidly developed in fields such as electronic devices and components, power circuitry module, large-scale surface-mounted integrated circuit, LED.
Being high saturated non-polar rubber after add-on type liquid silicon rubber sulfuration, main chain is made up of silicon atom and oxygen atom, arranges one layer of nonpolar organic group outside main chain, and molecular surface energy is low, thus the caking property of matrix material is low.Typically via primary coat or add viscosifier in LSR silicone rubber and improve the adhesive property of itself and base material.Using silane coupling agent to add production process and production time, reduce production efficiency, and the volatilization of primary coat solvent easily causes environmental pollution, therefore, adding viscosifier provides the adhesion strength at silicone rubber to be always up the study hotspot in this field.
Suitable viscosifier require good with the main component compatibility of addition-type silicon rubber, and do not affect the every Physical Mechanical after silicone rubber curing process and solidification, electrical property.At present, the preparation method of viscosifier, mainly to synthesize master, introduces various organic group in the structure of viscosifier.Specifically can be divided into following a few class: silane or the siloxane oligomer of allyl glycidyl ether and silicon hydrogen-based additive reaction are viscosifier；The siloxane oligomer of hydrosilyl group-containing and beta-diketon base is viscosifier；With the siloxane oligomer containing phenyl or ester group for viscosifier；With the polymethyl hydrogen siloxane containing phenyl for viscosifier；With Silatrane Derivatives for viscosifier；With the phenolic compound of olefin-containing base or double; two (trimethoxy silicon propyl group) fumarate and hydroxy-end capped (CH3)2SiO/CH2=CH(CH3) compound of SiO copolymer is viscosifier；With the product of trimethylolpropane diallyl, γ-glycidoxypropyltrimethoxy silane and tetraethyl orthosilicate for viscosifier.The viscosifier of these types all can increase the caking property of organosilicon and base material to a certain extent, but to there is also other not enough simultaneously, for instance preparation method is complicated, use condition harsh.Therefore, seek a kind of suitable viscosifier and become the task of top priority with the adhesive strength improving silicone rubber.
Summary of the invention
The invention solves the technical problem that and preparation method bad with rubber compatibility is complicated, use condition is harsh that the addition-type silicon rubber viscosifier adopted in prior art exist.
Specifically, the invention provides a kind of organic silicon rigidity-increasing stick, shown in the structure such as Formulas I or Formula II of described organic silicon rigidity-increasing stick:
[(R1)3SiO1/2]a[R2(R1’)SiO2/2]b[(R1’’)2SiO2/2]c[R3(R1’’’)SiO2/2]d
Formulas I
[(R1)3SiO1/2]a[R2(R1’)SiO2/2]b[(R1’’)2SiO2/2]c[R3R1’’’SiO3/2]d
Formula II
Wherein, R1, R1 ', to be each independently carbon atom be 1-8 alkyl for R1 ' ', R1 ' ' ', R2 is-CH=CH2Or H, R3 are the group containing cyclic ether；A, b, c, d are molar content, and a, b, d can not be 0, and a+b+c+d=1；And R2 is-CH=CH2Time, b≤0.2.
The preparation method that the present invention also provides for a kind of organic silicon rigidity-increasing stick, comprises the following steps:
S10, will provide for (R1)3SiO1/2The organic silicon monomer I of chain link, offer R2 (R1 ') SiO2/2The organic silicon monomer II of chain link, provide (R1 ' ')2SiO2/2The organic silicon monomer Ш of chain link, offer R3R1 ' ' ' SiO3/2Chain link or R3 (R1 ' ' ') SiO2/2The organic silicon monomer IV of chain link in proportion with organic solvent, water, catalyst mix after, be obtained by reacting the organic solution containing organo-silicon compound；
S20, the organic solution containing organo-silicon compound obtained by step S10 are washed to neutrality, and then heat up azeotropic removal of water, obtains pre-product；
In S30, removing pre-product, the silicone hydroxyl of residual, distillation of finally reducing pressure, obtain described organic silicon rigidity-increasing stick.
Finally, the invention provides a kind of addition-type silicon rubber compositions, containing organic silicon rigidity-increasing stick provided by the invention in described addition-type silicon rubber compositions.
