WO2024103503A1 - 一种粘合剂及其制备方法和应用 - Google Patents

一种粘合剂及其制备方法和应用 Download PDF

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Publication number
WO2024103503A1
WO2024103503A1 PCT/CN2022/143736 CN2022143736W WO2024103503A1 WO 2024103503 A1 WO2024103503 A1 WO 2024103503A1 CN 2022143736 W CN2022143736 W CN 2022143736W WO 2024103503 A1 WO2024103503 A1 WO 2024103503A1
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Prior art keywords
modified polysiloxane
adhesive
acrylate
diacrylate
monoacrylate
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PCT/CN2022/143736
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English (en)
French (fr)
Inventor
陈浩锦
黎达华
陈俊民
张银华
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广州回天新材料有限公司
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Publication of WO2024103503A1 publication Critical patent/WO2024103503A1/zh

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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the invention belongs to the field of polymer materials, and in particular relates to an adhesive and a preparation method and application thereof.
  • UV-curing adhesives do not contain volatile organic compounds (VOCs) and can be cured within tens of seconds under ultraviolet (UV) irradiation. They are green, environmentally friendly, energy-saving and efficient. Using UV-curing adhesives to quickly bond and assemble optical lens devices (including glass, plastic and metal) has become an industry trend.
  • VOCs volatile organic compounds
  • UVA and UVB ultraviolet rays contained in sunlight irradiate the adhesive material for a long time.
  • the carbonyl, aromatic and other light-absorbing groups in the adhesive cross-linking network and the residual photoinitiators, photosensitizers and other light-absorbing impurities will absorb UVB or even UVA, resulting in the rearrangement of chemical bonds and aging and deterioration.
  • molecular oxygen can be photosensitized to produce highly active singlet oxygen, which will add to macromolecular polymers to form oxidation products and photodegrade. It can also form peroxyl radicals to undergo hydrogen abstraction, cracking, cross-linking, rearrangement and other reactions, resulting in a decrease in the adhesive modulus, yellowing, embrittlement of the adhesive layer and debonding, water ingress and other problems, which seriously affect the service life of the camera.
  • the temperature changes in the outdoor environment the material expands and contracts with the temperature, resulting in stress concentration, which will cause long-term accumulation and lead to bonding failure. Water vapor and dust invade the camera cavity, resulting in reduced camera quality and life.
  • silicone adhesives Compared with the C-C bonds in ordinary polymers, silicone adhesives have better light and heat stability due to their unique Si-O-Si structure, so they have excellent outdoor weather resistance.
  • ordinary one-component room temperature vulcanized silicone needs to be cured through moisture condensation reaction, which has a slow curing speed and low efficiency; it also has high viscosity and large thixotropy, and cannot meet the requirements of narrow edge dispensing of optical lenses.
  • Addition-type silicone requires heating and curing, which takes a long time to cure, and has weak adhesion to the substrate, which also limits its application in optical cameras.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides an adhesive having good resistance to ultraviolet aging and high and low temperature aging, and can be used outdoors.
  • the invention also provides a preparation method and application of the adhesive.
  • an adhesive comprising the following components in parts by weight:
  • the acrylate-modified polysiloxane includes monoacrylate-modified polysiloxane and diacrylate-modified polysiloxane; the mass ratio of the monoacrylate-modified polysiloxane to the diacrylate-modified polysiloxane is 1:2-10.
  • the present invention has at least the following beneficial effects:
  • the invention adopts monoacrylate modified polysiloxane and diacrylate modified polysiloxane as base resin.
  • the polysiloxane contains a unique Si-O-Si structure, which can give the adhesive good weather resistance and aging resistance.
  • the acrylate modification enables the adhesive to be quickly formed by light curing to form a cross-linked network, improve mechanical properties, and have high curing efficiency.
  • the mass ratio of the monoacrylate modified polysiloxane and the diacrylate modified polysiloxane is controlled, so that the adhesive has a suitable cross-linking density, has good flexibility, and improves aging resistance.
  • the mass ratio of the monoacrylate-modified polysiloxane to the diacrylate-modified polysiloxane is 1:2-8, more preferably 1:2.5-6.
  • the adhesive comprises the following components in parts by weight:
  • the adhesive comprises the following components in parts by weight:
  • the reactive diluent is an acrylate monomer; there is no particular limitation on the acrylate monomer, including at least one of a monofunctional acrylate monomer and a multifunctional acrylate monomer.
  • a monofunctional acrylate monomer refers to an acrylate monomer containing one acrylate group in its molecular structure
  • a multifunctional acrylate monomer refers to an acrylate monomer containing two or more acrylate groups in its molecular structure.
  • the monofunctional acrylate monomer includes at least one of 2-hydroxyethyl acrylate, isobornyl acrylate, cyclopentadiene acrylate, lauryl acrylate, acryloylmorpholine, phenoxyethyl acrylate, N,N-dimethylacrylamide, tetrahydrofurfuryl acrylate, dicyclopentenyloxy acrylate, cyclotrimethylolpropane formal acrylate, and 4-tert-butylcyclohexyl acrylate.
  • the multifunctional acrylate monomer includes at least one of 1,4-butylene glycol diacrylate, tricyclodecane dimethanol diacrylate, polyethylene glycol diacrylate, and trimethylolpropane triacrylate.
  • the reactive diluent includes at least one of isobornyl acrylate, dicyclopentene acrylate, acryloyl morpholine, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, 4-tert-butylcyclohexyl acrylate, and tricyclodecane dimethanol diacrylate; more preferably, the reactive diluent includes at least one of isobornyl acrylate, cyclopentadiene acrylate, and tricyclodecane dimethanol diacrylate.
  • the use of a reactive diluent containing a cyclic structure can effectively increase the glass transition temperature of the adhesive, increase the bulk strength of the adhesive, reduce the shrinkage rate, and enhance the bonding strength between the adhesive and the substrate.
  • the thixotropic agent includes at least one of nano-calcium carbonate, fumed silica, bentonite, cellulose acetate, polymer elastic particles, and polyamide, more preferably fumed silica, and further preferably Wacker H20.
  • the coupling agent includes at least one of a titanate coupling agent and a silane coupling agent, more preferably at least one of isopropyl dioleyloxy (dioctylphosphoyloxy) titanate, isopropyl triisostearate titanate, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, mercaptopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; more preferably, the silane coupling agent Dowcorning's Z-6030.
  • silane coupling agent Dowcorning's Z-6030.
  • the photoinitiator includes at least one of benzoin ethers, ⁇ -hydroxy ketone derivatives, ⁇ -amino ketone derivatives, benzil and its derivatives, and acylphosphine peroxides; more preferably, it is a mixture of ethyl 2,4,6-trimethylbenzoylphenylphosphonate and di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; further preferably, IGM's Irgacure 2100.
