CN112552870B - High-strength high-hardness UV/moisture dual-curing MS glue and preparation method thereof - Google Patents
High-strength high-hardness UV/moisture dual-curing MS glue and preparation method thereof Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- 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
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- C09J11/04—Non-macromolecular additives inorganic
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Abstract
The invention discloses a high-strength high-hardness UV/moisture dual-curing MS adhesive and a preparation method thereof, and relates to the field of adhesives. The self-made high-modulus silane modified polyether polymer is obtained by adding difunctional polyether ammonia and acrylate modified epoxy resin to obtain a polyether ammonia intermediate of an acrylic-based epoxy resin block, continuously reacting with an isocyanate silane coupling agent, and applying the self-made high-modulus silane modified polyether polymer to MS glue.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a high-strength high-hardness UV/moisture dual-curing MS adhesive and a preparation method thereof.
Background
The silane modified polyether sealant (MS glue) structurally contains the characteristics of a terminal silane group and a main chain polyether bond, integrates the performance advantages of an organosilicon sealant and a polyurethane sealant in performance, has the advantages of wide bonding, good painting property, low content of non-volatile organic matters and the like, and is mainly based on a basic polymer. Usually, MS glue needs to be improved by adding a plurality of auxiliary agents such as an antioxidant, an ultraviolet light absorber, a light stabilizer and the like, but the auxiliary agents have a migration phenomenon which can have adverse effects on the glue. Research and development for improving the temperature resistance of MS have been increasing in recent years.
With the development of large-scale automatic continuous production and the improvement of environmental protection requirements at the present stage, the ultraviolet curing adhesive can be widely applied due to quick positioning, but in practical application, due to the existence of a non-illumination area, the color of the filler blocks light, the light intensity is weak, and a deep layer or shadow area is difficult to carry out ultraviolet curing, so that the bonding effect can be greatly influenced. Therefore, the technical defects of the existing stage can be well solved by the MS capable of realizing UV rapid positioning later stage moisture curing.
At present, for example, the invention patent with the publication number of CN111732933A discloses a high-strength high-hardness epoxy modified MS sealant and a preparation method thereof, the epoxy modified MS sealant comprises a silane modified polyether polymer and comprises the following components of difunctional polyether amine, low-molecular-weight epoxy resin, epoxy silane and an epoxy accelerator, in the technology, polyether amine and low-molecular-weight epoxy resin monomers are adopted for reaction, and finally, epoxy silane is used for sealing ends, so that the highest hardness can only reach 55D. The requirements of high strength and high hardness cannot be met.
Disclosure of Invention
The invention discloses a high-strength high-hardness UV/moisture dual-curing MS glue and a preparation method thereof, solves the problem of poor strength of the traditional MS glue, realizes the improvement of the bonding strength to a base material, has the characteristics of high hardness, low molding shrinkage and the like, and can be quickly positioned by UV for later-stage moisture curing.
In order to achieve the technical effect, the application discloses a high-strength high-hardness UV/moisture dual-curing MS adhesive, which comprises the following raw materials in parts by weight:
40-60 parts of a silane modified polyether polymer;
5-15 parts of an acrylic monomer;
10-15 parts of a reinforcing agent;
0.1-0.5 part of UV initiator;
0.5-1.5 parts of a dehydrating agent;
5-15 parts of a coupling agent;
0.1-1 part of a catalyst;
the silane modified polyether polymer consists of a general silane modified polyether polymer and a self-made high-modulus silane modified polyether polymer, wherein the weight proportion of the high-modulus silane modified polyether polymer in the silane modified polyether polymer is not less than 60%;
the high-modulus silane modified polyether polymer has a structure as shown in a formula (I)
Formula (I)
Wherein m = 200-.
Further, the high-modulus silane modified polyether polymer is obtained by adding difunctional polyether ammonia and acrylate modified epoxy resin to obtain a polyether ammonia intermediate of an acrylic-based epoxy resin block, and then continuously reacting with an isocyanate silane coupling agent.
Further, the difunctional polyether ammonia has a structure shown in a formula (II), the acrylate modified epoxy resin has a structure shown in a formula (III), and the isocyanate silane coupling agent is 3-isocyanate propyl trimethoxy silane and has a structure shown in a formula (IV);
formula (II);
formula (III);
formula (IV);
wherein m = 200-.