In the present invention, by providing the organic silicon rigidity-increasing stick of a kind of new structure, it contains epoxy radicals and si-h bond or silene key, wherein epoxide group provides good caking property, and si-h bond or silene key can react with silicone rubber system, to prevent the effusion of life-time service process small molecular, it is ensured that the outward appearance of rubber and performance.Described organic silicon rigidity-increasing stick preparation method provided by the invention, first pass through cohydrolysis and prepare organo-silicon compound, reaction conversion ratio is significantly high, then pass through the free water and Bound moisture that are azeotroped off in product, finally remove the silicone hydroxyl of residual in product, molecular weight of product can be made evenly, more to clarify clearly demarcated, thus its viscosifying action is also evenly.The addition-type silicon rubber compositions adopting organic silicon rigidity-increasing stick provided by the invention has good adhesive property with base material.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the organic silicon rigidity-increasing stick S1 that embodiment 1 prepares.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of organic silicon rigidity-increasing stick, shown in the structure such as Formulas I or Formula II of described organic silicon rigidity-increasing stick:
[(R1)3SiO1/2]a[R2(R1’)SiO2/2]b[(R1’’)2SiO2/2]c[R3(R1’’’)SiO2/2]d
Formulas I
[(R1)3SiO1/2]a[R2(R1’)SiO2/2]b[(R1’’)2SiO2/2]c[R3R1’’’SiO3/2]d
Formula II
Wherein, R1, R1 ', to be each independently carbon atom be 1-8 alkyl for R1 ' ', R1 ' ' ', R2 is-CH=CH2Or H, R3 are the group containing cyclic ether；A, b, c, d are molar content, and a, b, d can not be 0, and a+b+c+d=1；And R2 is-CH=CH2Time, b≤0.2.
It is with it may be noted that, as the known general knowledge of those skilled in the art, when the structural formula of organosiloxane or silane polymer or chemical name are write, when the group laid out in parallel being joined directly together with silicon atom is write, the group drawn together with bracket, represents that it is the group being joined directly together with silicon atom；And the group that unused bracket is drawn together, then it represents that it constitutes an overall group with other group above, is then connected with silicon atom again.
Such as, in the organic silicon rigidity-increasing stick shown in Formulas I provided by the invention, it contains 4 chain links, respectively (R1)3SiO1/2Chain link, R2 (R1 ') SiO2/2Chain link, (R1 ' ')2SiO2/2Chain link and R3 (R1 ' ' ') SiO2/2Chain link.And the organic silicon rigidity-increasing stick shown in Formula II is also containing 4 links, respectively (R1)3SiO1/2Chain link, R2 (R1 ') SiO2/2Chain link, (R1 ' ')2SiO2/2Chain link and R3R1 ' ' ' SiO3/2Chain link.
Wherein, (R1)3SiO1/2Chain link is single functionality chain link, and it is end-sealed type chain link, and silicon atom therein and three R1 bases are joined directly together, and residue is then connected with oxygen atom, and its structural formula is shown in Formula Il I:
Formula III.
R2(R1’)SiO2/2Chain link is bifunctionality chain link, and wherein silicon atom is joined directly together with R2 base and R1 ' base respectively, and residue is then connected with two oxygen atoms, and its structural formula is shown in following formula I V:
Formulas I V.
(R1’’)2SiO2/2Chain link is also bifunctionality chain link, and wherein silicon atom is joined directly together with two R1 ' ' bases respectively, and residue is then connected with two oxygen atoms, and its structural formula is shown in lower Formula V:
Formula V.
R3(R1’’’)SiO2/2Chain link is also bifunctionality chain link, and wherein silicon atom is joined directly together with R3 base and R1 ' ' ' base respectively, and residue is then connected with two oxygen atoms, and its structural formula is shown in lower Formula IV:
Formula IV.
And R3R1 ' ' ' SiO3/2Chain link is then three-functionality-degree chain link, the wherein as a whole group of R3R1 ' ' ', this entirety group and silicon atom are joined directly together, and R1 ' ' ' base is directly connected with silicon atom, the remainder of silicon atom is connected with three oxygen atoms again, shown in the following Formula VII of its structural formula:
Formula VII.
As previously mentioned, in the present invention, by providing the organic silicon rigidity-increasing stick of a kind of new structure, it contains epoxy radicals and si-h bond or silene key, wherein epoxide group provides good caking property, and si-h bond or silene key can react with silicone rubber system, to prevent the effusion of life-time service process small molecular, it is ensured that the outward appearance of rubber and performance.
Specifically, aforementioned R2 (R1 ') SiO2/2R2 in chain link is-CH=CH2Or H, namely this chain link is used for providing si-h bond or silene key.Inventor is by further testing discovery, when R2 is-CH=CH2Time, b≤0.2, otherwise silene linkage content is too high can suppress curing rate.
R3(R1’’’)SiO2/2Chain link or R3R1 ' ' ' SiO3/2R3 in chain link is the group containing cyclic ether, and it is then used for providing epoxy radicals, and this chain link content in organic silicon rigidity-increasing stick meets: 0 < d < 1.Under preferable case, 0.05≤d≤0.3.
And (R1)3SiO1/2Chain link is end-sealed type chain link, and this chain link content in organic silicon rigidity-increasing stick meets: 0 < a < 1.Under preferable case, 0 < a≤0.3.
(R1’’)2SiO2/2Chain link is then for the content of Molecular regulator structure, molecular weight and wherein si-h bond or silene key, therefore (R1 ' ')2SiO2/2Chain link can contain in the organic silicon rigidity-increasing stick of the present invention, it is possible to does not contain.Accordingly, this (R1 ' ')2SiO2/2Chain link content in organic silicon rigidity-increasing stick meets: 0≤c < 1.Under preferable case, 0≤c≤0.9.