  • the monoacrylate-modified polysiloxane has the following general formula:
  • R1 is selected from C1 - C5 alkyl or hydrogen atom, more preferably C1 - C3 alkyl or hydrogen atom, further preferably hydrogen atom or methyl;
  • R 3 , R 4 , R 7 , R 8 are independently selected from C 1 to C 4 alkoxy groups or C 1 to C 5 alkyl groups, more preferably R 3 , R 4 , R 7 , R 8 are independently selected from C 1 to C 3 alkyl groups, and further preferably R 3 , R 4 , R 7 , R 8 are independently selected from methyl, ethyl, isopropyl;
  • R2 is selected from the following group:
  • the monoacrylate-modified polysiloxane is prepared by a preparation method comprising the following steps:
  • the diacrylate monomer/prepolymer is reacted with the single-terminal hydrogen-containing polysiloxane to obtain the monoacrylate-modified polysiloxane.
  • the molar ratio of acrylate groups in the diacrylate monomer/prepolymer to hydrogen atoms in the single-end hydrogen-containing polysiloxane is 2.0-3.0:1, more preferably 2.0-2.5:1, including but not limited to 2.0:1, 2.2:1, 2.5:1, etc.
  • the reaction temperature of the diacrylate monomer/prepolymer and the single-terminal hydrogen-containing polysiloxane is 80-100° C., more preferably 80-90° C.; the reaction time is 3-6 hours, more preferably 3-4 hours.
  • the raw materials for preparing the monoacrylate-modified polysiloxane further include a catalyst, an inhibitor, and a solvent.
  • the solvent, the inhibitor, the catalyst, and the diacrylate monomer/oligomer are mixed, an inert gas is introduced, and the single-terminal hydrogen-containing polysiloxane is added dropwise to react to obtain the monoacrylate-modified polysiloxane.
  • the single-end hydrogen-containing polysiloxane is added dropwise for 0.5 to 1.5 hours, more preferably for 1 hour, and the system temperature is controlled at 800 to 100° C., more preferably at 90° C. during the addition process.
  • the temperature is lowered to 50-60° C., and the volatile components are removed by vacuum decompression.
  • the catalyst comprises at least one of chloroplatinic acid, chloroplatinic acid-divinyltetramethyldisiloxane complex, and platinum (0) divinyltetramethyldisiloxane.
  • the catalyst is added in the form of a solution, the concentration of the catalyst solution is 50 to 70 ppm, more preferably 60 ppm; the solvent of the catalyst solution is isopropanol.
  • the catalyst accounts for 0.01 to 0.1% of the total mass of the monoacrylate-modified polysiloxane raw material, and more preferably 0.04 to 0.05%.
  • the polymerization inhibitor comprises p-hydroxyanisole.
  • the mass of the polymerization inhibitor is 5-15% of the mass of the diacrylate monomer/oligomer, more preferably 5-7%.
  • the solvent comprises at least one of xylene and toluene; the volume mass ratio of the solvent to the diacrylate monomer/oligomer is 20-30 mL: 1 g, more preferably 20-25 mL: 1 g.
  • the hydrogen content of the single-ended hydrogen-containing polysiloxane is 0.01% to 0.03%, and RH-H222-3 provided by Runhe Silicone Company is more preferred.
  • the inert gas includes at least one of nitrogen, helium and argon.
  • the diacrylate-modified polysiloxane has the following general formula:
  • R 1 ' and R 10 ' are independently selected from C 1 to C 5 alkyl groups or hydrogen atoms, more preferably R 1 ' and R 10 ' are independently selected from C 1 to C 3 alkyl groups or hydrogen atoms, and further preferably R 1 ' and R 10 ' are independently selected from hydrogen atoms or methyl groups;
  • R 3 ', R 4 ', R 7 ', R 8 ' are independently selected from C 1 to C 4 alkoxy groups or C 1 to C 5 alkyl groups, more preferably R 3 ', R 4 ', R 7 ', R 8 ' are independently selected from C 1 to C 3 alkyl groups, and further preferably R 3 ', R 4 ', R 7 ', R 8 ' are independently selected from one of methyl, ethyl and isopropyl groups;
  • R 5 ' and R 6 ' are independently selected from C 1 to C 5 alkyl groups, more preferably R 5 ' and R 6 ' are independently selected from C 1 to C 3 alkyl groups, and further preferably R 5 ' and R 6 ' are independently selected from methyl and ethyl groups;
  • n is an integer of 1 to 600, more preferably an integer of 10 to 400;
  • R 2 ', R 9 ' are selected from the following group:
  • the diacrylate-modified polysiloxane is prepared by a preparation method comprising the following steps:
  • the diacrylate monomer/prepolymer is reacted with the double-terminal hydrogen-containing polysiloxane to obtain the diacrylate-modified polysiloxane.
  • the molar ratio of acrylate groups in the diacrylate monomer/prepolymer to hydrogen atoms in the double-terminal hydrogen-containing polysiloxane is 2.0-3.0:1, more preferably 2.0-2.5:1, including but not limited to 2.0:1, 2.2:1, 2.5:1, etc.
  • the reaction temperature of the diacrylate monomer/prepolymer and the double-terminal hydrogen-containing polysiloxane is 80-100°C, more preferably 80-90°C; the reaction time is 5-8h, more preferably 5-6h.
  • the raw materials for preparing the diacrylate-modified polysiloxane further include a catalyst, an inhibitor, and a solvent, specifically, the solvent, the inhibitor, the catalyst, and the diacrylate monomer/oligomer are mixed, an inert gas is introduced, and a double-terminal hydrogen-containing polysiloxane is added dropwise to react to obtain the diacrylate-modified polysiloxane.
  • the solvent, the inhibitor, and the catalyst can be the same or different from those used in preparing the monoacrylate-modified polysiloxane.
  • the mass of the inhibitor is 0.1 to 1% of the mass of the diacrylate monomer/oligomer, more preferably 0.2 to 0.5%.
  • the volume mass ratio of the solvent to the diacrylate monomer/oligomer is 10 to 20 mL: 1 g, more preferably 15 to 20 mL: 1 g.
  • the dropwise addition time of the dual-terminal hydrogen-containing polysiloxane is 0.5 to 1 h, more preferably 0.5 h, and the system temperature is controlled at 80 to 100° C., more preferably 90° C. during the dropwise addition.
  • the temperature is lowered to 50-60° C., and the volatile components are removed by vacuuming and reducing the pressure.
  • the inert gas includes at least one of nitrogen, helium and argon.
  • the hydrogen content of the double-terminal hydrogen-containing polysiloxane is 0.01% to 0.015%, and RH-DH-02 provided by Runhe Silicone Company is more preferred.
