CN105778100B - A kind of organic silicon rigidity-increasing stick and preparation method thereof and a kind of addition-type silicon rubber composition - Google Patents
A kind of organic silicon rigidity-increasing stick and preparation method thereof and a kind of addition-type silicon rubber composition Download PDFInfo
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Abstract
The present invention provides a kind of organic silicon rigidity-increasing stick and preparation method thereof, the structure of the organic silicon rigidity-increasing stick is as shown in Formulas I or Formula II.The present invention also provides the addition-type silicon rubber compositions containing the organic silicon rigidity-increasing stick.There is good adhesive property using the addition-type silicon rubber composition and substrate of organic silicon rigidity-increasing stick provided by the invention.
Description
Technical field
The invention belongs to silicon rubber technical field more particularly to a kind of organic silicon rigidity-increasing stick and preparation method thereof and contain this
The addition-type silicon rubber composition of organic silicon rigidity-increasing stick.
Background technique
Addition-type silicon rubber has many advantages, such as that no coupling product in sulfidation, shrinking percentage are low and profound can solidify,
The fields such as electronic component, power circuitry module, large-scale integrated circuit board, LED are rapidly developed.
It is the non-polar rubber of high saturation after add-on type liquid silicon rubber vulcanization, main chain is made of silicon atom and oxygen atom,
One layer of nonpolar organic group is arranged on the outside of main chain, molecular surface energy is low, thus low to the caking property of basis material.Generally
Tackifier are added by primary coat or in LSR silicon rubber to improve its adhesive property with substrate.Life is increased using silane coupling agent
Process and production time are produced, production efficiency is reduced, and the volatilization of primary coat solvent easily causes environmental pollution, therefore, adds tackifier
Offer is in the research hotspot that the adhesion strength of silicon rubber is always the field.
It is good with the main component compatibility of addition-type silicon rubber that suitable tackifier are required, and does not influence silicon rubber solidification work
Skill and every Physical Mechanical after solidifying, electrical property.Currently, the preparation method of tackifier mainly with synthesis based on, viscosifying
Various organic groups are introduced in the structure of agent.Following a few classes: allyl glycidyl ether and the addition of silicon hydrogen-based can be specifically divided into
The silane or siloxane oligomer of reaction are tackifier；The siloxane oligomer of hydrosilyl group-containing and beta-diketon base is tackifier；With
Siloxane oligomer containing phenyl or ester group is tackifier；Using the polymethyl hydrogen siloxane containing phenyl as tackifier；With miscellaneous nitrogen silicon
Tricyclic derivatives are tackifier；With the phenolic compound of olefin-containing base or bis- (trimethoxy silicon propyl) fumarates with it is hydroxy-end capped
(CH3)2SiO/CH2=CH(CH3) SiO copolymer compound be tackifier；With trimethylolpropane diallyl, γ-ring
The reaction product of the third oxygen propyl trimethoxy silicane of oxygen and ethyl orthosilicate is tackifier.The tackifier of these types are in certain journey
The caking property of organosilicon and substrate can be increased on degree, but simultaneously there is also other deficiencies, for example, preparation method it is complicated, use item
Part harshness etc..Therefore, seek a kind of suitable tackifier to improve the adhesive strength of silicon rubber and become the task of top priority.
Summary of the invention
The present invention solves existing for the addition-type silicon rubber tackifier used in the prior art and rubber compatibility
Bad and preparation method complexity, the technical problem of use condition harshness.
Specifically, the present invention provides a kind of organic silicon rigidity-increasing stick, the structure such as Formulas I or Formula II of the organic silicon rigidity-increasing stick
It is shown:
[(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 by R1 ' ', R1 ' ' ', R2 is-CH=CH2Or H, R3
For the group containing cyclic ether；A, b, c, d are molar content, and a, b, d cannot be 0, and a+b+c+d=1；And R2 is-CH=CH2When,
b≤0.2。
The present invention also provides a kind of preparation methods of organic silicon rigidity-increasing stick, comprising the following steps:
S10, (R1) will be provided3SiO1/2The organic silicon monomer I of chain link, R2 (R1 ') SiO is provided2/2The organosilicon list of chain link
Body II, (R1 ' ') is provided2SiO2/2The organic silicon monomer Ш of chain link, R3R1 ' ' ' SiO is provided3/2Chain link or R3 (R1 ' ' ') SiO2/2
After the organic silicon monomer IV of chain link is mixed with organic solvent, water, catalyst in proportion, reaction is obtained containing organo-silicon compound
Organic solution；
S20, the organic solution containing organo-silicon compound for obtaining step S10 are washed to neutrality, and then heat up azeotropic
Water is removed, pre-product is obtained；
S30, remaining silicone hydroxyl in pre-product is removed, is finally evaporated under reduced pressure, obtains the organic silicon rigidity-increasing stick.
Finally, containing in the addition-type silicon rubber composition the present invention provides a kind of addition-type silicon rubber composition
Organic silicon rigidity-increasing stick provided by the invention.
