CN111635729A - Silane modified polyurethane-epoxy composition and preparation method thereof - Google Patents
Silane modified polyurethane-epoxy composition and preparation method thereof Download PDFInfo
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/837—Chemically modified polymers by silicon containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- 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
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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
- C09J11/06—Non-macromolecular additives organic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Abstract
The invention discloses a silane modified polyurethane-epoxy composition and a preparation method thereof, belongs to the technical field of structural adhesives, and solves the problems of slow curing, narrow application range and the like of the existing structural adhesive. The silane modified polyurethane-epoxy composition consists of A, B parts; the component A comprises silane modified polyurethane, epoxy resin and inorganic filler; the component B comprises an epoxy curing agent, a silane coupling agent and a chelated tin catalyst. The structural adhesive has low viscosity, is not limited by adhesive dispensing equipment, and is suitable for most procedures.
Description
Technical Field
The invention belongs to the technical field of structural adhesives, and particularly relates to a silane modified polyurethane-epoxy composition and a preparation method thereof.
Background
Structural adhesive is needed to be used for bonding in the process of assembling household appliances, the structural adhesive used in the market of the household appliances at present mainly comprises single-component silicone adhesive and double-component epoxy adhesive, the curing speed of the single-component silicone adhesive is too slow, the production efficiency is influenced, the viscosity is too high and is limited by dispensing equipment, and part of the dispensing equipment is only suitable for low-viscosity adhesive, so that the application range is small; the bi-component epoxy adhesive has high bonding strength, but has slow curing speed, poor toughness and limited application range, and influences the production efficiency (the next step can be carried out after the adhesive reaches a certain strength after being cured). And the same household appliance needs to use a plurality of different adhesives according to the requirements and the applicability in the manufacturing process, so that the equipment investment is increased.
At present, no structural adhesive which can meet the requirements of rapid assembly and high strength in the current household appliance market and has a wide application range exists, in the existing structural adhesive, although the silicone adhesive has good toughness, the silicone adhesive has a slow curing speed and low mechanical strength, and although the epoxy adhesive has high mechanical strength, the epoxy adhesive has a slow curing speed (the two-component epoxy adhesive with a fast curing speed has low mechanical strength) and poor toughness.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a silane-modified polyurethane-epoxy composition and a preparation method thereof, so as to solve the problems of slow curing, narrow application range, etc. of the existing structural adhesive.
The purpose of the invention is mainly realized by the following technical scheme:
a silane modified polyurethane-epoxy composition, which consists of A, B parts; the component A comprises silane modified polyurethane, epoxy resin and inorganic filler; the component B comprises an epoxy curing agent, a silane coupling agent and a chelated tin catalyst.
Further, A, B comprises the following components in percentage by weight:
component A
100 parts of silane-modified polyurethane, namely 100 parts of,
30-80 parts of epoxy resin,
10-30 parts of inorganic filler;
b component
5-25 parts of an epoxy curing agent,
3-8 parts of a silane coupling agent,
1-3 parts of a chelated tin catalyst.
Further, the preparation method of the silane modified polyurethane comprises the following steps:
weighing polyether polyol according to a formula, heating to 120 ℃ for 100 ℃ and vacuum dehydration, cooling to below 50 ℃, adding diisocyanate and an organic tin catalyst according to the formula, heating to 75-80 ℃ for reaction for 1-2 hours, titrating the content of isocyanate groups to a target value R, adding silane coupling agent according to the formula, continuing to react for 1-2 hours at 75-80 ℃, titrating to detect that the isocyanate groups cannot terminate the reaction, and preparing the needed silane modified polyurethane which is put into a closed container for storage.
Further, the epoxy resin is one or more of bisphenol a epoxy resin E44, bisphenol a epoxy resin E51, bisphenol F epoxy resin F44, and bisphenol F epoxy resin F51.
Further, the epoxy curing agent is polyamide curing agent and/or 2,4,6-3 (dimethylaminomethyl) phenol.
