CN108359401B - High-strength multi-curing polyurethane adhesive and preparation method and use method thereof - Google Patents

High-strength multi-curing polyurethane adhesive and preparation method and use method thereof Download PDF

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CN108359401B
CN108359401B CN201810183996.2A CN201810183996A CN108359401B CN 108359401 B CN108359401 B CN 108359401B CN 201810183996 A CN201810183996 A CN 201810183996A CN 108359401 B CN108359401 B CN 108359401B
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curing
moisture
adhesive
prepolymer
polyurethane adhesive
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CN108359401A (en
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叶陈瑶
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Nanjing Zhonglan Intelligent Technology Co ltd
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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
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a preparation method of a high-strength multi-curing polyurethane adhesive, which realizes stable curing under high humidity and high temperature conditions and realizes the effect of excellent high-strength bonding performance of an adhesive structure by selecting the types of polyols and sealing agents in a moisture-curing oligomer in a compounding way. The scheme is as follows: (1) moisture-curing prepolymer: 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 a moisture-cured prepolymer with NCO content of 8-15%; (2) adding a sealing agent: and (3) adding caprolactam, sodium bisulfite and methyl ethyl ketoxime into the moisture-curing prepolymer in sequence, stirring uniformly, and adding a solvent according to the viscosity requirement to obtain the product.

