CN114231174B - Organic silicon coating adhesive and preparation method thereof - Google Patents
Organic silicon coating adhesive and preparation method thereof Download PDFInfo
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- CN114231174B CN114231174B CN202111681143.XA CN202111681143A CN114231174B CN 114231174 B CN114231174 B CN 114231174B CN 202111681143 A CN202111681143 A CN 202111681143A CN 114231174 B CN114231174 B CN 114231174B
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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
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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
- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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 removal agent, 50-100 parts of cross-linking 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 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
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 Conformal paints, coating glues, moisture-proof glues, insulating glues, and the like, are used under the english name Conformal 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 glue is generally coated on a circuit board of an electronic component (PCBA, also called a printed circuit board), and a layer of 0.02-0.2 mm insulating compact protective film is formed on the circuit board, so that the coating glue can prevent water vapor from penetrating and dust from polluting and has a 'three-proofing' effect. 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:
further, the structural formula of the methyl alkoxy phenyl silicone resin is shown as the formula (I):
(RMe 2 SiO 0.5 ) a (MePhSiO 0.5 ) b (MeSiO 1.5 ) c (SiO 2 ) Formula (I)
Wherein, R is methoxyl or ethoxyl, a = 0.2-0.4, b = 0.2-0.4, c = 0.8-1.1, a + b + c = 1.4-1.7;
the alkoxy content is 0.25wt%, and the molecular weight is 2000-5000.
The use of the resin has the beneficial effects that: 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-shaped link ensures the toughness of the adhesive layer; meanwhile, the introduction of phenyl greatly improves the weather resistance and the aging resistance.
Further, the viscosity of the phenyl polysiloxane terminated with the double end alkoxy group and/or the phenyl polysiloxane terminated with the single end alkoxy group is 50-5000 mPa & s;
the phenyl polysiloxane terminated with double end alkoxy groups and/or phenyl polysiloxane terminated with single end alkoxy groups has a structure shown in a formula (II):
wherein m is more than 1, and m and n are integers which enable the viscosity of the phenyl polysiloxane with double end alkoxy end capping and/or the phenyl polysiloxane with single end alkoxy end capping 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 2 hours 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 30min;
(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: isopropanol =1:100, respectively;
the addition amount of the chloroplatinic acid catalyst solution is 5-10 ppm of the double-terminal vinyl polydimethylsiloxane or the single-terminal vinyl phenyl polydimethylsiloxane based on the content of Pt.
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 1.0 to 1.2 in terms of a molar ratio Si-H/Si-Vi.
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 of growing day by day.
Further, the phenylmethylsilicone oil has the structure of formula (III):
(CH 3 ) 3 SiO[(C 6 H 5 ) 2 SiO] X [(CH 3 ) 2 SiO] Y Si(CH 3 ) 3 formula (III)
Wherein X >1, and X and Y are integers such that the viscosity of the phenylmethylsilicone oil satisfies 50 to 100 mPas.
The effects of using the phenyl methyl silicone oil are as follows: 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 a structure of formula (iv):
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:
the second step:
the third step:
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 removal 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 more 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 20min; adding a water removing agent with the thixotropic agent content of 2%, and mixing for 10min; heating to 102 ℃ and mixing for 1h; then heating to 120 ℃, and mixing for 1h; then heating to 150 ℃, and vacuumizing and mixing for 4h; 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, and discharging into a sealing tube to obtain the organic silicon coating adhesive.
Further, the phenyl polysiloxane terminated with both ends alkoxy or the phenyl polysiloxane terminated with single ends alkoxy 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 30min;
(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 500rpm.
