CN114231174A - Organic silicon coating adhesive and preparation method thereof - Google Patents

Organic silicon coating adhesive and preparation method thereof Download PDF

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CN114231174A
CN114231174A CN202111681143.XA CN202111681143A CN114231174A CN 114231174 A CN114231174 A CN 114231174A CN 202111681143 A CN202111681143 A CN 202111681143A CN 114231174 A CN114231174 A CN 114231174A
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alkoxy
phenyl
nitrogen
mixing
phenyl polysiloxane
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CN114231174B (en
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孙刚
林志秀
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Xintai Yonghe Yantai New Material Co ltd
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Yantai Tightsen Fine Chemicals Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
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Abstract

The invention discloses an organic silicon coating adhesive which comprises the following components in parts by weight: 30-50 parts of methyl alkoxy phenyl silicone resin, 650-750 parts of bi-end alkoxy end-blocked phenyl polysiloxane, 50-100 parts of single-end alkoxy end-blocked phenyl polysiloxane, 80-120 parts of phenyl methyl silicone oil, 10-50 parts of thixotropic agent, 1-5 parts of water removing agent, 50-100 parts of crosslinking agent, 10-30 parts of first coupling agent, 10-30 parts of second coupling agent and 5-15 parts of catalyst. The organic silicon coating adhesive disclosed by the invention has the advantages of no occurrence of viscosity peak, excellent aging resistance, improved storage stability and greatly improved bonding strength. The invention also provides a preparation method of the organic silicon coating adhesive.

Description

Organic silicon coating adhesive and preparation method thereof
Technical Field
The invention relates to the field of novel organic silicon materials, in particular to an organic silicon coating adhesive and a preparation method thereof.
Background
Coating glues, also known as three-proofing paints, Coating glues, moisture-proof glues, insulating glues, etc., are known under the english name of formal Coating. The coating glue can be divided into the following systems: silicone resin, acrylic resin, polyurethane, synthetic rubber, synthetic resin, modified resin, fluorosilicone resin, etc., wherein the silicone resin coating composition is applied in a wide range of applications due to its excellent properties of aging resistance, weather resistance, ultraviolet resistance, etc.
The coating adhesive is generally coated on a circuit board (PCBA, also called printed circuit board) of an electronic component, and a layer of 0.02-0.2 mm insulating compact protective film is formed on the circuit board, so that the penetration of water vapor and the pollution of dust are blocked, and the three-proofing effect is achieved. From the actual role, the coating glue has only three prevention functions, namely moisture prevention, salt mist prevention, mildew prevention, dust prevention, shock prevention, corrosion prevention, electric leakage prevention, aging prevention, insulation, life prolongation and the like; the application field is very wide: the protective film can protect electronic devices, circuit boards, communication devices and other precise components in the industries of electronic appliances, household appliance industry, digital electronics, led, automobile industry, aerospace, navigation, medical treatment and the like in all directions.
Because of the environmental requirements, the traditional solvent-based coating adhesives are gradually eliminated, and the solvent-free environmental protection (LOV) coating adhesives are more popular and accepted in the market.
The traditional room temperature dealcoholization condensation silica gel adopts hydroxyl-terminated silicone oil (commonly known as 107 glue) as a main raw material, has the defect of high viscosity, has a viscosity peak in the processing process, influences the processing and use, has poor stability in the storage process, greatly prolongs the surface drying time, and even does not solidify; the glue has poor toughness and low strength, and is easy to break or crack under the conditions of impact, pressing and the like, so that the protective effect of the glue is influenced. These problems have hindered the development of silicone coated adhesives and are urgently needed to be solved.
Disclosure of Invention
The object of the present invention is to solve the drawbacks of the prior art. The organic silicon coating adhesive provided by the invention has the advantages of no viscosity peak, excellent aging resistance, improved storage stability and greatly improved bonding strength.
The invention provides an organic silicon coating adhesive which comprises the following components in parts by weight:
Figure BDA0003449200810000021
further, the structural formula of the methyl alkoxy phenyl silicone resin is shown as the formula (I):
(RMe2SiO0.5)a(MePhSiO0.5)b(MeSiO1.5)c(SiO2) Formula (I)
Wherein R is methoxy or ethoxy, a is 0.2-0.4, b is 0.2-0.4, c is 0.8-1.1, and a + b + c is 1.4-1.7;
the alkoxy group content is 0.25 wt%, and the molecular weight is 2000-5000.