Furthermore, the silane coupling agent of the component B and the silane coupling agent for preparing the silane modified polyurethane are one or more than two of 3-aminopropyl trimethoxy silane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane, vinyl trimethoxy silane, gamma-aminopropyl triethoxy silane and gamma-glycidyl ether oxygen propyl trimethoxy silane.
Further, the inorganic filler is one or more than two of silica micropowder, calcium carbonate, silica and diatomite.
Further, the target value is that R is the molar ratio of isocyanate groups to hydroxyl groups, and R is between 2 and 3.
Further, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate.
The invention also provides a preparation method of the silane modified polyurethane-epoxy composition, which comprises the following steps:
the component A comprises: firstly, adding silane modified polyurethane and epoxy resin into a reaction kettle, keeping the vacuum degree less than-0.09 MPa, and stirring for 0.5-2 h at 70-100 ℃;
then, cooling to below 40 ℃, adding an inorganic filler, dispersing and stirring at a high speed for 0.5-2 h to uniformly mix the materials, defoaming in vacuum to obtain a component A, and sealing and storing;
and B component: and adding an epoxy curing agent, a catalyst and a silane coupling agent into the reaction kettle, stirring for 0.5-1 h to uniformly mix the materials, defoaming in vacuum to obtain a component B, and sealing and storing.
Compared with the prior art, the invention can at least realize one of the following technical effects:
1) the invention develops an adhesive which meets the assembly requirements of the existing household appliances, and has the advantages of wide application range, low viscosity, quick curing, good flexibility, high bonding strength, and good moisture-heat resistance and impact resistance. In the existing structural adhesive, the epoxy adhesive is slow in curing speed, poor in toughness, slow in curing speed of silicone adhesive, high in viscosity and small in application range.
The adhesive dispensing device is suitable for most of procedures, has the advantages that the viscosity is low, the adhesive dispensing device is not limited by adhesive dispensing equipment, some adhesive dispensing equipment is only suitable for using low-viscosity adhesive, high-viscosity adhesive cannot be used, a large amount of filler is added in the silicone adhesive for reinforcement, the viscosity is overhigh, and the adhesive dispensing device is only suitable for dispensing of a special adhesive dispensing machine. Some applications in household appliances, such as the bonding of display screens, have requirements on the thickness of a glue layer, a high-viscosity structural glue cannot be used, and a low-viscosity adhesive must be used. The invention fills the market gap.
2) According to the invention, silane modified polyurethane and epoxy resin are used as a component A, an epoxy curing agent, a chelated tin catalyst and a coupling agent are used as a component B, and A, B components are mixed, so that the epoxy resin and the epoxy curing agent react, the silane modified polyurethane reacts with moisture in the air under the catalytic action of the chelated tin, and an interpenetrating network (similar to a composite material) is formed when two different systems of glue are combined and cured, so that the silane modified polyurethane has a synergistic effect, the adhesive force is increased, the toughness is improved, and the curing speed is high (generally, the adhesive force with high curing speed is relatively poor). At present, no people use silane modified polyurethane and epoxy system for matching.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description.
Detailed Description
A silane-modified polyurethane-epoxy composition and a method for preparing the same are described in further detail below with reference to specific examples, which are provided for purposes of comparison and explanation only and to which the present invention is not limited.
A silane modified polyurethane-epoxy composition, which consists of A, B parts; the component A comprises silane modified polyurethane, epoxy resin and inorganic filler; the component B comprises an epoxy curing agent, a silane coupling agent and a chelated tin catalyst.
The component A is silane modified polyurethane and epoxy resin, the component B is epoxy curing agent, chelating tin catalyst and silane coupling agent, and the component A, B is mixed, the epoxy resin reacts with the epoxy curing agent, the silane modified polyurethane reacts with moisture in the air under the catalytic action of the chelating tin, and the glue of two different systems forms an interpenetrating network (similar to a composite material) during combined curing, so that the synergistic effect is achieved, the adhesive force is increased, the toughness is improved, and the curing speed is high (generally, the adhesive force with high curing speed is relatively poor).