  • the diacrylate monomer/prepolymer used in the preparation of monoacrylate-modified polysiloxane and diacrylate-modified polysiloxane is independently selected from the following raw materials:
  • the second aspect of the present invention provides a method for preparing the above-mentioned adhesive, comprising the following steps: mixing the components of the adhesive to obtain the adhesive.
  • the components are mixed, filtered, vacuum degassed, and centrifuged to obtain the adhesive composition.
  • the mixing speed is 1500-2000 rpm, and the mixing time is 1-2 hours.
  • the rotation speed of the vacuum degassing is 1000 to 1200 rpm
  • the vacuum degree is -0.08 to -0.1 MPa
  • the time is 10 to 20 min.
  • the third aspect of the present invention proposes the use of the adhesive in protecting outdoor equipment.
  • the outdoor equipment includes at least one of electronic communication equipment and lighting equipment, including but not limited to cameras, indicator lights, lighting lamps, etc.
  • the present invention has the following beneficial effects:
  • the adhesive of the present invention is easy to prepare, can withstand the effects of complex environmental conditions such as outdoor humidity and heat, temperature changes, ultraviolet aging, etc., and can be applied to the protection of outdoor equipment, such as the bonding and sealing of outdoor cameras. It will not cause the camera window seal failure, and can solve the bonding and sealing problems of high-definition outdoor cameras. It has excellent weather resistance and is suitable for promotion and application.
  • the adhesive of the present invention uses an acrylate-modified polysiloxane containing a cyclic structure obtained by reacting a diacrylate monomer/prepolymer with a hydrogen-containing silicone oil as a base resin.
  • a diacrylate monomer/prepolymer with a hydrogen-containing silicone oil as a base resin.
  • tricyclodecane dimethanol diacrylate (diacrylate monomer/prepolymer) is selected as an example for illustration. The cases where other diacrylate monomers/prepolymers are selected are similar.
  • the preparation method of monoacrylate modified polysiloxane is as follows:
  • 320g of xylene solution was added to a 1000mL four-necked round-bottom flask equipped with a mechanical stirrer (with a polytetrafluoroethylene stirring paddle), a dropping funnel, a thermometer and a reflux condenser, and then 1g of p-hydroxyanisole (provided by Aldrich reagent), 0.34g of chloroplatinic acid ( H2PtCl6H2O ) isopropanol solution (provided by Aldrich reagent) and 26.8g of tricyclodecane dimethanol diacrylate (provided by Sartomer) were added in sequence.
  • p-hydroxyanisole provided by Aldrich reagent
  • H2PtCl6H2O chloroplatinic acid
  • 26.8g of tricyclodecane dimethanol diacrylate provided by Sartomer
  • n 80 to 100.
  • the preparation method of diacrylate modified polysiloxane is as follows:
  • 320g of xylene solution was added to a 1000mL four-necked round-bottom flask equipped with a mechanical stirrer (with a polytetrafluoroethylene stirring blade), a dropping funnel, a thermometer and a reflux condenser, and then 1g of p-hydroxyanisole (provided by Aldrich reagent), 0.48g of chloroplatinic acid ( H2PtCl ⁇ 6H2O ) isopropanol solution (provided by Aldrich reagent) and 20.1g of tricyclodecane dimethanol diacrylate (provided by Sartomer) were added in sequence.
  • p-hydroxyanisole provided by Aldrich reagent
  • H2PtCl ⁇ 6H2O chloroplatinic acid
  • 20.1g of tricyclodecane dimethanol diacrylate provided by Sartomer
  • m 350 ⁇ 375.
  • Examples 1 to 5 prepare adhesives.
  • the specific amounts of each component are shown in Table 1.
  • the specific process is as follows: resin, reactive diluent, coupling agent, photoinitiator, and thixotropic agent are added to a dry container in proportion, and sheared and dispersed with a mechanical stirrer at a speed of 1500 rpm for 1 hour. Then take out and filter, put into a homogenizer for vacuum degassing after filtration, set the speed to 1200 rpm, the vacuum degree to -0.1 MPa, and the stirring time to 10 minutes. Finally, take out and put into a 50 mL centrifuge tube, centrifuge and degas, and obtain an adhesive composition.
  • CN965 polyurethane acrylate provided by Sartomer.
  • EB8411 Polyurethane acrylate supplied by Allnex.
  • SR506 NS Isobornyl acrylate supplied by Sartomer.
  • FA-513AS Dicyclopentenyl acrylate provided by Showa Denko.
  • SR833 NS Tricyclodecane dimethanol diacrylate supplied by Sartomer.
  • ISTA Isostearyl acrylate provided by Osaka organic chemical.
  • H20 Fumed silica provided by Wacker.
  • Z-6030 Methacryloxypropyltrimethoxysilane provided by Dowcorning.
  • Irgacure 2100 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester and di(2,4,6-trimethylbenzoylphenylphosphonic acid) provided by IGM
  • Irganox1010 Hindered phenolic antioxidant provided by BASF.
  • Tinuvin 400 Hydroxyphenyltriazine UV absorber provided by BASF.
  • This comparative example prepares an adhesive, which is mainly different from the embodiment in that CN965 polyurethane acrylate is used to replace the monoacrylate-modified polysiloxane and the diacrylate-modified polysiloxane in equal amounts.
  • the specific formula is shown in Table 1, and the specific process is similar to that of the embodiment.
  • This comparative example prepares an adhesive, which is mainly different from the embodiment in that EB8411 polyurethane acrylate is used to replace the monoacrylate-modified polysiloxane and the diacrylate-modified polysiloxane in equal amounts.
  • the specific formula is shown in Table 1, and the specific process is similar to the embodiment.
  • This comparative example prepares an adhesive, which is mainly different from the embodiment in that CN965 polyurethane acrylate is used to replace the monoacrylate-modified polysiloxane and the diacrylate-modified polysiloxane in equal amounts, and an antioxidant and a light stabilizer are additionally added.
  • the specific formula is shown in Table 1, and the specific process is similar to the embodiment.
  • This comparative example prepares an adhesive, which is mainly different from the example in that the amount of monoacrylate-modified polysiloxane is increased and the amount of diacrylate-modified polysiloxane is reduced.
  • the specific formula is shown in Table 1, and the specific process is similar to the example.
  • This comparative example prepares an adhesive, which is mainly different from the embodiment in that the linear isostearyl acrylate (ISTA) is used to replace the cyclic reactive diluent in equal amounts.
  • the specific formula is shown in Table 1, and the specific process is similar to that of the embodiment.
  • an adhesive is prepared.
  • the main difference from the embodiment is that a monoacrylate-modified polysiloxane without a ring structure (Formula V, marked as S-3) and a diacrylate-modified polysiloxane without a ring structure (Formula VI, marked as S-4) are used as base materials.
  • the specific formula is shown in Table 1, and the specific process is similar to that of the embodiment.
  • n 80 to 100;
  • m 350 ⁇ 375.
