CN108395847B - High-strength light-heat curing polyurethane adhesive and preparation method and use method thereof - Google Patents
High-strength light-heat curing polyurethane adhesive and preparation method and use method thereof Download PDFInfo
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- CN108395847B CN108395847B CN201810183902.1A CN201810183902A CN108395847B CN 108395847 B CN108395847 B CN 108395847B CN 201810183902 A CN201810183902 A CN 201810183902A CN 108395847 B CN108395847 B CN 108395847B
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
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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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Abstract
The invention relates to a preparation method of a high-strength light and heat cured polyurethane adhesive, which selects the compounding of polyol types in a moisture cured oligomer, and realizes the stable and rapid curing under the conditions of humidity and high temperature by using a light curing group and an end capping agent, thereby realizing the effect of excellent high-strength bonding performance of a bonding structure. The method specifically comprises the following steps: uniformly stirring the dried polycarbonate polyol, polyether polyol and isocyanate, adding a catalyst, reacting at 70-100 ℃ for 1-5h, cooling to 60-80 ℃, adding a chain extender, reacting for 0.5-2h, and adding a solvent for dilution to obtain a moisture-cured prepolymer with the NCO content of about 5-10%; cooling the prepolymer to below 50 ℃, sequentially adding a hydroxyl-containing acrylate monomer, a photoinitiator and a polymerization inhibitor into the prepolymer under the condition of keeping out of the sun, and uniformly stirring; and (3) under the condition of keeping out of the sun, adding caprolactam, sodium bisulfite and methyl ethyl ketoxime into the uniformly mixed mixture obtained in the step (2), uniformly stirring, and adding a solvent according to the viscosity requirement.
Description
Technical Field
The invention relates to the field of polyurethane adhesives, in particular to the field of polyurethane adhesives with high strength and photo-thermal dual curing, and also relates to a preparation method and a use method.
Background
Polyurethane resin belongs to a class of high-quality polymer resin substances, and is widely applied to various fields: for example, polyurethane artificial leather is widely used for manufacturing fur and clothes, and polyurethane adhesives, polyurethane coatings and polyurethane floor materials are all applied.
Since 1937, polyurethane materials developed very rapidly after their first synthesis, and various types of polyurethanes appeared in endless numbers, with thermoplastic polyurethane adhesives appearing in the middle of the 20 s, solvent-free polyurethane adhesives appearing in 1968, moisture-curing polyurethane adhesives appearing in 1978, and reactive hot-melt polyurethane adhesives appearing in 1984. Basic polyurethane adhesives are basically completed in the 20 th century, research in the last two decades mainly focuses on high-performance composite polyurethane adhesives, which are adhesive products for specific applications, and the research difficulty of general adhesives is gradually increased.
For the use of polymer materials, the inventors have conducted detailed studies on the curing modes of photo-thermal, wet-thermal and wet-optical, and have made respective patent applications. In actual use, how to obtain a high-strength and high-temperature-resistant polyurethane adhesive suitable for being used under photo-thermal conditions is a product class to be developed.
In view of the above technical problems, the inventor enterprises have conducted long-term research to obtain the present invention.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical problems introduced in the background technology, the polyurethane component is selected, and the NCO-terminated polyurethane oligomer is used as the basis to obtain a design of rapid light curing and multi-stage curing, so that rapid and stable curing at high temperature is realized, the curing degree at high temperature is increased, and the excellent effects of high-strength bonding, high-temperature resistance and rapid curing of the bonding structure can be realized.
It is another object of the present invention to provide a method for preparing a high-strength photo-and thermo-curing polyurethane adhesive.
It is another object of the present invention to provide a method of using a high intensity photo-thermal curing polyurethane adhesive.
In order to achieve the technical effects, the following technical scheme is adopted.
A preparation method of a high-strength light-heat curing polyurethane adhesive comprises the following steps:
(1) NCO-terminated polyurethane prepolymers
Respectively carrying out vacuum drying on polycarbonate polyol, polyether polyol and isocyanate;
uniformly stirring the dried polycarbonate polyol, polyether polyol and isocyanate, adding a catalyst, reacting at 70-100 ℃ for 1-5h, cooling to 60-80 ℃, adding a chain extender, reacting for 0.5-2h, and adding a solvent for dilution to obtain an NCO-terminated polyurethane prepolymer with an NCO content of about 5-10%.
