CN106800655A - A kind of organic silicon rigidity-increasing stick and preparation method thereof and a kind of silica-gel composition - Google Patents
A kind of organic silicon rigidity-increasing stick and preparation method thereof and a kind of silica-gel composition Download PDFInfo
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Abstract
The 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：[(R1)3SiO1/2]a[(R1’)2SiO2/2]b[R2R1’’(R1’’)SiO2/2]c[R1’’’SiO3/2]dFormulas I [(R1)3SiO1/2]a[(R1’)2SiO2/2]b[R2R1’’SiO3/2]c[R1’’’SiO3/2]dFormula II is present invention also offers the silica-gel composition containing the organic silicon rigidity-increasing stick.The silica-gel composition of the organic silicon rigidity-increasing stick provided using the present invention has good adhesive property with base material.
Description
Technical field
The invention belongs to silica gel technical field, more particularly to a kind of organic silicon rigidity-increasing stick and preparation method thereof and contain
There is the silica-gel composition of the organic silicon rigidity-increasing stick.
Background technology
Add-on type silica gel have the advantages that no coupling product in sulfidation, shrinkage factor it is low and can profound solidification,
It is rapidly developed in fields such as electronic component, power circuitry module, large-scale surface-mounted integrated circuit, LED.
Compare other macromolecular adhesives, silicone adhesive have high transparency, low temperature resistant, color inhibition high,
The characteristics such as long lifespan, this is because the bond energy of the repeat unit-Si-O- of organosilicon is much larger than general high molecular bonding
The C-C bond energys of agent, external environment is difficult to damage it, but anything has its dual character ,-Si-O-
Shortcoming as adhesive is that its polarity is weak, so it is generally very poor with the adhesion of base material, with base material shape
Into secondary bond power it is weak, and unmodified organic silica gel be also difficult to base material formed covalent bond, if so thinking
The adhesion of organosilicon and base material is improved, adds appropriate tackifier to be highly desirable to..
It is applied to suitable tackifier requirement on solar cell good with the main component compatibility of silica gel, and not
Every Physical Mechanical, electrical property, light transmittance after influence silica gel curing process and solidification.At present, viscosify
The preparation method of agent is main based on synthesis, and various organic groups are introduced in the structure of tackifier.Specifically may be used
To be divided into following a few classes：Allyl glycidyl ether and the silane or siloxane oligomer of silicon hydrogen-based addition reaction
It is tackifier；The siloxane oligomer of hydrosilyl group-containing and beta-diketon base is tackifier；With containing phenyl or ester group
Siloxane oligomer is tackifier；It is tackifier with the polymethyl hydrogen siloxane containing phenyl；With hetero nitrogen silicon tricyclic
Derivative is tackifier；With the phenolic compound of olefin-containing base or double (trimethoxy silicon propyl group) fumarates with
Hydroxy-end capped (CH3)2SiO/CH2=CH (CH3) SiO copolymers compound be tackifier；With trihydroxy methyl
The product of propane diallyl, γ-glycidoxypropyltrimethoxy silane and tetraethyl orthosilicate is thickening
Agent.The tackifier of these types can increase the caking property of organosilicon and base material to a certain extent, but simultaneously
There is also other not enough, such as preparation method complexity, use condition harshness etc..Therefore, seek a kind of suitable
Tackifier with improve silica gel adhesive strength turn into the task of top priority.
The content of the invention
The present invention solve that the silica gel for using in the prior art exists with tackifier it is bad with silica gel compatibility,
And the technical problem that preparation method is complicated, use condition is harsh.
Specifically, the invention provides a kind of organic silicon rigidity-increasing stick, the structure such as Formulas I of the organic silicon rigidity-increasing stick
Or shown in Formula II：
[(R1)3SiO1/2]a[(R1’)2SiO2/2]b[R2R1”(R1”)SiO2/2]c[R1”’SiO3/2]d
Formulas I
[(R1)3SiO1/2]a[(R1’)2SiO2/2]b[R2R1”SiO3/2]c[R1”’SiO3/2]d
Formula II
Wherein, it is at least in 1-8 alkyl and-CH=CH2 that R1, R1 ', R1 " ' are respectively selected from carbon atom
Kind, and at least one contain-CH=CH2 in R1, R1 ', R1 " '；R1 " is that carbon atom is 1-8 alkyl, R2
It is the group containing cyclic ether；A, b, c, d are molar content, a+b+c+d=1,0<a<1,0<b<1,0<c<1,
0<d<1。
The present invention also provides a kind of preparation method of organic silicon rigidity-increasing stick, comprises the following steps：
S10, will provide (R1)3SiO1/2The organochlorosilane monomer I of chain link, offer (R1 ') 2SiO2/2Chain link
Organochlorosilane monomer II, offer R1 " ' SiO3/2One or more in the organochlorosilane monomer III of chain link,
After mixing with organic solvent in proportion, alkaline aqueous solution is added dropwise thereto, reaction obtains containing Organosilicon Alcohol in Organic
Organic solution；
S20, the organic solution containing Organosilicon Alcohol in Organic for obtaining step S10, with offer (R1)3SiO1/2Chain link
Organosiloxane monomer IV, provide (R1 ')2SiO2/2The organosiloxane monomer V of chain link, offer
R1”’SiO3/2One or more, offer R2R1 of the organosiloxane monomer VI of chain link " (R1 ") SiO2/2Or
R2R1”SiO3/2The organosiloxane monomer VII, catalyst of chain link, proton solvent mixing, then heating up is carried out
Catalysis dealcoholization, obtains pre-product；
S30, the pre-product that S20 steps are obtained filter and then vacuum distillation, obtain the organic silicon rigidity-increasing
Stick.
