CN111892904B - Polyurethane adhesive and preparation method thereof - Google Patents
Polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN111892904B CN111892904B CN202010815899.8A CN202010815899A CN111892904B CN 111892904 B CN111892904 B CN 111892904B CN 202010815899 A CN202010815899 A CN 202010815899A CN 111892904 B CN111892904 B CN 111892904B
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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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- 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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- 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
- C09J11/08—Macromolecular 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2312/00—Crosslinking
Abstract
The invention provides a polyurethane adhesive and a preparation method thereof, wherein the polyurethane adhesive comprises the following components in parts by weight: 50-60 parts of polyurethane emulsion, 10-15 parts of organic silicon titanium modified epoxy resin, 2-4 parts of N- (4-hydroxyphenyl) maleimide, 2-4 parts of N-methyldiethanolamine, 1-3 parts of hydrogenated castor oil, 0.5-2 parts of composite fiber, 0-3 parts of functional auxiliary agent and 4-6 parts of nano aluminum oxide.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a polyurethane adhesive and a preparation method thereof.
Background
The polyurethane adhesive refers to an adhesive containing a carbamate group (-NHCOO-) or an isocyanate group (-NCO) in a molecular chain. Polyurethane adhesives are divided into two broad classes, polyisocyanates and polyurethanes. The molecular chain of the polyisocyanate contains isocyano (-NCO) and carbamate (-NH-COO-), so that the polyurethane adhesive shows high activity and polarity.
In any polyurethane adhesive, isocyanate groups in the system react with substances containing active hydrogen in or out of the system to generate polyurethane groups or polyurea, so that the system strength is greatly improved to realize the purpose of bonding, for example, the polyurethane adhesive is bonded with a substrate containing active hydrogen: the porous materials such as foam, plastic, wood, leather, fabric, paper, ceramic and the like, and the materials with smooth surfaces such as metal, glass, rubber, plastic and the like have excellent chemical bonding force.
The polyurethane adhesive is an important component in the polyurethane resin which is rapidly developed at present, has excellent performance, is widely applied in many aspects, is one of eight important varieties of synthetic adhesives, and has the defects of easy hydrolysis under high temperature and high humidity and reduced adhesive strength. For example, in the field of food packaging, different requirements such as pasteurization, high temperature, cooking at 121 ℃, cooking at 135 ℃, microwave packaging, vacuum packaging and the like can be met according to different foods. When the polyurethane is exposed to the high-temperature and high-humidity environment for a long time, the carbamate group in the polyurethane is easy to hydrolyze, the molecular weight is reduced, and the bonding effect is poor; in addition, the polyurethane material has poor thermal oxidation resistance, and adhesive products in the environments are easy to yellow, so that the application and popularization of the adhesive are also limited.
Disclosure of Invention
In view of the above, the invention aims to provide a polyurethane adhesive and a preparation method thereof, and the prepared polyurethane adhesive has excellent quick-drying adhesion, strong adhesive force, good heat resistance, obviously improved film forming mechanical property, obviously improved interlayer connection stability and is worthy of application and popularization by optimizing and improving the preparation method of raw materials and reasonably selecting raw material compatibility.
In order to achieve the purpose, the invention provides the following technical scheme:
a polyurethane adhesive comprises the following components in parts by weight: 50-60 parts of polyurethane emulsion, 10-15 parts of organic silicon titanium modified epoxy resin, 2-4 parts of N- (4-hydroxyphenyl) maleimide, 2-4 parts of N-methyldiethanolamine, 1-3 parts of hydrogenated castor oil, 0.5-2 parts of composite fiber, 0-3 parts of functional auxiliary agent and 4-6 parts of nano aluminum oxide. The particle size of the nano alumina is 100-150 nm.
As a further preference of the invention, the polyurethane emulsion comprises a component A and a component B in a volume ratio of 1:0.8-1.5, wherein the component A is a polyurethane adhesive emulsion with the isocyanate group content of 4.5-6%, and the component B is a modified polyurethane adhesive emulsion with the isocyanate group content of 5-8%.