The beneficial effects of using the resin are as follows: the silicone resin is used as an important node for constructing the main framework, so that the cured adhesive layer has high strength and high crosslinking density, and the adhesive layer has good water resistance and oil resistance; the T-link ensures the toughness of the adhesive layer; meanwhile, the introduction of the phenyl greatly improves the weather resistance and the aging resistance.
Further, the viscosity of the bi-terminal alkoxy end-capped phenyl polysiloxane and/or the mono-terminal alkoxy end-capped phenyl polysiloxane is 50-5000 mPa & s;
the bi-and/or mono-terminal alkoxy-terminated phenyl polysiloxane has the structure of formula (II):
Figure BDA0003449200810000031
wherein m is more than 1, and m and n are integers which enable the viscosity of the phenyl polysiloxane terminated by double end alkoxy and/or the phenyl polysiloxane terminated by single end alkoxy to be 50-5000 mPa & s;
r1 is vinyl or methyl.
Further, the phenyl polysiloxane terminated by two terminal alkoxy groups or the phenyl polysiloxane terminated by single terminal alkoxy groups is prepared by the following method:
(1) vacuumizing and stirring double-end vinyl phenyl polydimethylsiloxane or single-end vinyl phenyl polydimethylsiloxane at 150 ℃ for 2h to remove residual micromolecules and moisture in the interior, and then cooling to 30 ℃;
(2) introducing nitrogen, adding a chloroplatinic acid catalyst solution, and continuously mixing for 30 min;
(3) heating to 100 ℃ under the protection of nitrogen, slowly adding a certain amount of hydrogen-containing alkoxy silane, reacting for 2 hours at 100 ℃ after the addition is finished, vacuumizing and stirring for 2 hours at 120 ℃ after the reaction is finished, and removing low-boiling and unreacted raw materials;
(4) and cooling to 25 ℃ under the protection of nitrogen, adding graphite powder, adsorbing to remove chloroplatinic acid, and filtering to obtain the bi-alkoxy end-capped phenyl polysiloxane or the mono-alkoxy end-capped phenyl polysiloxane.
Further, the chloroplatinic acid catalyst solution comprises anhydrous chloroplatinic acid and isopropanol, and the weight ratio of the anhydrous chloroplatinic acid: 1-isopropyl alcohol: 100, respectively;
the amount of the chloroplatinic acid catalyst solution is 5-10 ppm of the double-end vinyl polydimethylsiloxane or the single-end vinyl phenyl polydimethylsiloxane in terms of Pt content.
The silicone oil synthesized by the method has the beneficial effects that: the introduction of Si-OH is avoided by adopting a hydrosilylation mode, dehydrating raw materials and protecting nitrogen in the whole process; the single-end vinyl phenyl polydimethylsiloxane can reduce the viscosity of a product, can participate in the reaction, reduces the hardness, improves the elongation and resilience, and does not generate the migration problem.
Further, the hydroalkoxysilane is triethoxysilane, and the addition amount thereof is such that the molar ratio Si-H/Si-Vi is 1.0 to 1.2.
Wherein Vi represents a vinyl group.
The silicone resin and the silicone oil have the beneficial effects that: no hydroxyl group, no viscosity peak, and greatly improved processability; compare 107 simultaneously and glue, have excellent storage stability, promoted the practicality of product, satisfy the automated production who develops day by day.
Further, the phenylmethylsilicone oil has the structure of formula (III):
(CH3)3SiO[(C6H5)2SiO]X[(CH3)2SiO]YSi(CH3)3formula (III)
Wherein X is greater than 1 and X, Y is an integer such that the viscosity of the phenylmethylsilicone oil satisfies 50 to 100 mPas.
The effect of using the above phenyl methyl silicone oil is: the silicone oil containing phenyl group has viscosity reducing effect, and also has improved compatibility with main resin and silicone oil, high temperature resistance, irradiation resistance and lubricity.
Further, the second coupling agent has the structure of formula (iv):
Figure BDA0003449200810000041
wherein, L is more than 0 and less than 5, and L is an integer.
The coupling agent with the structure has the beneficial effects that: the acrylate and the epoxy group in the molecule can effectively promote the adhesion of the product to different materials, especially the adhesion of a PCB (printed Circuit Board), simultaneously contain a certain amount of alkoxy groups, and can also participate in the reaction, so that the coupling agent molecule can play a role more stably, and the phenyl group is arranged, thereby enhancing the intermiscibility and the strength.