(2) Addition of the Photocurable component
And (3) cooling the prepolymer to below 50 ℃, sequentially adding a hydroxyl-containing acrylate monomer, a photoinitiator and a polymerization inhibitor into the prepolymer under the condition of keeping out of the sun, and uniformly stirring.
(3) Addition of blocking Agents
And (3) under the condition of keeping out of the sun, sequentially adding caprolactam, sodium bisulfite and methyl ethyl ketoxime into the uniformly mixed mixture obtained in the step (2), uniformly stirring, and adding a solvent according to the viscosity requirement to obtain the product.
As a preferable technical scheme, the polyether polyol is polyether triol, the molecular weight is 1000-5000, and the polycarbonate polyol is polycarbonate diol, the molecular weight is 1000-2000.
Preferably, the molar ratio of the polycarbonate polyol to the polyether polyol is 3-5: 1.
as a preferable technical solution, the total mole ratio of the polycarbonate polyol and the polyether polyol to the isocyanate mole ratio is 1: (1.2-2.3).
Preferably, the isocyanate is toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate.
As a preferred technical scheme, the solvent is toluene, xylene or acetone.
Preferably, the chain extender is 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, trimethylolpropane, castor oil, or the like.
As a preferable technical scheme, the photoinitiator is 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide or 2,4, 6-trimethylbenzoyl ethyl phosphonate.
According to a preferable technical scheme, the polymerization inhibitor is hydroquinone or p-benzoquinone.
As a preferable technical scheme, the total mass of the caprolactam, the sodium bisulfite and the methyl ethyl ketoxime accounts for 3-10 wt% of the solid content of the adhesive, and the weight ratio of the caprolactam, the sodium bisulfite and the methyl ethyl ketoxime is 1: (2-3): 1.
as a preferred technical scheme, the hydroxyl-containing acrylate monomer is hydroxyethyl acrylate, phenyl glycidyl ether acrylate and cyclohexane dimethoxy diacrylate with the proportion of 1 (0.8-1.5): (0.2-0.5) (molar ratio), the total mass of the above monomers accounts for 10-25% of the binder solids, and may be more preferably 11%, 13%, 15%, 17%, 19%, 21%, 23%.
The preparation method of the high-strength light and heat curing polyurethane adhesive can obtain the high-strength light and heat curing polyurethane adhesive.
A method for using high-strength light-heat-curing polyurethane adhesive comprises coating adhesive on one surface of an adherend, pressing an adherend II on the surface of the adherend coated with adhesive, clamping the connecting part with a clamp, irradiating with ultraviolet light for 3-10min, and curing at 60-80 deg.C for 1-3 h.
At least one of the first adherend and the second adherend is made of a material which is transparent to violet rays. Preferably, the first adherend and the second adherend are glass or a high-temperature resistant plastic, and the high-temperature resistant plastic is preferably PMMA, PC, PS, PPS, or the like.
Detailed Description
In order to provide the skilled person and the public with a more complete understanding of the technical solution of the present invention, the following description of the reaction mechanism and the example mode is provided.
The invention prepares the high-strength light and heat dual-curing polyurethane adhesive by a step method, and the key technical points in the two steps are respectively introduced below.
NCO-terminated polyurethane prepolymers
The preparation of the NCO-terminated polyurethane prepolymer is that dried polycarbonate polyol, polyether polyol and isocyanate are stirred uniformly, the mixture reacts for 1 to 5 hours at a temperature of between 70 and 100 ℃, the temperature is reduced to between 60 and 80 ℃, a chain extender is added for reaction for 0.5 to 2 hours, and a solvent is added for dilution to obtain the moisture-cured prepolymer with the NCO content of about 5 to 10 percent.
The polycarbonate polyol and the polyether polyol are matched for use, the polyether polyol has good flexibility, the polycarbonate polyol has good rigidity, the polycarbonate polyol and the polyether polyol are matched through a proper molar ratio, the obtained adhesive has good strength, and the good flexibility ensures the bonding property and the adhesiveness of the adhesive.
Because the adhesive is used for bonding high-strength materials, the cured materials have higher mechanical strength and adhesive strength, wherein the molar ratio of the polycarbonate polyol to the polyether polyol is 3-5:1, the polycarbonate polyol accounts for the main body, the mechanical strength is ensured by using the adhesive, and if the adhesive is not in the range, the adhesive strength is improved after the amount of the polyether polyol is increased, but the mechanical strength is greatly reduced; if the polyether polyol is not used or is used in an excessively small amount, the mechanical strength is increased but the adhesive strength is reduced due to excessively low affinity with the substrate, and the connector is easily broken when lateral movement or bending occurs.
