CN102994004A - Reinforcing addition type liquid silicone rubber bonding accelerant and preparation method and application thereof - Google Patents
Reinforcing addition type liquid silicone rubber bonding accelerant and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a reinforcing addition type liquid silicone rubber bonding accelerant and a preparation method and an application thereof. The bonding accelerant is a siloxane compound which contains polyalkenyl, epoxy groups and alkoxyl simultaneously. The preparation method comprises the steps of uniformly agitating a hydroxyl containing polyalkenyl ether compound and an epoxy siloxane compound at room temperature; adding a catalyst; heating to 60-130 DEG C to react for 1-10h; and then, continuously reacting for 1-6h at a reduced pressure. The bonding accelerant provided by the invention is simple and convenient in preparation process, low in cost of materials which are easy to get, green and environment-friendly and suitable for industrialized production. The bonding accelerant prepared by the method provided by the invention can remarkably improve the bonding performance of the liquid silicone rubber, is beneficial for fillers to be filled and dispersed in silicon rubber, improves the mechanical property of the silicon rubber, and has a wide application prospect in the fields of electronic apparatus packaging, semiconductor chip coating and photovoltaic module packaging and the like.
Description
Technical field
The present invention relates to the bonding and Strengthening Technology field of organosilicon material, in more detail can improve the adhesion promoters of add-on type liquid silicon rubber adhesiveproperties and mechanical property.The invention still further relates to the preparation method and application of described adhesion promoters.
Background technology
The world today, scientific and technical fast development, the mankind have entered the electronic information epoch.Along with the continuous progress of electronic technology, that electronic component, logical circuit are tending towards day by day is integrated, miniaturization and modularization, and Working environment is harsher, and the stability in use of electron device is had higher requirement.Encapsulation is one of important procedure of electronic devices and components, it can the strengthening electronic device globality, prevent moisture, dust and obnoxious flavour to the erosion of electronic devices and components, improve the resistibility to external shock, vibrations, stablize component parameter, and be conducive to miniaturization and the lightweight of device.
Electronic package material commonly used mainly contains Resins, epoxy, urethane and organosilicon material three major types at present.Wherein, add-on type liquid silicon rubber can keep elasticity at-60~200 ℃ long-term, does not absorb heat during curing, not heat release, do not shrink after the curing, and having good electrical property and chemical stability, energy water-fast, anti-ozone, weather-proof becomes one of high performance packaged material.Although add-on type liquid silicon rubber has the incomparable advantage of other packaged material, himself also has some problems.Be nonpolar organic group such as add-on type liquid silicon rubber in the sulfuration rear surface overwhelming majority, show low internal cohesive energy (Silicone sealants and structural adhesives.International Journal of Adhesion ﹠amp; Adhesives; 2001; 21 (5): 411-422); thereby poor to the cementability of other material; moisture causes corrosion and failure of insulation by the infiltration inside of electronic component of the space between silicon rubber and the base material easily in use; in the environment of harshness even can come off with base material, make electron device lose seal protection, limited to a certain extent its range of application.
In order to address the above problem, the cementability that how to improve add-on type liquid silicon rubber and base material some researchs have been carried out both at home and abroad.At present, mainly contain three kinds of methods: the one, substrate surface is processed, comprise that shortcoming is to need additional production process, has reduced production efficiency, has increased production cost with silane coupling agent pretreating substrates surface, with measures such as Cement Composite Treated by Plasma substrate surfaces; The 2nd, by changing the molecular structure of polysiloxane, make add-on type liquid silicon rubber itself have cementability, but because this preparation process more complicated realizes that suitability for industrialized production is subject to larger restriction with applying; The 3rd, by adding adhesion promoters, made add-on type liquid silicon rubber solidify the rear cementability that obtains.