Further, the second coupling agent is synthesized by the following route:
the first step is as follows:
Figure BDA0003449200810000051
the second step is that:
Figure BDA0003449200810000052
the third step:
Figure BDA0003449200810000061
wherein the catalyst-0 is a platinum catalyst, and the catalyst-1 and the catalyst-2 are both acid catalysts.
Further, the thixotropic agent is oleophylic hydrophobic white carbon black, and the specific surface area is 150-200; the water removing agent is hexamethyldisilazane; the cross-linking agent is one or more of phenyl trimethoxy silane, phenyl triethoxy silane, phenyl vinyl dimethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, methyl orthosilicate and ethyl orthosilicate which are mixed randomly.
Further, the first coupling agent is any mixture of one or more of KH-550, KH-560, KH-570, A-186 and KH-792.
The technical scheme has the beneficial effects that a large number of adhesive groups are provided, the adhesion between the adhesive layer and the surface of the base material is enhanced, and meanwhile, the raw materials are wide in source and great in cost advantage.
Further, the catalyst is one or a mixture of several of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, n-butyl titanate, tetraisopropyl titanate, TYZOR-9000, TYZOR-722 and TYZOR-726.
The invention also provides a preparation method of the organic silicon coating adhesive, which comprises the following steps:
(1) mixing the phenyl methyl silicone oil and the thixotropic agent for 30min according to the parts by weight; then adding distilled water with the thixotropic agent accounting for 1 percent, and continuously mixing for 20 min; adding a water removing agent with the thixotropic agent content of 2%, and mixing for 10 min; heating to 102 ℃ and mixing for 1 h; then heating to 120 ℃, and mixing for 1 h; then heating to 150 ℃, and vacuumizing and mixing for 4 h; then vacuumizing, stirring and cooling to 25 ℃, keeping the temperature constant, and protecting with nitrogen;
(2) adding the methyl alkoxy phenyl silicone resin, the bi-end alkoxy end-capped phenyl polysiloxane and the mono-end alkoxy end-capped phenyl polysiloxane according to the weight parts, and mixing for 30min under the protection of nitrogen; then adding the rest of the water removing agent, the cross-linking agent, the first coupling agent and the second coupling agent, and mixing for 30min under the protection of nitrogen; finally, adding the catalyst, and mixing for 20min under the protection of nitrogen;
(3) vacuumizing and stirring for 20min, breaking vacuum by nitrogen, discharging into a sealing tube, and obtaining the organic silicon coating adhesive.
Further, the phenyl polysiloxane terminated by two terminal alkoxy groups or the phenyl polysiloxane terminated by single terminal alkoxy groups is prepared by the following method:
(1) vacuumizing and stirring double-end vinyl phenyl polydimethylsiloxane or single-end vinyl phenyl polydimethylsiloxane at 150 ℃ for 2 hours, and then cooling to 30 ℃;
(2) introducing nitrogen, adding a chloroplatinic acid catalyst solution, and continuously mixing for 30 min;
(3) heating to 100 ℃ under the protection of nitrogen, slowly adding a certain amount of hydrogen-containing alkoxy silane, reacting for 2 hours at 100 ℃ after the addition is finished, and vacuumizing and stirring for 2 hours at 120 ℃;
(4) and cooling to 25 ℃ under the protection of nitrogen, adding graphite powder, and filtering to obtain the bi-end alkoxy end-capped phenyl polysiloxane or the mono-end alkoxy end-capped phenyl polysiloxane.
Further, in the preparation method of the silicone coated gum, the mixing of the phenylmethylsilicone oil and the thixotropic agent in the step (1) and the mixing in the step (2) are all carried out under mechanical stirring, and the rotation speed of the mechanical stirring is 500 rpm.
On the basis of the technical scheme, different fillers such as pigment, fluorescent whitening agent, flame retardant powder, heat conducting powder and the like can be added according to different requirements.