Finally, the invention provides a kind of silica-gel composition, provided containing the present invention in the silica-gel composition
Organic silicon rigidity-increasing stick.
In the present invention, by providing a kind of organic silicon rigidity-increasing stick of new structure, it contains epoxy radicals and silene
Key, its epoxide epoxy group group provides good caking property, and silene key can react with silica gel system, to prevent
The effusion of long-term use process small molecular, it is ensured that the outward appearance and performance of silica gel.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the organic silicon rigidity-increasing stick A1 that embodiment 1 is prepared.
Specific embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect become more apparent, with
Under in conjunction with the embodiments, the present invention will be described in further detail.It should be appreciated that described herein specific
Embodiment is only used to explain the present invention, is not intended to limit the present invention.
The 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[(R1’)2SiO2/2]b[R2R1”(R1”)SiO2/2]c[R1”’SiO3/2]d
Formulas I
[(R1)3SiO1/2]a[(R1’)2SiO2/2]b[R2R1”SiO3/2]c[R1”’SiO3/2]d
Formula II
Wherein, it is at least in 1-8 alkyl and-CH=CH2 that R1, R1 ', R1 " ' are respectively selected from carbon atom
Kind, and at least one contain-CH=CH2 in R1, R1 ', R1 " '；R1 " is that carbon atom is 1-8 alkyl, R2
It is the group containing cyclic ether；A, b, c, d are molar content, a+b+c+d=1,0<a<1,0<b<1,0<c<1,
0<d<1。
It may be noted that ground is, it is poly- in organosiloxane or silane as the common knowledge of those skilled in the art
When the structural formula or chemical name of compound are write, when the group laid out in parallel being joined directly together with silicon atom is write,
The group included with bracket, represents that it is the group being joined directly together with silicon atom；And the base that unused bracket is included
Group, then it represents that it constitutes a group for entirety with other groups above, is then connected with silicon atom again.
For example, the present invention provide Formulas I shown in organic silicon rigidity-increasing stick in, it contains 4 chain links, respectively
(R1)3SiO1/2Chain link, (R1 ')2SiO2/2Chain link, R2R1 " (R1 ") SiO2/2Chain link and R1 " ' SiO3/2Chain link.
And the organic silicon rigidity-increasing stick shown in Formula II is also to contain 4 chain links, respectively (R1)3SiO1/2Chain link,
(R1’)2SiO2/2Chain link, R2R1 " SiO3/2Chain link and R1 " ' SiO3/2Chain link.
Wherein, (R1)3SiO1/2Chain link is single functionality chain link, and it is end-sealed type chain link, silicon atom therein with
Three R1 bases are joined directly together, remaining then be connected with oxygen atom, and its structural formula is shown in Formula Il I：
(R1’)2SiO2/2Chain link is bifunctionality chain link, and wherein silicon atom is joined directly together with two R1 ' bases, remaining
Then it is connected with two oxygen atoms, its structural formula is shown in following formula I V：
R2R1”(R1”)SiO2/2Chain link is also bifunctionality chain link, wherein R2 and one of R1 " it is connected,
Silicon atom respectively with two R1 " base is joined directly together, remaining then be connected with two oxygen atoms, under its structural formula is
Shown in Formula V：
R1”’SiO3/2Chain link is then three-functionality-degree chain link, wherein silicon atom and R1 " ' base is joined directly together, it is remaining then
It is connected with three oxygen atoms, its structural formula is shown in lower Formula IV：
R2R1”SiO3/2Chain link is also three-functionality-degree chain link, wherein R2R1 " it is an overall group, the entirety
Group is joined directly together with silicon atom, and R1 " base is directly connected with silicon atom, the remainder of silicon atom again with
Three oxygen atoms are connected, shown in the following Formula VII of its structural formula：
As it was previously stated, in the present invention, by providing a kind of organic silicon rigidity-increasing stick of new structure, it contains ring
Epoxide and silene key, its epoxide epoxy group group provide good caking property, and silene key can be anti-with silica gel system
Should, to prevent the effusion of long-term use process small molecular, it is ensured that the outward appearance and performance of silica gel.
Specifically, foregoing (R1)3SiO1/2Chain link, (R1 ')2SiO2/2R1 in chain link and R1 " ' SiO3/2 chain links,
It is at least one in 1-8 alkyl and-CH=CH2 that R1 ', R1 " ' is respectively selected from carbon atom, and R1, R1 ',
At least one can be used to provide silene containing at least one chain link in-CH=CH2, i.e. these chain links in R1 " '
Key.Inventor is by further experiment discovery ,-CH=CH2Content should≤0.2, otherwise silene linkage content is too
Height can suppress curing rate.