Description

High-strength multi-curing polyurethane adhesive and preparation method and use method thereof
Technical Field
The invention relates to the field of polyurethane adhesives, in particular to the field of high-strength multi-curing polyurethane adhesives, 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 high polymer materials, damp and hot are environmental factors avoided as much as possible, and how to obtain a high-strength and high-temperature-resistant polyurethane adhesive suitable for being used under the damp and hot condition is an urgent problem to be solved.
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 invention obtains a design of multi-curing and multi-stage curing by selecting polyurethane components, realizes stable curing under high temperature and high humidity, increases the curing degree under high temperature, and can realize the effects of high-strength bonding of an adhesive structure and excellent high-temperature resistance.
It is another object of the present invention to provide a method for preparing a high strength multiple cure polyurethane adhesive.
It is another object of the present invention to provide a method of using a high strength multi-cure polyurethane adhesive.
In order to achieve the technical effects, the following technical scheme is adopted.
A preparation method of a high-strength multi-curing polyurethane adhesive comprises the following steps:
(1) moisture-curing prepolymers
Respectively carrying out vacuum drying on polycarbonate polyol, polyether polyol and isocyanate;
and uniformly stirring the dried polycarbonate polyol, polyether polyol and isocyanate, reacting for 1-5h at 70-100 ℃, 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 8-15%.
(2) Addition of blocking Agents
And (3) adding caprolactam, sodium bisulfite and methyl ethyl ketoxime into the moisture-curing prepolymer in sequence, stirring uniformly, and adding a solvent according to the viscosity requirement to obtain the product.
Preferably, the polyether polyol is polyether triol, the molecular weight is 1000-5000-.
Preferably, the molar ratio of the polycarbonate polyol to the polyether polyol is 3-5:1, more preferably 4: 1.
Preferably, the total molar ratio of the polycarbonate polyol and the polyether polyol to the isocyanate is 1: (3-10).
Preferably, the isocyanate is toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate, and is preferably toluene diisocyanate or diphenylmethane diisocyanate or a mixture with isophorone diisocyanate.
Preferably, the chain extender is 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, trimethylolpropane, castor oil, or the like.
Preferably, the solvent is toluene, xylene or acetone.
Preferably, the weight ratio of caprolactam to sodium bisulfite to methyl ethyl ketoxime is 1: (2-3): 1.
preferably, the total mass of caprolactam, sodium bisulfite and methyl ethyl ketoxime accounts for 5-15wt% of the solid content of the binder.
The invention also claims a preparation method of the high-strength multi-curing polyurethane adhesive to obtain the high-strength multi-curing polyurethane adhesive.
The application method of the high-strength multi-curing polyurethane adhesive comprises the steps of coating the adhesive on one surface of an adherend, compacting a second adherend on the one surface of the adherend coated with the adhesive, clamping a connecting part by using a clamp, and curing for 1-3 hours at the temperature of 60-80 ℃ and at the humidity of 40-60.
Preferably, the first adherend and the second adherend are made of metal, such as stainless steel, copper, iron, or an alloy, plastic, such as PMMA, PC, PE, PP, PS, PPs, or SAN, or cloth, such as polyester, polyamide, aramid, PTT, ultra-high molecular weight polyethylene fiber, vinylon, or spandex.
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 multi-stage curing polyurethane adhesive by a step-by-step method, and the key technical points in the two steps are respectively introduced below.
Moisture-curing prepolymers
The preparation of the moisture curing prepolymer is that the dried polycarbonate polyol, polyether polyol and isocyanate are evenly stirred and react for 1 to 5 hours at the temperature of 70 to 100 ℃, the temperature is reduced to 60 to 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 curing prepolymer with the NCO content of about 8 to 15 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 proper molar ratio is adopted, the obtained adhesive has good strength, and the good flexibility ensures the bonding property and the adhesiveness of the adhesive.
When the adhesive is used, a high-strength material is bonded, and the cured material has high 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 polycarbonate polyol is not in the range, the adhesive strength is improved to a certain extent after 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: (3-10) which aims to obtain a moisture-curable prepolymer with an NCO content of about 8-15%, wherein the NCO content can ensure that the prepolymer can be reacted with a blocking agent containing active hydrogen used in the next step, and the isocyanate content is high, so that a certain amount of NCO residue can be ensured after the reaction with the blocking agent, and the moisture-curable specific adhesive can be obtained finally.
In the moisture curing process, residual-NCO reacts with water or water vapor in an adherend or air to obtain-NH 2, and then the-NCO and-NH 2 are subjected to crosslinking reaction, so that the moisture curing effect is realized.
Addition of blocking Agents
The invention has the important invention point that the sealant is selected, the adhesive capable of being thermally cured in sections 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.
In the invention, caprolactam, sodium bisulfite and methyl ethyl ketoxime are added into the moisture-cured prepolymer in sequence, the mixture is stirred uniformly, and a solvent is added according to the viscosity requirement, thus obtaining the product. 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 5-15wt% of the solid content of the adhesive, and the dosage is selected according to the strength requirement of the used product.
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 specific curing conditions are that moisture curing is needed and preliminary heat curing is guaranteed (the dissociation temperature of sodium bisulfite is about 60 ℃ as a low-temperature section sealant), so that the humidity is 40-60, and the temperature is 60-80 ℃ for curing for 1-3 h.
The first and second adherends can be selected from metals, plastics, cloth, etc. as the first and second adherends are selected, the invention is suitable for high temperature solidification, which is generally a metal with high temperature requirement, and can be stainless steel, copper, iron, alloy, etc.
Advantageous technical effects
The structural design main body of the invention is a multi-curing adhesive, mainly involving moisture curing and thermocuring, the moisture curing can realize slow curing, and the thermocuring can realize stage curing.
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; the introduction of thermosetting groups, mainly selected in specific proportions of caprolactam, sodium bisulfite and methyl ethyl ketoxime, imparts stage curability to the adhesive. 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 75g 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 an NCO content of about 14% (the NCO content is the mass content of the prepolymer, and the same applies below).
(2) Addition of blocking Agents
And (2) sequentially adding 5g of caprolactam, 10g of sodium bisulfite and 5g of methyl ethyl ketoxime into the moisture-curing prepolymer, uniformly stirring, and adding xylene according to the viscosity requirement to obtain the high-strength multi-curing 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-;
stirring dried 65g of polycarbonate diol L6001 and 75g of diphenylmethane diisocyanate uniformly, 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 for dilution to obtain a moisture-cured prepolymer with the NCO content of about 14% (the NCO content is the mass content of the prepolymer).
(2) Addition of blocking Agents
And (2) sequentially adding 5g of caprolactam, 10g of sodium bisulfite and 5g of methyl ethyl ketoxime into the moisture-curing prepolymer, uniformly stirring, and adding xylene according to the viscosity requirement to obtain the high-strength multi-curing 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-;
20g of dried polycarbonate diol L6001, 55g of polyether triol N330 and 75g of diphenylmethane diisocyanate are uniformly stirred, 0.5g of dibutyltin dilaurate serving as a catalyst is added, the reaction is carried out for 1 to 5 hours at the temperature of 80 ℃, the temperature is reduced to 60 ℃, 4g of chain extender 1, 4-butanediol is added for reaction for 1 hour, and xylene is added for dilution, so that a moisture-curing prepolymer with the NCO content of about 14% (the NCO content is the content of the prepolymer) is obtained.
(2) Addition of blocking Agents
And (2) sequentially adding 5g of caprolactam, 10g of sodium bisulfite and 5g of methyl ethyl ketoxime into the moisture-curing prepolymer, uniformly stirring, and adding xylene according to the viscosity requirement to obtain the high-strength multi-curing polyurethane adhesive.
Comparative example 3
(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 44g of dried polycarbonate diol L6001, 33g of polyether triol VORANOL3010 and 80g 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 1, 4-butanediol serving as a chain extender, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 14% (the NCO content accounts for the content of the prepolymer).
(2) Addition of blocking Agents
And (2) sequentially adding 5g of caprolactam, 10g of sodium bisulfite and 5g of methyl ethyl ketoxime into the moisture-curing prepolymer, uniformly stirring, and adding xylene according to the viscosity requirement to obtain the high-strength multi-curing 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 38g 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 7.5% (the NCO content accounts for the content of the prepolymer).
(2) Addition of blocking Agents
And (2) sequentially adding 5g of caprolactam, 10g of sodium bisulfite and 5g of methyl ethyl ketoxime into the moisture-curing prepolymer, uniformly stirring, and adding xylene according to the viscosity requirement to obtain the high-strength multi-curing 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 90g 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 16% (the NCO content accounts for the content of the prepolymer).
(2) Addition of blocking Agents
And (2) sequentially adding 5g of caprolactam, 10g of sodium bisulfite and 5g of methyl ethyl ketoxime into the moisture-curing prepolymer, uniformly stirring, and adding xylene according to the viscosity requirement to obtain the high-strength multi-curing 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 75g 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 14% (the NCO content is the content of the prepolymer).
(2) Addition of blocking Agents
And sequentially adding 20g of sodium bisulfite into the moisture-curing prepolymer, uniformly stirring, and adding dimethylbenzene according to the viscosity requirement to obtain the high-strength multi-curing 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 75g 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 14% (the NCO content is the content of the prepolymer).
(2) Addition of blocking Agents
And (2) sequentially adding 5g of caprolactam and 15g of sodium bisulfite into the moisture-curing prepolymer, 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 75g 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 14% (the NCO content is the content of the prepolymer).
(2) Addition of blocking Agents
And sequentially adding 10g of caprolactam and 10g of methyl ethyl ketoxime into the moisture-curing prepolymer, uniformly stirring, and adding dimethylbenzene according to viscosity requirements to obtain the high-strength multi-curing polyurethane adhesive.
Comparative example 9
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 75g 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 1, 4-butanediol serving as a chain extender, reacting for 1h, and adding xylene to dilute to obtain a moisture-cured prepolymer with the NCO content of about 14% (the NCO content accounts for the content of the prepolymer).
[ 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, placing at the humidity of 50 and the temperature of 65 ℃, curing for 2 hours, 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 the PMMA test piece, compacting the adherend on the surface of the PMMA test piece coated with the adhesive, clamping the connecting part by using a clamp, placing at the humidity of 50 and the temperature of 65 ℃, curing for 2 hours, further placing at the humidity of 50 and the temperature of 160 ℃ again, curing for 30 minutes, and testing according to the method to obtain the high-temperature tensile shear strength.
2. Three point plastic bend test
The three-point bending test standard is carried out according to GB/T9341-2000, and the test piece is prepared by the following method: the adhesive was coated on a release film, and the other side was covered with the release film, and a sample having a thickness of 4mm, a width of 10mm, and a length of 80mm was obtained by the above-mentioned curing method 1. The flexural modulus (MPa) and flexural strength (MPa) were recorded.
[ test results ]
Figure BDA0001589434710000111
The experimental data verify the content of the specification, the NCO content, the proportion of the polycarbonate polyol and the polyether polyol, the type selection of the sealing agent and the like all have important influence on the performance of a final product, meanwhile, the type of the sealing agent realizes stage curing, and the performances of curing strength and the like at a high-temperature section are realized.