Compared with the prior art, the invention provides an organic silicon coating adhesive and a preparation method thereof, and the organic silicon coating adhesive has the following technical effects:
the organic silicon coating adhesive prepared by the invention can not generate a viscosity peak, and the processability is greatly improved; meanwhile, the anti-aging and storage stability of the product is excellent, the practicability of the product is improved, and the increasingly developed automatic production is met; the organic silicon coating adhesive prepared by the invention has greatly improved bonding strength to different materials, especially PCB boards, and prolonged service life.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure. While the invention will be described in conjunction with the preferred embodiments, it is not intended that features of the invention be limited to these embodiments. On the contrary, the invention is described in connection with the embodiments for the purpose of covering alternatives or modifications that may be extended based on the claims of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be practiced without these particulars. Moreover, some of the specific details have been left out of the description in order to avoid obscuring or obscuring the focus of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example 1
Synthesis of a double-end alkoxy-terminated phenyl polysiloxane:
vacuumizing 1000g of double-end vinyl phenyl polydimethylsiloxane (R1 is vinyl and the vinyl content is 1.7 wt%) with the viscosity of 50 mPas and the structural formula of (II) at 150 ℃ for stirring for 2h, continuously stirring, vacuumizing and cooling to 30 ℃; breaking vacuum with nitrogen (anhydrous) and protecting, adding 1.1g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol 1: 100), and mixing for 30 min; under the protection of nitrogen, heating to 100 ℃, adding 110g of hydrogen-containing alkoxy silane, slowly adding the hydrogen-containing alkoxy silane, and reacting for 2 hours at 100 ℃; vacuumizing and stirring for 2h at 120 ℃ after the time is reached, and removing low-boiling and unreacted raw materials; cooling to 25 ℃ under the protection of nitrogen, adding graphite powder to adsorb and remove chloroplatinic acid; filtering to obtain the required bi-end alkoxy end-capped phenyl polysiloxane-1;
synthesis of single terminal alkoxy-terminated phenyl polysiloxane:
1000g of single-ended vinyl phenyl polydimethylsiloxane (R1 is methyl, the vinyl content is 0.85 wt%) with the viscosity of 50 mPas and the structural formula of (II) is vacuumized and stirred for 2h at 150 ℃, and the mixture is continuously stirred, vacuumized and cooled to 30 ℃; breaking vacuum with nitrogen (anhydrous) and protecting, adding 1.1g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol 1: 100), and mixing for 30 min; heating to 100 ℃ under the protection of nitrogen, adding 55g of hydrogen-containing alkoxy silane, slowly adding the hydrogen-containing alkoxy silane, and reacting for 2 hours at 100 ℃; vacuumizing and stirring for 2h at 120 ℃ after the time is reached, and removing low-boiling and unreacted raw materials; cooling to 25 ℃ under the protection of nitrogen, adding graphite powder to adsorb and remove chloroplatinic acid; filtering to obtain the required phenyl polysiloxane-1 with the end sealed by the single end alkoxy;
preparation of a phenyl-containing, one-component, clear, room temperature dealcoholized cured silicone coating gum:
80g of phenyl methyl silicone oil with the viscosity of 100 mPas and shown in a structural formula (III) and 50g of oleophylic hydrophobic white carbon black with the specific surface area of 200 are mixed for 30min at 500 rpm; then adding 0.5g of distilled water, and continuing to mix for 20 min; then adding 1.0g of hexamethyldisilazane and mixing for 10 min; heating to 102 ℃ and mixing for 1 h; then heating to 120 ℃, and mixing for 1 h; then heating to 150 ℃, and vacuumizing and mixing for 4 h; then vacuumizing, stirring and cooling to 25 ℃, keeping the temperature constant, and protecting with nitrogen; adding 50g of methylalkoxy phenyl silicone resin (with alkoxy content of 0.25 wt% and molecular weight of 5000) with the structural formula shown in (I), 650g of double-end alkoxy end-capped phenyl polysiloxane-1 and 50g of single-end alkoxy end-capped phenyl polysiloxane-1, and mixing for 30min at 500rpm under the protection of nitrogen; mixing the mixture for 30min at 500rpm under the protection of nitrogen by adding 1.5g of hexamethyldisilazane, 50g of phenylvinyldimethoxysilane, 10gKH-560 and 10g of a second coupling agent (wherein L is 4) with the structural formula shown in the specification; adding 5g of dibutyltin dilaurate, and mixing for 20min at 500rpm under the protection of nitrogen; vacuumizing and stirring for 20min, breaking the vacuum by nitrogen, discharging into a sealing tube, and obtaining the phenyl-containing single-component transparent room-temperature dealcoholized and cured organic silicon coating adhesive 1.