  • the preparation method of the compounds of formula V and formula VI is a conventional method known in the art.
  • the preparation method disclosed in patent US6140444A is used to prepare the compounds of formula V and formula VI.
  • This test example tests the performance of the adhesives prepared in the examples and comparative examples.
  • Test method for bonding strength between glass and metal aluminum The prepared adhesive is applied to the overlapped surface of the metal aluminum of 25mm ⁇ 100mm ⁇ 2mm through a syringe, and a glass sheet of 25mm ⁇ 100mm ⁇ 2mm is overlapped on the PC sheet, with an overlapped area of 12.5mm ⁇ 25mm and a thickness of 0.2mm. Then the specimen is irradiated with LED 395nm ultraviolet light, with an irradiation energy of 6000mJ/ cm2 . Then the specimen is tested for tensile shear strength on a universal electronic tensile machine, with a tensile speed of 10mm/min, and the test results are recorded.
  • the adhesive was cured under LED 395nm ultraviolet light at 6000mJ/ cm2 energy, and cut according to the specifications of 20mm*5mm*1mm in length, width and height.
  • the dynamic mechanical analyzer DMA850 was used to perform tensile storage modulus test under the conditions of 20 ⁇ m amplitude, 1Hz frequency, 0.1N preload, 2°C/min heating rate, and -50°C ⁇ 95°C heating range, and the test results were recorded.
  • Camera lens sealing and bonding air tightness test method Use an automatic glue dispenser to evenly apply the adhesive to the glue dispensing groove of the cast aluminum metal lens base with polyester coating, control the glue line width to 1-2mm, glue thickness to 0.15mm, and cover the glass lens. Then put the sample into the UV LED 395nm curing box, cure it with 6000mJ/cm2 energy, and finally assemble the camera sample with the back plastic cavity.
  • the adhesive prepared in Examples 1 to 5 of the present invention is formed by UV curing, with fast curing speed and high efficiency.
  • the cured adhesive has suitable shear strength.
  • the storage modulus is low, the storage modulus at low temperature (-40°C) is 6.85 to 50.6 MPa, and the storage modulus at high temperature is 2.19 to 12.6 MPa.
  • the storage modulus is low, the flexibility of the adhesive is good, and the temperature has little effect on the storage modulus, showing a high resistance to high and low temperature impact, which can ensure that the adhesive always maintains good flexibility during use (temperature alternation).
  • the adhesive prepared by the present invention also has excellent resistance to ultraviolet aging and moisture and heat aging. After rigorous aging tests, the air tightness still meets the standards; it can be used for sealing and bonding outdoor equipment, such as cameras.
  • Comparative Example 3 adds antioxidants and light stabilizers on the basis of Comparative Example 1. Although the weather resistance will be improved to a certain extent, the airtightness effect cannot be achieved.
  • Comparative Example 4 uses too much S-1 (monoacrylate modified polysiloxane) and too little S-2 (diacrylate modified polysiloxane) to obtain an adhesive with fewer cross-linking points and significantly worse airtightness.