R2R1”(R1”)SiO2/2Chain link or R2R1 " SiO3/2R2 in chain link is the group containing cyclic ether, its
For providing epoxy radicals, content of the chain link in organic silicon rigidity-increasing stick meets：0<c<1.In some embodiments
In, 0.05≤c≤0.2.
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.In certain embodiments, 0<a≤0.2.
(R1’)2SiO2/2Chain link is then used for Molecular regulator structure, molecular weight and the wherein content of silene key, also
Can be used to adjust intermiscibility of the tackifier in silica gel system, caused not with making up the presence of epoxy ether group
Mix.Accordingly, content of this chain link in organic silicon rigidity-increasing stick meets：(0<b<1).In some embodiments
In, 0.3≤b≤0.7.
R1”’SiO3/2Chain link can be used for Molecular regulator structure, molecular weight and the wherein content of silene key,
Its humidification of silica gel system can also be made up epoxy ether group and there is the mechanical performance decline for causing.
Accordingly, content of this chain link in organic silicon rigidity-increasing stick meets：0<d<1.In certain embodiments,
0.05≤d≤0.5。
As it was previously stated, R1, R1 ', R1 " ' be respectively selected from carbon atom in 1-8 alkyl and-CH=CH2 extremely
At least one contains-CH=CH2 in few one kind, and R1, R1 ', R1 " '.That is R1, R1 ', R1 " ' can be with
Identical, it is also possible to different, R1, R1 ', R1 " ' at least one contain-CH=CH2.Wherein carbon atom is 1-8
Alkyl can for methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
Isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl, tertiary pentyl, isohesyl, hexamethylene
Base.
During it is understood that R1, R1, ', R1 " ' can be 1-8 alkyl selected from-CH=CH2 and carbon atom
Multiple, for example, R1 ' can include-CH=CH2, while can also comprising carbon atom be 1-8 alkyl, such as
(R1’)2SiO2/2Chain link can be [CH2=CH (CH3) SiO2/2]；Equally, R1 ' can also individually for carbon is former
Son is 1-8 alkyl, such as-CH3.It is understood that in certain embodiments, it is same in Formulas I and Formula II
R1, R1 in chain link ', R1 " ' can be simultaneously respectively different groups.By taking R1 ' as an example, in Formulas I
(R1’)2SiO2/2Chain link can be simultaneously [CH2=CH (CH3) SiO2/2] and [(CH3)2SiO2/2], then in Formulas I
(R1’)2SiO2/2The molar content of chain link is [CH2=CH (CH3) SiO2/2] and [(CH3)2SiO2/2] both mole
The total amount of content.Also it is in this way, will not be described here for other chain links in Formulas I and Formula II.
As it was previously stated, R2 is the group containing cyclic ether.In certain embodiments, the R2 is glycidol
Base or expoxycyclohexyl.Wherein, the glycidyl is selected from 2,3- epoxypropyls, 3,4- epoxy radicals fourths
Base, 4,5- epoxypentyls, 2- glycidoxyethyls, 3- glycidoxypropyl groups, 4- glycidoxy fourths
Any one in base, but it is not limited to this.The expoxycyclohexyl can be 2- (3,4- epoxycyclohexyethylSiOis
Base) ethyl or 3- (3,4- expoxycyclohexyl) propyl group, but it is not limited to this.
The present invention also provides a kind of preparation method of organic silicon rigidity-increasing stick, comprises the following steps：
S10, will provide (R1)3SiO1/2The organochlorosilane monomer I of chain link, offer (R1 ') 2SiO2/2Chain link
Organochlorosilane monomer II, offer R1 " ' SiO3/2One or more in the organochlorosilane monomer III of chain link,
After mixing with organic solvent in proportion, alkaline aqueous solution is added dropwise thereto, reaction obtains containing Organosilicon Alcohol in Organic
Organic solution；
S20, the organic solution containing Organosilicon Alcohol in Organic for obtaining step S10, with offer (R1)3SiO1/2Chain link
Organosiloxane monomer IV, provide (R1 ')2SiO2/2The organosiloxane monomer V of chain link, offer
R1”’SiO3/2One or more, offer R2R1 of the organosiloxane monomer VI of chain link " (R1 ") SiO2/2Or
R2R1”SiO3/2The organosiloxane monomer VII, catalyst of chain link, proton solvent mixing, then heating up is carried out
Catalysis dealcoholization, obtains pre-product；
S30, the pre-product that S20 steps are obtained filter and then vacuum distillation, obtain the organic silicon rigidity-increasing
Stick.
Wherein, the organochlorosilane monomer I is used to provide (R1)3SiO1/2Chain link, i.e. the organochlorosilane list
Body I is a chlorosilane monomer.This chlorosilane monomer can be used to Molecular regulator amount, Molecular regulator medium vinyl
Content and epoxy group content.Specifically, in step S10, the organochlorosilane monomer I can be selected from three
Methylchlorosilane, chlorotriethyl silane, three normal propyl chloride silane, dimethyl vinyl chlorosilane, diethyl
One or more in vinyl chlorosilane, Methylethyl vinyl chlorosilane, but it is not limited to this.