Further, the high modulus silane modified polyether polymer is prepared by the following method:
s1, adding bifunctional polyether amine into a reaction kettle, starting stirring, and slowly heating to 50-60 ℃; slowly dropping acrylate modified epoxy resin into the reaction kettle for addition reaction, slowly heating to 50-80 ℃, stirring for 1-2h, and vacuum degassing for 15-20min under the pressure of not higher than-0.09 MPa to obtain a polyetheramine intermediate with an acrylate-based epoxy resin block;
wherein the polyetheramine intermediate having an acrylate-based epoxy resin block has a structure according to formula (V):
formula (V)
S2, dehydrating the polyether amine intermediate with the acrylate-based epoxy resin block prepared in the step S1 at 100 ℃ under reduced pressure for 2 hours, and cooling to 50-110 ℃ under the protection of nitrogen; adding 3-isocyanatopropyl trimethoxy silane and 0-0.1% dibutyltin dilaurate according to a certain proportion, mixing and stirring, measuring and monitoring the content of NCO by adopting a di-n-butylamine-hydrochloric acid method, and finishing the reaction when the content of NCO is not changed any more; adding 0.1 percent of absolute ethyl alcohol by mass percent to remove possible residual trace 3-isocyanate propyl trimethoxy silane; then adding 0.5 percent of vinyl trimethoxy silane and 0.01 percent of activated carbon adsorbent by mass fraction, stirring for 2h at 60 ℃ in nitrogen atmosphere, adsorbing and removing the tin catalyst in the system, vacuum degassing for 15-20min at the pressure of less than or equal to-0.09 MPa, filtering, sealing and storing to obtain the silane modified polyether polymer without free isocyanate.
Further, the acrylic monomer is selected from one or more of tetrahydrofuran methacrylate, dodecyl acrylate, 2-phenoxyethyl methacrylate, 3,5 trimethylcyclohexane acrylate, isobornyl methacrylate, trimethylolpropane formal acrylate, polyethylene glycol (600) dimethacrylate, polyethylene glycol (600) diacrylate and tricyclodecane dimethanol diacrylate;
the reinforcing agent is selected from one or more of heavy calcium carbonate, nano calcium carbonate, aluminum hydroxide, kaolin, silicon dioxide, titanium dioxide, carbon black and fumed silica;
the UV initiator is selected from one or more of 2, 4, 6- (trimethylbenzoyl) diphenylphosphine oxide, 2, 4, 6-trimethylbenzoyl phosphonic acid ethyl ester and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone;
the dehydrating agent is one or a mixture of two of vinyltrimethoxysilane and vinyltriethoxysilane;
the coupling agent is selected from one or more of aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane or N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane;
the catalyst is selected from one or more of organic tin catalyst, organic bismuth catalyst and amine catalyst.
The invention also discloses a preparation method of the high-strength high-hardness UV/moisture dual-curing MS glue, which comprises the following steps:
(1) according to the proportion, adding the silane modified polyether polymer and the reinforcing agent into a reaction kettle, starting a stirrer, wherein the revolution speed is 20-40rpm, the dispersion rotation speed is 500 plus 1800rpm, the temperature is increased to 100 plus 115 ℃, the vacuum is less than or equal to-0.098 MPa, and the stirring time is 1-2 h;
(2) cooling to below 50 ℃, adding acrylic monomer, revolving at 20-40rpm, dispersing at 500-1000rpm, stirring for 10-30min, and keeping the vacuum at-0.098 MPa;
(3) adding a dehydrating agent, wherein the revolution speed is 20-40rpm, the dispersion rotation speed is 500-1000rpm, the stirring time is 10-30min, and the vacuum is less than or equal to-0.098 MPa;
(4) adding a UV initiator, a coupling agent and a catalyst, stirring for 10-30min at a revolution speed of 5-40rpm and a dispersion rotation speed of 200-1000rpm, then starting vacuum at the pressure of less than or equal to-0.098 MPa and stirring for 10-30min, and discharging to obtain the high-strength high-hardness UV/moisture dual-curing MS adhesive.
The beneficial effects of the invention include:
the invention adopts epoxy resin with acrylate functional group capable of being cured by UV, excess polyether amine is successfully introduced into flexible polyether chain segment after ring opening, and then isocyanate silane coupling agent is used for blocking and introducing hydrolyzable cured siloxane group, so that the resin system can realize UV moisture dual curing.
(1) The dual-curing MS not only keeps the excellent and traditional performances of MS, but also introduces the bisphenol A epoxy chain segment, thereby obviously improving the bonding strength of the glue film to the base material, the cohesive force of the glue, the water resistance, the solvent resistance and the chemical resistance.