As it was previously stated, R1, R1 ', R1 ' ', R1 ' ' ' are each independently carbon atom be 1-8 alkyl, i.e. R1, R1 ', R1 ' ', R1 ' ' ' can be identical, it is also possible to different.Under preferable case, described R1, R1 ', R1 ' ', R1 ' ' ' be each independently selected from methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl, tertiary pentyl, isohesyl, cyclohexyl.
As it was previously stated, R3 is the group containing cyclic ether.Under preferable case, described R3 is glycidyl or expoxycyclohexyl.Wherein, described glycidyl is selected from any one in 2,3-epoxypropyl, 3,4-epoxy radicals butyl, 4,5-epoxypentyl, 2-glycidoxyethyl, 3-glycidoxypropyl group, 4-glycidoxy butyl, but is not limited to this.Described expoxycyclohexyl can be 2-(3,4-expoxycyclohexyl) ethyl or 3-(3,4-expoxycyclohexyl) propyl group, but is not limited to this.
The preparation method that the present invention also provides for a kind of organic silicon rigidity-increasing stick, comprises the following steps:
S10, will provide for (R1)3SiO1/2The organic silicon monomer I of chain link, offer R2 (R1 ') SiO2/2The organic silicon monomer II of chain link, provide (R1 ' ')2SiO2/2The organic silicon monomer Ш of chain link, offer R3R1 ' ' ' SiO3/2Chain link or R3 (R1 ' ' ') SiO2/2The organic silicon monomer IV of chain link in proportion with organic solvent, water, catalyst mix after, be obtained by reacting the organic solution containing organo-silicon compound；
S20, the organic solution containing organo-silicon compound obtained by step S10 are washed to neutrality, and then heat up azeotropic removal of water, obtains pre-product；
In S30, removing pre-product, the silicone hydroxyl of residual, distillation of finally reducing pressure, obtain described organic silicon rigidity-increasing stick.
Described organic silicon rigidity-increasing stick preparation method provided by the invention, first pass through cohydrolysis and prepare organo-silicon compound, reaction conversion ratio is significantly high, then pass through the free water and Bound moisture that are azeotroped off in product, finally remove the silicone hydroxyl of residual in product, molecular weight of product can be made evenly, more to clarify clearly demarcated, thus its viscosifying action is also evenly.
Wherein, described organic silicon monomer I is used for providing (R1)3SiO1/2Chain link, namely this organic silicon monomer I is monoalkoxysilane monomer.Specifically, in step S10, described organosilane monomers I can be selected from one or more in trimethylmethoxysilane, trimethylethoxysilane, triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, three n-pro-pyl methoxy silane, three n-pro-pyl Ethoxysilanes, hexamethyl disiloxane, hexaethyldisiloxane, but is not limited to this.
In step S10, described organic silicon monomer II is for providing R2 (R1 ') SiO2/2The organic silicon monomer of chain link, namely it is for providing the dialkoxy silicane monomer of silicon hydrogen-based or silylene group.
Wherein, it is provided that the organic silicon monomer of silicon hydrogen-based can be one or more in methyl dimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, ethyl diethoxy silane, but is not limited to this.
And the organic silicon monomer of silylene group is provided, in the present invention then for providing the organic silicon monomer of silico ethylene base, can be selected from methylvinyldimethoxysilane, methyl vinyl diethoxysilane, ethyl vinyl dimethoxysilane, ethyl vinyl diethoxy silane one or more, but be not limited to this.
In step S10, described organic silicon monomer Ш is for providing (R1 ' ')2SiO2/2The organic silicon monomer of chain link, it is also dialkoxy silicane monomer.This bis-alkoxysilane monomer is then used to Molecular regulator amount, Molecular regulator medium vinyl content and epoxy group content.Specifically, described organic silicon monomer III can be selected from one or more in dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, but is not limited to this.
In step S10, described organic silicon monomer IV is used for providing R3R1 ' ' ' SiO3/2Chain link or R3 (R1 ' ' ') SiO2/2Chain link, namely this organic silicon monomer is used for providing epoxide group.
Wherein, it is provided that and R3 (R1 ' ' ') SiO2/2The organic silicon monomer IV of chain link is bis-alkoxysilane monomer, its can be selected from 3-glycidoxypropyl group (methyl) dimethoxysilane, 3-glycidoxypropyl group (methyl) diethoxy silane, 3-glycidoxypropyl group (methyl) dibutoxy silane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2-(3,4-expoxycyclohexyl) hexyl (methyl) dimethoxysilane, 2-(3,4-expoxycyclohexyl) one or more in hexyl (methyl) diethoxy silane, but it is not limited to this.