In step S10, the organochlorosilane monomer II is used to provide (R1 ')2SiO2/2Chain link, i.e., this is organic
Silane monomer II is dichlorosilane monomer.This dichlorosilane monomer can be used to Molecular regulator amount, Molecular regulator
Medium vinyl content and epoxy group content.Specifically, in step S10, the organochlorosilane monomer II
Dimethyldichlorosilane, diethyl dichlorosilane, dipropyl dichlorosilane, Methylethyl dichloro can be selected from
Silane, methyl-propyl dichlorosilane, ethyl propyl dichlorosilane, methylvinyldichlorosilane, ethyl second
One or more in alkenyl dichlorosilane, propyl ethylene base dichlorosilane, but it is not limited to this.
In step S10, the organochlorosilane monomer III is offer R1 " ' SiO3/2The organic silicon monomer of chain link,
It is also trichlorosilane monomer.This trichlorosilane monomer can be used to ethene in Molecular regulator amount, Molecular regulator
Base content and epoxy group content.Specifically, the organochlorosilane monomer III can be selected from methyl trichlorine silicon
One or more in alkane, ethyl trichlorosilane, n-propyltrichlorosilan, vinyl trichlorosilane, but not
It is confined to this.
In step S20, the organosiloxane monomer IV is used to provide (R1)3SiO1/2Chain link, it is single alcoxyl
Base silane monomer.This monoalkoxysilane monomer can be used to Molecular regulator amount, Molecular regulator medium vinyl and contain
Amount and epoxy group content.Specifically, the organosiloxane monomer IV can be selected from trimethyl methoxy silicon
Alkane, trimethylethoxysilane, triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, three n-propyl first
TMOS, three n-propyl Ethoxysilanes, dimethylvinylmethoxysiiane, dimethyl ethenyl second
TMOS, diethoxy vinyl methoxy silane, diethyl vinylethoxysilane, diη-propyl
Vinyl methoxy silane, diη-propyl vinylethoxysilane, tetramethyl divinyl disiloxane,
One or more in HMDO, hexaethyldisiloxane, but it is not limited to this.
In step S20, the organosiloxane monomer V is used to provide (R1 ')2SiO2/2Chain link, it is double alkane
TMOS monomer.This bis-alkoxysilane monomer can be used to Molecular regulator amount, Molecular regulator medium vinyl
Content and epoxy group content.Specifically, the organosiloxane monomer V can be selected from dimethylformamide dimethyl oxygen
Base silane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane,
Diη-propyl dimethoxysilane, diη-propyl diethoxy silane, methylvinyldimethoxysilane,
Methyl vinyl diethoxysilane, ethyl vinyl dimethoxysilane, ethyl vinyl diethoxy silicon
One or more in alkane, n-propyl vinyl dimethoxysilane, n-propyl vinyl diethoxy silane,
But it is not limited to this.
In step S20, the organosiloxane monomer VI is used to provide R1 " ' SiO3/2Chain link, it is three alcoxyls
Base silane monomer.This trialkoxy silane monomer can be used to Molecular regulator amount, Molecular regulator medium vinyl and contain
Amount and epoxy group content.Specifically, the organosiloxane monomer VI can be selected from methyl trimethoxy epoxide silicon
Alkane, MTES, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl front three
TMOS, n-propyl triethoxysilane, vinyltrimethoxy silane, VTES
In one or more, but be not limited to this.
In step S20, the organosiloxane monomer VII is used to provide R2R1 " (R1 ") SiO2/2Or
R2R1”SiO3/2Chain link, the organosilane monomers are used to provide epoxide group.
Wherein, for providing R2 (R1 ")2SiO2/2The organosiloxane monomer VII of chain link is bis-alkoxysilane list
Body, it can be selected from 3- glycidoxypropyl groups (methyl) dimethoxysilane, 3- glycidoxypropyl group (first
Base) diethoxy silane, 3- glycidoxypropyl groups (methyl) dibutoxy silane, 2,3- epoxypropyls
(methyl) dimethoxysilane, 2- (3,4- expoxycyclohexyls) hexyl (methyl) dimethoxysilane,
One or more in 2- (3,4- expoxycyclohexyl) hexyl (methyl) diethoxy silane, but do not limit to
In this.
And be used to provide R2R1 " SiO3/2The organosiloxane monomer IV of chain link is then trialkoxy silane, and it can
With selected from 3- glycidyl ether oxygen propyl trimethoxy silicanes, 3- glycidoxypropyltrietandysilane andysilanes,
2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl triethoxy silicane
One or more in alkane, but it is not limited to this.