In the present invention, by providing a kind of new structural organic silicon rigidity-increasing stick, contain epoxy group and si-h bond or silicon
Ethylene linkage, epoxide epoxy group group provides good caking property, and si-h bond or silene key can be reacted with silicon rubber system, to prevent
The evolution of long-term use process small molecular guarantees the appearance and performance of rubber.The organic silicon rigidity-increasing stick provided by the invention
Preparation method first passes through cohydrolysis and prepares organo-silicon compound, and reaction conversion ratio is very high, then by being azeotroped off in product
Free water and combine water, finally remove remaining silicone hydroxyl in product, can make molecular weight of product more evenly, more clarification it is clearly demarcated,
Also more evenly to its tackifying effect.Using the addition-type silicon rubber composition and substrate of organic silicon rigidity-increasing stick provided by the invention
With good adhesive property.
Detailed description of the invention
Fig. 1 is the infrared spectrogram for the organic silicon rigidity-increasing stick S1 that embodiment 1 is prepared.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
The present invention provides a kind of organic silicon rigidity-increasing stick, the structure of the organic silicon rigidity-increasing stick is as shown in Formulas I or Formula II:
[(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 by R1 ' ', R1 ' ' ', R2 is-CH=CH2Or H, R3
For the group containing cyclic ether；A, b, c, d are molar content, and a, b, d cannot be 0, and a+b+c+d=1；And R2 is-CH=CH2When,
b≤0.2。
It may be noted that ground is, as the common knowledge of those skilled in the art, in organosiloxane or silane polymer
When structural formula or chemical name are write, when the group laid out in parallel being connected directly with silicon atom is write, the group included with bracket,
Indicate that it is the group being connected directly with silicon atom；And the group that unused bracket includes, then it represents that other groups of itself and front
The group for constituting an entirety, is then connected with silicon atom again.
For example, containing 4 chain links, respectively (R1) in organic silicon rigidity-increasing stick shown in Formulas I provided by the invention3SiO1/2Chain link, R2 (R1 ') SiO2/2Chain link, (R1 ' ')2SiO2/2Chain link and R3 (R1 ' ' ') SiO2/2Chain link.And shown in Formula II
Organic silicon rigidity-increasing stick is also to link containing 4, respectively (R1)3SiO1/2Chain link, R2 (R1 ') SiO2/2Chain link, (R1 ' ')2SiO2/2
Chain link and R3R1 ' ' ' SiO3/2Chain link.
Wherein, (R1)3SiO1/2Chain link is single functionality chain link, is end-sealed type chain link, silicon atom therein and three R1
Base is connected directly, remaining then be connected with oxygen atom, and structural formula is shown in Formula Il I:
Formula III.
R2(R1’)SiO2/2Chain link is bifunctionality chain link, and wherein silicon atom is connected directly with R2 base and R1 ' base respectively, is remained
Yu Ze is connected with two oxygen atoms, and structural formula is shown in following formula I V:
Formula IV.
(R1’’)2SiO2/2Chain link is also bifunctionality chain link, and wherein silicon atom is connected directly with two R1 ' ' bases respectively,
Remaining then be connected with two oxygen atoms, 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 direct with R3 base and R1 ' ' ' base respectively
It is connected, remaining then be connected with two oxygen atoms, structural formula is shown in lower Formula IV:
Formula IV.
And R3R1 ' ' ' SiO3/2Chain link is then three-functionality-degree chain link, and wherein R3R1 ' ' ' is a whole group, the entirety base
Group is connected directly with silicon atom, and R1 ' ' ' base is directly connected with silicon atom, the remainder of silicon atom again with three oxygen atom phases
Even, shown in the following Formula VII of structural formula:
Formula VII.
As previously mentioned, by providing a kind of new structural organic silicon rigidity-increasing stick, containing epoxy group and silicon in the present invention
Hydrogen bond or silene key, epoxide epoxy group group provides good caking property, and si-h bond or silene key can be anti-with silicon rubber system
It answers, to prevent the evolution of long-term use process small molecular, guarantees the appearance and performance of rubber.
Specifically, aforementioned R2 (R1 ') SiO2/2R2 in chain link is-CH=CH2Or H, i.e., the chain link is for providing si-h bond
Or silene key.Inventor is by further experiment discovery, when R2 is-CH=CH2When, b≤0.2, otherwise silene linkage content is too high
It can inhibit curing rate.
R3(R1’’’)SiO2/2Chain link or R3R1 ' ' ' SiO3/2R3 in chain link is the group containing cyclic ether, then is used to mention
For epoxy group, content of the chain link 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 content of the chain link in organic silicon rigidity-increasing stick meets: 0 < a < 1.
Under preferable case, 0 < a≤0.3.
(R1’’)2SiO2/2Chain link is then used to adjust molecular structure, molecular weight and wherein si-h bond or silene key contain
Amount, therefore (R1 ' ')2SiO2/2Chain link can contain in organic silicon rigidity-increasing stick of the invention, and can be free of has.Accordingly, this
(R1’’)2SiO2/2Content of the chain link in organic silicon rigidity-increasing stick meets: 0≤c < 1.Under preferable case, 0≤c≤0.9.
As previously mentioned, R1, R1 ', R1 ' ', R1 ' ' ' be each independently carbon atom be 1-8 alkyl, i.e. R1, R1 ',
R1 ' ', R1 ' ' ' may be the same or different.Under preferable case, described R1, R1 ', R1 ' ', R1 ' ' ' select each independently
From methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, isobutyl group, sec-butyl, uncle
Butyl, isopentyl, neopentyl, tertiary pentyl, isohesyl, cyclohexyl.