And R3R1 ' ' ' SiO is provided3/2The organic silicon monomer IV of chain link is then trialkoxy silane, it can be selected from 3-glycidyl ether oxygen propyl trimethoxy silicane, 3-glycidoxypropyltrietandysilane andysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) one or more in ethyl triethoxysilane, but it is not limited to this.
According to preparation method provided by the invention, first by 4 kinds of organic silicon monomer cohydrolysis condensations, obtain organo-silicon compound.Calculating with the total mole number of the siloxy group in all organic silicon monomers, the consumption of water is its more than 1 times, it is preferred to 1-5 times.
The temperature of cohydrolysis condensation reaction can be that room temperature is to 100 DEG C, it is preferred to 50-90 DEG C.Response time can be 4-12h.
Aforementioned cohydrolysis condensation reaction carries out in the presence of a catalyst.Wherein, described catalyst is various acidic catalysts common in prior art and/or base catalyst, without adopting expensive platinum catalyst in prior art.Specifically, wherein, described acidic catalyst is selected from one or more in hydrochloric acid, sulphuric acid, acetic acid, sulfonic acid, and described base catalyst is selected from one or more in potassium hydroxide, sodium hydroxide, Lithium hydrate, ammonia, triethylamine.The consumption of catalyst is without too much, only needing it to carry out by catalytic hydrolysis reaction.Under preferable case, with the gross mass of all organic silicon monomers for benchmark, the consumption of catalyst is 0.1-10%.
As previously described, because heretofore described organic silicon rigidity-increasing stick is prepared by the hydrolysis of various organic silicon monomers, therefore reaction system is Aquo System.And the various reactive groups (such as silicone hydroxyl, epoxide group) that the hydrone in this Aquo System is easily and in organo-silicon compound form chemical bonding, it is difficult to directly remove with desiccant.Therefore, in the present invention, for the various free waters remained in removing system and Bound moisture, this reaction carries out in organic solvent, after cohydrolysis reaction completes, then can pass through organic solvent and water azeotropic, utilize high temperature azeotropic to destroy afore mentioned chemical bonding, such that it is able to the residual water in thorough removing system.
In the present invention, by various organic solvents of the prior art are carried out specific experiment, it has been found that following several organic solvents can remove the free water in system and Bound moisture: benzene,toluene,xylene, normal hexane, normal heptane.Inventor also finds by experiment, and the azeotropic point of these solvents and water is below 100 DEG C.More preferably in situation, with the gross mass of all organic silicon monomers for benchmark, the consumption of organic solvent is 50-200%.
The method according to the invention, after various organic silicon monomer cohydrolysis complete, system can be carried out intensification azeotropic removal of water, and prevent in azeotropic process other side reaction in system at high temperature to carry out, therefore reacted mixed system first need to be washed by the present invention before azeotropic, be neutral system to system.The step of washing is conventionally known to one of skill in the art, repeats no more herein.Then again this neutrality mixed system is carried out azeotropic water removing, pre-product can be obtained.
In the present invention, after various organic silicon monomer cohydrolysis, its product can remain part silicone hydroxyl.This silicone hydroxyl one side hydrone easily and in product system forms chemical bonding, cause that water in products is difficult to remove, it is susceptible to self dehydrating condensation between this silicone hydroxyl on the other hand when follow-up decompression distillation, product is made to be partially formed macromole, make molecular weight distribution extremely uneven, make the final product prepared muddy.Therefore, in the present invention before decompression distillation, the silicone hydroxyl of residual in pre-product can be removed in advance.In the present invention, inventor have found that, organochlorosilane can react with silicone hydroxyl and generate HCl, thus removing silicone hydroxyl, thereby may be ensured that molecular weight of product more uniformly spreads, the viscosifying action of silicone rubber is also more uniformly distributed；Therefore, in the present invention, the raw material adopted except silicone hydroxyl preferably employs organochlorosilane.And organochlorosilane is very sensitive to steam, also can react with water, cause that the efficiency removing silicone hydroxyl can be substantially reduced.Therefore adopt organochlorosilane as in the present invention except the raw material of silicone hydroxyl, the water content in product system in the present invention is proposed requirements at the higher level so that except the azeotropic water removing step before silicone hydroxyl even more important.
In the present invention, described organochlorosilane can be the organochlorosilane containing si-h bond, silene key or silane capital construction, to ensure that the pre-product that itself and step S20 obtain can have good dispersibility.Specifically, when described organochlorosilane end-capping reagent contains si-h bond, it can be selected from dimethylchlorosilane and/or diethyl chlorosilane.And when described organochlorosilane end-capping reagent contains silene base key, it can be selected from dimethyl vinyl chlorosilane and/or diethyl vinyl chlorosilane.When described organochlorosilane end-capping reagent contains silane base key, it can be selected from trim,ethylchlorosilane and/or chlorotriethyl silane.