Step S10 using chlorosilane easily with water reaction generation Organosilicon Alcohol in Organic and the principle of HCl, by water droplet plus
Enter in chlorosilane solution, wherein the Organosilicon Alcohol in Organic for generating is dissolved in organic solvent, silanol can be avoided to connect with water
The condensation touched and produce, HCl and the alkali reaction in water phase of generation are removed.Described organic solvent can be
Ether, butyl ether, toluene and dimethylbenzene etc..Described alkali should can so ensure with the water equimolar being added dropwise
Hydrolyze the HCl and alkali reaction with same mole of generation, it is to avoid excessive HCl or the alkali residual of excess can promote silanol
Condensation reaction.Described alkali requirement can be dissolved or dispersed in water, such as NaOH, potassium hydroxide,
Barium carbonate, sodium acid carbonate, triethylamine etc..
Step S20 using alcoholic extract hydroxyl group and the organosiloxane monomer of Organosilicon Alcohol in Organic alkoxy in certain circumstances
Meeting dealcoholysis forms the principle of condensation product, and the dealcoholization is under the collective effect of catalyst and proton solvent
Carry out.Described catalyst is base catalyst.In certain embodiments, the catalyst be magnesium, calcium,
The hydroxide or oxide of strontium, barium；With the Organosilicon Alcohol in Organic in step S20, organosiloxane monomer IV,
The integral molar quantity of organosiloxane monomer V, organosiloxane monomer VI and organosiloxane monomer VII is base
Standard, the consumption of catalyst is 0.0005-5mol%.Proton solvent is selected from water, methyl alcohol, ethanol or 2- propyl alcohol
Any one, with the Organosilicon Alcohol in Organic in step S20, organosiloxane monomer IV, organosiloxane monomer
Vth, on the basis of the integral molar quantity of organosiloxane monomer VI and organosiloxane monomer VII, proton solvent
Consumption is 0.02-200mol%.In certain embodiments, proton solvent is water, and its consumption is 0.02-8mol%.
In some embodiments of the invention, the temperature of the dealcoholization condensation reaction is 50-100 DEG C.Using the method
Obtained tackifier molecular weight distribution evenly, is more beneficial for its intermiscibility with silica gel.
In step S30, solvent and low-boiling point material can be boiled off by vacuum distillation, can mistake by filtering
Insoluble catalyst is filtered, so as to obtain the organic silicon rigidity-increasing stick.Vacuum distillation and filtering can be using these
The conventional method in field is carried out, and the present invention is not particularly limited, and is not described in detail herein.
The organic silicon rigidity-increasing stick that the present invention is provided, its adhesive property that can be used in silica gel improve silica gel and base material.
Therefore, invention also provides a kind of silica-gel composition, provided containing the present invention in the silica-gel composition
Organic silicon rigidity-increasing stick.The silica-gel composition of the organic silicon rigidity-increasing stick provided using the present invention has good with base material
Good adhesive property.
The silica-gel composition is known to those skilled in the art, typically by the siloxanes containing vinyl, contains
The components such as the siloxanes of hydrogen, catalyst and inhibitor are mixed according to a certain percentage, without spy in the present invention
It is different to limit.The silica-gel composition can be used to encapsulate the association areas such as solar battery sheet.
The silica-gel composition that the present invention is provided, its organic silicon rigidity-increasing stick that present invention offer is provided.In the present invention
Some embodiments in, on the basis of the gross mass of the silica-gel composition, wherein, organic silicon rigidity-increasing stick
Content is 0.1-2.5%.
Make specific explanations explanation to the present invention with reference to embodiments.Raw material employed in embodiment and comparative example
It is commercially available, the present invention is not particularly limited.
Embodiment 1
The present embodiment is used to illustrate the organic silicon rigidity-increasing stick A1 and silica-gel composition B1 of present invention offer.
16.296g trim,ethylchlorosilanes (M=108.64, n=0.15mol) are taken as organic silicon monomer I, 12.906g
Dimethyldichlorosilane (M=129.06, n=0.1mol) is used as organosilane monomers II, 41.1g methyl trichlorosilanes
(M=149.4536, n=0.275mol) is used as organic silicon monomer Ш, 26.447g methyl ethylene dimethoxy silicon
Alkane (M=132.2331, n=0.2mol) is used as organic silicon monomer V, 30.65g MTMSs
(M=136.22, n=0.225mol) is used as organic silicon monomer VI, 11.017g3- glycidoxypropyl groups (methyl)
Dimethoxysilane (M=220.34, n=0.05mol) is used as organic silicon monomer VII.
Organic silicon monomer I, II, Ш and 150g toluene is well mixed, then the water of barium carbonate is added dropwise thereto
Dispersion liquid (content of barium carbonate is 50%), continues to react 1h after completion of dropwise addition, and then stratification removes water
Layer, the toluene layer for obtaining is the toluene solution of trimethyl silanol, Dimethylsilanediol and methyl silanetriol；Will
After toluene solution is removed water with anhydrous sodium sulfate drying, then it is added to organic silicon monomer V, VI, VII, 3.7g
Calcium hydroxide (M=74, n=0.05mol) and 64g methyl alcohol (M=32, n=2mol), after being warming up to 80 DEG C of reaction 4h
Terminate reaction, be then filtered off insoluble calcium hydroxide, be warming up to 150 DEG C of vacuum distillations and obtain clear
The present embodiment siliceous vinyl organic silicon rigidity-increasing stick, be designated as A1.Its theoretical construct formula is：
By the dimethyl of the end-blocking of the vinyldimethylsiloxane with 0.15mmol/g contents of ethylene of 100g
Polysiloxanes mixes with the methyl polysiloxane with 5.5mmol/g hydrogen contents of 5g, then before adding 2.625g
Inhibitor, the 0.2g platinum catalysts of organic silicon rigidity-increasing stick A1,0.1g are stated, stirring makes to be well mixed, and obtains this
The addition-type silicon rubber composition of embodiment, is designated as B1.