As previously mentioned, R3 is the group containing cyclic ether.Under preferable case, the R3 is glycidyl or epoxycyclohexyethylSiOi
Base.Wherein, the glycidyl is selected from 2,3- epoxypropyl, 3,4- epoxy group butyl, 4,5- epoxypentyl, 2- epoxy
Among, 3- glycidoxypropyl group, any one in 4- glycidoxy butyl, but not limited to this.The ring
Oxygroup cyclohexyl can be 2- (3,4- expoxycyclohexyl) ethyl or 3- (3,4- expoxycyclohexyl) propyl, but be not limited to
This.
The present invention also provides a kind of preparation methods of organic silicon rigidity-increasing stick, comprising the following steps:
S10, (R1) will be provided3SiO1/2The organic silicon monomer I of chain link, R2 (R1 ') SiO is provided2/2The organosilicon list of chain link
Body II, (R1 ' ') is provided2SiO2/2The organic silicon monomer Ш of chain link, R3R1 ' ' ' SiO is provided3/2Chain link or R3 (R1 ' ' ') SiO2/2
After the organic silicon monomer IV of chain link is mixed with organic solvent, water, catalyst in proportion, reaction is obtained containing organo-silicon compound
Organic solution；
S20, the organic solution containing organo-silicon compound for obtaining step S10 are washed to neutrality, and then heat up azeotropic
Water is removed, pre-product is obtained；
S30, remaining silicone hydroxyl in pre-product is removed, is finally evaporated under reduced pressure, obtains the organic silicon rigidity-increasing stick.
The organic silicon rigidity-increasing stick preparation method provided by the invention, first passes through cohydrolysis and prepares organo-silicon compound, instead
It answers conversion ratio very high, then by the free water that is azeotroped off in product and combines water, finally remove remaining silicon hydroxyl in product
Base, can make molecular weight of product more evenly, more clarification it is clearly demarcated, so that its tackifying effect is also more evenly.
Wherein, the organic silicon monomer I is for providing (R1)3SiO1/2Chain link, i.e. organic silicon monomer I are monoalkoxy
Silane monomer.Specifically, in step S10, the organosilane monomers I can be selected from trimethylmethoxysilane, trimethyl second
Oxysilane, triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, three n-propyl methoxy silanes, three n-propyl ethyoxyls
One of silane, hexamethyldisiloxane, hexaethyldisiloxane are a variety of, but not limited to this.
In step S10, the organic silicon monomer II is to provide R2 (R1 ') SiO2/2The organic silicon monomer of chain link, i.e., it is to mention
For silicon hydrogen-based or the dialkoxy silicane monomer of silylene group.
Wherein, the organic silicon monomer for providing silicon hydrogen-based can be methyl dimethoxysilane, methyldiethoxysilane, second
One of base dimethoxysilane, ethyl diethoxy silane are a variety of, but not limited to this.
And the organic silicon monomer of silylene group is provided, it, can be in the present invention then to provide the organic silicon monomer of silico ethylene base
Selected from methylvinyldimethoxysilane, methyl vinyl diethoxysilane, ethyl vinyl dimethoxysilane, ethyl
One of methylvinyldiethoxysilane is a variety of, but not limited to this.
In step S10, the organic silicon monomer Ш is to provide (R1 ' ')2SiO2/2The organic silicon monomer of chain link is also two
Alkoxy silane monomer.This bis-alkoxysilane monomer be then for adjust molecular weight, adjust molecule medium vinyl content and
Epoxy group content.Specifically, the organic silicon monomer III can be selected from dimethyldimethoxysil,ne, dimethyl diethoxy
One of silane, diethyldimethoxysilane, diethyldiethoxysilane are a variety of, but not limited to this.
In step S10, the organic silicon monomer IV is for providing R3R1 ' ' ' SiO3/2Chain link or R3 (R1 ' ' ') SiO2/2Chain
Section, the i.e. organic silicon monomer are for providing epoxy group.
Wherein, R3 (R1 ' ' ') SiO is provided2/2The organic silicon monomer IV of chain link is bis-alkoxysilane monomer, can be selected
From 3- glycidoxypropyl group (methyl) dimethoxysilane, 3- glycidoxypropyl group (methyl) diethoxy silane, 3- ring
Oxygen propoxypropyl (methyl) dibutoxy silane, 2,3- epoxypropyl (methyl) dimethoxysilane, 2-(3,4- epoxy group
Cyclohexyl) hexyl (methyl) dimethoxysilane, 2-(3,4- expoxycyclohexyl) in hexyl (methyl) diethoxy silane
It is one or more, but not limited to this.
And provide R3R1 ' ' ' SiO3/2The organic silicon monomer IV of chain link is then trialkoxy silane, can be shunk selected from 3-
Glycerol ether oxygen propyl trimethoxy silicane, 3- glycidoxypropyltrietandysilane andysilane, 2-(3,4- epoxycyclohexyl) second
Base trimethoxy silane, 2-(3,4- epoxycyclohexyl) one of ethyl triethoxysilane or a variety of, but not limited to this.