(2) The adhesive has the advantages of low molding shrinkage, low VOC (volatile organic compounds), UV (ultraviolet) curing, rapid 30S positioning, no influence on the next process when the thickness of the adhesive shell reaches 0.2mm, maximum adhesive strength after 48 hours, and hardness of 50-70D.
(3) The system is made into electronic black glue, and is widely applied to bonding sealing and protection in the electronic packaging industry to replace low-temperature curing glue, UV glue and other application points on CCM assembly.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, those who do not specify specific conditions are performed according to conventional conditions or conditions recommended by the manufacturer, and those who do not specify the reagents or instruments used are conventional products commercially available.
The general silane modified polyether polymer is selected from the following components: japanese brillouin brand: MS951
The high modulus silane modified polyether polymer is prepared according to the following steps:
s1, adding 100 parts of difunctional polyetheramine D2000 into a reaction kettle, starting stirring, and slowly heating to 60 ℃; slowly dripping 25 mass percent of acrylate modified epoxy resin (with the viscosity of 10000-50000 CP) into a reaction kettle for addition reaction, slowly heating to 80 ℃, stirring for 2 hours, and carrying out vacuum degassing for 20min under the pressure of less than or equal to-0.09 MPa to obtain a polyetheramine intermediate with an acrylate-based epoxy resin block;
s2, dehydrating the polyetheramine intermediate with the acrylate-based epoxy resin block prepared by the S1 at 100 ℃ under reduced pressure for 2h, and cooling to 80 ℃ under the protection of nitrogen; adding 3-isocyanatopropyl trimethoxy silane and 0.1% dibutyltin dilaurate by mass percent, mixing and stirring, measuring and monitoring the content of NCO by adopting a di-n-butylamine-hydrochloric acid method, and finishing the reaction when the content of NCO is not changed any more; adding 0.1 percent of absolute ethyl alcohol by mass percent to remove possible residual trace 3-isocyanate propyl trimethoxy silane; then adding 0.5 percent of vinyl trimethoxy silane and 0.01 percent of activated carbon adsorbent by mass fraction, stirring for 2h at 60 ℃ in nitrogen atmosphere, adsorbing and removing a tin catalyst in the system, vacuum degassing for 15-20min at the pressure of less than or equal to-0.09 MPa, filtering, sealing and storing to obtain the high-modulus silane modified polyether polymer without free isocyanate.
The high modulus silane modified polyether polymers used in examples 1-3 below were all high modulus silane modified polyether polymers prepared by the above procedure.
Example 1
Adding 40 parts of high-modulus silane modified polyether polymer, 20 parts of Brillouin MS951 and 15 parts of reinforcing agent into a reaction kettle, starting a stirrer, raising the revolution speed to 20rpm and the dispersion speed to 1000rpm, raising the temperature to 110 ℃, and keeping the vacuum at less than or equal to-0.098 MPa for 1-2 h; cooling to below 50 ℃, adding 10 parts of tetrahydrofuran methacrylate, revolving at 20rpm, dispersing at 1000rpm, stirring for 30min, and keeping the vacuum at less than or equal to-0.098 MPa; adding 1 part of vinyl trimethoxy silane, wherein the revolution speed is 20rpm, the dispersion speed is 800rpm, the stirring time is 30min, and the vacuum is less than or equal to-0.098 MPa; adding 0.5 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 10 parts of aminopropyltrimethoxysilane, 0.5 part of a mixture of DBU and bismuth neodecanoate (the weight ratio is 2: 3), revolving at the speed of 15rpm, dispersing at the speed of 800rpm, stirring for 10-30min, then starting vacuum, stirring for 30min at the vacuum pressure of less than or equal to-0.098 MPa, and discharging to obtain the high-strength high-hardness UV/moisture dual-curing MS adhesive.
Example 2
Adding 40 parts of high-modulus silane modified polyether polymer, 10 parts of Brillouin MS951 and 15 parts of reinforcing agent into a reaction kettle, starting a stirrer, raising the revolution speed to 20rpm and the dispersion speed to 1000rpm, raising the temperature to 110 ℃, and keeping the vacuum at less than or equal to-0.098 MPa for 1-2 h; cooling to below 50 ℃, adding 10 parts of tetrahydrofuran methacrylate, revolving at 20rpm, dispersing at 1000rpm, stirring for 30min, and keeping the vacuum at less than or equal to-0.098 MPa; adding 1 part of vinyl trimethoxy silane, wherein the revolution speed is 20rpm, the dispersion speed is 800rpm, the stirring time is 30min, and the vacuum is less than or equal to-0.098 MPa; adding 0.5 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 10 parts of aminopropyltrimethoxysilane, 0.5 part of a mixture of DBU and bismuth neodecanoate (the weight ratio is 2: 3), revolving at the speed of 15rpm, dispersing at the speed of 800rpm, stirring for 10-30min, then starting vacuum, stirring for 30min at the vacuum pressure of less than or equal to-0.098 MPa, and discharging to obtain the high-strength high-hardness UV/moisture dual-curing MS adhesive.