In the present invention, described organochlorosilane is only used for away in pre-product the part silicone hydroxyl of residual, and therefore its content is without too high, will not the structure of final organic silicon rigidity-increasing stick and molecular weight be impacted.Under preferable case, with the gross mass of all organic silicon monomers for benchmark, the consumption of organochlorosilane is 0.1-0.5%.
After removing the silicone hydroxyl in pre-product by above-mentioned steps, system can be carried out decompression distillation and process, finally give the organic silicon rigidity-increasing stick of clear.The step of described decompression distillation is decompression distilation steps common in prior art, is not particularly limited, repeats no more herein in the present invention.
Organic silicon rigidity-increasing stick provided by the invention, its adhesive property that can be used for improving silicone rubber and base material in silicone rubber.Therefore, the present invention finally provides a kind of addition-type silicon rubber compositions, namely contains organic silicon rigidity-increasing stick provided by the invention in described addition-type silicon rubber compositions.The addition-type silicon rubber compositions adopting organic silicon rigidity-increasing stick provided by the invention has good adhesive property with base material.
Described addition-type silicon rubber is conventionally known to one of skill in the art, is generally mixed according to a certain percentage by components such as the siloxanes containing vinyl, hydrogeneous siloxanes, catalyst and inhibitor, is not particularly limited in the present invention.
Addition-type silicon rubber compositions provided by the invention, uniquely the difference is that only with silicone rubber of the prior art, wherein contains organic silicon rigidity-increasing stick provided by the invention.Under preferable case, with the gross mass of described addition-type silicon rubber compositions for benchmark, wherein, the content of organic silicon rigidity-increasing stick is 0.5-2.5%.
Below in conjunction with embodiment, the present invention done specific explanations explanation.In embodiment and comparative example, adopted raw material is each through being commercially available, and the present invention is not particularly limited.
Embodiment 1
The present embodiment is used for organic silicon rigidity-increasing stick A1 and addition-type silicon rubber compositions B1 provided by the invention is described.
Take 13.4g methyldiethoxysilane (M=134, n=0.2mol) as organic silicon monomer II, 38.4g triethyl group methoxy silane (M=160, n=0.24mol) as organic silicon monomer I, 61.36g3-glycidyl ether oxygen propyl trimethoxy silicane (M=236, n=0.26mol) as organic silicon monomer IV, 56.4g di-n-butyl dimethoxysilane (M=188, n=0.3mol) as organic silicon monomer III.
Above 4 kinds of organic silicon monomers and 140g dimethylbenzene, 100g aqueous acetic acid (acetic acid content 8.5%) will mix, be warming up to 60 DEG C of reaction 8h.After reaction terminates, with separatory funnel separating dimethyl benzene solution, wash with water until neutral；Again water washed xylene solution is warming up to 100 DEG C of azeotropic until system water is except clean, add 0.42g dimethylchlorosilane stirring 1h again, then heat to 150 DEG C of decompression distillations, boil off dimethylbenzene and low-boiling-point substance, obtain the organic silicon rigidity-increasing stick of the hydrosilyl group-containing of the present embodiment of clear, being designated as A1, its structural formula is
。
The dimethyl polysiloxane of the vinyldimethylsiloxane end-blocking with 0.15mmol/g contents of ethylene of 100g is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, add the inhibitor of 0.63g aforementioned organic silicon viscosifier A1,0.1g, 0.2g platinum catalyst again, stirring makes mix homogeneously, obtain the addition-type silicon rubber compositions of the present embodiment, be designated as B1.
Embodiment 2
The present embodiment is used for organic silicon rigidity-increasing stick A2 and addition-type silicon rubber compositions B2 provided by the invention is described.
Take 13.2g methylvinyldimethoxysilane (M=132, n=0.1mol) as organic silicon monomer II, 16.2g hexamethyl disiloxane (M=162, n=0.1mol) as organic silicon monomer I, 22g3-glycidoxypropyl group (methyl) dimethoxysilane (M=220, n=0.1mol) as organic silicon monomer IV, 90g dimethyldiethoxysilane (M=148, n=0.6mol) as organic silicon monomer III.
Above 4 kinds of organic silicon monomers and 77g toluene, 60g hydrochloric acid (HCl content 25%) will mix, be warming up to 90 DEG C of reaction 4h.Reaction isolates toluene solution with separatory funnel after terminating, and washes with water until neutral；Again water washed toluene solution is warming up to 100 DEG C of azeotropic until system water is except clean, add 0.16g dimethyl vinyl chlorosilane stirring 1h again, then heat to 150 DEG C of decompression distillations, boil off toluene and low-boiling-point substance, obtain the organic silicon rigidity-increasing stick of the siliceous vinyl of the present embodiment of clear, being designated as A2, its structural formula is
。
The dimethyl polysiloxane of the vinyldimethylsiloxane end-blocking with 0.15mmol/g contents of ethylene of 100g is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, add the inhibitor of 1.575g aforementioned organic silicon viscosifier A2,0.1g, 0.2g platinum catalyst again, stirring makes mix homogeneously, obtain the addition-type silicon rubber compositions of the present embodiment, be designated as B2.