4 kinds of organic silicon monomer cohydrolysis are first condensed, obtain organosilicon compound by the preparation method provided according to the present invention
Object.It is calculated with the total mole number of the siloxy group in all organic silicon monomers, the dosage of water is its 1 times or more, preferably 1-5
Times.
The temperature of cohydrolysis condensation reaction can be room temperature to 100 DEG C, preferably 50-90 DEG C.Reaction time can be 4-
12h。
Aforementioned cohydrolysis condensation reaction carries out in the presence of a catalyst.Wherein, the catalyst is common in the art
Various acidic catalysts and/or basic catalyst, without using expensive platinum catalyst in the prior art.Specifically
Ground, wherein the acidic catalyst is selected from one of hydrochloric acid, sulfuric acid, acetic acid, sulfonic acid or a variety of, the basic catalyst choosing
From one of potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, triethylamine or a variety of.The dosage of catalyst is not necessarily to excessively,
Only need it can catalytic hydrolysis reaction progress.Under preferable case, on the basis of the gross mass of all organic silicon monomers, catalyst
Dosage be 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 hydrone in the Aquo System is easy and the various reactivity in organo-silicon compound
Group (such as silicone hydroxyl, epoxy group) forms chemical bonding, it is difficult to directly be removed with desiccant.Therefore, in the present invention, in order to
In removing system remaining various free waters and combine water, which carries out in organic solvent, after the completion of cohydrolysis reaction,
Then afore mentioned chemical can be destroyed using high temperature azeotropic and is bonded, so as to thoroughly remove system by by organic solvent azeotrope with water
In residual water.
In the present invention, by carrying out specific experiment to various organic solvents in the prior art, discovery is following several organic
Solvent can remove free water in system and combine water: benzene,toluene,xylene, n-hexane, normal heptane.Inventor passes through experiment
It has also been found that the azeotropic point of these solvents and water is below 100 DEG C.In more preferable situation, with the gross mass of all organic silicon monomers
On the basis of, the dosage of organic solvent is 50-200%.
According to the method for the present invention, after the completion of various organic silicon monomer cohydrolysis, heating azeotropic can be carried out to system
Water is removed, and prevents in azeotropic process that other side reactions carry out at high temperature in system, therefore need to be before azeotropic first in the present invention
Mixed system after reaction is washed, until system is neutral system.The step of washing, is known to those skilled in the art,
Details are not described herein again.Then the neutrality mixed system is subjected to azeotropic water removing again, pre-product can be obtained.
In the present invention, after various organic silicon monomer cohydrolysis, part silicone hydroxyl can be remained in reaction product.The silicon
On the one hand hydroxyl is easy to be formed with the hydrone in product system to be chemically bonded, cause water in products to be difficult to remove, on the other hand
Itself dehydrating condensation is easy to happen between the silicone hydroxyl in subsequent vacuum distillation, so that product is partially formed macromolecular, so that
Molecular weight distribution is extremely uneven, keeps final product obtained muddy.Therefore, it can be removed in advance before vacuum distillation in the present invention
Remove remaining silicone hydroxyl in pre-product.In the present invention, the generation inventors have found that organochlorosilane can react with silicone hydroxyl
HCl thereby may be ensured that molecular weight of product is more uniformly spread to remove silicone hydroxyl, also more to the tackifying effect of silicon rubber
It is uniform；Therefore, in the present invention, except raw material used by silicone hydroxyl preferably uses organochlorosilane.And organochlorosilane is to water
Vapour is very sensitive, can also react with water, and the efficiency except silicone hydroxyl is caused to will be greatly reduced.Therefore using organochlorosilane as this
The raw material that silicone hydroxyl is removed in invention proposes requirements at the higher level to the water content in product system in the present invention, so that removing silicone hydroxyl
Azeotropic water removing step before is even more important.
In the present invention, the organochlorosilane can be the organochlorosilane containing si-h bond, silene key or silane capital construction,
To guarantee that it can have good dispersibility with the obtained pre-product of step S20.Specifically, the organochlorosilane end-capping reagent contains
When having si-h bond, dimethylchlorosilane and/or diethyl chlorosilane can be selected from.And when the organochlorosilane end-capping reagent contains
When having silylene group key, dimethyl vinyl chlorosilane and/or diethyl vinyl chlorosilane can be selected from.When the organochlorine
When silane end-cappers contain silylation key, trim,ethylchlorosilane and/or chlorotriethyl silane can be selected from.
In the present invention, the organochlorosilane is only used for away remaining part silicone hydroxyl in pre-product, therefore its content
Without excessively high, will not structure to final organic silicon rigidity-increasing stick and molecular weight impact.Under preferable case, with all organic
On the basis of the gross mass of silicon monomer, the dosage of organochlorosilane is 0.1-0.5%.
After removing the silicone hydroxyl in pre-product through the above steps, vacuum distillation processing can be carried out to system, it is final to obtain
To the organic silicon rigidity-increasing stick of clear.The step of vacuum distillation is vacuum distillation step common in the art, this
It is not particularly limited in invention, details are not described herein again.
Organic silicon rigidity-increasing stick provided by the invention can be used in silicon rubber improving the adhesive property of silicon rubber and substrate.
Therefore, the present invention finally provides a kind of addition-type silicon rubber composition, contains this in the addition-type silicon rubber composition
The organic silicon rigidity-increasing stick provided is provided.Using the addition-type silicon rubber composition and substrate of organic silicon rigidity-increasing stick provided by the invention
With good adhesive property.