As a further preferred aspect of the present invention, in the raw materials of the polyurethane adhesive emulsion of component A, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with a molar ratio of 0-0.5:1, the active hydrogen compound is polyoxypropylene glycol with a molecular weight of 1500-.
In the component B polyurethane adhesive emulsion raw material, the isocyanate group is isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with a molar ratio of 0.5:1, and the active hydrogen compound is epoxy modified polyoxypropylene triol and pentaerythritol polyoxypropylene tetraol with a molar ratio of 1:0-0.3, wherein the molecular weight of the modified polyoxypropylene triol is 3500-5000, the hydroxyl value is 38-43mgKOH/g, the molecular weight of the pentaerythritol polyoxypropylene tetraol is 580-650, and the hydroxyl value is 1000-1200 mgKOH/g.
The preparation method of the modified polyoxypropylene triol is further preferable in the invention, the preparation method comprises the steps of taking glycerin, bisphenol A and dimethylolbutyric acid as initial compounds, taking potassium hydroxide as a catalyst, heating to 90-100 ℃ in a reaction kettle under the atmosphere of nitrogen, then removing water in the catalyst by vacuum dehydration, adding propylene oxide and ethylene oxide into the reaction kettle after dehydration, adjusting the internal pressure of the kettle to 0.25-0.3MPa and the temperature to 110-115 ℃ for block polycondensation reaction, after the reaction is completed, carrying out reduced pressure distillation, and then sequentially carrying out neutralization, filtration and refining to obtain the modified polyoxypropylene triol.
Further preferably, the composite fiber is a fiber obtained by mixing the following components in a mass ratio of 1: 0.2-0.5: 0.2-0.3 of sepiolite fiber, alumina fiber and polyhydroxyalkanoate fiber composite.
The functional auxiliary agent further preferably comprises a defoaming agent, a silane coupling agent and a surfactant, wherein the defoaming agent is a polysiloxane defoaming agent or a polyether modified organic silicon type defoaming agent, the silane coupling agent is vinyl tri-tert-butyl hydroperoxide silane, and the surfactant is sodium dodecyl benzene sulfonate.
As a further preferred aspect of the present invention, the polyurethane adhesive comprises the following steps:
1) weighing raw materials in parts by weight, placing the composite fiber in an acetone-ethanol mixed solution, soaking at normal temperature for 3-5min, taking out, blending with N- (4-hydroxyphenyl) maleimide and organic silicon titanium modified epoxy resin, heating and blending at 80-90 ℃ for 5-10min, adding hydrogenated castor oil, continuously heating to 95 ℃, heating and blending for 3-5min to obtain a first mixture for later use;
2) and (2) blending the functional auxiliary agent, N-methyldiethanolamine and nano-alumina, then adding the mixture into the first mixture, firstly heating and stirring for 10min, then adding the mixture into polyurethane emulsion, and continuously stirring and mixing for 5-20min or carrying out ultrasonic treatment for 5-15min to obtain the polyurethane emulsion.
As a further preferred mode of the invention, the temperature rise and the stirring in the step 2) are 45 ℃, 300-500rpm and the ultrasonic treatment is 28-30 KHz.
The invention has the beneficial effects that: according to the invention, by optimizing and improving the preparation method of the raw materials and reasonably selecting the raw materials for compatibility, the prepared polyurethane adhesive has excellent quick-drying adhesion, strong adhesive force, good heat resistance, obviously improved film forming mechanical property, obviously improved interlayer connection stability and high application and popularization value.