  • Comparative Example 5 uses an active diluent (isostearyl acrylate) without a ring structure to obtain an adhesive with significantly reduced shear strength, reduced bonding strength with the substrate, and insufficient airtightness.
  • the adhesive obtained by using conventional acrylate-modified polysiloxane without a ring structure as the base resin has significantly reduced shear strength, reduced bonding strength with the substrate, poor resistance to ultraviolet aging and moisture-heat aging, and fails to meet the airtightness requirements.
  • the adhesive of the present invention is used for bonding and sealing of outdoor cameras. It can withstand the influence of complex environmental conditions such as outdoor humidity and heat, temperature alternation, ultraviolet aging, etc., and will not cause failure of the camera window seal. It can solve the bonding and sealing problems of high-definition outdoor cameras, has excellent weather resistance, and is suitable for promotion and application.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明属于高分子材料领域，具体涉及一种粘合剂及其制备方法和应用。本发明的粘合剂包括如下重量份的组分：丙烯酸酯改性聚硅氧烷50～80份；活性稀释剂20～40份；触变剂0～8份；偶联剂0～3份；光引发剂0.5～2份；所述丙烯酸酯改性聚硅氧烷包括单丙烯酸酯改性聚硅氧烷、双丙烯酸酯改性聚硅氧烷；所述单丙烯酸酯改性聚硅氧烷与所述双丙烯酸酯改性聚硅氧烷的质量比为1∶2～10。粘合剂能够经受户外湿热和温度交变，紫外线老化等复杂环境条件的作用，可应用于户外设备的防护，如户外摄像头的粘接密封，不会造成摄像头视窗密封失效，能够解决高清户外摄像头的粘接密封问题，耐候性优异，适合推广应用。

Description

一种粘合剂及其制备方法和应用 技术领域
本发明属于高分子材料领域，具体涉及一种粘合剂及其制备方法和应用。
背景技术
随着光学摄像头市场的快速发展，行业对环保、生产效率和产品可靠性的要求不断提高。紫外光固化粘合剂不含有机挥发物(VOC)，可在紫外线(UV)照射下数十秒内固化，具有绿色环保、节能高效的优点，使用紫外光固化粘合剂对光学镜头器件(包括玻璃、塑料和金属)进行快速粘接组装已经成为行业的趋势。
户外监控摄像头长期暴露在太阳底下，经常受到日晒雨淋，因此不仅要求粘合剂具有良好的粘接密封性，而且对其耐紫外线和耐高低温老化性能提出了更大的挑战。日光中含有的UVA及UVB紫外线长时间照射粘合剂材料，粘合剂交联网络中的羰基、芳基等吸光基团以及残余光引发剂、光敏剂等吸光杂质会吸收UVB甚至UVA导致化学键的重排而老化变质。在户外有氧条件下分子氧可以被光敏化，产生活性高的单线态氧对大分子聚合物加成形成氧化产物而光降解，也可以形成过氧自由基而发生夺氢、裂解、交联、重排等反应，从而造成粘合剂模量变小、黄变、胶层脆化而脱粘，进水等问题，严重影响摄像头的使用寿命。此外，户外环境中的温度变化，材料随温度变化发生热胀冷缩，产生应力集中，长期累积会导致粘接失效，水汽和灰尘侵入摄像头腔体内部导致摄像头使用质量和寿命降低。
相关专利文献(CN111534267A、CN109337591A、CN112795347A)报道了使用紫外光固化胶粘剂对摄像头进行粘接密封组装，虽然具有较好的粘接性和气密性，但是耐紫外线老化和耐高低温冲击性能相对较差，不能应用于户外光学摄像头的粘接密封。
相对于普通高分子聚合物中的C-C健，有机硅粘合剂由于独特的Si-O-Si结构，光、热稳定性更好，因此具有优异的户外耐候性。但是普通单组份室温硫化硅胶需要通过湿气缩合反应固化，固化速度慢、效率低；且黏度高、触变性大，无法满足光学镜头窄边点胶的要求。加成型硅胶需要加热固化，固化时间长，且对基材的粘接力较弱，同样限制了其在光学摄像头上的应用。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种粘合剂，具有良好的耐紫外线老化和耐高低温老化性，可应用于户外。
本发明还提出一种上述粘合剂的制备方法和应用。
本发明的第一方面，提出一种粘合剂，包括如下重量份的组分：
Figure PCTCN2022143736-appb-000001
所述丙烯酸酯改性聚硅氧烷包括单丙烯酸酯改性聚硅氧烷、双丙烯酸酯改性聚硅氧烷；所述单丙烯酸酯改性聚硅氧烷与所述双丙烯酸酯改性聚硅氧烷的质量比为1∶2～10。
根据本发明的第一方面，本发明至少具有如下的有益效果：
本发明采用单丙烯酸酯改性聚硅氧烷、双丙烯酸酯改性聚硅氧烷作为基体树脂，聚硅氧烷含有独特的Si-O-Si结构，能够赋予粘合剂良好的耐候性、耐老化性；丙烯酸酯改性使得粘合剂能够通过光固化快速成型，形成交联网络，提高力学性能，且固化效率高；而且控制单丙烯酸酯改性聚硅氧烷、双丙烯酸酯改性聚硅氧烷的质量比，使得粘合剂具有合适的交联密度，具有良好柔韧性的同时，提高耐老化性能。
优选地，所述粘合剂包括如下重量份的组分：
Figure PCTCN2022143736-appb-000002
优选地，所述单丙烯酸酯改性聚硅氧烷与所述双丙烯酸酯改性聚硅氧烷的质量比为1∶2～8，更优选1∶2.5～6。
优选地，所述粘合剂包括如下重量份的组分：
Figure PCTCN2022143736-appb-000003
优选地，所述粘合剂包括如下重量份的组分：
Figure PCTCN2022143736-appb-000004
优选地，所述活性稀释剂为丙烯酸酯单体；对丙烯酸酯单体没有特别限制，包括单官能的丙烯酸酯单体、多官能的丙烯酸酯单体中的至少一种。在本发明中，单官能的丙烯酸酯单体指的是分子结构内含有一个丙烯酸酯基的丙烯酸酯单体；多官能的丙烯酸酯单体指的是分子结构内含有两个或两个以上的丙烯酸酯基的丙烯酸酯单体。