Example 3
Adding 40 parts of silane modified polyether polymer, 0 part of Brillouin MS951 and 15 parts of reinforcing agent into a reaction kettle, starting a stirrer, heating to 110 ℃ at a revolution speed of 20rpm and a dispersion rotation speed of 1000rpm, and stirring for 1-2 hours under the vacuum condition of less than or equal to-0.098 MPa; cooling to below 50 ℃, adding 10 parts of tetrahydrofuran methacrylate, revolving at 20rpm, dispersing at 1000rpm, stirring for 30min, and keeping the vacuum at less than or equal to-0.098 MPa; adding 1 part of vinyl trimethoxy silane, wherein the revolution speed is 20rpm, the dispersion speed is 800rpm, the stirring time is 30min, and the vacuum is less than or equal to-0.098 MPa; adding 0.5 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 10 parts of aminopropyltrimethoxysilane, 0.5 part of a mixture of DBU and bismuth neodecanoate (the weight ratio is 2: 3), revolving at the speed of 15rpm, dispersing at the speed of 800rpm, stirring for 10-30min, then opening the vacuum, keeping the vacuum at the pressure of less than or equal to-0.098 MPa, stirring for 30min, and discharging to obtain the high-strength high-hardness UV/moisture dual-curing MS adhesive.
Comparative example 1
Adding 40 parts of universal silane modified polyether-Brillouin MS951 and 15 parts of reinforcing agent into a reaction kettle, starting a stirrer, revolving at the speed of 20rpm and the speed of 1000rpm, heating to 110 ℃, and stirring for 1-2 hours under the vacuum condition of less than or equal to-0.098 MPa; cooling to below 50 ℃, adding 10 parts of tetrahydrofuran methacrylate, revolving at 20rpm, dispersing at 1000rpm, stirring for 30min, and keeping the vacuum at less than or equal to-0.098 MPa; adding 1 part of vinyl trimethoxy silane, wherein the revolution speed is 20rpm, the dispersion speed is 800rpm, the stirring time is 30min, and the vacuum is less than or equal to-0.098 MPa; adding 0.5 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 10 parts of aminopropyltrimethoxysilane, 0.5 part of a mixture of DBU and bismuth neodecanoate (the weight ratio is 2: 3), the revolution speed is 15rpm, the dispersion rotation speed is 800rpm, the stirring time is 10-30min, then, starting vacuum, the vacuum is less than or equal to-0.098 MPa, the stirring time is 30min, and discharging to obtain the high-strength high-hardness UV/moisture dual-curing MS adhesive.
Comparative example 2
Adding 40 parts of bisphenol A epoxy modified acrylic resin and 15 parts of reinforcing agent into a reaction kettle, starting a stirrer, revolving at a speed of 20rpm and a dispersion speed of 1000rpm, heating to 110 ℃, and stirring for 1-2 hours under a vacuum condition of less than or equal to-0.098 MPa; cooling to below 50 ℃, adding 10 parts of tetrahydrofuran methacrylate, revolving at 20rpm, dispersing at 1000rpm, stirring for 30min, and keeping the vacuum at less than or equal to-0.098 MPa; adding 1 part of vinyl trimethoxy silane, wherein the revolution speed is 20rpm, the dispersion speed is 800rpm, the stirring time is 30min, and the vacuum is less than or equal to-0.098 MPa; adding 0.5 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 10 parts of aminopropyltrimethoxysilane, 0.5 part of a mixture of DBU and bismuth neodecanoate (the weight ratio is 2: 3), revolving at the speed of 15rpm, dispersing at the speed of 800rpm, stirring for 10-30min, then opening the vacuum, keeping the vacuum at the pressure of less than or equal to-0.098 MPa, stirring for 30min, and discharging to obtain the high-strength high-hardness UV/moisture dual-curing MS adhesive.
Experimental detection
1, materials and methods:
1.1 test site: futai Xinyou New Material Co, Ltd laboratory.