The addition-type silicon rubber is known to those skilled in the art, generally by the siloxanes, hydrogeneous containing vinyl
The components such as siloxanes, catalyst and inhibitor mix according to a certain percentage, are not particularly limited in the present invention.
Addition-type silicon rubber composition provided by the invention only exists with the unique difference of silicon rubber in the prior art
In wherein containing organic silicon rigidity-increasing stick provided by the invention.Under preferable case, with total matter of the addition-type silicon rubber composition
On the basis of amount, wherein the content of organic silicon rigidity-increasing stick is 0.5-2.5%.
Specific explanations explanation is made to the present invention with reference to embodiments.Raw material employed in embodiment and comparative example passes through
It is commercially available, the present invention is not particularly limited.
Embodiment 1
The present embodiment is for illustrating organic silicon rigidity-increasing stick A1 and addition-type silicon rubber composition B1 provided by the invention.
Take 13.4g methyldiethoxysilane (M=134, n=0.2mol) as organic silicon monomer II, 38.4g triethyl group first
Oxysilane (M=160, n=0.24mol) is used as organic silicon monomer I, 61.36g3- glycidyl ether oxygen propyl trimethoxy silicon
Alkane (M=236, n=0.26mol) is used as organic silicon monomer IV, 56.4g di-n-butyl dimethoxysilane (M=188, n=0.3mol)
As organic silicon monomer III.
4 kinds of front organic silicon monomer and 140g dimethylbenzene, 100g aqueous acetic acid (acetic acid content 8.5%) are mixed, heating
To 60 DEG C of reaction 8h.After reaction, xylene solution is isolated with separatory funnel, be washed with water until neutral；It again will be water washed
Xylene solution be warming up to 100 DEG C of azeotropic until system water is except clean, then adds 0.42g dimethylchlorosilane stirring 1h, so
After be warming up to 150 DEG C of vacuum distillations, boil off dimethylbenzene and low-boiling-point substance, obtain having for the hydrosilyl group-containing of the present embodiment of clear
Machine silicon tackifier, are denoted as A1, and structural formula is
。
By the poly- silicon of dimethyl of the vinyldimethylsiloxane sealing end with 0.15mmol/g contents of ethylene of 100g
Oxygen alkane is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, then adds 0.63g aforementioned organic silicon tackifier
Inhibitor, the 0.2g platinum catalyst of A1,0.1g, stirring make to be uniformly mixed, and obtain the addition-type silicon rubber composition of the present embodiment,
It is denoted as B1.
Embodiment 2
The present embodiment is for illustrating organic silicon rigidity-increasing stick A2 and addition-type silicon rubber composition B2 provided by the invention.
Take 13.2g methylvinyldimethoxysilane (M=132, n=0.1mol) as organic silicon monomer II, 16.2g six
Tetramethyldisiloxane (M=162, n=0.1mol) is used as organic silicon monomer I, 22g3- glycidoxypropyl group (methyl) dimethoxy
Silane (M=220, n=0.1mol) is made as organic silicon monomer IV, 90g dimethyl diethoxysilane (M=148, n=0.6mol)
For organic silicon monomer III.
4 kinds of front organic silicon monomer and 77g toluene, 60g hydrochloric acid (HCl content 25%) are mixed, 90 DEG C of reactions are warming up to
4h.After reaction, toluene solution is isolated with separatory funnel, be washed with water until neutral；Again by water washed toluene solution liter
Temperature is to 100 DEG C of azeotropic until system water is except clean, then adds 0.16g dimethyl vinyl chlorosilane stirring 1h, then heats to
150 DEG C of vacuum distillations, boil off toluene and low-boiling-point substance, obtain the organosilicon thickening of the siliceous vinyl of the present embodiment of clear
Agent, is denoted as A2, and structural formula is
。
By the poly- silicon of dimethyl of the vinyldimethylsiloxane sealing end with 0.15mmol/g contents of ethylene of 100g
Oxygen alkane is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, then adds 1.575g aforementioned organic silicon thickening
Inhibitor, the 0.2g platinum catalyst of agent A2,0.1g, stirring make to be uniformly mixed, and obtain the addition-type silicon rubber combination of the present embodiment
Object is denoted as B2.
Embodiment 3
The present embodiment is for illustrating organic silicon rigidity-increasing stick A3 and addition-type silicon rubber composition B3 provided by the invention.
Take 16g methyl vinyl diethoxysilane (M=160, n=0.1mol) as organic silicon monomer II, 4.72g front three
Base oxethyl silane (M=118, n=0.04mol) is used as organic silicon monomer I, 14.4g2-(3,4- epoxycyclohexyl) three second of ethyl
Oxysilane (M=288, n=0.05mol) as organic silicon monomer IV, 119.88g dimethyl diethoxysilane (M=148, n=
0.81mol) it is used as organic silicon monomer III.