Chinese patent CN102408869A discloses a kind of with vinyl front three (second) TMOS and γ-(2,3-epoxy the third oxygen) propyl group front three (second) TMOS has the add-on type liquid silicon rubber adhesion promoters of certain cementability by hydrolysis reaction or both hydrolysis reaction products and γ-aminopropyl front three (second) TMOS reaction preparation to aluminium, but there is the bad control of hydrolysis reaction condition of siloxanes, reaction process produces gel easily, and nitrogenous compound makes the shortcomings such as Pt catalyst poisoning easily.European patent EP 2158285B1 has reported a kind of synthetic silicoorganic compound with at least one benzene ring structure, at least one alicyclic epoxy base and at least one Si-H base of addition reaction of silicon with hydrogen that utilize, and it is added in the silicon rubber can make the sealing material that the electrolytic thin-membrane in the fuel cell is produced good bonding.Chinese patent CN102010598A also reported a kind of utilize addition reaction of silicon with hydrogen synthetic contain the organo-siloxane that has allyl group, epoxy group(ing) and organic siloxy-on trimerization isocyanide acyl ring and the per 1 molecule trimerization isocyanide acyl ring; by add this adhesion promoters to silicon rubber, can make the thermoplasticss such as itself and liquid crystalline polymers produce good bonding.But all have the bad control of addition reaction of silicon with hydrogen condition, platinum catalyst is removed the shortcomings such as difficulty.
Although at present to the more existing reports of the adhesion promoters that improves the add-on type liquid silicon rubber cementability, but adhesiveproperties is only studied in these work mostly, does not but have relevant report for the adhesion promoters that can improve simultaneously add-on type liquid silicon rubber adhesiveproperties and mechanical property.Because organo-silicone rubber has the amorphism structure, its macromolecular chain is very submissive, and is extremely low without the organo-silicone rubber intensity of reinforcement a little less than the interchain interaction power, almost has no value for use.Therefore, developing the add-on type liquid silicon rubber adhesion promoters with strengthening action has great importance.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of add-on type liquid silicon rubber adhesion promoters with strengthening action and preparation method thereof is provided.
The invention still further relates to the application of adhesion promoters in add-on type liquid silicon rubber, this adhesion promoters is added in the add-on type liquid silicon rubber, can obtain good adhesive property and mechanical property.
Purpose of the present invention is achieved through the following technical solutions:
A kind of add-on type liquid silicon rubber adhesion promoters with strengthening action contains the silicone compounds of polyene-based, epoxy group(ing) and alkoxyl group simultaneously, and its general molecular formula is:
R wherein
1For-CH (CH
2OCH
2CH=CH
2)
2,-CH
2C (CH
2CH
3) (CH
2OCH
2CH=CH
2)
2Or-CH
2C (CH
2OCH
2CH=CH
2)
3R
2For-CH
3Or-CH
2CH
3R
3For-CH
3,-CH
2CH
3,-OCH
3Or-OCH
2CH
3R
4For-CH
2CH
2CH
2OCH
2R
5Or-CH
2CH
2R
6, R wherein
5Be epoxy group(ing), R
6It is 3,4-epoxy group(ing)-cyclohexyl.
Preparation method with add-on type liquid silicon rubber adhesion promoters of strengthening action: polyene-based ether compound and the epoxy group(ing) silicone compounds of hydroxyl were at room temperature stirred in 0.8: 1 in molar ratio~1.4: 1, then 0.5~4% the organic titanate catalyzer that under agitation condition, adds the reactant total mass, being to react 1~10h under 60~130 ℃ of conditions in temperature, is to continue reaction 1~6h under 0.01~30kPa condition to obtain the add-on type liquid silicon rubber adhesion promoters in vacuum tightness;
The polyene-based ether compound of described hydroxyl is one or more in glycerine diallyl ether, trimethylolpropane allyl ether and the pentaerythritol triallyl ether; Structural formula is respectively:
Glycerine diallyl ether trimethylolpropane allyl ether pentaerythritol triallyl ether
Described epoxy group(ing) silicone compounds is 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, 3-(2,3-epoxy the third oxygen) propyl group methyl dimethoxysilane, 3-(2,3-epoxy the third oxygen) propyl-triethoxysilicane, 3-(2,3-epoxy the third oxygen) propyl group methyldiethoxysilane, 2-(3,4-epoxy cyclohexane base) one or more in ethyl trimethoxy silane and 2-(3, the 4-epoxy cyclohexane base) ethyl triethoxysilane;
Described organic titanate catalyzer is one or more in tetraethyl titanate, titanium isopropylate, tetrabutyl titanate, metatitanic acid four tert-butyl esters and the bis(acetylacetonate) titanium acid diisopropyl ester.
Further, the mol ratio of the polyene-based ether compound of described hydroxyl and epoxy group(ing) silicone compounds be preferably 1: 1~1.2: 1.Described temperature is the time of reacting under 60~130 ℃ of conditions to be preferably 1.5~7.5h.Described vacuum tightness is the time of continuing reaction under 0.01~30kPa condition to be preferably 2~4h.