Example 2
Synthesis of a double-end alkoxy-terminated phenyl polysiloxane:
vacuumizing 1000g of double-end vinyl phenyl polydimethylsiloxane (R1 is vinyl and the vinyl content is 0.32 wt%) with the viscosity of 1000 mPas and the structural formula of (II) at 150 ℃ for stirring for 2h, continuously stirring, vacuumizing and cooling to 30 ℃; breaking vacuum with nitrogen (anhydrous) and protecting, adding 1.7g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol 1: 100), and mixing for 30 min; under the protection of nitrogen, heating to 100 ℃, adding 22g of hydrogen-containing alkoxy silane, slowly adding the hydrogen-containing alkoxy silane, and reacting for 2 hours at 100 ℃; vacuumizing and stirring for 2h at 120 ℃ after the time is reached, and removing low-boiling and unreacted raw materials; cooling to 25 ℃ under the protection of nitrogen, adding graphite powder to adsorb and remove chloroplatinic acid; filtering to obtain the required bi-end alkoxy end-capped phenyl polysiloxane-2;
synthesis of single terminal alkoxy-terminated phenyl polysiloxane:
vacuumizing 1000g of single-end vinyl phenyl polydimethylsiloxane (R1 is methyl, the vinyl content is 0.16 wt%) with the viscosity of 1000 mPas and the structural formula of (II) at 150 ℃ for stirring for 2h, continuously stirring, vacuumizing and cooling to 30 ℃; breaking vacuum with nitrogen (anhydrous) and protecting, adding 1.7g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol 1: 100), and mixing for 30 min; heating to 100 ℃ under the protection of nitrogen, adding 11g of hydrogen-containing alkoxy silane, slowly adding the hydrogen-containing alkoxy silane, and reacting for 2 hours at 100 ℃; vacuumizing and stirring for 2h at 120 ℃ after the time is reached, and removing low-boiling and unreacted raw materials; cooling to 25 ℃ under the protection of nitrogen, adding graphite powder to adsorb and remove chloroplatinic acid; filtering to obtain the required phenyl polysiloxane-2 with the end sealed by the single end alkoxy;
preparation of a phenyl-containing, one-component, clear, room temperature dealcoholized cured silicone coating gum:
100g of phenyl methyl silicone oil with the viscosity of 80 mPas and the structural formula (III) and 25g of oleophylic and hydrophobic white carbon black with the specific surface area of 180 are mixed for 30min at 500 rpm; then adding 0.25g of distilled water, and continuing to mix for 20 min; then adding 0.5g of hexamethyldisilazane and mixing for 10 min; heating to 102 ℃ and mixing for 1 h; then heating to 120 ℃, and mixing for 1 h; then heating to 150 ℃, and vacuumizing and mixing for 4 h; then vacuumizing, stirring and cooling to 25 ℃, keeping the temperature constant, and protecting with nitrogen; adding 40g of methylalkoxyphenyl silicone resin (with an alkoxy content of 0.25 wt% and a molecular weight of 3500) having the structural formula (I), 700g of double-end alkoxy-terminated phenyl polysiloxane-2 and 75g of single-end alkoxy-terminated phenyl polysiloxane-2, and mixing for 30min at 500rpm under the protection of nitrogen; adding 3g of hexamethyldisilazane, 15g of phenylvinyldimethoxysilane, 60g of phenyltrimethoxysilane, 10gKH-560, 10gKH570 and 20g of a second coupling agent (wherein L is 3) with the structural formula of (IV), and mixing for 30min at 500rpm under the protection of nitrogen; adding 10g of n-butyl titanate, and mixing for 20min at 500rpm under the protection of nitrogen; vacuumizing and stirring for 20min, breaking the vacuum by nitrogen, discharging into a sealing tube, and obtaining the phenyl-containing single-component transparent room-temperature dealcoholized and cured organic silicon coating adhesive 2.