The silane modified polyurethane-epoxy composition has the advantages that through the synergistic effect of the silane modified polyurethane and the epoxy resin, the silane modified polyurethane-epoxy composition has the high flexibility of polyurethane after being cured, has the high bonding strength of epoxy resin glue, has the humidity resistance and heat resistance, good impact resistance, high curing speed and low viscosity, can meet the requirements of current household electric quick equipment, and has wide application range and the requirements of impact resistance and humidity resistance. The adhesive is mainly used for bonding materials such as metal, plastic, ceramics and the like.
A. The weight ratio of the component B is as follows:
component A
100 parts of silane-modified polyurethane, namely 100 parts of,
30-80 parts of epoxy resin,
10-30 parts of inorganic filler;
b component
5-25 parts of an epoxy curing agent,
3-8 parts of a silane coupling agent,
1-3 parts of a chelated tin catalyst.
In the component A, the weight ratio of the epoxy resin is 30-80 parts, the strength of the cured body of the adhesive is increased along with the increase of the ratio of the epoxy resin, the hardness is increased, the adhesive force is reduced, the mass ratio of the epoxy resin is in a relatively balanced state within the range of 30-80 parts, and if the mass ratio is too low or too high, the comprehensive performance is greatly reduced. The most suitable epoxy resin proportion is 50, and 50 parts of epoxy resin can balance the performances of the adhesive in all aspects, so that the adhesive is in an optimal state.
The weight ratio of the inorganic filler is 10-30 parts, the inorganic filler is mainly added for reinforcement, the higher the addition amount is, the better the mechanical property is, but the viscosity is influenced by the excessively high addition amount, and the application range of the structural adhesive is reduced.
In the component B, 3-8 parts of silane coupling agent (first silane coupling agent) by weight is used for improving the adhesive force and assisting in catalyzing the reaction of silane modified polyurethane and moisture, and the adhesion is influenced when the silane coupling agent is added too low and other performances are influenced when the silane coupling agent is added too high.
The weight ratio of the chelated tin catalyst is 1-3 parts, the silane modified polyurethane reacts with moisture in the air under the catalysis of the chelated tin, and the higher the catalyst content is, the faster the silane modified polyurethane is cured; however, the excessive content of the chelated tin catalyst can cause the excessive curing after mixing, a certain operation time is needed in the actual process, the excessive curing can cause the surface of the structural adhesive which is not finished to be dried and cured, and the weight ratio of the chelated tin catalyst is preferably 2 parts.
Specifically, the preparation method of the silane modified polyurethane in the component A comprises the following steps:
weighing 100 parts (mass parts) of polyether polyol according to the formula ratio, heating to 100-120 ℃, and dehydrating in vacuum for 2 hours, wherein the vacuum degree is-0.09 to-0.1 MPa;
then cooling to below 50 ℃ (when the temperature is too high, a sudden polymerization phenomenon occurs in the synthesis process), then adding 25-38 parts of diisocyanate and 0.1-0.5 part of organic tin catalyst according to the formula amount, heating to 75-80 ℃ for reaction for 1-2 hours (when the reaction temperature is too low, the reaction rate is too slow or the reaction effect cannot be achieved, and when the temperature is too high, a sudden polymerization phenomenon occurs in the synthesis process), and titrating the content of the isocyanate group (NCO) to a target value R;
adding 12-24 parts of silane coupling agent (second silane coupling agent) with the formula amount, continuing to react for 1-2 hours at 75-80 ℃ for blocking, and stopping the reaction until no isocyanate group (NCO) is detected by titration to prepare the needed silane modified polyurethane, and storing the silane modified polyurethane in a closed container.
Calculated by taking 100 parts of the polyether polyol as a basis, the lower the content of diisocyanate, the lower the R value, the higher the molecular weight of the synthesized polyurethane and the higher the viscosity, and the higher the content of diisocyanate, the higher the R value, the lower the molecular weight and the lower the viscosity, but the higher the R value, the lower the stability of the synthesized polyurethane, and the target value is mainly to control the R value (the R value is the molar ratio of NCO to hydroxyl) to be 2-3.