The polyether polyol is polyether triol, the molecular weight is 1000-5000, the molecular weight is preferably 2500-3500, and the polycarbonate polyol is polycarbonate diol, the molecular weight is 1000-2000. The above-mentioned selection should not be too large in molecular weight, low in hydroxyl value, low in post-crosslinking degree, and low in mechanical strength, and if too small in molecular weight, too large in crosslinking degree, and tends to decrease in adhesive strength.
The polyol selection is preferably: the polycarbonate polyol is polycarbonate diol (PCDL), and can be selected from Asahi chemical industry trademark L6001, molecular weight 1000, hydroxyl value 110 +/-10, acid value 0.05mgKOH/g, viscosity 1100-; l5651, molecular weight 1000, hydroxyl number 110. + -.10, acid number 0.05mgKOH/g, viscosity 1200-; the polyether polyol is polyether triol, and can be selected from N330, molecular weight of 3000 +/-200, hydroxyl value of 56 +/-3, acid value of less than or equal to 0.1mgKOH/g and viscosity of 500 +/-75 mPas.
The isocyanate is not specifically limited and may be any isocyanate commonly used, and preferably, the isocyanate is toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate, more preferably toluene diisocyanate or diphenylmethane diisocyanate or a mixture with isophorone diisocyanate, and further preferably a combination of an aromatic isocyanate and a non-aromatic isocyanate, and has balanced strength and flexibility.
In the reaction of the polyol and the isocyanate, the total molar ratio of the polycarbonate polyol and the polyether polyol to the isocyanate molar ratio is 1: (1.2-2.3) which is intended to obtain an NCO-terminated polyurethane prepolymer having an NCO content of about 5-10% which is capable of reacting with a photo-curing group containing active hydrogen and a blocking agent to be used in the next step.
Introduction of photo-curing group
The NCO-terminated polyurethane prepolymers described above have a high number of isocyanate end groups which can be reacted with isocyanates via hydroxyl-containing acrylates or blocking agents.
And (3) sequentially adding a hydroxyl-containing acrylate monomer, a photoinitiator and a polymerization inhibitor into the prepolymer, uniformly stirring, and adding a solvent according to viscosity requirements to obtain the product.
The monomer selection is related, hydroxyethyl acrylate is used as a main monomer and is used as the most common basic hydroxyl-containing acrylate, and the comprehensive performance is excellent; the phenyl glycidyl ether acrylate contains phenyl, so that the strength can be provided, and meanwhile, hydroxyl can slowly react with an epoxy group and be cured, so that the later-stage crosslinking degree is improved; because of early-stage moisture curing and benzene-containing acrylate curing, the strength is continuously improved, but the adhesive force is obviously reduced; the cyclooctane dimethoxy diacrylate is used as an adhesion enhancement monomer, SR406 can be adopted, and the monomer has the advantages of fast curing, strong adhesion, photolysis resistance, high temperature resistance, strong adhesion to plastics and chemical corrosion resistance, and is selected to make up for the differences.
As a preferred technical scheme, the hydroxyl-containing acrylate monomer is hydroxyethyl acrylate, phenyl glycidyl ether acrylate and cyclohexane dimethoxy diacrylate with the proportion of 1 (0.8-1.5): (0.2-0.5) (molar ratio). Because the invention is used for bonding high-strength materials in a targeted way, the using amount of the phenyl glycidyl ether acrylate is larger, the self-strength of the adhesive can be greatly improved, and if the using amount is too small, the strength is not enhanced enough; however, due to the above effect on the adhesive properties, cyclohexane dimethoxy diacrylate was creatively selected in the present invention, which remedies the above disadvantages, but is not too large, which decreases the strength, and if not added or added in the smallest amount, the adhesive properties of the adhesive decrease. The total mass of which is such as to ensure that the final hydroxyl-containing monomer and the blocking agent can react all the NCO completely, without excluding the case where the final product contains NCO groups.