优选地，所述单官能丙烯酸酯单体包括丙烯酸-2-羟基乙酯、丙烯酸异冰片酯、环戊二烯丙烯酸酯、丙烯酸月桂酯、丙烯酰吗啉、丙烯酸苯氧基乙酯、N，N-二甲基丙烯酰胺、丙烯酸四氢糠基酯、丙烯酸二环戊烯氧基酯、环三羟甲基丙烷缩甲醛丙烯酸酯、4-叔丁基环己基丙烯酸酯中的至少一种。
优选地，所述多官能丙烯酸酯单体包括如二丙烯酸-1，4-丁二醇酯、三环癸烷二甲醇二丙烯酸酯、聚乙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯中的至少一种。
优选地，所述活性稀释剂包括丙烯酸异冰片酯、二环戊烯丙烯酸酯、丙烯酰吗啉、丙烯酸苯氧基乙酯、丙烯酸四氢糠基酯、4-叔丁基环己基丙烯酸酯、三环癸烷二甲醇二丙烯酸酯中的至少一种；更优选的活性稀释剂包括丙烯酸异冰片酯、环戊二烯丙烯酸酯、三环癸烷二甲醇二丙烯酸酯中的至少一种。在本发明中，采用含有环状结构的活性稀释剂，能够有效提高粘合剂的玻璃转化温度，提高粘结剂本体强度，降低收缩率，增强粘 合剂与基材之间的粘接强度。
优选地，所述触变剂包括纳米碳酸钙、气相二氧化硅、膨润土、醋酸纤维素、聚合物弹性粒子、聚酰胺中的至少一种，更优选气相二氧化硅，进一步优选Wacker H20。
优选地，所述偶联剂包括钛酸酯偶联剂、硅烷偶联剂中的至少一种，更优选异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、三异硬脂酸钛酸异丙酯、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、3-(2，3-环氧丙氧)丙基三甲氧基硅烷、巯丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷中的至少一种；更优选硅烷偶联剂Dowcorning的Z-6030。
优选地，所述光引发剂包括苯偶姻醚类、α-羟基酮衍生物、α-胺基酮衍生物、苯偶酰及其衍生物、酰基膦过氧化物中的至少一种；更优选2，4，6-三甲基苯甲酰基苯基膦酸乙酯和二(2，4，6-三甲基苯甲酰基)-苯基氧化膦的混合物；进一步优选IGM的Irgacure 2100。
优选地，所述单丙烯酸酯改性聚硅氧烷具有如下通式：
Figure PCTCN2022143736-appb-000005
其中，R 1选自C 1～C 5的烷基或氢原子，更优选C 1～C 3的烷基或氢原子，进一步优选氢原子或甲基；
R 3、R 4、R 7、R 8独立地选自C 1～C 4的烷氧基或C 1～C 5的烷基，更优选的R 3、R 4、R 7、R 8独立地选自C 1～C 3的烷基，进一步优选的R 3、R 4、R 7、R 8独立地选自甲基、乙基、异丙基中的一种；
R 5、R 6、R 9独立地选自C 1～C 5的烷基，更优选的R 5、R 6、R 9独立地选自C 1～C 3的烷基，进一步优选的R 5、R 6、R 9独立地选自甲基、乙基、丙基中的一种；
n为1～600的整数，更优选10～400的整数；
R 2选自下组：
Figure PCTCN2022143736-appb-000006
优选地，所述单丙烯酸酯改性的聚硅氧烷由包括如下步骤的制备方法制备得到：
将二丙烯酸酯类单体/预聚体与单端含氢聚硅氧烷反应，得到单丙烯酸酯改性的聚硅氧烷。
优选地，所述二丙烯酸酯类单体/预聚体中的丙烯酸酯基与单端含氢聚硅氧烷中的氢原子的摩尔比为2.0～3.0∶1，更优选2.0～2.5∶1，包括但不限于2.0∶1，2.2∶1，2.5∶1等。
优选地，所述二丙烯酸酯类单体/预聚体与单端含氢聚硅氧烷反应的温度为80～100℃，更优选80～90℃；所述反应的时间为3～6h，更优选3～4h。
优选地，单丙烯酸酯改性的聚硅氧烷的制备原料还包括催化剂、阻聚剂、溶剂，具 体为将溶剂、阻聚剂、催化剂、二丙烯酸酯单体/低聚体混合，通入惰性气体，滴加单端含氢聚硅氧烷，反应得到所述单丙烯酸酯改性的聚硅氧烷。
优选地，所述单端含氢聚硅氧烷的滴加时间为0.5～1.5h，更优选1h，滴加过程中控制体系温度在800～100℃，更优选90℃。
优选地，所述二丙烯酸酯单体/低聚体与单端含氢聚硅氧烷反应结束后降温至50～60℃，抽真空减压除去挥发性组分。
优选地，所述催化剂包括氯铂酸、氯铂酸-二乙烯基四甲基二硅氧烷络合物、铂(0)二乙烯基四甲基二硅氧烷中的至少一种。所述催化剂以溶液的形式加入，所述催化剂溶液的浓度为50～70ppm，更优选60ppm；所述催化剂溶液的溶剂为异丙醇。
优选地，所述催化剂占单丙烯酸酯改性的聚硅氧烷原料总质量的0.01～0.1％，更优选0.04～0.05％。
优选地，所述阻聚剂包括对羟基苯甲醚。所述阻聚剂的质量为二丙烯酸酯单体/低聚体的质量的5～15％，更优选5～7％。
所述溶剂包括二甲苯、甲苯中的至少一种；所述溶剂与二丙烯酸酯单体/低聚体的体积质量比为20～30mL∶1g，更优选20～25mL∶1g。
优选地，所述单端含氢聚硅氧烷的含氢量为0.01％～0.03％，更优选润禾有机硅公司提供的RH-H222-3。
优选地，所述惰性气体包括氮气、氦气、氩气中的至少一种。
优选地，所述双丙烯酸酯改性聚硅氧烷具有如下通式：
Figure PCTCN2022143736-appb-000007
其中，R 1’、R 10’独立地选自C 1～C 5的烷基或氢原子，更优选的R 1’、R 10’独立地选自C 1～C 3的烷基或氢原子，进一步优选的R 1’、R 10’独立地选自氢原子或甲基；
R 3’、R 4’、R 7’、R 8’独立地选自C 1～C 4的烷氧基或C 1～C 5的烷基，更优选的R 3’、R 4’、R 7’、R 8’独立地选自C 1～C 3的烷基，进一步优选的R 3’、R 4’、R 7’、R 8’独立地选自甲基、乙基、异丙基中的一种；
R 5’、R 6’独立地选自C 1～C 5的烷基，更优选的R 5’、R 6’独立地选自C 1～C 3的烷基，进一步优选的R 5’、R 6’独立地选自甲基、乙基中的一种；
m为1～600的整数，更优选10～400的整数；
R 2’、R 9’选自下组：
Figure PCTCN2022143736-appb-000008
优选地，所述双丙烯酸酯改性的聚硅氧烷由包括如下步骤的制备方法制备得到：
将二丙烯酸酯类单体/预聚体与双端含氢聚硅氧烷反应，得到所述双丙烯酸酯改性的聚硅氧烷。
优选地，所述二丙烯酸酯类单体/预聚体中的丙烯酸酯基与双端含氢聚硅氧烷的氢原子的摩尔比为2.0～3.0∶1，更优选2.0～2.5∶1，包括但不限于2.0∶1，2.2∶1，2.5∶1等。
优选地，所述二丙烯酸酯类单体/预聚体与双端含氢聚硅氧烷反应的温度为 80～100℃，更优选80～90℃；所述反应的时间为5～8h，更优选5～6h。
优选地，双丙烯酸酯改性的聚硅氧烷的制备原料还包括催化剂、阻聚剂、溶剂，具体为将溶剂、阻聚剂、催化剂、二丙烯酸酯单体/低聚体混合，通入惰性气体，滴加双端含氢聚硅氧烷，反应得到所述双丙烯酸酯改性的聚硅氧烷。所述溶剂、阻聚剂、催化剂可选用与制备单丙烯酸酯改性的聚硅氧烷使用的相同或不同。所述阻聚剂的质量为二丙烯酸酯单体/低聚体的质量的0.1～1％，更优选0.2～0.5％。所述溶剂与二丙烯酸酯单体/低聚体的体积质量比为10～20mL∶1g，更优选15～20mL∶1g。