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 is given by way of example of the present invention and other advantages and features of the present invention will become apparent to those skilled in the art from the following detailed description. 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 included to provide a thorough understanding of the invention. The invention may be practiced without these particulars. Moreover, some of the specific details have been omitted from the description in order not to obscure or obscure 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 Biterminal alkoxy-terminated phenyl polysiloxane:
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) is vacuumized and stirred for 2h at the temperature of 150 ℃, and the stirring, the vacuumizing and the temperature reduction are continued to 30 ℃; breaking vacuum and protecting with nitrogen (anhydrous), adding 1.1g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol =1 = 100), and continuing mixing for 30min; heating to 100 ℃ under the protection of nitrogen, 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 reaching the time, 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 needed bi-end alkoxy end-capped phenyl polysiloxane-1;
synthesis of mono-terminal alkoxy-terminated phenyl polysiloxane:
1000g of single-end 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 and protecting with nitrogen (anhydrous), adding 1.1g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol =1 = 100), and continuing mixing for 30min; heating to 100 ℃ under the protection of nitrogen, adding 55g of hydrogen-containing alkoxy silane, slowly adding the hydrogen-containing alkoxy silane, and reacting at 100 ℃ for 2 hours; vacuumizing and stirring for 2h at 120 ℃ after reaching the time, 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 20min; then adding 1.0g of hexamethyldisilazane and mixing for 10min; heating to 102 ℃ and mixing for 1h; then heating to 120 ℃, and mixing for 1h; then heating to 150 ℃, and vacuumizing and mixing for 4h; 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 0.25wt% 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 with 1.5g hexamethyldisilazane, 50g phenylvinyldimethoxysilane, 10g KH-560, 10g of a second coupling agent of formula (IV) (where L = 4), under nitrogen blanket at 500rpm for 30min; adding 5g of dibutyltin dilaurate, and mixing for 20min at 500rpm under the protection of nitrogen; vacuumizing and stirring for 20min, breaking vacuum by nitrogen, discharging into a sealed tube to obtain the single-component transparent room-temperature dealcoholized and cured organosilicon coating adhesive 1 containing phenyl.
Example 2
Synthesis of a Biterminal alkoxy-terminated phenyl polysiloxane:
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) is vacuumized and stirred for 2h at the temperature of 150 ℃, and the stirring, the vacuumizing and the temperature reduction are continued to 30 ℃; breaking vacuum and protecting with nitrogen (anhydrous), adding 1.7g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol = 1; 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 needed 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 and 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 and protecting with nitrogen (anhydrous), adding 1.7g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol =1 = 100), and continuing mixing for 30min; under the protection of nitrogen, heating to 100 ℃, 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 reaching the time, 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 single end alkoxy end capping;
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 0.25g of distilled water is added, and the mixture is continuously mixed for 20min; then adding 0.5g of hexamethyldisilazane and mixing for 10min; heating to 102 ℃ and mixing for 1h; then heating to 120 ℃, and mixing for 1h; then heating to 150 ℃, and vacuumizing and mixing for 4h; then vacuumizing, stirring and cooling to 25 ℃, keeping the temperature constant, and protecting with nitrogen; adding 40g of methylalkoxyphenyl silicone resin (with the alkoxy content of 0.25wt% and the molecular weight of 3500) with the structural formula shown in (I), 700g of double-end alkoxy end-capped phenyl polysiloxane-2 and 75g of single-end alkoxy end-capped phenyl polysiloxane-2, and mixing for 30min at 500rpm under the protection of nitrogen; after adding 3g of hexamethyldisilazane, 15g of phenylvinyldimethoxysilane, 60g of phenyltrimethoxysilane, 10g of KH-560, 10g of KH570, 20g of the second coupling agent of the formula (IV) (where L = 3), under nitrogen blanket 500rpm, mix for 30min; adding 10g of n-butyl titanate, and mixing for 20min at 500rpm under the protection of nitrogen; vacuumizing and stirring for 20min, breaking vacuum by nitrogen, discharging into a sealed tube to obtain the single-component transparent room-temperature dealcoholized and cured organosilicon coating adhesive 2 containing phenyl.