Addition of blocking Agents
The invention has the important invention point that the sealant is selected, the adhesive capable of realizing segmented thermosetting is obtained by selecting the sealant, and the adhesive is divided into the sealant of a low temperature section, a medium temperature section and a high temperature section, wherein the sealant of the low temperature section is subjected to curing reaction in primary curing, the strength in the bonding process is ensured, the sealant of the medium temperature section and the high temperature section is subjected to unblocking at high temperature to perform curing reaction, the crosslinking degree is improved, and the high temperature resistance is improved.
After the light curing group is added into the NCO-terminated polyurethane prepolymer, under the condition of keeping out of the sun, caprolactam, sodium bisulfite and methyl ethyl ketoxime are sequentially added, the mixture is uniformly stirred, and a solvent is added according to the viscosity requirement, so that the product is obtained. Wherein the low-temperature section sealant is sodium bisulfite with a dissociation temperature of 60 ℃, the medium-temperature section sealant is methyl ethyl ketoxime with a dissociation temperature of 125-130 ℃, the high-temperature section sealant is caprolactam with a dissociation temperature of 160 ℃. The three sealing agents are unsealed at different temperatures, and then the segmented curing effect of the invention is realized.
The weight ratio of the caprolactam to the sodium bisulfite to the methyl ethyl ketoxime is 1: (2-3): the method has the advantages that 1, the usage amount of sodium bisulfite is the largest, the primary basic adhesive force is ensured, the mechanical strength is also ensured, and the subsequent molar weight of methyl ethyl ketoxime and caprolactam is gradually reduced. The total mass of caprolactam, sodium bisulfite and methyl ethyl ketoxime accounts for 3-10 wt% of the solid content of the adhesive, and the dosage is selected according to the strength requirement of the used product.
Due to the dosage of the light-curing monomer and the end-capping agent added in the subsequent step, residual NCO exists in some cases, but the residual quantity is not large, and the overall performance is not influenced. In essence the present invention relies on part of the water to effect a further crosslinking at elevated temperatures.
Meanwhile, the light-curing components in the examples of the present invention, and the examples and comparative examples of the step-curing are described in detail in other patents on the same day, and the effects are proved, which are not described in detail in the present application.
Application method
The invention provides a specific using method which is selected according to the basic performance of an adhesive, and specifically comprises the following steps: since the adhesive needs a long period of time for curing, the adhesive is applied to one surface of an adherend, and the adherend is pressed against the surface of the adherend to which the adhesive is applied, and the connecting portion is held by a clip to ensure that it does not shift.
The use time is more conventional for the photo-curing condition, the ultraviolet light is irradiated for 3-10min, and the subsequent free radical polymerization crosslinking can be completed in the subsequent thermal curing. As for the thermal curing conditions, the temperature is selected from 60-80 ℃ for curing for 1-3h due to the need of moisture curing and the guarantee of primary thermal curing (the dissociation temperature of the low-temperature section sealant is sodium bisulfite is 60 ℃).
As the selection of the adherend, the first adherend and the second adherend may be ultraviolet-permeable materials, and as a preferable example, the first adherend and the second adherend are glass or high-temperature-resistant plastics, and the high-temperature-resistant plastics are preferably PMMA, PC, PS, PPS, or the like.
Advantageous technical effects
The structural design main body of the invention introduces hydroxyl-containing photocuring monomer and end-capping agent through NCO end-capped prepolymer, so that the hydroxyl-containing photocuring monomer and end-capping agent have photocuring and segmented curing adhesives which are matched with each other, photocuring can realize rapid curing, end-capping curing can realize segmented high-temperature curing, and high-temperature resistance is improved.
According to the invention, the polycarbonate polyol and polyether polyol with specific dosage and molecular weight are selected as the end NCO moisture curing prepolymer, so that the balance of mechanical strength and adhesion force is realized; introducing a photocuring group, and mainly selecting acrylic monomers of hydroxyethyl acrylate, phenyl glycidyl ether acrylate and cyclohexane dimethanol diacrylate in a specific ratio to further balance the mechanical strength and the adhesive force; introducing a blocking agent, and sequentially adding caprolactam, sodium bisulfite and methyl ethyl ketoxime under the condition of keeping out of the sun to realize three-stage curing. Meanwhile, the invention also preferably provides a use method matched with the components, so that the effects are better realized.
In order to make the technical solutions of the present invention more intuitive for the skilled person, the following exemplary examples and comparative examples are selected for description, and these examples are not to be construed as limiting the scope of the present invention, and any embodiments that do not depart from the basic concept of the present invention are within the scope of the present invention.