The epoxy resin is exemplified by one or more of bisphenol a type epoxy resin E44, bisphenol a type epoxy resin E51, bisphenol F type epoxy resin F44, or bisphenol F type epoxy resin F51, preferably F51. The epoxy curing agent can be one or more of polyamide curing agents GX-3090, LITE 3040, 2,4,6-3 (dimethylaminomethyl) phenol from Caddy, and preferably 2,4,6-3 (dimethylaminomethyl) phenol.
The first silane coupling agent a and the second silane coupling agent b can be one or more than two of 3-aminopropyl trimethoxy silane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxy silane, vinyl trimethoxy silane, gamma-aminopropyl triethoxy silane and gamma-glycidyl ether oxygen propyl trimethoxy silane, and the first silane coupling agent a and the second silane coupling agent b can be the same silane coupling agent or different silane coupling agents. An amino coupling agent is needed for end sealing during synthesis, a first silane coupling agent a used in a finished product formula is used for improving the adhesive force, and a second silane coupling agent b used during synthesis of the silane modified polyurethane plays an end sealing role.
The inorganic filler is one or more than two of silica micropowder, calcium carbonate, silica and diatomite. The polyether polyol is one or more of GX-9005, GX-9201 and 3050D of optimizing chemistry of Kadela company;
the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate.
In addition, the invention can adjust the curing speed by various factors, such as controlling the moisture content in the inorganic filler, controlling the dosage of the chelated tin catalyst, controlling the dosage of the coupling agent, and the like.
The concrete method for adjusting the curing speed by controlling the moisture content in the component A comprises the following steps:
in the first method, before the component A is prepared, the filler is baked. The moisture content of the baked filler is different from that of the unbaked filler, and the unbaked filler has high moisture content, so that the reaction speed is accelerated;
and in the second method, after the preparation of the component A is finished, the component A is heated to 100-120 ℃, and then vacuum dehydration is carried out.
The curing speed can be adjusted by controlling the dosage of the coupling agent and the like, the coupling agent such as A-171 can play a role of a water removal agent, moisture can preferentially react with the coupling agent in the reaction process, the dosage of the coupling agent is increased, and the curing speed is reduced.
The curing speed can be adjusted by controlling the amount of the chelated tin catalyst. The silane modified polyurethane reacts with moisture in the air under the catalysis of the chelated tin, and the weight ratio of the chelated tin catalyst is 1-3 parts; the higher the catalyst content is, the faster the silane-modified polyurethane is cured; however, the excessive content of the chelated tin catalyst can cause the excessive curing after mixing, a certain operation time is needed in the actual process, the excessive curing can cause the surface of the structural adhesive which is not finished to be dried and cured, and the weight ratio of the chelated tin catalyst is preferably 2 parts.
Example 1
TABLE 1 content of ingredients of silane-modified polyurethane-epoxy composition in example 1
Example 2
TABLE 2 content of ingredients of silane-modified polyurethane-epoxy composition in example 2
Example 3
TABLE 3 content of ingredients of silane-modified polyurethane-epoxy composition in example 3
Example 4
TABLE 4 content of ingredients of silane-modified polyurethane-epoxy composition in example 4
Example 5
TABLE 5 content of ingredients of silane-modified polyurethane-epoxy composition in example 5
Example 6
A preparation method of a silane modified polyurethane-epoxy composition comprises the following steps:
the component A comprises: firstly, adding silane modified polyurethane and epoxy resin into a reaction kettle, keeping the vacuum degree less than-0.09 MPa, stirring for 0.5-2 h at 70-100 ℃, exemplarily stirring for 1h at 90 ℃.
Then, cooling to below 40 ℃ by circulating water, adding an inorganic filler, dispersing and stirring at a high speed for 0.5-2 h (exemplarily stirring for 1 h) to uniformly mix the materials, keeping the vacuum degree less than-0.09 MPa, and defoaming in vacuum for 0.5 h to obtain a component A, and filling the component A into a two-component sealant rubber tube A for sealed storage;
and B component: adding an epoxy curing agent, a catalyst and a silane coupling agent a into a reaction kettle, stirring for 0.5-1 h to uniformly mix the materials, keeping the vacuum degree less than-0.08 MPa, defoaming for 0.5 h in vacuum to obtain a component B, and filling the component B into a tube B of a two-component sealed rubber tube for sealed storage.