The application of described adhesion promoters in add-on type liquid silicon rubber: successively the 1-ethynyl of adhesion promoters, containing hydrogen silicone oil and 0.004~0.03 mass parts of the aluminum oxide of the vinyl silicone oil of 100 mass parts, 120~200 mass parts, 0.8~6 mass parts-1-hexalin is added kneader, at room temperature stir, and then the adding platinum content is the divinyl tetramethyl disiloxane complex compound of the Platinic chloride of 1500~4500ppm, stir, deaeration 8~25min under vacuum tightness 0.5~50kPa is at last in 110~150 ℃ of lower curing 1~5h moulding; In the described containing hydrogen silicone oil in si-h bond and vinyl silicone oil and the adhesion promoters mol ratio of two key summations be 1: 1~1.6: 1; Described platinum atom content accounts for 2~40ppm of total quality of material.
The present invention compared with prior art has following advantage:
1, the adhesion promoters of the present invention's preparation can significantly improve the adhesiveproperties of add-on type liquid silicon rubber, adds a small amount of (being generally less than 2.5 mass parts) adhesion promoters in silicon rubber, and bonding strength can improve more than 150%.
2, the adhesion promoters of the present invention's preparation can significantly improve the mechanical property of add-on type liquid silicon rubber.This adhesion promoters contains polyene-based, can form the Concentrative crosslinking structure when add-on type liquid silicon rubber solidifies, and the ability of add-on type liquid silicon rubber opposing external force is strengthened, and intensity improves.
3, the adhesion promoters of the present invention's preparation can improve the consistency of filler and add-on type liquid silicon rubber, is conducive to filling and the dispersion of filler in silicon rubber, improves processing characteristics.
4, preparation technology of the present invention is easy, and raw material is cheap and easy to get, and environmental protection is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the infrared spectrum of the adhesion promoters 1 of preparation among the embodiment 1;
Fig. 2 is the nucleus magnetic hydrogen spectrum of the adhesion promoters 1 of preparation among the embodiment 1;
Fig. 3 is the infrared spectrum of the adhesion promoters 6 of preparation among the embodiment 6;
Fig. 4 is the nucleus magnetic hydrogen spectrum of the adhesion promoters 6 of preparation among the embodiment 6.
Embodiment
For a better understanding of the present invention, below in conjunction with embodiment the present invention is done further explanation, but embodiments of the present invention are not limited to this.
Embodiment 1
With 12.82g pentaerythritol triallyl ether (APE) and 11.82g 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH-560) adds the there-necked flask with thermometer and condensing reflux pipe, at room temperature stir, then under agitation condition, drip the 0.25g tetrabutyl titanate, be warming up to 80 ℃ of reaction 2h, under vacuum tightness 0.5kPa, continue at last reaction 2h and get product adhesion promoters 1.
Infrared spectrum (Fig. 1) to adhesion promoters 1 is analyzed, at 2844cm
-1The absorption peak of methoxyl group appears in the place, at 1646cm
-1The absorption peak of two keys appears in the place, at 922cm
-1C-H absorption peak in the thiazolinyl and the absorption peak of epoxy group(ing) appear in the place.
Nucleus magnetic hydrogen spectrum (Fig. 2) to adhesion promoters 1 is analyzed, the peak at chemical shift 5~6ppm place is produced by the hydrogen proton in two keys, the peak at chemical shift 3.54ppm place is produced by the hydrogen proton in the methoxyl group, and the peak at chemical shift 2.5~3.2ppm place is produced by the hydrogen proton in the epoxy group(ing).
Can determine that by infrared spectrum and nucleus magnetic hydrogen spectrum adhesion promoters 1 is for containing simultaneously the compound of polyene-based, epoxy group(ing) and alkoxyl group.Wherein, polyene-based can participate in the curing of add-on type liquid silicon rubber, forms the Concentrative crosslinking structure, has improved the mechanical property of silicon rubber; And epoxy group(ing), alkoxyl group isopolarity group can improve the reactive force of add-on type liquid silicon rubber and base material, make silicon rubber have good cementability.Above-mentioned preparation process can adopt reaction formula to be expressed as:
Be the vinyl silicone oil of 300mPas with 40 mass parts viscosity successively, the vinyl silicone oil of 60 mass parts 1000mPas, 150 mass parts median sizes are the aluminum oxide of 5 μ m, the adhesion promoters 1 of 2 mass parts, 7.12 the mass parts hydrogen content is 0.5% containing hydrogen silicone oil and 0.01 mass parts 1-ethynyl-1-hexalin adding kneader, at room temperature stir, and then add the divinyl tetramethyl disiloxane complex compound that 0.38 mass parts platinum content is the Platinic chloride of 2600ppm, stir, deaeration 15min under vacuum tightness 2kPa is at last in 130 ℃ of lower curing 2h moulding.The performance of sample is as shown in table 1, and testing method sees Table 1 explanation.Its bonding tensile shear strength (is called for short shearing resistance, together lower) be 1.19MPa, tensile strength is 3.19MPa, shearing resistance (0.34MPa) and tensile strength (2.23MPa) with respect to comparative example 1 have improved respectively 250% and 43%, illustrate that the adhesion promoters 1 with APE and KH-560 preparation can improve adhesiveproperties and the mechanical property of add-on type liquid silicon rubber significantly.