Specific examples and comparative examples are as follows：
Example 1
(1) Moisture-curing prepolymers
Respectively carrying out vacuum drying on polycarbonate diol (PCDL, L6001, molecular weight of 1000, hydroxyl value of 110 +/-10, acid value of 0.05mgKOH/g, viscosity of 1100-;
uniformly stirring 40g of dried polycarbonate diol L6001, 30g of polyether triol N330 and 40g of diphenylmethane diisocyanate, adding 0.5g of dibutyltin dilaurate serving as a catalyst, reacting at 80 ℃ for 1-5h, cooling to 60 ℃, adding 4g of chain extender 1, 4-butanediol, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 8% (the NCO content is the mass content of the prepolymer, and the same applies below).
(2) Addition of Photocurable groups
And (2) cooling the moisture-cured prepolymer to below 50 ℃, sequentially adding 8g of hydroxyethyl acrylate, 20g of phenyl glycidyl ether acrylate, 7g of cyclohexane dimethanol diacrylate, 0.5g of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 0.3g of polymerization inhibitor hydroquinone into the prepolymer under the condition of keeping out of the sun, and uniformly stirring.
(3) Addition of blocking agent
And sequentially adding 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime into the moisture-cured prepolymer under the condition of keeping out of the sun, uniformly stirring, and adding dimethylbenzene according to the viscosity requirement to obtain the high-strength multi-cured polyurethane adhesive.
Comparative example 1
(1) Moisture-curing prepolymers
Respectively carrying out vacuum drying on polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 +/-10, acid value 0.05mgKOH/g, viscosity 1100-;
uniformly stirring 62g of dried polycarbonate diol L6001 and 40g of diphenylmethane diisocyanate, adding 0.5g of dibutyltin dilaurate serving as a catalyst, reacting at 80 ℃ for 1-5h, cooling to 60 ℃, adding 4g of chain extender 1, 4-butanediol, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 8% (the NCO content is the content of the prepolymer).
(2) Addition of Photocurable groups
And (2) cooling the moisture-cured prepolymer to below 50 ℃, sequentially adding 8g of hydroxyethyl acrylate, 20g of phenyl glycidyl ether acrylate, 7g of cyclohexane dimethanol diacrylate, 0.5g of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 0.3g of polymerization inhibitor hydroquinone into the prepolymer under the condition of keeping out of the sun, and uniformly stirring.
(3) Addition of blocking agent
And sequentially adding 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime into the moisture-cured prepolymer under the condition of keeping out of the sun, uniformly stirring, and adding dimethylbenzene according to the viscosity requirement to obtain the high-strength multi-cured polyurethane adhesive.
Comparative example 2
(1) Moisture-curing prepolymers
Respectively carrying out vacuum drying on polycarbonate diol (PCDL, L6001, molecular weight of 1000, hydroxyl value of 110 +/-10, acid value of 0.05mgKOH/g, viscosity of 1100-;
uniformly stirring 30g of dried polycarbonate diol L6001, 43g of polyether triol N330 and 40g of diphenylmethane diisocyanate, adding 0.5g of dibutyltin dilaurate serving as a catalyst, reacting at 80 ℃ for 1-5h, cooling to 60 ℃, adding 4g of chain extender 1, 4-butanediol, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 8% (the NCO content is the content of the prepolymer).
(2) Addition of Photocurable groups
And (2) cooling the moisture-cured prepolymer to below 50 ℃, sequentially adding 8g of hydroxyethyl acrylate, 20g of phenyl glycidyl ether acrylate, 7g of cyclohexane dimethanol diacrylate, 0.5g of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 0.3g of polymerization inhibitor hydroquinone into the prepolymer under the condition of keeping out of the sun, and uniformly stirring.
(3) Addition of blocking agent
And sequentially adding 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime into the moisture-cured prepolymer under the condition of keeping out of the sun, uniformly stirring, and adding dimethylbenzene according to the viscosity requirement to obtain the high-strength multi-cured polyurethane adhesive.
Comparative example 3
(1) The moisture curing prepolymer is prepared by respectively vacuum drying polycarbonate diol (PCDL, L6001, molecular weight 1000, hydroxyl value 110 +/-10, acid value 0.05mgKOH/g, viscosity 1100-;
uniformly stirring 40g of dried polycarbonate diol L6001, 35g of polyether diol VORANOL3010 and 40g of diphenylmethane diisocyanate, adding 0.5g of dibutyltin dilaurate serving as a catalyst, reacting at 80 ℃ for 1-5h, cooling to 60 ℃, adding 4g of chain extender 1, 4-butanediol, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with NCO content of about 8% (NCO content is the content of the prepolymer).