Embodiment 2
The present embodiment is used to illustrate the organic silicon rigidity-increasing stick A2 and silica-gel composition B2 of present invention offer.
88.38g diethyl dichlorosilanes (M=157.12, n=0.5625mol) are used as organosilane monomers II, 5.913g
Trimethylethoxysilane (M=118.25, n=0.05mol) is used as organic silicon monomer IV, 15.429g diethyl two
Ethoxysilane (M=176.3287, n=0.0875mol) is used as organic silicon monomer V, 7.512g ethyl trimethoxies
Base silane (M=150.2484, n=0.05mol), 9.516g VTESs
(M=190.31, n=0.05mol) is used as organic silicon monomer VI, 47.28g3- glycidoxypropyl group trimethoxy silicon
Alkane (M=236.4, n=0.2mol) is used as organic silicon monomer VII.
Organic silicon monomer II and 150g ether is well mixed, then sodium hydrate aqueous solution (carbon is added dropwise thereto
68.97%), after completion of dropwise addition to continue to react 1h, then stratification removes water layer to the content of sour hydrogen sodium,
The ether layer for obtaining is the diethyl ether solution of diethyl silicon diol；Diethyl ether solution is removed water with anhydrous sodium sulfate drying
Afterwards, then it is added to organic silicon monomer IV, V, VI, VII, 0.000855g barium hydroxides
(M=171, n=0.000005mol) and 0.09g water (M=18, n=0.005mol), is warming up to 100 DEG C of reaction 5h
After terminate reaction, be then filtered off insoluble barium hydroxide, being warming up to 150 DEG C of vacuum distillations, to obtain clarification saturating
The organic silicon rigidity-increasing stick of the siliceous vinyl of bright the present embodiment, is designated as A2.Its theoretical construct formula is：
By the dimethyl of the end-blocking of the vinyldimethylsiloxane with 0.15mmol/g contents of ethylene of 100g
Polysiloxanes mixes with the methyl polysiloxane with 5.5mmol/g hydrogen contents of 5g, then before adding 0.525g
Inhibitor, the 0.2g platinum catalysts of organic silicon rigidity-increasing stick A2,0.1g are stated, stirring makes to be well mixed, and obtains this
The addition-type silicon rubber composition of embodiment, is designated as B2.
Embodiment 3
The present embodiment is used to illustrate the organic silicon rigidity-increasing stick A3 and silica-gel composition B3 of present invention offer.
The normal propyl chloride silane (M=192.8015, n=0.05mol) of 9.64g tri- is taken as organosilane monomers I,
70.704g diethyl dichlorosilanes (M=157.12, n=0.45mol) are used as organosilane monomers II, 10.013g first
Base trichlorosilane (M=149.4536, n=0.067mol) is used as organic silicon monomer Ш, 5.812g dimethyl ethenyls
Methoxy silane (M=116.23, n=0.05mol) is used as organosilane monomers IV, 6.617g methyl ethylene diformazans
TMOS (M=132.33, n=0.05mol) is used as organic silicon monomer V, 38.276g n-propyl trimethoxy silicon
Alkane (M=164.2749, n=0.233mol) is used as organic silicon monomer VI, 28.846g2- (3,4- 7-oxa-bicyclo[4.1.0) ethyl
Triethoxysilane (M=288.4552, n=0.1mol) is used as organic silicon monomer VII.
Organic silicon monomer I, II, Ш and 150g dimethylbenzene is well mixed, then triethylamine is added dropwise thereto
The aqueous solution (content of triethylamine is 84.9%), continues to react 1h after completion of dropwise addition, and then stratification is removed
Water layer, the diformazan benzene layer for obtaining is three n-propyl silanols, Dimethylsilanediol, the dimethylbenzene of the silanol of methyl three
Solution；By xylene solution with anhydrous sodium sulfate drying remove water after, then be added to organic silicon monomer IV, V,
VIth, VII, 0.4g magnesia (M=40, n=0.01mol) and 60g2- propyl alcohol (M=60, n=1mol), are warming up to
Terminate reaction after 50 DEG C of reaction 4h, be then filtered off insoluble calcium hydroxide, be warming up to 150 DEG C of vacuum distillations
The organic silicon rigidity-increasing stick of the siliceous vinyl of the present embodiment of clear is obtained, A3 is designated as.Its theory knot
Structure formula is：
By the poly- silicon of dimethyl of the end-blocking of the vinyldimethylsiloxane with 0.15mmol/g contents of ethylene of 100g
Oxygen alkane mixes with the methyl polysiloxane with 5.5mmol/g hydrogen contents of 5g, then adds that 1.365g is foregoing to be had
Inhibitor, the 0.2g platinum catalysts of machine silicon tackifier A3,0.1g, stirring make to be well mixed, and obtain this implementation
The addition-type silicon rubber composition of example, is designated as B3.