Example 3
Synthesis of a Biterminal 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 5000mPa & s and the structural formula of (II) at 150 ℃ for stirring for 2h, and continuously stirring, vacuumizing and cooling to 30 ℃; breaking vacuum and protecting with nitrogen (anhydrous), adding 2.1g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol =1 = 100), and continuing mixing for 30min; 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 reaching the time, 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-ended vinyl phenyl polydimethylsiloxane (R1 is methyl and the vinyl content is 0.08 wt%) with the viscosity of 5000mPa & s and the structural formula as (II) at 150 ℃ for stirring for 2h, continuously stirring, vacuumizing and cooling to 30 ℃; breaking vacuum and protecting with nitrogen (anhydrous), adding 2.1g chloroplatinic acid catalyst solution (weight ratio, anhydrous chloroplatinic acid: isopropanol = 1; heating to 100 ℃ under the protection of nitrogen, adding 6g of hydrogen-containing alkoxy silane, slowly adding the hydrogen-containing alkoxy silane, and reacting at 100 ℃ for 2 hours; 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 single end alkoxy end capping;
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 shown in a 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 20min; then adding 0.2g of hexamethyldisilazane and mixing for 10min; heating to 102 ℃ and mixing for 1h; then heating to 120 ℃, and mixing for 1h; then heating to 150 ℃, and vacuumizing and mixing for 4h; 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 0.25wt% 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 5g of hexamethyldisilazane, 50g of phenylvinyldimethoxysilane, 50g of vinyltrimethoxysilane, 30g of A-186 and 30g of a second coupling agent (wherein, L = 2) with the structural formula shown as (IV) are added and mixed 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 20min; then 0.2g of hexamethyldisilazane is added and mixed for 10min; heating to 102 ℃ and mixing for 1h; then heating to 120 ℃, and mixing for 1h; then heating to 150 ℃, and vacuumizing and mixing for 4h; 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; mixing with 5g hexamethyldisilazane, 50g phenylvinyldimethoxysilane, 50g vinyltrimethoxysilane, 30g A-186, 30g of a second coupling agent of formula (IV) (wherein L = 2), and nitrogen at 500rpm for 30min; 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 alkoxy-terminated silicone oil is the main coating rubber in the market.
Comparative example 3
Preparation of a phenyl-containing, single-component, clear, room temperature dealcoholized, cured silicone:
100g of phenyl methyl silicone oil with the viscosity of 50 mPas and shown in a 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 20min; then 0.2g of hexamethyldisilazane is added and mixed for 10min; heating to 102 ℃ and mixing for 1h; then heating to 120 ℃, and mixing for 1h; then heating to 150 ℃, and vacuumizing and mixing for 4h; 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 0.25wt% and molecular weight of 2000) with the structural formula (I), 750g of phenyl polysiloxane-3 terminated with double end alkoxy and 100g of phenyl polysiloxane-3 terminated with single end alkoxy, and mixing for 30min at 500rpm under the protection of nitrogen; after adding 5g hexamethyldisilazane, 50g phenylvinyldimethoxysilane, 50g vinyltrimethoxysilane, 60g A-186, and mixing for 30min at 500rpm under nitrogen protection; 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 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: lightly touching the surface of the sealant with hand every one minute at 23 + -2 deg.C and 50 + -5% RH for surface skinning time, i.e. 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 the surface of the copper sheet is rusted or discolored or not is observed by the coating glue:
(1) Aging for 100 hours by using double 85 aging;
(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
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 (4)
1. The organic silicon coating adhesive is characterized by comprising the following components in parts by weight:
30 to 50 portions of methyl alkoxy phenyl silicone resin,
650 to 750 portions of bi-end alkoxy end-capped phenyl polysiloxane,