(2) Addition of Photocurable groups
And (2) cooling the moisture-cured prepolymer to below 50 ℃, sequentially adding 8g of hydroxyethyl acrylate, 20g of phenyl glycidyl ether acrylate, 7g of cyclohexane dimethanol diacrylate, 0.5g of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 0.3g of polymerization inhibitor hydroquinone into the prepolymer under the condition of keeping out of the sun, and uniformly stirring.
(3) Addition of blocking agent
And sequentially adding 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime into the moisture-cured prepolymer under the condition of keeping out of the sun, uniformly stirring, and adding dimethylbenzene according to the viscosity requirement to obtain the high-strength multi-cured polyurethane adhesive.
Comparative example 4
(1) Moisture-curing prepolymers
Respectively carrying out vacuum drying on polycarbonate diol (PCDL, L6001, molecular weight of 1000, hydroxyl value of 110 +/-10, acid value of 0.05mgKOH/g, viscosity of 1100-;
uniformly stirring 40g of dried polycarbonate diol L6001, 30g of polyether triol N330 and 40g of diphenylmethane diisocyanate, adding 0.5g of dibutyltin dilaurate serving as a catalyst, reacting at 80 ℃ for 1-5h, cooling to 60 ℃, adding 4g of chain extender 1, 4-butanediol, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 8% (the NCO content accounts for the content of the prepolymer).
(2) Addition of Photocurable groups
And (2) cooling the moisture-cured prepolymer to below 50 ℃, sequentially adding 10g of hydroxyethyl acrylate, 23g of phenyl glycidyl ether acrylate, 0.5g of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 0.3g of polymerization inhibitor hydroquinone into the prepolymer under the condition of keeping out of the sun, and uniformly stirring.
(3) Addition of blocking agent
And sequentially adding 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime into the moisture-cured prepolymer under the condition of keeping out of the sun, uniformly stirring, and adding dimethylbenzene according to the viscosity requirement to obtain the high-strength multi-cured polyurethane adhesive.
Comparative example 5
(1) Moisture-curing prepolymers
Respectively carrying out vacuum drying on polycarbonate diol (PCDL, L6001, molecular weight of 1000, hydroxyl value of 110 +/-10, acid value of 0.05mgKOH/g, viscosity of 1100-;
uniformly stirring 40g of dried polycarbonate diol L6001, 30g of polyether triol N330 and 40g of diphenylmethane diisocyanate, adding 0.5g of dibutyltin dilaurate serving as a catalyst, reacting at 80 ℃ for 1-5h, cooling to 60 ℃, adding 4g of chain extender 1, 4-butanediol, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 8% (the NCO content accounts for the content of the prepolymer).
(2) Addition of Photocurable groups
And (2) cooling the moisture-cured prepolymer to below 50 ℃, sequentially adding 20g of hydroxyethyl acrylate, 5g of phenyl glycidyl ether acrylate, 10g of cyclohexane dimethanol diacrylate, 0.5g of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 0.3g of polymerization inhibitor hydroquinone into the prepolymer under the condition of keeping out of the sun, and uniformly stirring.
(3) Addition of blocking agent
And sequentially adding 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime into the moisture-cured prepolymer under the condition of keeping out of the sun, uniformly stirring, and adding dimethylbenzene according to the viscosity requirement to obtain the high-strength multi-cured polyurethane adhesive.
Comparative example 6
(1) Moisture-curing prepolymers
Respectively carrying out vacuum drying on polycarbonate diol (PCDL, L6001, molecular weight of 1000, hydroxyl value of 110 +/-10, acid value of 0.05mgKOH/g, viscosity of 1100-;
uniformly stirring 40g of dried polycarbonate diol L6001, 30g of polyether triol N330 and 40g of diphenylmethane diisocyanate, adding 0.5g of dibutyltin dilaurate serving as a catalyst, reacting at 80 ℃ for 1-5h, cooling to 60 ℃, adding 4g of chain extender 1, 4-butanediol, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 8% (the NCO content accounts for the content of the prepolymer).