By 4 kinds of front organic silicon monomer and 300g n-hexane, 180g sodium hydrate aqueous solution (sodium hydrate content
0.17%) it mixes, is warming up to 30 DEG C of reaction 12h.After reaction, isolate hexane solution with separatory funnel, be washed with water until
It is neutral；Water washed hexane solution is warming up to 100 DEG C of azeotropic until system water removes completely, then adds 0.83g trimethyl again
Chlorosilane stirs 1h, then heats to 150 DEG C of vacuum distillations, boils off n-hexane and low-boiling-point substance, obtain this implementation of clear
The organic silicon rigidity-increasing stick of the siliceous vinyl of example, is denoted as A3, structural formula is
。
By the poly- silicon of dimethyl of the vinyldimethylsiloxane sealing end with 0.15mmol/g contents of ethylene of 100g
Oxygen alkane is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, then adds 2.625g aforementioned organic silicon thickening
Inhibitor, the 0.2g platinum catalyst of agent A3,0.1g, stirring make to be uniformly mixed, and obtain the addition-type silicon rubber combination of the present embodiment
Object is denoted as B3.
Embodiment 4
The present embodiment is for illustrating organic silicon rigidity-increasing stick A4 and addition-type silicon rubber composition B6 provided by the invention.
Take 80.4g methyldiethoxysilane (M=134, n=0.6mol) as organic silicon monomer II, 31.2g trimethyl first
Oxysilane (M=104, n=0.3mol) is used as organic silicon monomer I, 23.6g3- glycidyl ether oxygen propyl trimethoxy silicane
(M=236, n=0.1mol) is used as organic silicon monomer IV.
3 kinds of front organic silicon monomer and 140g normal heptane, 90g aqueous sulfuric acid (sulfuric acid content 1.5%) are mixed, heating
To 60 DEG C of reaction 8h.After reaction, n-heptane solution is isolated with separatory funnel, be washed with water until neutral；It again will be water washed
N-heptane solution be warming up to 100 DEG C of azeotropic until system water is except clean, then adds 0.3g dimethylchlorosilane stirring 1h, then
150 DEG C of vacuum distillations are warming up to, normal heptane and low-boiling-point substance is boiled off, obtains the organic of the hydrosilyl group-containing of the present embodiment of clear
Silicon tackifier, are denoted as A4, and structural formula is
。
By the poly- silicon of dimethyl of the vinyldimethylsiloxane sealing end with 0.15mmol/g contents of ethylene of 100g
Oxygen alkane is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, then adds 1.05g aforementioned organic silicon tackifier
Inhibitor, the 0.2g platinum catalyst of A4,0.1g, stirring make to be uniformly mixed, and obtain the addition-type silicon rubber composition of the present embodiment,
It is denoted as B4.
Comparative example 1
This comparative example is used to illustrate the addition-type silicon rubber composition without containing organic silicon rigidity-increasing stick provided by the invention
DB1。
By the poly- silicon of dimethyl of the vinyldimethylsiloxane sealing end with 0.15mmol/g contents of ethylene of 100g
Oxygen alkane is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, then add the inhibitor of 0.1g, 0.2g platinum is urged
Agent, stirring make to be uniformly mixed, obtain the addition-type silicon rubber composition of this comparative example, be denoted as DB1.
Comparative example 2
This comparative example is used to illustrate the organic silicon rigidity-increasing stick DA2 and addition-type silicon rubber composition DB2 that non-present invention provides.
Take 16.2g hexamethyldisiloxane (M=162, n=0.1mol) as organic silicon monomer I, 66g3- glycidoxy
Propyl (methyl) dimethoxysilane (M=220, n=0.3mol) is used as organic silicon monomer IV, 133.2g dimethyl diethoxy silicon
Alkane (M=148, n=0.5mol) is used as organic silicon monomer III.
3 kinds of front organic silicon monomer and 77g toluene, 60g hydrochloric acid (HCl content 35%) are mixed, 90 DEG C of reactions are warming up to
4h.After reaction, toluene solution is isolated with separatory funnel, be washed with water until neutral；Again by water washed toluene solution liter
Temperature is to 100 DEG C of azeotropic until system water is except clean, then adds 0.22g trim,ethylchlorosilane stirring 1h, then heats to 150 DEG C and subtracts
Pressure distillation, boils off toluene and low-boiling-point substance, obtains the organic silicon rigidity-increasing stick of the present embodiment of clear, be denoted as DA2, structural formula
For
。
By the poly- silicon of dimethyl of the vinyldimethylsiloxane sealing end with 0.15mmol/g contents of ethylene of 100g
Oxygen alkane is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, then adds 1.575g aforementioned organic silicon thickening
Inhibitor, the 0.2g platinum catalyst of agent DA2,0.1g, stirring make to be uniformly mixed, and obtain the addition-type silicon rubber combination of the present embodiment
Object is denoted as DB2.
Comparative example 3
This comparative example is used to illustrate the organic silicon rigidity-increasing stick DA3 and addition-type silicon rubber composition DB3 that non-present invention provides.
Take 16g methyl vinyl diethoxysilane (M=160, n=0.1mol) as organic silicon monomer II, 16.2g six
Tetramethyldisiloxane (M=162, n=0.1mol) as organic silicon monomer I, 103.6g dimethyl diethoxysilane (M=148, n=
0.7mol) it is used as organic silicon monomer III.