Example 3
Synthesis of a double-end alkoxy-terminated phenyl polysiloxane:
vacuumizing 1000g of double-end vinyl phenyl polydimethylsiloxane (R1 is vinyl and the vinyl content is 0.16 wt%) with the viscosity of 5000 mPas and the structural formula as (II) at 150 ℃ for stirring for 2h, continuously stirring, vacuumizing and cooling to 30 ℃; breaking vacuum with nitrogen (anhydrous) and protecting, adding 2.1g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol 1: 100), and mixing for 30 min; under the protection of nitrogen, heating to 100 ℃, adding 12g of hydrogen-containing alkoxy silane, slowly adding the hydrogen-containing alkoxy silane, and reacting for 2 hours at 100 ℃; vacuumizing and stirring for 2h at 120 ℃ after the time is reached, and removing low-boiling and unreacted raw materials; cooling to 25 ℃ under the protection of nitrogen, adding graphite powder to adsorb and remove chloroplatinic acid; filtering to obtain the required bi-end alkoxy end-capped phenyl polysiloxane-3;
synthesis of single terminal alkoxy-terminated phenyl polysiloxane:
vacuumizing 1000g of single-end vinyl phenyl polydimethylsiloxane (R1 is methyl, the vinyl content is 0.08 wt%) with the viscosity of 5000 mPas and the structural formula as (II) at 150 ℃ for stirring for 2h, continuously stirring, vacuumizing and cooling to 30 ℃; breaking vacuum with nitrogen (anhydrous) and protecting, adding 2.1g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol 1: 100), and mixing for 30 min; under the protection of nitrogen, heating to 100 ℃, adding 6g of hydrogen-containing alkoxy silane, slowly adding the hydrogen-containing alkoxy silane, and reacting for 2 hours at 100 ℃; vacuumizing and stirring for 2h at 120 ℃ after the time is reached, and removing low-boiling and unreacted raw materials; cooling to 25 ℃ under the protection of nitrogen, adding graphite powder to adsorb and remove chloroplatinic acid; filtering to obtain the required phenyl polysiloxane-3 with the end sealed by the single end alkoxy;
preparation of a phenyl-containing, one-component, clear, room temperature dealcoholized cured silicone coating gum:
100g of phenyl methyl silicone oil with the viscosity of 50 mPas and the structural formula (III) and 10g of oleophylic and hydrophobic white carbon black with the specific surface area of 150 are mixed for 30min at 500 rpm; then adding 0.1g of distilled water, and continuing to mix for 20 min; then adding 0.2g of hexamethyldisilazane and mixing for 10 min; heating to 102 ℃ and mixing for 1 h; then heating to 120 ℃, and mixing for 1 h; then heating to 150 ℃, and vacuumizing and mixing for 4 h; then vacuumizing, stirring and cooling to 25 ℃, keeping the temperature constant, and protecting with nitrogen; adding 50g of methylalkoxy phenyl silicone resin (with alkoxy content of 0.25 wt% and molecular weight of 2000) with the structural formula shown in (I), 750g of double-end alkoxy end-capped phenyl polysiloxane-3 and 100g of single-end alkoxy end-capped phenyl polysiloxane-3, and mixing for 30min at 500rpm under the protection of nitrogen; then adding 5g of hexamethyldisilazane, 50g of phenyl vinyl dimethoxysilane, 50g of vinyl trimethoxy silane, 30g of A-186 and 30g of a second coupling agent (wherein L is 2) with the structural formula shown as (IV), and mixing for 30min at 500rpm under the protection of nitrogen; adding 10g of n-butyl titanate and 5g of tetraisopropyl titanate, and mixing for 20min at 500rpm under the protection of nitrogen; vacuumizing and stirring for 20min, breaking the vacuum by nitrogen, discharging into a sealing tube, and obtaining the phenyl-containing single-component transparent room-temperature dealcoholized and cured organic silicon coating adhesive 3.
Comparative example 1
100g of dimethyl silicone oil with the viscosity of 50mPa & s and 10g of oleophylic and hydrophobic white carbon black with the specific surface area of 150 are mixed for 30min at 500 rpm; then adding 0.1g of distilled water, and continuing to mix for 20 min; then adding 0.2g of hexamethyldisilazane and mixing for 10 min; heating to 102 ℃ and mixing for 1 h; then heating to 120 ℃, and mixing for 1 h; then heating to 150 ℃, and vacuumizing and mixing for 4 h; then vacuumizing, stirring and cooling to 25 ℃, keeping the temperature constant, and protecting with nitrogen; adding 900g of 107 glue with the viscosity of 5000mPa.s, and mixing for 30min at 500rpm under the protection of nitrogen; adding 5g of hexamethyldisilazane, 50g of phenyl vinyl dimethoxysilane, 50g of vinyl trimethoxy silane, 30g of A-186 and 30g of a second coupling agent (wherein L is 2) with the structural formula of (IV), and mixing for 30min at 500rpm under the protection of nitrogen; adding 10g of n-butyl titanate and 5g of tetraisopropyl titanate, and mixing for 20min at 500rpm under the protection of nitrogen; vacuumizing and stirring for 20min, breaking the vacuum by nitrogen, discharging into a sealing tube, and obtaining the phenyl-containing single-component transparent organic silica gel which is dealcoholized and cured at room temperature.
Comparative example 2
The main flow of alkoxy-terminated silicone oil is commercially available as coating gum.