(2) Addition of photoinitiating groups
And (2) cooling the moisture-cured prepolymer to below 50 ℃, sequentially adding 8g of hydroxyethyl acrylate, 20g of phenyl glycidyl ether acrylate, 7g of cyclohexane dimethanol diacrylate, 0.5g of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 0.3g of polymerization inhibitor hydroquinone into the prepolymer under a dark condition, uniformly stirring, and adding xylene according to viscosity requirements to obtain the high-strength moisture-heat dual-cured polyurethane adhesive.
Comparative example 7
(1) Moisture-curing prepolymers
Respectively carrying out vacuum drying on polycarbonate diol (PCDL, L6001, molecular weight of 1000, hydroxyl value of 110 +/-10, acid value of 0.05mgKOH/g, viscosity of 1100-;
uniformly stirring 40g of dried polycarbonate diol L6001, 30g of polyether triol N330 and 40g of diphenylmethane diisocyanate, adding 0.5g of dibutyltin dilaurate serving as a catalyst, reacting at 80 ℃ for 1-5h, cooling to 60 ℃, adding 4g of chain extender 1, 4-butanediol, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 8% (the NCO content accounts for the content of the prepolymer).
(2) Addition of Photocurable groups
And (2) cooling the moisture-cured prepolymer to below 50 ℃, sequentially adding 8g of hydroxyethyl acrylate, 20g of phenyl glycidyl ether acrylate, 7g of cyclohexane dimethanol diacrylate, 0.5g of photoinitiator 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 0.3g of polymerization inhibitor hydroquinone into the prepolymer under the condition of keeping out of the sun, and uniformly stirring.
(3) Addition of blocking agent
And sequentially adding 14g of sodium bisulfite into the moisture-curing prepolymer under the condition of keeping out of the sun, uniformly stirring, and adding dimethylbenzene according to the viscosity requirement to obtain the high-strength multi-curing polyurethane adhesive.
Comparative example 8
(1) Moisture-curing prepolymers
Respectively carrying out vacuum drying on polycarbonate diol (PCDL, L6001, molecular weight of 1000, hydroxyl value of 110 +/-10, acid value of 0.05mgKOH/g, viscosity of 1100-;
uniformly stirring 40g of dried polycarbonate diol L6001, 30g of polyether triol N330 and 40g of diphenylmethane diisocyanate, adding 0.5g of dibutyltin dilaurate serving as a catalyst, reacting at 80 ℃ for 1-5h, cooling to 60 ℃, adding 4g of chain extender 1, 4-butanediol, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 8% (the NCO content accounts for the content of the prepolymer).
(2) Addition of blocking Agents
And 3.5g of caprolactam, 7g of sodium bisulfite and 3.5g of methyl ethyl ketoxime are sequentially added into the moisture-curing prepolymer, the mixture is uniformly stirred, and dimethylbenzene is added according to the viscosity requirement, so that the high-strength moisture-light dual-curing polyurethane adhesive is obtained.
[ test methods ]
1. Tensile shear strength
The test standard was carried out with reference to GB/T13936-92, replacing the metal sheet with a PMMA test sheet, replacing the vulcanized rubber with the adhesives of the examples and comparative examples of the invention, under the same conditions as GB/T13936-92, and recording the failure mode of the fracture surface.
Sample curing method 1: and (3) coating an adhesive on the PMMA test piece, compacting the other PMMA test piece on the surface of the PMMA test piece coated with the adhesive, clamping the connecting part by using a clamp, irradiating by using ultraviolet rays for 10min, placing at the humidity of 50 and the temperature of 65 ℃, curing for 2h, and testing according to the method to obtain the low-temperature tensile shear strength and record the fracture condition.
Sample curing method 2: and (3) coating an adhesive on a PMMA test piece, compacting an adherend on the surface of the PMMA test piece coated with the adhesive, clamping a connecting part by using a clamp, irradiating for 10min by using ultraviolet rays, placing at the humidity of 50 and the temperature of 65 ℃, curing for 2h, further placing at the humidity of 50 and the temperature of 160 ℃ again, curing for 30 min, and testing according to the method to obtain the high-temperature tensile shear strength.
2. Three point plastic bend test
The three-point test standard is carried out according to GB/T9341-2000, and the test piece is prepared by the following method: and coating the adhesive on a release film, covering the release film on the other side, and obtaining a sample with the thickness of 4mm, the width of 10mm and the length of 80mm by adopting the curing method. The flexural modulus (MPa) and flexural strength (MPa) were recorded.