With 12.82g APE and 18.02g 2-(3,4-epoxy cyclohexane base) ethyl triethoxysilane (KH-567) adds the there-necked flask with thermometer and condensing reflux pipe, at room temperature stir, then under agitation condition, drip the 0.15g tetrabutyl titanate, be warming up to 130 ℃ of reaction 1h, under vacuum tightness 0.01kPa, continue at last reaction 1h and get product adhesion promoters 2.
Be the vinyl silicone oil of 300mPas with 40 mass parts viscosity successively, the vinyl silicone oil of 60 mass parts 1000mPas, 120 mass parts median sizes are the aluminum oxide of 5 μ m, 2.5 the adhesion promoters 2 of mass parts, 6.33 the mass parts hydrogen content is 0.5% containing hydrogen silicone oil and 0.004 mass parts 1-ethynyl-1-hexalin adding kneader, at room temperature stir, and then add the divinyl tetramethyl disiloxane complex compound that 0.3 mass parts platinum content is the Platinic chloride of 1500ppm, stir, deaeration 25min under vacuum tightness 50kPa is at last in 110 ℃ of lower curing 5h moulding.The performance of sample is as shown in table 1, its shearing resistance is 0.81MPa, tensile strength is 2.89MPa, compare with tensile strength (2.06MPa) with the shearing resistance (0.31MPa) of comparative example 2 and to have improved respectively 161% and 40%, illustrate that the adhesion promoters 2 with APE and KH-567 preparation can improve adhesiveproperties and the mechanical property of add-on type liquid silicon rubber preferably.
Embodiment 3
The present embodiment difference from Example 1 is KH-560 is changed into 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane (KH-566), and its consumption is 12.32g, makes adhesion promoters 3.
Adhesion promoters 3 is carried out infrared spectrum and nucleus magnetic hydrogen spectrum analysis as can be known, and its structure is:
Adhesion promoters 1 is changed into adhesion promoters 3, and its consumption is 1.5 mass parts, the consumption of corresponding containing hydrogen silicone oil is reduced to 6.3 mass parts, and the consumption of the divinyl tetramethyl disiloxane complex compound of Platinic chloride is changed into 1.52 mass parts.The performance of solidifying sample is as shown in table 1, its shearing resistance is 0.96MPa, tensile strength is 3.01MPa, shearing resistance and tensile strength with respect to comparative example 1 have improved respectively 182% and 35%, illustrate that KH-566 replaces the adhesion promoters 3 of KH-560 preparation can significantly improve adhesiveproperties and the mechanical property of add-on type liquid silicon rubber.
With 10.72g trimethylolpropane allyl ether (TMPDE) and 9.94g 3-(2,3-epoxy the third oxygen) propyl-triethoxysilicane (KH-561) adds the there-necked flask with thermometer and condensing reflux pipe, at room temperature stir, then under agitation condition, drip the 0.83g tetrabutyl titanate, be warming up to 60 ℃ of reaction 10h, under vacuum tightness 30kPa, continue at last reaction 6h and get product adhesion promoters 4.
Be the vinyl silicone oil of 300mPas with 40 mass parts viscosity successively, the vinyl silicone oil of 60 mass parts 1000mPas, 200 mass parts median sizes are the aluminum oxide of 5 μ m, the adhesion promoters 4 of 6 mass parts, 13.88 the mass parts hydrogen content is 0.5% containing hydrogen silicone oil and 0.03 mass parts 1-ethynyl-1-hexalin adding kneader, at room temperature stir, and then add the divinyl tetramethyl disiloxane complex compound that 2.84 mass parts platinum contents are the Platinic chloride of 4500ppm, stir, deaeration 8min under vacuum tightness 0.5kPa is at last in 150 ℃ of lower curing 1h moulding.The performance of sample is as shown in table 1, its shearing resistance is 1.43MPa, tensile strength is 3.34MPa, compare with comparative example 3 and to have improved respectively 297% and 27%, illustrate that the adhesion promoters 4 with TMPDE and KH-561 preparation can improve adhesiveproperties and the mechanical property of add-on type liquid silicon rubber significantly.