Embodiment 3
The present embodiment is used for organic silicon rigidity-increasing stick A3 and addition-type silicon rubber compositions B3 provided by the invention is described.
Take 16g methyl vinyl diethoxysilane (M=160, n=0.1mol) as organic silicon monomer II, 4.72g trimethylethoxysilane (M=118, n=0.04mol) as organic silicon monomer I, 14.4g2-(3,4-epoxycyclohexyl) ethyl triethoxysilane (M=288, n=0.05mol) as organic silicon monomer IV, 119.88g dimethyldiethoxysilane (M=148, n=0.81mol) as organic silicon monomer III.
Above 4 kinds of organic silicon monomers and 300g normal hexane, 180g sodium hydrate aqueous solution (sodium hydrate content 0.17%) will mix, be warming up to 30 DEG C of reaction 12h.Reaction isolates hexane solution with separatory funnel after terminating, and washes with water until neutral；Again water washed hexane solution is warming up to 100 DEG C of azeotropic until system water is except clean, add 0.83g trim,ethylchlorosilane stirring 1h again, then heat to 150 DEG C of decompression distillations, boil off normal hexane and low-boiling-point substance, obtain the organic silicon rigidity-increasing stick of the siliceous vinyl of the present embodiment of clear, being designated as A3, its structural formula is
。
The dimethyl polysiloxane of the vinyldimethylsiloxane end-blocking with 0.15mmol/g contents of ethylene of 100g is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, add the inhibitor of 2.625g aforementioned organic silicon viscosifier A3,0.1g, 0.2g platinum catalyst again, stirring makes mix homogeneously, obtain the addition-type silicon rubber compositions of the present embodiment, be designated as B3.
Embodiment 4
The present embodiment is used for organic silicon rigidity-increasing stick A4 and addition-type silicon rubber compositions B6 provided by the invention is described.
Take 80.4g methyldiethoxysilane (M=134, n=0.6mol) as organic silicon monomer II, 31.2g trimethylmethoxysilane (M=104, n=0.3mol) as organic silicon monomer I, 23.6g3-glycidyl ether oxygen propyl trimethoxy silicane (M=236, n=0.1mol) as organic silicon monomer IV.
Above 3 kinds of organic silicon monomers and 140g normal heptane, 90g aqueous sulfuric acid (sulfuric acid content 1.5%) will mix, be warming up to 60 DEG C of reaction 8h.Reaction isolates n-heptane solution with separatory funnel after terminating, and washes with water until neutral；Again water washed n-heptane solution is warming up to 100 DEG C of azeotropic until system water is except clean, add 0.3g dimethylchlorosilane stirring 1h again, then heat to 150 DEG C of decompression distillations, boil off normal heptane and low-boiling-point substance, obtain the organic silicon rigidity-increasing stick of the hydrosilyl group-containing of the present embodiment of clear, being designated as A4, its structural formula is
。
The dimethyl polysiloxane of the vinyldimethylsiloxane end-blocking with 0.15mmol/g contents of ethylene of 100g is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, add the inhibitor of 1.05g aforementioned organic silicon viscosifier A4,0.1g, 0.2g platinum catalyst again, stirring makes mix homogeneously, obtain the addition-type silicon rubber compositions of the present embodiment, be designated as B4.
Comparative example 1
This comparative example is for illustrating not contain the addition-type silicon rubber compositions DB1 of organic silicon rigidity-increasing stick provided by the invention.
The dimethyl polysiloxane of the vinyldimethylsiloxane end-blocking with 0.15mmol/g contents of ethylene of 100g is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, add the inhibitor of 0.1g, 0.2g platinum catalyst again, stirring makes mix homogeneously, obtain the addition-type silicon rubber compositions of this comparative example, be designated as DB1.
Comparative example 2
This comparative example is used for organic silicon rigidity-increasing stick DA2 and the addition-type silicon rubber compositions DB2 that non-invention provides is described.
Take 16.2g hexamethyl disiloxane (M=162, n=0.1mol) as organic silicon monomer I, 66g3-glycidoxypropyl group (methyl) dimethoxysilane (M=220, n=0.3mol) as organic silicon monomer IV, 133.2g dimethyldiethoxysilane (M=148, n=0.5mol) as organic silicon monomer III.
Above 3 kinds of organic silicon monomers and 77g toluene, 60g hydrochloric acid (HCl content 35%) will mix, be warming up to 90 DEG C of reaction 4h.Reaction isolates toluene solution with separatory funnel after terminating, and washes with water until neutral；Again water washed toluene solution is warming up to 100 DEG C of azeotropic until system water is except clean, then adds 0.22g trim,ethylchlorosilane stirring 1h, then heat to 150 DEG C of decompression distillations, boil off toluene and low-boiling-point substance, obtaining the organic silicon rigidity-increasing stick of the present embodiment of clear, be designated as DA2, its structural formula is
。
The dimethyl polysiloxane of the vinyldimethylsiloxane end-blocking with 0.15mmol/g contents of ethylene of 100g is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, add the inhibitor of 1.575g aforementioned organic silicon viscosifier DA2,0.1g, 0.2g platinum catalyst again, stirring makes mix homogeneously, obtain the addition-type silicon rubber compositions of the present embodiment, be designated as DB2.