Comparative example: the comparative example is a two-component epoxy adhesive used in the household appliance market, REH-0080 of Shaoqi (Xiamen) electronic technology Co.
When in use, the component A and the component B are mixed and quickly and uniformly stirred.
Test sample preparation:
preparation of shear strength and peel strength test pieces: surface treatment of a 304 stainless steel sheet, wiping with alcohol, preparing a shear strength test piece and a T-shaped peeling strength test piece after gluing the surface-treated 304 stainless steel sheet, and testing the shear strength and the peeling strength after curing for a certain time at room temperature.
Cold and hot impact aging test: after preparing the shear strength and peel strength test pieces, curing for 1 day, placing the test pieces into a cold-hot impact test box, keeping the temperature at minus 20 ℃ for 30 minutes, heating to 60 ℃ and keeping the temperature for 30 minutes, and after circulating for 1000 times, testing the shear strength and peel strength at room temperature.
High temperature and high humidity aging test: after preparing the shear strength and peel strength test pieces, curing for 1 day, placing the test pieces in a constant temperature and humidity test box, standing the test pieces at the temperature of 60 ℃ and the humidity of 90% for 1000 hours, and testing the shear strength and the peel strength at room temperature.
TABLE 6 results of Performance test of examples 1-5 and comparative examples
According to the invention, through the synergistic effect of the silane modified polyurethane and the epoxy resin, the flexibility and the bonding strength of a cured substance are improved, the moisture-heat resistance and the cold-heat shock resistance are good, the flexibility can be judged from the hardness and the elongation at break, the hardness of the structural adhesive is Shore A50-70, and the hardness of a comparative example is Shore D75-85; the elongation at break of the cured product of the present invention was 200%, and the elongation at break of the comparative example was 15%, which revealed that the flexibility of the cured product of the present invention was significantly improved.
The peeling force can reach more than 20N/mm after 4 hours of curing, the production efficiency is greatly improved, the overall viscosity is reduced by using the low-viscosity epoxy resin, the mechanical property is excellent, the application range is expanded, and the adhesive dispensing device is not limited.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A silane modified polyurethane-epoxy composition is characterized by consisting of A, B parts; the component A comprises silane modified polyurethane, epoxy resin and inorganic filler; the component B comprises an epoxy curing agent, a silane coupling agent and a chelated tin catalyst.
2. The silane-modified polyurethane-epoxy composition of claim 1, wherein A, B comprises the following components in parts by weight:
component A
100 parts of silane-modified polyurethane, namely 100 parts of,
30-80 parts of epoxy resin,
10-30 parts of inorganic filler;
b component
5-25 parts of an epoxy curing agent,
3-8 parts of a silane coupling agent,
1-3 parts of a chelated tin catalyst.
3. The silane-modified polyurethane-epoxy composition according to claim 1, wherein the silane-modified polyurethane is prepared by the following method:
weighing polyether polyol according to a formula, heating to 120 ℃ for 100 ℃ and vacuum dehydration, cooling to below 50 ℃, adding diisocyanate and an organic tin catalyst according to the formula, heating to 75-80 ℃ for reaction for 1-2 hours, titrating the content of isocyanate groups to a target value R, adding silane coupling agent according to the formula, continuing to react for 1-2 hours at 75-80 ℃, titrating to detect that the isocyanate groups cannot terminate the reaction, and preparing the needed silane modified polyurethane which is put into a closed container for storage.
4. The silane-modified polyurethane-epoxy composition according to claim 1, wherein the epoxy resin is one or more of bisphenol a epoxy resin E44, bisphenol a epoxy resin E51, bisphenol F epoxy resin F44, and bisphenol F epoxy resin F51.
5. The silane-modified polyurethane-epoxy composition according to claim 1, wherein the epoxy curing agent is a polyamide curing agent and/or 2,4,6-3 (dimethylaminomethyl) phenol.