Comparative example 3
Preparation of a phenyl-containing, one-component, clear, room temperature dealcoholized and cured silicone gum:
100g of phenyl methyl silicone oil with the viscosity of 50 mPas and the structural formula (III) and 10g of oleophylic and hydrophobic white carbon black with the specific surface area of 150 are mixed for 30min at 500 rpm; then adding 0.1g of distilled water, and continuing to mix for 20 min; then adding 0.2g of hexamethyldisilazane and mixing for 10 min; heating to 102 ℃ and mixing for 1 h; then heating to 120 ℃, and mixing for 1 h; then heating to 150 ℃, and vacuumizing and mixing for 4 h; then vacuumizing, stirring and cooling to 25 ℃, keeping the temperature constant, and protecting with nitrogen. Adding 50g of methylalkoxy phenyl silicone resin (with alkoxy content of 0.25 wt% and molecular weight of 2000) with the structural formula shown in (I), 750g of double-end alkoxy end-capped phenyl polysiloxane-3 and 100g of single-end alkoxy end-capped phenyl polysiloxane-3, and mixing for 30min at 500rpm under the protection of nitrogen; mixing 5g of hexamethyldisilazane, 50g of phenylvinyldimethoxysilane, 50g of vinyltrimethoxysilane and 60g A-186 at 500rpm under the protection of nitrogen for 30 min; adding 10g of n-butyl titanate and 5g of tetraisopropyl titanate, and mixing for 20min at 500rpm under the protection of nitrogen; vacuumizing and stirring for 20min, breaking the vacuum by nitrogen, discharging into a sealing tube, and obtaining the phenyl-containing single-component transparent organic silica gel which is dealcoholized and cured at room temperature.
The silicone coating adhesives obtained in the examples and comparative examples of the present invention were subjected to performance testing:
1. surface drying time: the surface of the sealant is touched by hands every other minute under the conditions of 23 +/-2 ℃ and 50 +/-5% RH, and the surface skinning time is the surface drying time;
2. and (3) aging test: after the surface of the copper sheet is subjected to rust removal treatment, coating glue is sprayed, after the copper sheet is completely cured, the following aging process is carried out, and whether rust and color change exist on the surface of part of the copper sheet protected by the coating glue is observed:
(1) aging for 100 hours by using a double-85 aging method;
(2) aging at high temperature for 100h (100 ℃);
(3) the cold and hot impact is carried out for 100 cycles (-40 ℃ to 85 ℃).
The results of the performance tests of the silicone coating gums of each example and comparative example are shown in table 1.
TABLE 1 Performance test results of the silicone coating gums of the examples and comparative examples
Figure BDA0003449200810000131
As can be seen from Table 1, through the data analysis of the example 3 and the comparative example 3, the organic silicon coating adhesive prepared by the self-synthesized coupling agent of the invention has obvious enhancement effect on the adhesion of PCB materials; according to the data analysis of the example 3 and the comparative examples 1 and 2, the alkoxy-terminated silicone oil is obviously better than a 107 glue system in viscosity peak and storage stability; in addition, the introduction of alkoxy end capping of a phenyl system and alkoxy phenyl silicone resin obviously improves the strength and greatly improves the aging resistance.
While the invention has been described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more particular description of the invention than is possible with reference to the specific embodiments, which are not to be construed as limiting the invention. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (10)

1. The organic silicon coating adhesive is characterized by comprising the following components in parts by weight:
Figure FDA0003449200800000011
2. the silicone-coated gum of claim 1, wherein the methylalkoxyphenyl silicone resin has the structural formula of formula (I):
(RMe2SiO0.5)a(MePhSiO0.5)b(MeSiO1.5)c(SiO2) Formula (I)
Wherein R is methoxy or ethoxy, a is 0.2-0.4, b is 0.2-0.4, c is 0.8-1.1, and a + b + c is 1.4-1.7;
the alkoxy group content is 0.25 wt%, and the molecular weight is 2000-5000.
3. The silicone coating gum of claim 1, wherein the viscosity of the both-end alkoxy-terminated phenyl polysiloxane and/or the single-end alkoxy-terminated phenyl polysiloxane is 50 to 5000 mPa-s;
the bi-and/or mono-terminal alkoxy-terminated phenyl polysiloxane has the structure of formula (II):
Figure FDA0003449200800000012
wherein m is more than 1, and m and n are integers which enable the viscosity of the phenyl polysiloxane terminated by double end alkoxy and/or the phenyl polysiloxane terminated by single end alkoxy to be 50-5000 mPa & s;
r1 is vinyl or methyl.