优选地，所述双端含氢聚硅氧烷的滴加时间为0.5～1h，更优选0.5h，滴加过程中控制体系温度在80～100℃，更优选90℃。
优选地，所述二丙烯酸酯单体/低聚体与双端含氢聚硅氧烷反应结束后降温至50～60℃，抽真空减压除去挥发性组分。
优选地，所述惰性气体包括氮气、氦气、氩气中的至少一种。
优选地，所述双端含氢聚硅氧烷的含氢量为0.01％～0.015％，更优选润禾有机硅公司提供的RH-DH-02。
优选地，在制备单丙烯酸酯改性聚硅氧烷、双丙烯酸酯改性聚硅氧烷中使用的二丙烯酸酯单体/预聚体独立地选自如下原料：
Figure PCTCN2022143736-appb-000009
本发明的第二方面，提出一种上述粘合剂的制备方法，包括如下步骤：将所述粘合剂得到各组分混合，得到所述粘合剂。
优选地，将各组分混合后，过滤、真空脱泡、离心脱泡后得到所述粘合剂组合物。
优选地，所述混合的转速为1500～2000rpm，混合的时间为1～2h。
优选地，所述真空脱泡的转速为1000～1200rpm，真空度为-0.08～-0.1MPa，时间为10～20min。
本发明的第三方面，提出所述粘合剂在户外设备防护中的应用。
优选地，所述户外设备包括电子通信设备、照明设备中的至少一种，包括但不限于摄像头、指示灯、照明灯等。
与现有技术相比，本发明具有如下的有益效果：
聚硅氧烷材料本身的强度一般较低，采用丙烯酸酯改性使其交联固化，形成交联网络，改善力学性能，与此同时基体树脂中还包括环状结构，环状结构的引入能够有效提高粘合剂对基材的粘接力，提高玻璃化转变温度和耐湿热老化性能；同时搭配使用含环状结构的活性稀释剂，进一步降低收缩率，增强粘合剂对基材的粘接强度，提高粘合剂的本体强度和玻璃化转变温度，配合其他组分，得到的粘合剂具有良好的柔韧性、粘接强度，以及耐老化性能。
本发明的粘合剂制备简单，能够经受户外湿热和温度交变，紫外线老化等复杂环境条件的作用，可应用于户外设备的防护，如户外摄像头的粘接密封，不会造成摄像头视窗密封失效，能够解决高清户外摄像头的粘接密封问题，耐候性优异，适合推广应用。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
以下实施例中所用的原料，如无特殊说明，均可从常规商业途径得到；所采用的工艺，如无特殊说明，均采用本领域的常规工艺；所采用的操作温度，如无特殊说明，均为室温(20±5℃)。
本发明粘合剂采用由二丙烯酸酯类单体/预聚体与含氢硅油反应得到的含环状结构的丙烯酸酯改性聚硅氧烷作为基体树脂，具体实施方式中选用三环癸烷二甲醇二丙烯酸酯(二丙烯酸酯类单体/预聚体)为例进行说明，二丙烯酸酯类单体/预聚体选用其他的情况与此相似。
单丙烯酸酯改性聚硅氧烷的制备方法如下：
将320g二甲苯溶液加入装配好机械搅拌器(带聚四氟乙烯搅拌桨)、滴液漏斗、温度计和回流冷凝管的1000mL四颈圆底烧瓶中，然后依次加入1g对羟基苯甲醚(Aldrich试剂提供)，0.34g氯铂酸(H 2PtCl·6H 2O)异丙醇溶液(Aldrich试剂提供)和26.8g三环癸烷二甲醇二丙烯酸酯(Sartomer公司提供)。通入干燥氮气，开启搅拌，搅拌速度控制在100rpm，控制料温在90℃，温度恒定10min之后通过滴液漏斗缓慢滴加400g单端含氢硅油RH-H222-3(润禾有机硅公司提供)，滴加时间1h，反应时间4h。待温度 降至50℃停止搅拌，过滤，然后抽真空减压除去挥发性组分，得到单丙烯酸酯改性聚硅氧烷，在本发明中称S-1，经测试，具有如下化学式：
Figure PCTCN2022143736-appb-000010
n为80～100。
双丙烯酸酯改性聚硅氧烷的制备方法如下：
将320g二甲苯溶液加入装配好机械搅拌器(带聚四氟乙烯搅拌桨)、滴液漏斗、温度计和回流冷凝管的1000mL四颈圆底烧瓶中，然后依次加入1g对羟基苯甲醚(Aldrich试剂提供)，0.48g氯铂酸(H 2PtCl·6H 2O)异丙醇溶液(Aldrich试剂提供)和20.1g三环癸烷二甲醇二丙烯酸酯(Sartomer公司提供)。通入干燥氮气，开启搅拌，搅拌速度控制在100rpm，控制料温在90℃，温度恒定10min之后通过滴液漏斗缓慢滴加400g双端侧含氢硅油RH-LHC-3(润禾有机硅公司提供)，滴加时间0.5h，反应时间6h。待温度降至50℃停止搅拌，过滤，然后抽真空减压除去挥发性组分，得到双丙烯酸酯改性聚硅氧烷，在本发明中称S-2；经测试，具有如下的结构式：
Figure PCTCN2022143736-appb-000011
m为350～375。
实施例1～5
实施例1～5制备粘合剂，各组分具体用量见表1，具体过程为：将树脂、活性稀释剂、偶联剂、光引发剂、触变剂按比例添加至干燥容器中，用机械搅拌机剪切分散，转速1500rpm，搅拌时间1h。然后取出过滤，过滤完放入均质机真空脱泡，设置转速1200rpm，真空度为-0.1MPa，搅拌时间10min。最后取出装入50mL离心管，离心脱泡，得到粘合剂组合物。
表1实施例和对比例的粘合剂的成分配比表(重量份)
Figure PCTCN2022143736-appb-000012
表格中原料的相关信息如下：
CN965：Sartomer公司提供的聚氨酯丙烯酸酯。
EB8411：Allnex公司提供的聚氨酯丙烯酸酯。
SR506 NS：Sartomer公司提供的丙烯酸异冰片酯。
FA-513AS：Showa Denko公司提供的二环戊烯基丙烯酸酯。
SR833 NS：Sartomer公司提供的三环癸烷二甲醇二丙烯酸酯。
ISTA：Osaka organic chemical公司提供的丙烯酸异十八酯。
H20：Wacker公司提供的气相法白炭黑。
Z-6030：Dowcorning公司提供的甲基丙烯酰氧基丙基三甲氧基硅烷。
Irgacure 2100：IGM公司提供的2，4，6-三甲基苯甲酰基苯基膦酸乙酯和二(2，4，6-三甲
基苯甲酰基)-苯基氧化膦的混合物。
Irganox1010：BASF公司提供的受阻酚类抗氧剂。
Tinuvin 400：BASF公司提供的羟基苯基三嗪紫外线吸收剂。
对比例1
本对比例制备了一种粘合剂，与实施例的主要区别在于采用CN965聚氨酯丙烯酸酯等量替换单丙烯酸酯改性聚硅氧烷和双丙烯酸酯改性聚硅氧烷，具体配方见表1，具体过程与实施例相似。
对比例2
本对比例制备了一种粘合剂，与实施例的主要区别在于采用EB8411聚氨酯丙烯酸酯等量替换单丙烯酸酯改性聚硅氧烷和双丙烯酸酯改性聚硅氧烷，具体配方见表1，具体过程与实施例相似。
对比例3
本对比例制备了一种粘合剂，与实施例的主要区别在于采用CN965聚氨酯丙烯酸酯等量替换单丙烯酸酯改性聚硅氧烷和双丙烯酸酯改性聚硅氧烷，以及额外增加了抗氧剂和光稳定剂，具体配方见表1，具体过程与实施例相似。
对比例4
本对比例制备了一种粘合剂，与实施例的主要区别在于增加了单丙烯酸酯改性聚硅氧烷的用量和降低了双丙烯酸酯改性聚硅氧烷的用量，具体配方见表1，具体过程与实施例相似。
对比例5
本对比例制备了一种粘合剂，与实施例的主要区别在于采用直链结构的丙烯酸异十八酯ISTA等量替换了环状结构的活性稀释剂，具体配方见表1，具体过程与实施例相似。
对比例6
本对比例制备了一种粘合剂，与实施例的主要区别在于采用不含环状结构的单丙烯酸酯改性聚硅氧烷(式V，标记为S-3)和不含环状结构的双丙烯酸酯改性聚硅氧烷(式VI，标记为S-4)作为基体材料，具体配方见表1，具体过程与实施例相似。