6. The silane-modified polyurethane-epoxy composition according to claim 3, wherein the silane coupling agent of the component B and the silane coupling agent for preparing the silane-modified polyurethane are each one or more of 3-aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, vinyltrimethoxysilane, γ -aminopropyltriethoxysilane, and γ -glycidoxypropyltrimethoxysilane.
7. The silane-modified polyurethane-epoxy composition according to claims 1 to 6, wherein the inorganic filler is one or more of fine silica powder, calcium carbonate, silica, and diatomaceous earth.
8. The silane-modified polyurethane-epoxy composition of claim 3, wherein the target value R is the molar ratio of isocyanate groups to hydroxyl groups, and R is between 2 and 3.
9. The silane-modified polyurethane-epoxy composition according to claim 3, wherein the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate.
10. A preparation method of a silane modified polyurethane-epoxy composition is characterized by comprising the following steps:
the component A comprises: firstly, adding silane modified polyurethane and epoxy resin into a reaction kettle, keeping the vacuum degree less than-0.09 MPa, and stirring for 0.5-2 h at 70-100 ℃;
then, cooling to below 40 ℃, adding an inorganic filler, dispersing and stirring at a high speed for 0.5-2 h to uniformly mix the materials, defoaming in vacuum to obtain a component A, and sealing and storing;
and B component: and adding an epoxy curing agent, a catalyst and a silane coupling agent into the reaction kettle, stirring for 0.5-1 h to uniformly mix the materials, defoaming in vacuum to obtain a component B, and sealing and storing.
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| CN202010586631.1A CN111635729A (en) | 2020-06-24 | 2020-06-24 | Silane modified polyurethane-epoxy composition and preparation method thereof |
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| CN112592688A (en) * | 2020-11-20 | 2021-04-02 | 浙江海泰新材料有限公司 | Polyurethane-epoxy two-component structural adhesive |
| CN114058308A (en) * | 2021-11-26 | 2022-02-18 | 迪马新材料科技（苏州）有限公司 | Epoxy heat-conducting glue and preparation method thereof |
| CN114479751A (en) * | 2022-02-11 | 2022-05-13 | 东莞市承林电子有限公司 | High-strength high-elasticity two-component polyurethane structural adhesive and preparation method thereof |
| CN114806415A (en) * | 2022-01-29 | 2022-07-29 | 北京东方雨虹防水技术股份有限公司 | Reaction curing type organic-inorganic composite elastic multi-component ceramic tile bonding material and preparation method thereof |
| CN114907079A (en) * | 2022-06-09 | 2022-08-16 | 新化县天马建筑新材料科技有限公司 | High-adhesion waterproof tile joint filling mortar and preparation method thereof |
| CN115011297A (en) * | 2022-07-15 | 2022-09-06 | 北京新风航天装备有限公司 | Adhesive for ceramic materials and preparation method thereof |
| CN114806415B (en) * | 2022-01-29 | 2024-04-26 | 北京东方雨虹防水技术股份有限公司 | Reaction-curing organic-inorganic composite elastic multi-component ceramic tile bonding material and preparation method thereof |
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| CN112592688A (en) * | 2020-11-20 | 2021-04-02 | 浙江海泰新材料有限公司 | Polyurethane-epoxy two-component structural adhesive |
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| CN114058308B (en) * | 2021-11-26 | 2023-10-27 | 迪马新材料科技（苏州）有限公司 | Epoxy heat-conducting adhesive and preparation method thereof |
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| CN114479751A (en) * | 2022-02-11 | 2022-05-13 | 东莞市承林电子有限公司 | High-strength high-elasticity two-component polyurethane structural adhesive and preparation method thereof |
| CN114907079A (en) * | 2022-06-09 | 2022-08-16 | 新化县天马建筑新材料科技有限公司 | High-adhesion waterproof tile joint filling mortar and preparation method thereof |
| CN115011297A (en) * | 2022-07-15 | 2022-09-06 | 北京新风航天装备有限公司 | Adhesive for ceramic materials and preparation method thereof |
| CN115011297B (en) * | 2022-07-15 | 2023-01-20 | 北京新风航天装备有限公司 | Adhesive for ceramic material and preparation method thereof |
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