3 kinds of front organic silicon monomer and 77g toluene, 55g sulfuric acid (sulfuric acid content 2.5%) are mixed, 60 DEG C of reactions are warming up to
4h.After reaction, toluene solution is isolated with separatory funnel, be washed with water until neutral；Again by water washed toluene solution liter
Temperature is to 100 DEG C of azeotropic until system water is except clean, then adds 0.27g trim,ethylchlorosilane stirring 1h, then heats to 150 DEG C and subtracts
Pressure distillation, boils off toluene and low-boiling-point substance, obtains the organic silicon rigidity-increasing stick of the siliceous vinyl of the present embodiment of clear, be denoted as
DA3, structural formula are
。
By the poly- silicon of dimethyl of the vinyldimethylsiloxane sealing end with 0.15mmol/g contents of ethylene of 100g
Oxygen alkane is mixed with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen content of 5g, then adds 1.575g aforementioned organic silicon thickening
Inhibitor, the 0.2g platinum catalyst of agent DA3,0.1g, stirring make to be uniformly mixed, and obtain the addition-type silicon rubber combination of the present embodiment
Object is denoted as DB3.
Performance test
(1) examination of infrared spectrum
Examination of infrared spectrum is carried out to the organic silicon rigidity-increasing stick S1 that embodiment 1 is prepared, 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 in the product
Key.909cm-1Place is the characteristic absorption peak of epoxy group, it follows that there is also epoxy groups in product.
(2) adhesive property is tested
According to GB/T 13936-92 " vulcanized rubber and metal bond tensile shear strength measuring method " each rubber group of test
Close the shear strength after object solidifies.Test condition: heat cure 1h at 100 DEG C.
Test result is as follows shown in table 1.
Table 1
。
It can be seen that in addition-type silicon rubber composition B1-B4 provided by the invention from the test result of upper table 1 due to dividing
Organic silicon rigidity-increasing stick A1-A4 provided by the invention Dui Ying not be used, the shear strength after solidifying is 1MPa or more, hence it is evident that excellent
In the silicon rubber sample DB1-DB3 of comparative example 1-3, that is, illustrate addition-type silicon rubber composition provided by the invention due to using
New structural organic silicon rigidity-increasing stick provided by the invention, so that it has good adhesive property with substrate.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (16)
1. a kind of preparation method of organic silicon rigidity-increasing stick, the structure of the organic silicon rigidity-increasing stick is as shown in Formulas I or Formula II:
[(R1)3SiO1/2]a[R2(R1’)SiO2/2]b[(R1”)2SiO2/2]c[R3(R1”’)SiO2/2]dFormulas I
[(R1)3SiO1/2]a[R2(R1’)SiO2/2]b[(R1”)2SiO2/2]c[R3R1”’SiO3/2]dFormula II
Wherein, it is 1-8 alkyl that R1, R1 ', R1 ", R1 " ', which are each independently carbon atom, and R2 is-CH=CH2Or H, R3 are containing ring-type
The group of ether；A, b, c, d are molar content, and a, b, d cannot be 0, and a+b+c+d=1；And R2 is-CH=CH2When, b≤0.2；
It is characterized in that, the preparation method of the organic silicon rigidity-increasing stick the following steps are included:
S10, (R1) will be provided3SiO1/2The organic silicon monomer I of chain link, R2 (R1 ') SiO is provided2/2The organic silicon monomer II of chain link,
It provides (R1 ")2SiO2/2The organic silicon monomer Ш of chain link, R3R1 " ' SiO is provided3/2Chain link or R3 (R1 " ') SiO2/2Chain link has
After machine silicon monomer IV is mixed with organic solvent, water, catalyst in proportion, reaction obtains organic molten containing organo-silicon compound
Liquid；
S20, the organic solution containing organo-silicon compound for obtaining step S10 are washed to neutrality, and then heating is azeotroped off
Water obtains pre-product；
S30, remaining silicone hydroxyl in pre-product is removed, is finally evaporated under reduced pressure, obtains the organic silicon rigidity-increasing stick；Remove pre-product
In raw material used by remaining silicone hydroxyl be organochlorosilane；
The R3R1 " ' SiO3/2Chain link is three-functionality-degree chain link, and wherein R3R1 " ' is a whole group, the entirety group with
Silicon atom is connected directly, and R1 " ' base is directly connected with silicon atom, and the remainder of silicon atom is connected with three oxygen atoms again.
2. preparation method according to claim 1, which is characterized in that 0 < a≤0.3,0≤c≤0.9,0.05≤d≤0.3.
It is selected each independently ', R1 ", R1 " ' 3. preparation method according to claim 1, which is characterized in that described R1, R1
From methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, isobutyl group, sec-butyl, uncle
Butyl, isopentyl, neopentyl, tertiary pentyl, isohesyl, cyclohexyl.
4. preparation method according to claim 1, which is characterized in that the R3 is selected from 2,3- epoxypropyl, 3,4- ring
Oxygroup butyl, 4,5- epoxypentyl, 2- glycidoxyethyl, 3- glycidoxypropyl group, 4- glycidoxy butyl, 2-
Any one in (3,4- expoxycyclohexyl) ethyl, 3- (3,4- expoxycyclohexyl) propyl.
5. preparation method according to claim 1, which is characterized in that in step S10, the organic silicon monomer I is selected from three
Methylmethoxysilane, trimethylethoxysilane, triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, three n-propyl first
One of oxysilane, three n-propyl Ethoxysilanes, hexamethyldisiloxane, hexaethyldisiloxane are a variety of.