Comparative example 3
This comparative example is used for organic silicon rigidity-increasing stick DA3 and the addition-type silicon rubber compositions DB3 that non-invention provides is described.
Take 16g methyl vinyl diethoxysilane (M=160, n=0.1mol) as organic silicon monomer II, 16.2g hexamethyl disiloxane (M=162, n=0.1mol) as organic silicon monomer I, 103.6g dimethyldiethoxysilane (M=148, n=0.7mol) as organic silicon monomer III.
Above 3 kinds of organic silicon monomers and 77g toluene, 55g sulphuric acid (sulfuric acid content 2.5%) will mix, be warming up to 60 DEG C of reaction 4h.Reaction isolates toluene solution with separatory funnel after terminating, and washes with water until neutral；Again water washed toluene solution is warming up to 100 DEG C of azeotropic until system water is except clean, add 0.27g trim,ethylchlorosilane stirring 1h again, then heat to 150 DEG C of decompression distillations, boil off toluene and low-boiling-point substance, obtain the organic silicon rigidity-increasing stick of the siliceous vinyl of the present embodiment of clear, being designated as DA3, its structural formula is
。
The dimethyl polysiloxane of the vinyldimethylsiloxane end-blocking with 0.15mmol/g contents of ethylene of 100g is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, add the inhibitor of 1.575g aforementioned organic silicon viscosifier DA3,0.1g, 0.2g platinum catalyst again, stirring makes mix homogeneously, obtain the addition-type silicon rubber compositions of the present embodiment, be designated as DB3.
Performance test
(1) examination of infrared spectrum
The organic silicon rigidity-increasing stick S1 that embodiment 1 is prepared carries out examination of infrared spectrum, as shown in Figure 1.
As shown in Figure 1,2154cm-1Place is the characteristic absorption peak of Si--H bond.It follows that there is also Si--H bond in the product.909cm-1Place is the characteristic absorption peak of epoxide group, it follows that there is also epoxide group in product.
(2) adhesive property test
The shear strength after each rubber composition solidifies is tested according to GB/T13936-92 " vulcanite and metal bonding tensile shear strength assay method ".Test condition: heat cure 1h at 100 DEG C.
Test result is as shown in table 1 below.
Table 1
。
Can be seen that from the test result of upper table 1, owing to correspondence respectively have employed organic silicon rigidity-increasing stick A1-A4 provided by the invention in addition-type silicon rubber compositions B1-B4 provided by the invention, shear strength after its solidification is more than 1MPa, it is substantially better than the silicone rubber sample DB1-DB3 of comparative example 1-3, namely illustrate that addition-type silicon rubber compositions provided by the invention is owing to have employed the organic silicon rigidity-increasing stick of new structure provided by the invention so that itself and base material have good adhesive property.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (17)
1. an organic silicon rigidity-increasing stick, it is characterised in that shown in the structure such as Formulas I or Formula II of described organic silicon rigidity-increasing stick:
[(R1)3SiO1/2]a[R2(R1’)SiO2/2]b[(R1’’)2SiO2/2]c[R3(R1’’’)SiO2/2]d
Formulas I
[(R1)3SiO1/2]a[R2(R1’)SiO2/2]b[(R1’’)2SiO2/2]c[R3R1’’’SiO3/2]d
Formula II
Wherein, R1, R1 ', to be each independently carbon atom be 1-8 alkyl for R1 ' ', R1 ' ' ', R2 is-CH=CH2Or H, R3 are the group containing cyclic ether；A, b, c, d are molar content, and a, b, d can not be 0, and a+b+c+d=1；And R2 is-CH=CH2Time, b≤0.2.
2. organic silicon rigidity-increasing stick according to claim 1, it is characterised in that 0 < a≤0.3,0≤c≤0.9,0.05≤d≤0.3.
3. organic silicon rigidity-increasing stick according to claim 1, it is characterized in that, described R1, R1 ', R1 ' ', R1 ' ' ' be each independently selected from methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl, tertiary pentyl, isohesyl, cyclohexyl.
4. organic silicon rigidity-increasing stick according to claim 1, it is characterised in that described R3 is glycidyl or expoxycyclohexyl；
Wherein, described glycidyl is selected from any one in 2,3-epoxypropyl, 3,4-epoxy radicals butyl, 4,5-epoxypentyl, 2-glycidoxyethyl, 3-glycidoxypropyl group, 4-glycidoxy butyl；
Described expoxycyclohexyl can be 2-(3,4-expoxycyclohexyl) ethyl or 3-(3,4-expoxycyclohexyl) propyl group.