50 to 100 portions of phenyl polysiloxane terminated with single end alkoxy,
80 to 120 portions of phenyl methyl silicone oil,
10-50 parts of a thixotropic agent,
1 to 5 parts of a water removing agent,
50-100 parts of a cross-linking agent,
10-30 parts of a first coupling agent,
10-30 parts of a second coupling agent,
5-15 parts of a catalyst;
the structural formula of the methylalkoxy phenyl silicone resin is shown as the formula (I):
(RMe 2 Si O 0.5 ) a (MePhSiO 0.5 ) b (Me SiO 1.5 ) c (SiO 2 ) Formula (I)
Wherein R is methoxy or ethoxy, a =0.2 to 0.4, b =0.2 to 0.4, c =0.8 to 1.1, a +, b +, c =1.4 to 1.7; the content of the alkoxy is 0.25wt%, and the molecular weight is 2000 to 5000;
the viscosity of the phenyl polysiloxane with the double end alkoxy end capping and/or the phenyl polysiloxane with the single end alkoxy end capping is 50 to 5000mPa & s;
the phenyl polysiloxane terminated with the double end alkoxy or the phenyl polysiloxane terminated with the single end alkoxy 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 30min;
(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) Cooling to 25 ℃ under the protection of nitrogen, adding graphite powder, and filtering to obtain the bi-terminal alkoxy end-capped phenyl polysiloxane or the mono-terminal alkoxy end-capped phenyl polysiloxane;
the phenyl methyl silicone oil has a structure of a formula (III):
(CH 3 ) 3 SiO[(C 6 H 5 ) 2 SiO]X[(CH 3 ) 2 SiO]YSi(CH 3 ) 3 formula (III)
Wherein X is more than 1, and X and Y are integers which enable the viscosity of the phenyl methyl silicone oil to satisfy 50 to 100mPa & s;
the first coupling agent is any mixture of one or more of KH-550, KH-560, KH-570, A-186 and KH-792;
the second coupling agent has a structure of formula (IV):
formula (IV)
Wherein L is more than 0 and less than 5 and is an integer;
the second coupling agent is synthesized by the following route:
the first step is as follows:
the second step is that:
the third step:
wherein the catalyst-0 is a platinum catalyst, and the catalyst-1 and the catalyst-2 are both acid catalysts.
2. The silicone coating gum of claim 1, wherein the chloroplatinic acid catalyst solution comprises anhydrous chloroplatinic acid, isopropyl alcohol, the weight ratio of the anhydrous chloroplatinic acid: isopropanol =1:100;
the amount of the chloroplatinic acid catalyst solution added is 5 to 10ppm of the vinyl-terminated polydimethylsiloxane or the vinyl-terminated phenyl polydimethylsiloxane in terms of Pt content.
3. The silicone coating according to claim 1, wherein the hydroalkoxysilane is triethoxysilane in an amount of 1.0 to 1.2 in a molar ratio Si-H/Si-Vi; wherein Vi represents a vinyl group.
4. A method of preparing the silicone coated gum of any one of claims 1-3, 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 20min; adding a water removing agent with the concentration of 2% of the thixotropic agent, and mixing for 10min; heating to 102 ℃ and mixing for 1h; then heating to 120 ℃, and mixing for 1h; then heating to 150 ℃, and vacuumizing and mixing for 4h; then vacuumizing, stirring and cooling to 25 ℃, keeping the temperature constant and protecting with nitrogen;
(2) According to the weight parts, adding the methyl alkoxy phenyl silicone resin, the phenyl polysiloxane with double end alkoxy end capping and the phenyl polysiloxane with single end alkoxy end capping, 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.
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| JPS63318944A (en) * | 1987-06-23 | 1988-12-27 | Daikyo Rubber Seiko:Kk | Sanitary rubbery product coated with modified polysiloxane and preparation thereof |
| CN110003842A (en) * | 2019-01-24 | 2019-07-12 | 烟台德邦科技有限公司 | A kind of single-component dealcoholization-type room-temperature vulcanized organic polyorganosiloxane composition |
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| CN105524281B (en) * | 2016-01-25 | 2018-06-26 | 广东恒大新材料科技有限公司 | A kind of borosilicate alkane modified silicone resin and add-on type resin combination and application |
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| CN110003842A (en) * | 2019-01-24 | 2019-07-12 | 烟台德邦科技有限公司 | A kind of single-component dealcoholization-type room-temperature vulcanized organic polyorganosiloxane composition |
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