Figure PCTCN2022143736-appb-000013
n为80～100；
Figure PCTCN2022143736-appb-000014
m为350～375。
式V与式VI化合物的制备方法为本领域已知常规方法制备得到，本对比例参考专利US6140444A所公开的制备方法制备得到式V和式VI化合物。
试验例
本试验例测试了实施例和对比例制备的粘合剂的性能。其中：
玻璃与金属铝的粘接强度测试方法：将配制好的上述粘合剂通过针筒点在25mm×100mm×2mm的金属铝的搭接面上，将25mm×100mm×2mm的玻璃片搭接在PC片上，搭接面积12.5mm×25mm，胶层厚度0.2mm。然后经过LED 395nm紫外光照射，照射能量6000mJ/cm 2。然后将样条在设备万能电子拉力机上进行拉剪强度测试，拉伸速度10mm/min，记录测试结果。
储能模量测试方法：将粘合剂在LED 395nm紫外线下，以6000mJ/cm 2能量进行固化，按照长宽高20mm*5mm*1mm的规格裁剪。采用动态力学分析仪DMA850，在振幅为20μm，频率为1Hz，预载力为0.1N，升温速率2℃/min，升温区间-50℃～95℃的条件下进行拉伸储能模量测试，记录测试结果。
摄像头透镜密封粘接气密性测试方法：用自动点胶机将粘合剂均匀地涂到带有聚酯涂层的铸铝金属镜片底座的点胶槽内，控制胶线宽度为1～2mm，胶厚0.15mm，盖上玻璃镜片。然后将样件放入UV LED 395nm固化箱中，以6000mJ/cm2能量进行固化，最后将摄像头样件与背部塑料腔体进行组装。随后分别进行湿热老化(温湿85℃/85％RH，1000h；温度循环-40到85℃，1h/cycle，1000cycles；高温老化85℃，1000hrs)和紫外线老化(340nm氙灯，0.51W/m 2.nm，65±3℃黑板温度，38±2℃、50±5RH％光照120min，18min喷淋并伴随光照，共计1000hrs)试验。最后验证摄像头视窗与玻璃镜片密封粘接的气密性：将组装好的样件完全浸没在25℃水中，然后利用气管接口往摄像头样件内部腔体施加0.05MPa压力的空气，观察水中有没有气泡产生，如果无气泡产生，表明气密 性测试通过，记录OK，观察粘合剂的外观并做记录；反之则不通过，记录NG，观察粘合剂的外观并做记录。
表2：粘合剂的性能测试结果
Figure PCTCN2022143736-appb-000015
本发明实施例1～5制备的粘合剂通过紫外光固化成型，固化速度快，效率高，固化后的粘合剂具有适宜的剪切强度；同时储能模量较低，低温(-40℃)下的储能模量为6.85～50.6MPa，高温下的储能模量为2.19～12.6MPa，储存模量较低，粘合剂的柔韧性较好，而且温度对储能模量的影响较小，表现出较高的抗高低温冲击性能，能够保证粘合剂在使用过程(温度交变)中始终保证良好的柔韧性。除此以外，本发明制备的粘合 剂还具有极佳的耐紫外线老化和耐湿热老化性能，经过严苛的老化测试后，气密性仍达标；可用于户外设备的密封粘结，如摄像头。
相较于实施例，对比例1～2采用不恰当的基体树脂(聚氨酯丙烯酸酯)得到粘合剂柔韧性受温度影响大，低温(-40℃)易脆性开裂、密封性下降；而且耐紫外线老化性能和耐湿热老化性能不佳，紫外线和湿热加速测试后，失去密封性，导致摄像头腔体漏气，不适合应用于户外。对比例3在对比例1的基础上增加抗氧化剂、光稳定剂，虽然耐候性会有一定程度的改善，但是无法达到气密性效果。对比例4采用过多量的S-1(单丙烯酸酯改性聚硅氧烷)和过少量的S-2(双丙烯酸酯改性聚硅氧烷)得到粘合剂交联点减少，气密性明显变差。对比例5采用不含环状结构的活性稀释剂(丙烯酸异十八酯)得到的粘合剂的剪切强度明显下降，与基材的粘接强度下降，气密性不足。对比例6采用常规的不含环状结构的丙烯酸酯改性聚硅氧烷作为基体树脂得到的粘合剂剪切强度明显降低，与基材的粘接强度下降，耐紫外线老化和耐湿热老化性能都较差，达不到气密性的要求。
本发明粘合剂应用于户外摄像头粘接密封，能够经受户外湿热和温度交变，紫外线老化等复杂环境条件的影响，不会造成摄像头视窗密封失效，能够解决高清户外摄像头的粘接密封问题，耐候性优异，适合推广应用。
上面对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种粘合剂，其特征在于，包括如下重量份的组分：
    Figure PCTCN2022143736-appb-100001
    所述丙烯酸酯改性聚硅氧烷包括单丙烯酸酯改性聚硅氧烷、双丙烯酸酯改性聚硅氧烷；所述单丙烯酸酯改性聚硅氧烷与所述双丙烯酸酯改性聚硅氧烷的质量比为1∶2～10。
  2. 根据权利要求1所述的粘合剂，其特征在于，所述单丙烯酸酯改性聚硅氧烷与所述双丙烯酸酯改性聚硅氧烷的质量比为1∶2～8。
  3. 根据权利要求1所述的粘合剂，其特征在于，所述单丙烯酸酯改性聚硅氧烷具有如下通式：
    Figure PCTCN2022143736-appb-100002
    其中，R 1选自C 1～C 5的烷基或氢原子，R 3、R 4、R 7、R 8独立地选自C 1～C 4的烷氧基或C 1～C 5的烷基，R 5、R 6、R 9独立地选自C 1～C 5的烷基，n为1～600的整数；
    R 2选自下组：
    Figure PCTCN2022143736-appb-100003
  4. 根据权利要求1所述的粘合剂，其特征在于，所述双丙烯酸酯改性聚硅氧烷具有如下通式：
    Figure PCTCN2022143736-appb-100004
    其中，R 1’、R 10’独立地选自C 1～C 5的烷基或氢原子，R 3’、R 4’、R 7’、R 8’独立地选自C 1～C 4的烷氧基或C 1～C 5的烷基，R 5’、R 6’独立地选自C 1～C 5的烷基，m为1～600的整数；
    R 2’、R 9’选自下组：
    Figure PCTCN2022143736-appb-100005
  5. 根据权利要求1所述的粘合剂，其特征在于，所述活性稀释剂包括丙烯酸异冰片酯、二环戊烯丙烯酸酯、丙烯酰吗啉、丙烯酸苯氧基乙酯、丙烯酸四氢糠基酯、4-叔丁基环己基丙烯酸酯、三环癸烷二甲醇二丙烯酸酯中的至少一种。
  6. 根据权利要求1-5任一项所述的粘合剂，其特征在于，所述粘合剂包括如下重量份的组分：
    Figure PCTCN2022143736-appb-100006
    Figure PCTCN2022143736-appb-100007
  7. 根据权利要求1所述的粘合剂，其特征在于，所述触变剂包括纳米碳酸钙、气相二氧化硅、膨润土、醋酸纤维素、聚合物弹性粒子、聚酰胺中的至少一种。
  8. 权利要求1-7任一项所述的粘合剂的制备方法，其特征在于，包括如下步骤：将所述粘合剂的各组分混合，得到所述粘合剂。
  9. 权利要求1-7任一项所述的粘合剂在户外设备防护中的应用。
  10. 根据权利要求9所述的应用，其特征在于，所述户外设备包括电子通信设备、照明设备中的至少一种。
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