5. the preparation method of the organic silicon rigidity-increasing stick described in claim 1, it is characterised in that comprise the following steps:
S10, will provide for (R1)3SiO1/2The organic silicon monomer I of chain link, offer R2 (R1 ') SiO2/2The organic silicon monomer II of chain link, provide (R1 ' ')2SiO2/2The organic silicon monomer Ш of chain link, offer R3R1 ' ' ' SiO3/2Chain link or R3 (R1 ' ' ') SiO2/2The organic silicon monomer IV of chain link in proportion with organic solvent, water, catalyst mix after, be obtained by reacting the organic solution containing organo-silicon compound；
S20, the organic solution containing organo-silicon compound obtained by step S10 are washed to neutrality, and then heat up azeotropic removal of water, obtains pre-product；
In S30, removing pre-product, the silicone hydroxyl of residual, distillation of finally reducing pressure, obtain described organic silicon rigidity-increasing stick.
6. preparation method according to claim 5, it is characterized in that, in step S10, described organic silicon monomer I is selected from one or more in trimethylmethoxysilane, trimethylethoxysilane, triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, three n-pro-pyl methoxy silane, three n-pro-pyl Ethoxysilanes, hexamethyl disiloxane, hexaethyldisiloxane.
7. preparation method according to claim 5, it is characterised in that in step S10, described organic silicon monomer II is for providing the organic silicon monomer of silicon hydrogen-based or silylene group；
Wherein, it is provided that the organic silicon monomer of silicon hydrogen-based is selected from one or more in methyl dimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, ethyl diethoxy silane；
The organic silicon monomer providing silylene group is selected from one or more in methylvinyldimethoxysilane, methyl vinyl diethoxysilane, ethyl vinyl dimethoxysilane, ethyl vinyl diethoxy silane.
8. preparation method according to claim 5, it is characterized in that, in step S10, described organic silicon monomer III is selected from one or more in dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane.
9. preparation method according to claim 5, it is characterised in that in step S10, it is provided that and R3 (R1 ' ' ') SiO2/2The organic silicon monomer IV of chain link selected from 3-glycidoxypropyl group (methyl) dimethoxysilane, 3-glycidoxypropyl group (methyl) diethoxy silane, 3-glycidoxypropyl group (methyl) dibutoxy silane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2-(3,4-expoxycyclohexyl) hexyl (methyl) dimethoxysilane, 2-(3,4-expoxycyclohexyl) one or more in hexyl (methyl) diethoxy silane；
R3R1SiO is provided3/2The organic silicon monomer IV of chain link is selected from 3-glycidyl ether oxygen propyl trimethoxy silicane, 3-glycidoxypropyltrietandysilane andysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) one or more in ethyl triethoxysilane.
10. preparation method according to claim 5, it is characterised in that in step S10, described organic solvent selected from benzene,toluene,xylene, normal hexane, normal heptane any one；
With the gross mass of all organic silicon monomers for benchmark, the consumption of organic solvent is 50-200%.
11. preparation method according to claim 5, it is characterised in that in step S10, calculating with the total mole number of the siloxy group in all organic silicon monomers, the consumption of water is its 1-5 times.
12. preparation method according to claim 5, it is characterised in that in step S10, described catalyst is acidic catalyst and/or base catalyst；Wherein, described acidic catalyst is selected from one or more in hydrochloric acid, sulphuric acid, acetic acid, sulfonic acid, and described base catalyst is selected from one or more in potassium hydroxide, sodium hydroxide, Lithium hydrate, ammonia, triethylamine；
With the gross mass of all organic silicon monomers for benchmark, the consumption of catalyst is 0.1-10%.
13. preparation method according to claim 5, it is characterised in that in step S10, reaction temperature be room temperature to 100 DEG C, the response time is 4-12h.
14. preparation method according to claim 5, it is characterised in that in step S30, removing the raw material that in pre-product, the silicone hydroxyl of residual adopts is organochlorosilane；And at least one that described organochlorosilane is in dimethylchlorosilane, diethyl chlorosilane, dimethyl vinyl chlorosilane, diethyl vinyl chlorosilane, trim,ethylchlorosilane, chlorotriethyl silane.
15. preparation method according to claim 14, it is characterised in that with the gross mass of all organic silicon monomers for benchmark, the consumption of organochlorosilane is 0.1-0.5%.
16. an addition-type silicon rubber compositions, it is characterised in that containing the organic silicon rigidity-increasing stick described in any one of claim 1-4 in described addition-type silicon rubber compositions.
17. addition-type silicon rubber compositions according to claim 16, it is characterised in that with the gross mass of described addition-type silicon rubber compositions for benchmark, wherein, the content of organic silicon rigidity-increasing stick is 0.5-2.5%.
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