The polyurethane emulsion consists of A, B two components which are matched with each other in a synergistic manner, has corresponding advantages in rheology and connectivity, effectively ensures the cohesiveness and the activation of the adhesive, and has good reaction and cooperation effect with other raw material components. The polyether glycol in the component B takes glycerol, bisphenol A and dimethylolbutyric acid as initial compounds, the glycerol is relatively slow in the initial period of forming a network structure, the contact reaction among the components is effectively promoted, the surface layer molecular space resistance is small, and compared with the matching of bisphenol A, the formed network structure has excellent shear strength and the stability among molecules is obviously improved through the reasonable alternative embedding connection of aromatic and heterocyclic rings with large rigidity and stable structure and soft and hard sections. Compared with single-component polyurethane emulsion, the double components adopt reasonable mixing proportion, so that the synergistic performance of the polyurethane adhesive is facilitated, and the polyurethane adhesive has good auxiliary promotion to other raw material reactions.
In the polyurethane adhesive emulsion main body, silicon-titanium modified epoxy resin is added in an auxiliary manner, so that the heat-resistant and oxidation-resistant effects are effectively improved, meanwhile, the silicon-titanium modified epoxy resin is matched with a multifunctional maleimide monomer to further ensure the performance reinforcement and stability of effective molecules of the polyurethane adhesive, the self-catalysis of amine groups also effectively complements the improvement of the chemical bonding reactivity among molecules, and the reinforced composite fibers are matched to form a cross-linked structure serving as a reinforced aggregate net layer.
The invention increases the fluidity of the adhesive and reduces the surface tension of the substance by introducing the nano-alumina into the polyurethane adhesive, and can carry out nano-modification on the surface properties of the raw material components so as to uniformly disperse the raw material components; the invention adopts the nano alumina with the particle size range of 100-150nm, not only improves the shearing strength of the adhesive, but also improves the wear resistance, aging resistance and weather resistance of the adhesive.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1:
a polyurethane adhesive comprises the following components in parts by weight: 55 parts of polyurethane emulsion, 10 parts of organic silicon titanium modified epoxy resin, 3 parts of N- (4-hydroxyphenyl) maleimide, 4 parts of N-methyldiethanolamine, 2 parts of hydrogenated castor oil, 1.5 parts of composite fiber, 2 parts of functional assistant and 4 parts of nano aluminum oxide. The particle size of the nano alumina is 100 nm.
The polyurethane adhesive comprises the following preparation steps:
1) weighing raw materials in parts by weight, placing the composite fiber in an acetone-ethanol mixed solution, soaking at normal temperature for 3-5min, taking out, blending with N- (4-hydroxyphenyl) maleimide and organic silicon titanium modified epoxy resin, heating and blending at 80-90 ℃ for 5-10min, adding hydrogenated castor oil, continuously heating to 95 ℃, heating and blending for 3-5min to obtain a first mixture for later use;
2) and (3) blending the functional auxiliary agent, N-methyldiethanolamine and nano-alumina, adding the mixture into the first mixture, stirring the mixture for 10min at 45 ℃ and 500rpm, adding the mixture into polyurethane emulsion, and continuously stirring and mixing the mixture for 5-20min or carrying out ultrasonic treatment on the mixture for 5-15min at 28-30KHz (continuously stirring and mixing the mixture in examples 1-3, and carrying out ultrasonic treatment in examples 4-6) to obtain the polyurethane emulsion.
Wherein the polyurethane emulsion comprises a component A and a component B in a volume ratio of 1:1.
The component A is polyurethane adhesive emulsion with 5.0% of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component A, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with the molar ratio of 0.5:1, the active hydrogen compound is polyoxypropylene glycol, the molecular weight of the polyoxypropylene glycol is 1500, and the hydroxyl value is 113 mgKOH/g.
The component B is a modified polyurethane adhesive emulsion with 8 percent of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component B, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with a molar ratio of 0.5:1, and the active hydrogen compounds are epoxy modified polyoxypropylene triol and pentaerythritol polyoxypropylene tetraol with a molar ratio of 1:0.2, wherein the molecular weight of the modified polyoxypropylene triol is 3500, and the hydroxyl value is 42mgKOH/g, and the molecular weight of the pentaerythritol polyoxypropylene tetraol is 610, and the hydroxyl value is 1055 mgKOH/g.