4. The silicone coating gum of claim 1, wherein the double end alkoxy-terminated phenyl polysiloxane or the single end alkoxy-terminated phenyl polysiloxane is prepared by the following method:
(1) vacuumizing and stirring double-end vinyl phenyl polydimethylsiloxane or single-end vinyl phenyl polydimethylsiloxane at 150 ℃ for 2 hours, and then cooling to 30 ℃;
(2) introducing nitrogen, adding a chloroplatinic acid catalyst solution, and continuously mixing for 30 min;
(3) heating to 100 ℃ under the protection of nitrogen, slowly adding a certain amount of hydrogen-containing alkoxy silane, reacting for 2 hours at 100 ℃ after the addition is finished, and vacuumizing and stirring for 2 hours at 120 ℃;
(4) and cooling to 25 ℃ under the protection of nitrogen, adding graphite powder, and filtering to obtain the bi-end alkoxy end-capped phenyl polysiloxane or the mono-end alkoxy end-capped phenyl polysiloxane.
5. The silicone coating gum of claim 4, wherein the chloroplatinic acid catalyst solution comprises anhydrous chloroplatinic acid, isopropanol, and the weight ratio of the anhydrous chloroplatinic acid: 1-isopropyl alcohol: 100, respectively;
the amount of the chloroplatinic acid catalyst solution is 5-10 ppm of the double-end vinyl polydimethylsiloxane or the single-end vinyl phenyl polydimethylsiloxane in terms of Pt content.
6. The silicone coating gum of claim 4, wherein the hydroalkoxysilane is triethoxysilane in a molar ratio Si-H/Si-Vi of 1.0 to 1.2.
7. The silicone coated gum of claim 1, wherein the phenylmethylsilicone oil has the structure of formula (III):
(CH3)3SiO[(C6H5)2SiO]X[(CH3)2SiO]YSi(CH3)3formula (III)
Wherein X is greater than 1 and X, Y is an integer such that the viscosity of the phenylmethylsilicone oil satisfies 50 to 100 mPas.
8. The silicone coated gum of claim 1, wherein the second coupling agent has the structure of formula (iv):
Figure FDA0003449200800000031
wherein, L is more than 0 and less than 5, and L is an integer.
9. A method of preparing the silicone coated gum of any one of claims 1-8, comprising the steps of:
(1) mixing the phenyl methyl silicone oil and the thixotropic agent for 30min according to the parts by weight; then adding distilled water with the thixotropic agent accounting for 1 percent, and continuously mixing for 20 min; adding a water removing agent with the thixotropic agent content of 2%, and mixing for 10 min; heating to 102 ℃ and mixing for 1 h; then heating to 120 ℃, and mixing for 1 h; then heating to 150 ℃, and vacuumizing and mixing for 4 h; then vacuumizing, stirring and cooling to 25 ℃, keeping the temperature constant, and protecting with nitrogen;
(2) adding the methyl alkoxy phenyl silicone resin, the bi-end alkoxy end-capped phenyl polysiloxane and the mono-end alkoxy end-capped phenyl polysiloxane according to the weight parts, and mixing for 30min under the protection of nitrogen; then adding the rest of the water removing agent, the cross-linking agent, the first coupling agent and the second coupling agent, and mixing for 30min under the protection of nitrogen; finally, adding the catalyst, and mixing for 20min under the protection of nitrogen;
(3) vacuumizing and stirring for 20min, breaking vacuum by nitrogen, discharging into a sealing tube, and obtaining the organic silicon coating adhesive.
10. The method of preparing a silicone coating gum of claim 9, wherein the double end alkoxy-terminated phenyl polysiloxane or the single end alkoxy-terminated phenyl polysiloxane is prepared by the following method:
(1) vacuumizing and stirring double-end vinyl phenyl polydimethylsiloxane or single-end vinyl phenyl polydimethylsiloxane at 150 ℃ for 2 hours, and then cooling to 30 ℃;
(2) introducing nitrogen, adding a chloroplatinic acid catalyst solution, and continuously mixing for 30 min;
(3) heating to 100 ℃ under the protection of nitrogen, slowly adding a certain amount of hydrogen-containing alkoxy silane, reacting for 2 hours at 100 ℃ after the addition is finished, and vacuumizing and stirring for 2 hours at 120 ℃;
(4) and cooling to 25 ℃ under the protection of nitrogen, adding graphite powder, and filtering to obtain the bi-end alkoxy end-capped phenyl polysiloxane or the mono-end alkoxy end-capped phenyl polysiloxane.
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