Claims (5)

1. A preparation method of a high-strength multi-curing polyurethane adhesive is characterized by comprising the following steps: the method comprises the following steps:
(1) moisture-curing 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 a moisture-cured prepolymer with the NCO content of 8-15%;
(2) addition of blocking Agents
Adding caprolactam, sodium bisulfite and methyl ethyl ketoxime into the moisture-curing prepolymer in sequence, stirring uniformly, and adding a solvent according to the viscosity requirement to obtain a product;
the total mass of the caprolactam, the sodium bisulfite and the methyl ethyl ketoxime accounts for 5 to 15 weight percent of the solid content of the adhesive;
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 total mole ratio of polycarbonate polyol and polyether polyol to isocyanate mole ratio is 1: (3-10);
the weight ratio of caprolactam, sodium bisulfite and methyl ethyl ketoxime is 1: (2-3): 1;
the molar ratio of the polycarbonate polyol to the polyether polyol is 3-5: 1.
2. the method of preparing a high strength multi-cure polyurethane adhesive according to claim 1, wherein: the isocyanate is toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate.
3. The method of preparing a high strength multi-cure polyurethane adhesive according to claim 1, wherein: the solvent is toluene, xylene or acetone.
4. The method of making a high strength multi-cure polyurethane adhesive of any one of claims 1-3, resulting in a high strength multi-cure polyurethane adhesive.
5. The method of using a high strength multi-cure polyurethane adhesive as defined in claim 4, wherein: applying an adhesive on one surface of an adherend, compacting a second adherend on the one surface of the adherend coated with the adhesive, clamping the connecting part by using a clamp, and curing for 1-3h at the temperature of 60-80 ℃ and the humidity of 40-60.
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