Embodiment 5
The present embodiment difference from Example 1 is KH-560 is changed into KH-561, and its consumption is 13.92g, accordingly the tetrabutyl titanate consumption is brought up to 0.27g, makes adhesion promoters 5.
Adhesion promoters 5 is carried out infrared spectrum and nucleus magnetic hydrogen spectrum analysis as can be known, and its structure is:
Adhesion promoters 1 is changed into adhesion promoters 5, and its consumption is 1.5 mass parts, the consumption of corresponding containing hydrogen silicone oil is reduced to 6.22 mass parts.The performance of sample is as shown in table 1, its shearing resistance is 1.04MPa, tensile strength is 3.15MPa, shearing resistance and tensile strength with respect to comparative example 1 have improved respectively 206% and 41%, illustrate with KH-561 to replace the adhesion promoters 5 of KH-560 preparation can improve significantly adhesiveproperties and the mechanical property of add-on type liquid silicon rubber.
The present embodiment difference from Example 1 is APE is changed into TMPDE, and its consumption is 10.72g, accordingly the tetrabutyl titanate consumption is reduced to 0.22g, makes adhesion promoters 6.Adhesion promoters 6 is carried out infrared spectrum (Fig. 3) and nucleus magnetic hydrogen spectrum (Fig. 4) analyze as can be known, its structure is:
Adhesion promoters 1 is changed into adhesion promoters 6, and its consumption is 1.5 mass parts, the consumption of corresponding containing hydrogen silicone oil is reduced to 5.73 mass parts, and the consumption of the divinyl tetramethyl disiloxane complex compound of Platinic chloride is changed into 0.76 mass parts.The performance of sample is as shown in table 1, its shearing resistance is 0.92MPa, tensile strength is 3.06MPa, compare with tensile strength with the shearing resistance of comparative example 1 and to have improved respectively 170% and 37%, illustrate with TMPDE to replace the adhesion promoters 6 of APE preparation can improve preferably adhesiveproperties and the mechanical property of add-on type liquid silicon rubber.
Comparative example 1
Be that the vinyl silicone oil of vinyl silicone oil, the 60 mass parts 1000mPas of 300mPas, aluminum oxide, 4.03 mass parts hydrogen contents that 150 mass parts median sizes are 5 μ m are that containing hydrogen silicone oil and 0.01 mass parts 1-ethynyl-1-hexalin of 0.5% add kneader successively with 40 mass parts viscosity, under 30 ℃, stir, and then add the vinylsiloxane complex compound that 0.38 mass parts platinum content is the Platinic chloride of 2600ppm, stir, be deaeration 20min under the 2kPa in vacuum tightness, in 130 ℃ of lower curing 2h moulding, the performance of sample is as shown in table 1 at last.
Comparative example 2
Be the vinyl silicone oil of 300mPas with 40 mass parts viscosity successively, the vinyl silicone oil of 60 mass parts 1000mPas, 120 mass parts median sizes are the aluminum oxide of 5 μ m, 3.39 the mass parts hydrogen content is 0.5% containing hydrogen silicone oil and 0.004 mass parts 1-ethynyl-1-hexalin adding kneader, at room temperature stir, and then add the divinyl tetramethyl disiloxane complex compound that 0.3 mass parts platinum content is the Platinic chloride of 1500ppm, stir, deaeration 25min under vacuum tightness 50kPa, in 110 ℃ of lower curing 5h moulding, the performance of sample is as shown in table 1 at last.
Comparative example 3
Be the vinyl silicone oil of 300mPas with 40 mass parts viscosity successively, the vinyl silicone oil of 60 mass parts 1000mPas, 200 mass parts median sizes are the aluminum oxide of 5 μ m, 5.37 the mass parts hydrogen content is 0.5% containing hydrogen silicone oil and 0.03 mass parts 1-ethynyl-1-hexalin adding kneader, at room temperature stir, and then add the divinyl tetramethyl disiloxane complex compound that 2.71 mass parts platinum contents are the Platinic chloride of 4500ppm, stir, deaeration 8min under vacuum tightness 0.5kPa, in 150 ℃ of lower curing 1h moulding, the performance of sample is as shown in table 1 at last.