Comparative example 1
This comparative example is used for the silica-gel composition DB1 for illustrating not containing the organic silicon rigidity-increasing stick that the present invention is provided.
By the dimethyl of the end-blocking of the vinyldimethylsiloxane with 0.15mmol/g contents of ethylene of 100g
Polysiloxanes mixes with the methylhydrogenpolysi,oxane with 5.5mmol/g hydrogen contents of 5g, then adds 0.1g's
Inhibitor, 0.2g platinum catalysts, stirring make to be well mixed, and obtain the silica-gel composition of this comparative example, are designated as
DB1。
Performance test
(1) examination of infrared spectrum
The organic silicon rigidity-increasing stick A1 prepared to embodiment 1 carries out examination of infrared spectrum, as shown in Figure 1.
1650cm as shown in Figure 1-1It is the characteristic absorption peak of C=C keys to locate.It follows that also depositing in the product
In C=C keys.906cm-1Locate the characteristic absorption peak for epoxide group, it follows that also there is epoxy in product
Group.
(2) adhesive property test
According to GB/T 13936-92《Vulcanized rubber bonds tensile shear strength assay method with metal》Test
Shear strength after each rubber composition solidification.Test condition：100 DEG C of heat cure 1h.Test result such as table 1
It is shown.
(3) light transmittance test
The light transmittance tested after each rubber composition solidifies using all band light transmittance tester
Test result is as shown in table 1.
Table 1
| Silicon rubber sample | Shear strength (MPa) | Light transmittance (%) |
| B1 | 1.03 | 91.9% |
| B2 | 1.69 | 91.6% |
| B3 | 1.46 | 91.9% |
| DB1 | 0.36 | 92% |
The silica-gel composition that can be seen that present invention offer from the test result of upper table 1 employs the present invention and carries
The organic silicon rigidity-increasing stick of confession, the shear strength after its solidification is substantially better than the silica gel sample DB1 of comparative example, and
Transmittance data is not substantially reduced, that is, illustrate the silica-gel composition of present invention offer as a result of the present invention
The organic silicon rigidity-increasing stick of the new structure of offer so that it has good adhesive property with base material, and not
Light transmittance can be reduced.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in this hair
Any modification, equivalent and improvement made within bright spirit and principle etc., should be included in the present invention
Protection domain within.
Claims (17)
1. a kind of organic silicon rigidity-increasing stick, it is characterised in that the structure of the organic silicon rigidity-increasing stick is as shown in Formulas I or Formula II：
[(R1)3SiO1/2]a[(R1’)2SiO2/2]b[R2R1’’(R1’’)SiO2/2]c[R1’’’SiO3/2]d
Formulas I
[(R1)3SiO1/2]a[(R1’)2SiO2/2]b[R2R1’’SiO3/2]c[R1’’’SiO3/2]d
Formula II
Wherein, at least one contains-CH=CH2 in R1, R1 ', to be respectively selected from carbon atom be at least one in 1-8 alkyl and-CH=CH2 to R1 ' ' ', and R1, R1 ', R1 ' ' '；R1 ' ' is that carbon atom is 1-8 alkyl, and R2 is the group containing cyclic ether；A, b, c, d are molar content, a+b+c+d=1,0<a<1,0<b<1,0<c<1,0<d<1.
2. organic silicon rigidity-increasing stick according to claim 1, it is characterised in that 0<A≤0.2,0.3≤b≤0.7,0.05≤c≤0.2,0.05≤d≤0.5.
3. organic silicon rigidity-increasing stick according to claim 1, characterized in that, described R1, R1 ', R1 ' ' ' be each independently selected from methyl, ethyl, n-propyl, 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 the R2 is glycidyl or expoxycyclohexyl；
Wherein, the glycidyl is selected from any one in 2,3- epoxypropyls, 3,4- epoxy radicals butyl, 4,5- epoxypentyls, 2- glycidoxyethyls, 3- glycidoxypropyl groups, 4- glycidoxy butyl；
The expoxycyclohexyl can be 2- (3,4- expoxycyclohexyls) ethyls or 3- (3,4- expoxycyclohexyls) 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 (R1)3SiO1/2The organochlorosilane monomer I of chain link, offer (R1 ') 2SiO2/2The organochlorosilane monomer II of chain link, offer R1 ' ' ' SiO3/2One or more in the organochlorosilane monomer III of chain link, after mixing with organic solvent in proportion, alkaline aqueous solution is added dropwise thereto, reaction obtains the organic solution containing Organosilicon Alcohol in Organic；
S20, the organic solution containing Organosilicon Alcohol in Organic for obtaining step S10, with offer (R1)3SiO1/2The organosiloxane monomer IV of chain link, offer (R1 ')2SiO2/2The organosiloxane monomer V of chain link, offer R1 ' ' ' SiO3/2One or more, offer R2R1 ' ' (R1 ' ') SiO of the organosiloxane monomer VI of chain link2/2Or R2R1 ' ' SiO3/2The organosiloxane monomer VII, catalyst of chain link, proton solvent mixing, then heating up carries out catalysis dealcoholization, obtains pre-product；
S30, the pre-product that S20 steps are obtained filter and then vacuum distillation, obtain the organic silicon rigidity-increasing stick.