6. preparation method according to claim 1, which is characterized in that in step S10, the organic silicon monomer II is to provide
The organic silicon monomer of silicon hydrogen-based or silylene group；
Wherein, the organic silicon monomer for providing silicon hydrogen-based is selected from methyl dimethoxysilane, methyldiethoxysilane, ethyl diformazan
One of oxysilane, ethyl diethoxy silane are a variety of；
There is provided silylene group organic silicon monomer be selected from methylvinyldimethoxysilane, methyl vinyl diethoxysilane,
One of ethyl vinyl dimethoxysilane, ethyl vinyl diethoxy silane are a variety of.
7. preparation method according to claim 1, which is characterized in that in step S10, the organic silicon monomer III is selected from
Dimethyldimethoxysil,ne, dimethyl diethoxysilane, diethyldimethoxysilane, in diethyldiethoxysilane
It is one or more.
8. preparation method according to claim 1, which is characterized in that in step S10, provide R3 (R1 " ') SiO2/2Chain link
Organic silicon monomer IV be selected from 3- glycidoxypropyl group (methyl) dimethoxysilane, 3- glycidoxypropyl group (methyl) two
Ethoxysilane, 3- glycidoxypropyl group (methyl) dibutoxy silane, 2,3- epoxypropyl (methyl) dimethoxy silicon
Alkane, 2- (3,4- expoxycyclohexyl) hexyl (methyl) dimethoxysilane, 2- (3,4- expoxycyclohexyl) hexyl (methyl)
One of diethoxy silane is a variety of；
R3R1 " ' SiO is provided3/2The organic silicon monomer IV of chain link is selected from 3- glycidyl ether oxygen propyl trimethoxy silicane, 3- contracts
Water glycerol ether oxygen propyl triethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4- epoxy hexamethylene
Base) one of ethyl triethoxysilane or a variety of.
9. preparation method according to claim 1, which is characterized in that in step S10, the organic solvent is selected from benzene, first
Benzene, dimethylbenzene, n-hexane, any one in normal heptane；
On the basis of the gross mass of all organic silicon monomers, the dosage of organic solvent is 50-200%.
10. preparation method according to claim 1, which is characterized in that in step S10, in all organic silicon monomers
The total mole number of siloxy group calculates, and the dosage of water is its 1-5 times.
11. preparation method according to claim 1, which is characterized in that in step S10, the catalyst is acidic catalyst
Agent and/or basic catalyst；Wherein, the acidic catalyst is selected from one of hydrochloric acid, sulfuric acid, acetic acid, sulfonic acid or a variety of, institute
It states basic catalyst and is selected from one of potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, triethylamine or a variety of；
On the basis of the gross mass of all organic silicon monomers, the dosage of catalyst is 0.1-10%.
12. preparation method according to claim 1, which is characterized in that in step S10, reaction temperature is room temperature to 100
DEG C, reaction time 4-12h.
13. preparation method according to claim 1, which is characterized in that in step S30, the organochlorosilane is selected from two
Methylchlorosilane, diethyl chlorosilane, dimethyl vinyl chlorosilane, diethyl vinyl chlorosilane, trim,ethylchlorosilane, three
At least one of ethyl chlorosilane.
14. preparation method according to claim 13, which is characterized in that using the gross mass of all organic silicon monomers as base
Standard, the dosage of organochlorosilane are 0.1-0.5%.
15. a kind of addition-type silicon rubber composition, which is characterized in that contain in the addition-type silicon rubber composition and wanted by right
The organic silicon rigidity-increasing stick for asking the preparation method of the described in any item organic silicon rigidity-increasing sticks of 1-14 to be prepared.
16. addition-type silicon rubber composition according to claim 15, which is characterized in that with the addition-type silicon rubber group
On the basis of the gross mass for closing object, wherein the content of organic silicon rigidity-increasing stick is 0.5-2.5%.
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| EP0336854A1 (en) * | 1988-03-24 | 1989-10-11 | Rhone-Poulenc Chimie | Diorganopolysiloxane which contains vinyl groups and epoxy-substituted organic groups |
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| CN103755963A (en) * | 2013-12-27 | 2014-04-30 | 深圳市安品有机硅材料有限公司 | Polysiloxane thickening agent and preparation method thereof |
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| JP5505991B2 (en) * | 2010-04-30 | 2014-05-28 | 信越化学工業株式会社 | High adhesion silicone resin composition and optical semiconductor device using the composition |
| CN103212386B (en) * | 2012-12-20 | 2014-12-03 | 北京化工大学 | High purity full porous silica gel-bonded chromatography immobile phase preparation method |
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| EP0336854A1 (en) * | 1988-03-24 | 1989-10-11 | Rhone-Poulenc Chimie | Diorganopolysiloxane which contains vinyl groups and epoxy-substituted organic groups |
| CN101954766A (en) * | 2009-06-29 | 2011-01-26 | 信越化学工业株式会社 | The heat-conducting silicon rubber composite sheet |
| CN103755963A (en) * | 2013-12-27 | 2014-04-30 | 深圳市安品有机硅材料有限公司 | Polysiloxane thickening agent and preparation method thereof |
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