The product performance testing method is as follows in the table 1:
1, according to the viscosity of GB/T 2794-1995 with rotary viscosity design determining silicon rubber.
2, measure the bonding tensile shear strength of silicon rubber and aluminium according to GB/T 13936-1992.
3, measure tensile strength and the elongation at break of silicon rubber according to GB/T 528-2009.
4, measure the Shore A hardness of silicon rubber according to GB/T 531-2008.
Table 1 add-on type liquid silicon rubber the performance test results
Claims (6)
1. add-on type liquid silicon rubber adhesion promoters with strengthening action is characterized in that: promotor is for containing simultaneously the silicone compounds of polyene-based, epoxy group(ing) and alkoxyl group, and its general molecular formula is:
R wherein
1For-CH (CH
2OCH
2CH=CH
2)
2,-CH
2C (CH
2CH
3) (CH
2OCH
2CH=CH
2)
2Or-CH
2C (CH
2OCH
2CH=CH
2)
3R
2For-CH
3Or-CH
2CH
3R
3For-CH
3,-CH
2CH
3,-OCH
3Or-OCH
2CH
3R
4For-CH
2CH
2CH
2OCH
2R
5Or-CH
2CH
2R
6, R wherein
5Be epoxy group(ing), R
6It is 3,4-epoxy group(ing)-cyclohexyl.
2. the preparation method with add-on type liquid silicon rubber adhesion promoters of strengthening action claimed in claim 1, it is characterized in that: polyene-based ether compound and the epoxy group(ing) silicone compounds of hydroxyl were at room temperature stirred in 0.8: 1 in molar ratio~1.4: 1, then 0.5~4% the organic titanate catalyzer that under agitation condition, adds the reactant total mass, being to react 1~10h under 60~130 ℃ of conditions in temperature, is to continue reaction 1~6h under 0.01~30kPa condition to obtain the add-on type liquid silicon rubber adhesion promoters in vacuum tightness;
The polyene-based ether compound of described hydroxyl is one or more in glycerine diallyl ether, trimethylolpropane allyl ether and the pentaerythritol triallyl ether;
Described epoxy group(ing) silicone compounds is 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, 3-(2,3-epoxy the third oxygen) propyl group methyl dimethoxysilane, 3-(2,3-epoxy the third oxygen) propyl-triethoxysilicane, 3-(2,3-epoxy the third oxygen) propyl group methyldiethoxysilane, 2-(3,4-epoxy cyclohexane base) one or more in ethyl trimethoxy silane and 2-(3, the 4-epoxy cyclohexane base) ethyl triethoxysilane;
Described organic titanate catalyzer is one or more in tetraethyl titanate, titanium isopropylate, tetrabutyl titanate, metatitanic acid four tert-butyl esters and the bis(acetylacetonate) titanium acid diisopropyl ester.
3. preparation method according to claim 2, it is characterized in that: the polyene-based ether compound of described hydroxyl and the mol ratio of epoxy group(ing) silicone compounds are 1: 1~1.2: 1.
4. preparation method according to claim 2, it is characterized in that: described temperature is that the time of reacting under 60~130 ℃ of conditions is 1.5~7.5h.
5. preparation method according to claim 2 is characterized in that: described vacuum tightness is that the time of continuing reaction under 0.01~30kPa condition is 2~4h.
6. the application of adhesion promoters claimed in claim 1 in add-on type liquid silicon rubber, it is characterized in that: successively with the vinyl silicone oil of 100 mass parts, the aluminum oxide of 120~200 mass parts, 0.8 the adhesion promoters of~6 mass parts, the 1-ethynyl of containing hydrogen silicone oil and 0.004~0.03 mass parts-1-hexalin adds kneader, at room temperature stir, and then the adding platinum content is the divinyl tetramethyl disiloxane complex compound of the Platinic chloride of 1500~4500ppm, stir, deaeration 8~25min under vacuum tightness 0.5~50kPa is at last in 110~150 ℃ of lower curing 1~5h moulding; In the described containing hydrogen silicone oil in si-h bond and vinyl silicone oil and the adhesion promoters mol ratio of two key summations be 1: 1~1.6: 1; Described platinum atom content accounts for 2~40ppm of total quality of material.
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