[ test results ]
Remarking: comparative example 8 cured slowly at the early stage and the strength rise was very slow.
The above experimental data verify that the ratio of polycarbonate polyol and polyether polyol, the selection of the type of the photo-curing monomer and the selection of the type of the sealant all have important influence on the performance of the final product, and if the ratio is not within the technical scope of the invention, the shear strength, the modulus, the strength and the curing rate are difficult to balance, and the requirements of high strength and rapid curing are difficult to adapt.
Claims (6)
1. A preparation method of high-strength light-heat curing polyurethane adhesive is characterized in that: the method comprises the following steps:
(1) NCO-terminated polyurethane prepolymers
Respectively carrying out vacuum drying on polycarbonate polyol, polyether polyol and isocyanate for later use;
uniformly stirring the dried polycarbonate polyol, polyether polyol and isocyanate, adding a catalyst, reacting at 70-100 ℃ for 1-5h, cooling to 60-80 ℃, adding a chain extender, reacting for 0.5-2h, and adding a solvent for dilution to obtain an NCO-terminated polyurethane prepolymer with the NCO content of 5-10%;
(2) addition of the Photocurable component
Cooling the prepolymer to below 50 ℃, sequentially adding a hydroxyl-containing acrylate monomer, a photoinitiator and a polymerization inhibitor into the prepolymer under the condition of keeping out of the sun, and uniformly stirring;
(3) addition of blocking Agents
Under the condition of keeping out of the sun, adding caprolactam, sodium bisulfite and methyl ethyl ketoxime into the uniformly mixed mixture obtained in the step (2) in sequence, stirring uniformly, and adding a solvent according to the viscosity requirement to obtain a product;
the molar ratio of the polycarbonate polyol to the polyether polyol is 3-5: 1;
the total mass of the caprolactam, the sodium bisulfite and the methyl ethyl ketoxime accounts for 3-10 wt% of the solid components of the adhesive, and the weight ratio of the caprolactam, the sodium bisulfite and the methyl ethyl ketoxime is 1: (2-3): 1;
the polyether polyol is polyether triol with the molecular weight of 1000-5000, and the polycarbonate polyol is polycarbonate diol with the molecular weight of 1000-2000;
the hydroxyl-containing acrylate monomer is hydroxyethyl acrylate, phenyl glycidyl ether acrylate and cyclohexane dimethoxy diacrylate with the molar ratio of 1 (0.8-1.5): (0.2-0.5) in an amount of 10-25% by mass based on the total mass of the monomers.
2. The method of preparing a high intensity photo-thermally-curable polyurethane adhesive of claim 1, wherein: the total mole ratio of polycarbonate polyol and polyether polyol to isocyanate mole ratio is 1: (1.2-2.3).
3. The method of preparing a high intensity photo-thermally-curable polyurethane adhesive of claim 1, wherein: the isocyanate is toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate.
4. The method of preparing a high intensity photo-thermally-curable polyurethane adhesive of claim 1, wherein: the solvent is toluene, xylene or acetone.
5. The method of making a high intensity light, heat-curable polyurethane adhesive of any of claims 1-4, resulting in a high intensity light, heat-curable polyurethane adhesive.
6. The method of using a high intensity photo-thermally-curable polyurethane adhesive of claim 5, wherein: coating the adhesive on one surface of an adherend, compacting the adherend II on the surface of the adherend coated with the adhesive, clamping the connecting part by using a clamp, irradiating by using ultraviolet light for 3-10min, and curing at 60-80 ℃ for 1-3 h.
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| CN112898533A (en) * | 2021-01-25 | 2021-06-04 | 韶关东森合成材料有限公司 | Multi-curing polyurethane latent curing agent and preparation method thereof |
| CN113234199A (en) * | 2021-06-10 | 2021-08-10 | 淄博华天橡塑科技有限公司 | High-toughness 3D printing photosensitive resin composition and 3D printing method |
| CN114716964B (en) * | 2021-12-30 | 2023-11-28 | 无锡市万力粘合材料股份有限公司 | UV (ultraviolet) curing glue for bonding solar backboard material and preparation method thereof |
| CN116651715A (en) * | 2023-05-12 | 2023-08-29 | 佛山市奥川顺新材料实业有限公司 | Polyurethane adhesive coating film forming process |
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