6. preparation method according to claim 5, it is characterized in that, in step S10, the organochlorosilane monomer I is selected from one or more in trim,ethylchlorosilane, chlorotriethyl silane, three normal propyl chloride silane, dimethyl vinyl chlorosilane, diethyl vinyl chlorosilane, Methylethyl vinyl chlorosilane.
7. preparation method according to claim 5, it is characterized in that, in step S10, the organochlorosilane monomer II is selected from one or more in dimethyldichlorosilane, diethyl dichlorosilane, dipropyl dichlorosilane, Methylethyl dichlorosilane, methyl-propyl dichlorosilane, ethyl propyl dichlorosilane, methylvinyldichlorosilane, ethyl vinyl dichlorosilane, propyl ethylene base dichlorosilane.
8. preparation method according to claim 5, it is characterised in that in step S10, the organochlorosilane monomer III is selected from one or more in methyl trichlorosilane, ethyl trichlorosilane, n-propyltrichlorosilan, vinyl trichlorosilane.
9. preparation method according to claim 5, it is characterized in that, in step S20, the organosiloxane monomer IV is selected from trimethylmethoxysilane, trimethylethoxysilane, triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, three n-propyl methoxy silanes, three n-propyl Ethoxysilanes, dimethylvinylmethoxysiiane, Vinyldimethylethoxysilane, diethoxy vinyl methoxy silane, diethyl vinylethoxysilane, diη-propyl vinyl methoxy silane, diη-propyl vinylethoxysilane, tetramethyl divinyl disiloxane, HMDO, one or more in hexaethyldisiloxane.
10. preparation method according to claim 5, it is characterized in that, in step S20, the organosiloxane monomer V is selected from dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diη-propyl dimethoxysilane, diη-propyl diethoxy silane, methylvinyldimethoxysilane, methyl vinyl diethoxysilane, ethyl vinyl dimethoxysilane, ethyl vinyl diethoxy silane, n-propyl vinyl dimethoxysilane, one or more in n-propyl vinyl diethoxy silane.
11. preparation methods according to claim 5, it is characterized in that, in step S20, the organosiloxane monomer VI is selected from one or more in MTMS, MTES, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl trimethoxy silane, n-propyl triethoxysilane, vinyltrimethoxy silane, VTES.
12. preparation methods according to claim 5, it is characterised in that in step S20, there is provided R2R1 ' ' (R1 ' ') SiO2/2The organosiloxane monomer VII of chain link is selected from 3- glycidoxypropyl groups（Methyl）Dimethoxysilane, 3- glycidoxypropyl groups（Methyl）Diethoxy silane, 3- glycidoxypropyl groups（Methyl）Dibutoxy silane, 2,3- epoxypropyls（Methyl）Dimethoxysilane, 2-（3,4- expoxycyclohexyls）Hexyl（Methyl）Dimethoxysilane, 2-（3,4- expoxycyclohexyls）Hexyl（Methyl）One or more in diethoxy silane；
R2R1 ' ' SiO are provided3/2The organosiloxane monomer VII of chain link is selected from 3- glycidyl ether oxygen propyl trimethoxy silicanes, 3- glycidoxypropyltrietandysilane andysilanes, 2-（3,4- epoxycyclohexyls）Ethyl trimethoxy silane, 2-（3,4- epoxycyclohexyls）One or more in ethyl triethoxysilane.
13. preparation methods according to claim 5, it is characterised in that in step S10, the organic solvent is selected from any one in ether, butyl ether, toluene and dimethylbenzene；The alkali is selected from any one in NaOH, potassium hydroxide, barium carbonate, sodium acid carbonate, triethylamine.
14. preparation methods according to claim 5, it is characterised in that in step S20, the catalyst is base catalyst；The base catalyst is selected from any one in magnesium, calcium, strontium, the hydroxide of barium or oxide；
On the basis of the integral molar quantity of the Organosilicon Alcohol in Organic in step S20, organosiloxane monomer IV, organosiloxane monomer V, organosiloxane monomer VI and organosiloxane monomer VII, the consumption of catalyst is 0.0005-5mol%；The consumption of the proton solvent is 0.02-200mol%；Reaction temperature is 50-100 DEG C.
15. preparation methods according to claim 14, it is characterised in that the proton solvent is water, methyl alcohol, ethanol or 2- propyl alcohol.
16. a kind of silica-gel compositions, it is characterised in that contain the organic silicon rigidity-increasing stick described in claim any one of 1-4 in the silica-gel composition.
17. silica-gel compositions according to claim 16, it is characterised in that on the basis of the gross mass of the silica-gel composition, wherein, the content of organic silicon rigidity-increasing stick is 0.1-2.5%.
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