1.2 test detection:
curing condition: 0.1g of glueQuantity, LED 365nm 500mw/cm 2 And measuring the thickness of the adhesive film by light intensity irradiation of multiplied by 10S, and standing the sample piece at room temperature for 24h after being shielded from light to test the curing depth.
Tensile shear strength: and (3) testing according to GB/T7124 + 2008 standard, wherein the materials are as follows: PC/PC, curing conditions: LED 365nm 200mw/cm 2 After 30S, the mixture is placed for 24h at room temperature.
Adhesion (cross-hatch) test:
and (3) coating glue on a test board (PCB), curing to form a film, cutting marks with the interval of 1nn in the transverse direction and the longitudinal direction on the poplar board by using a blade and a graduated scale, intersecting 100 squares, testing three different positions, and calculating the integrity degree of the lattices.
Hardness: according to GB/T531.1-2008 "method for testing the indentation hardness of vulcanized rubber or thermoplastic rubber
Dividing into: the predetermined test of Shore Durometer method (Shore hardness) was performed; according to Shore A hardness instrument LX-D, curing conditions are as follows: LED 365nm 200mw/cm 2 X 120S, and then the mixture is placed at room temperature for 7 days.
Tensile strength: the detection is carried out according to the GB 1040-1992 standard, and the curing conditions are as follows: LED 365nm 200mw/cm 2 X 120S, and then the mixture is placed at room temperature for 7 days.
Elongation at break: detection was carried out according to GB 1040-: the LED 365nm 200mw/cm 2X 120S is placed for 7 days at room temperature.
Retention rate of cold and hot impact strength: circulating for 100 times at-40-120 ℃ for 1h each time
Double 85 strength retention: at 85 deg.C and 85% humidity for 500 hr
1.3 test materials: the results were compared for example 1, example 2, example 3, and comparative example 1 to comparative example 2.
Except for different experimental treatments, the operation of the experiment is consistent.
2 results and analysis:
and (4) conclusion:
examples 1-3 can form a film through UV illumination fast curing, dark curing is carried out in the later stage, the curing depth is increased after 24h, the bonding strength, the adhesive force and the hardness are obviously improved compared with those of comparative example 1, and are slightly worse than those of comparative example 2, but the cold and hot impact and the elongation at break are greatly improved. Overall performance example 3 is optimal.
Therefore, the high-strength high-hardness UV/moisture dual-curing MS adhesive synthesized by the invention can obviously improve the adhesive strength of the adhesive film to a base material, the cohesive force of the adhesive and the water resistance, and still has good flexibility and reliability.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
Claims (6)
1. The high-strength high-hardness UV/moisture dual-curing MS adhesive is characterized by comprising the following raw materials in parts by weight:
40-60 parts of a silane modified polyether polymer;
5-15 parts of an acrylic monomer;
10-15 parts of a reinforcing agent;
0.1-0.5 part of UV initiator;
0.5-1.5 parts of a dehydrating agent;
5-15 parts of a coupling agent;
0.1-1 part of a catalyst;
the silane modified polyether polymer consists of a general silane modified polyether polymer and a self-made high-modulus silane modified polyether polymer, wherein the weight proportion of the high-modulus silane modified polyether polymer in the silane modified polyether polymer is not less than 60%;
the high-modulus silane modified polyether polymer has a structure as shown in a formula (I)
Formula (I)
Wherein m = 200-.
2. The high-strength high-hardness UV/moisture dual-cured MS glue according to claim 1, wherein: the high-modulus silane modified polyether polymer is obtained by adding difunctional polyether ammonia and acrylate modified epoxy resin to obtain a polyether ammonia intermediate of an acrylic-based epoxy resin block, and then continuously reacting with an isocyanate silane coupling agent.
3. The high-strength high-hardness UV/moisture dual-cured MS glue according to claim 2, wherein: the difunctional polyether ammonia has a structure shown in a formula (II), the acrylate modified epoxy resin has a structure shown in a formula (III), and the isocyanate silane coupling agent is 3-isocyanate propyl trimethoxy silane and has a structure shown in a formula (IV);
formula (II);
formula (III);
formula (IV);
wherein m = 200-.
4. The high-strength high-hardness UV/moisture dual-cured MS glue according to claim 3, wherein: the high modulus silane modified polyether polymer is prepared by the following method:
s1, adding bifunctional polyether amine into a reaction kettle, starting stirring, and slowly heating to 50-60 ℃; slowly dropping acrylate modified epoxy resin into the reaction kettle for addition reaction, slowly heating to 50-80 ℃, stirring for 1-2h, and vacuum degassing for 15-20min under the pressure of not higher than-0.09 MPa to obtain a polyetheramine intermediate with an acrylate-based epoxy resin block;
s2, dehydrating the polyetheramine intermediate with the acrylate-based epoxy resin block prepared in the step S1 at 100 ℃ under reduced pressure for 2 hours, and then cooling to 50-110 ℃ under the protection of nitrogen; adding 3-isocyanatopropyl trimethoxy silane and 0-0.1% dibutyltin dilaurate according to a certain proportion, mixing and stirring, measuring and monitoring the content of NCO by adopting a di-n-butylamine-hydrochloric acid method, and finishing the reaction when the content of NCO is not changed any more; adding 0.1 percent of absolute ethyl alcohol by mass percent to remove possible residual trace 3-isocyanate propyl trimethoxy silane; then adding 0.5 percent of vinyl trimethoxy silane and 0.01 percent of activated carbon adsorbent by mass fraction, stirring for 2h at 60 ℃ in nitrogen atmosphere, adsorbing and removing a tin catalyst in the system, vacuum degassing for 15-20min at the pressure of less than or equal to-0.09 MPa, filtering, sealing and storing to obtain the silane modified polyether polymer without free isocyanate.
5. The high-strength high-hardness UV/moisture dual-cured MS glue according to claim 1, wherein:
the acrylic monomer is selected from one or more of tetrahydrofuran methacrylate, dodecyl acrylate, 2-phenoxyethyl methacrylate, 3, 5-trimethylcyclohexane acrylate, isobornyl methacrylate, trimethylolpropane formal acrylate, polyethylene glycol (600) dimethacrylate, polyethylene glycol (600) diacrylate and tricyclodecane dimethanol diacrylate;
the reinforcing agent is selected from one or more of heavy calcium carbonate, nano calcium carbonate, aluminum hydroxide, silica micropowder, kaolin, titanium dioxide, carbon black and fumed silica;
the UV initiator is selected from one or more of 2, 4, 6- (trimethylbenzoyl) diphenylphosphine oxide, 2, 4, 6-trimethylbenzoyl phosphonic acid ethyl ester and 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone;
the dehydrating agent is one or a mixture of two of vinyltrimethoxysilane and vinyltriethoxysilane;
the coupling agent is selected from one or more of aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane or N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane;
the catalyst is selected from one or more of organic tin catalyst, organic bismuth catalyst and amine catalyst.
6. A method for preparing a high-strength high-hardness UV/moisture dual-curable MS glue according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) according to the proportion, adding the silane modified polyether polymer and the reinforcing agent into a reaction kettle, starting a stirrer, wherein the revolution speed is 20-40rpm, the dispersion rotation speed is 500 plus 1800rpm, the temperature is increased to 100 plus 115 ℃, the vacuum is less than or equal to-0.098 MPa, and the stirring time is 1-2 h;
(2) cooling to below 50 ℃, adding acrylic monomer, revolving at 20-40rpm, dispersing at 500-1000rpm, stirring for 10-30min, and keeping the vacuum at-0.098 MPa;
(3) adding a dehydrating agent, wherein the revolution speed is 20-40rpm, the dispersion rotation speed is 500-1000rpm, the stirring time is 10-30min, and the vacuum is less than or equal to-0.098 MPa;
(4) adding a UV initiator, a coupling agent and a catalyst, stirring for 10-30min at a revolution speed of 5-40rpm and a dispersion rotation speed of 200-1000rpm, then starting vacuum at the pressure of less than or equal to-0.098 MPa and stirring for 10-30min, and discharging to obtain the high-strength high-hardness UV/moisture dual-curing MS adhesive.
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| CN115785368A (en) * | 2022-12-09 | 2023-03-14 | 上海氯碱化工股份有限公司 | Modified polyether resin with UV/moisture dual-curing characteristic and preparation method thereof |
| CN117987064B (en) * | 2024-04-02 | 2024-05-28 | 广州布鲁奥申新材料科技有限公司 | High-limit modified bi-component heat-conducting adhesive for power battery and preparation method thereof |
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| CN102344539B (en) * | 2011-07-15 | 2013-11-27 | 深圳职业技术学院 | Silicon-containing dual curing group resin and preparation method thereof |
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| CN110028664B (en) * | 2019-04-28 | 2021-08-03 | 上海元业体育科技有限公司 | Silane-terminated polyether and preparation method thereof |
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