Further, the preparation method of the modified polyoxypropylene triol comprises the steps of taking glycerin, bisphenol A and dimethylolbutyric acid as initial compounds, taking potassium hydroxide as a catalyst, heating to 90-100 ℃ in a reaction kettle in the nitrogen atmosphere, then carrying out vacuum dehydration to remove water in the catalyst, adding epoxypropane and epoxyethane into the reaction kettle after dehydration, adjusting the internal pressure of the kettle to be 0.25-0.3MPa and the temperature to be 110-115 ℃ for block polycondensation reaction, carrying out reduced pressure distillation after the reaction is completed, and then sequentially carrying out neutralization, filtration and refining to obtain the modified polyoxypropylene triol.
The composite fiber is prepared from the following components in a mass ratio of 1: 0.2: 0.2 sepiolite fibers, alumina fibers, polyhydroxyalkanoate fiber composites.
The functional assistant comprises a defoaming agent, a silane coupling agent and a surfactant, wherein the defoaming agent is a polysiloxane defoaming agent or a polyether modified organic silicon type defoaming agent (SH-300 is adopted in the embodiment, the same is adopted in the following), the silane coupling agent is vinyl tri-tert-butyl hydroperoxide silane, and the surfactant is sodium dodecyl benzene sulfonate.
Example 2:
a polyurethane adhesive comprises the following components in parts by weight: 60 parts of polyurethane emulsion, 15 parts of organic silicon titanium modified epoxy resin, 4 parts of N- (4-hydroxyphenyl) maleimide, 4 parts of N-methyldiethanolamine, 2 parts of hydrogenated castor oil, 1.5 parts of composite fiber, 3 parts of functional assistant and 4.5 parts of nano aluminum oxide. The particle size of the nano alumina is 110 nm.
The preparation method of the polyurethane adhesive is the same as that of example 1.
Wherein the polyurethane emulsion comprises a component A and a component B in a volume ratio of 1: 1.5.
The component A is polyurethane adhesive emulsion with 5.5 percent of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component A, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with the molar ratio of 0.5:1, the active hydrogen compound is polyoxypropylene glycol, the molecular weight of the polyoxypropylene glycol is 2000, and the hydroxyl value is 110 mgKOH/g.
The component B is a modified polyurethane adhesive emulsion with the isocyanate group content of 7 percent, in the raw materials of the polyurethane adhesive emulsion of the component B, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with the molar ratio of 0.5:1, and the active hydrogen compounds are epoxy modified polyoxypropylene triol and pentaerythritol polyoxypropylene tetraol with the molar ratio of 1:0.2, wherein the molecular weight of the modified polyoxypropylene triol is 3700, the hydroxyl value is 41mgKOH/g, the molecular weight of the pentaerythritol polyoxypropylene tetraol is 600, and the hydroxyl value is 1080 mgKOH/g; the modified polyoxypropylene triol was prepared as in example 1.
The composite fiber is prepared from the following components in a mass ratio of 1: 0.5: 0.2 sepiolite fibers, alumina fibers, polyhydroxyalkanoate fiber composites. The functional assistant was the same as in example 1.
Example 3:
a polyurethane adhesive comprises the following components in parts by weight: 50 parts of polyurethane emulsion, 10 parts of organic silicon titanium modified epoxy resin, 2 parts of N- (4-hydroxyphenyl) maleimide, 3 parts of N-methyldiethanolamine, 2 parts of hydrogenated castor oil, 0.5 part of composite fiber, 1 part of functional assistant and 5 parts of nano aluminum oxide. The particle size of the nano alumina is 120 nm.
The preparation method of the polyurethane adhesive is the same as that of example 1.
Wherein the polyurethane emulsion comprises a component A and a component B in a volume ratio of 1: 1.5.
The component A is polyurethane adhesive emulsion with 4.5 percent of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component A, the isocyanate group is polymethylene polyphenyl polyisocyanate, the active hydrogen compound is polyoxypropylene glycol, and the molecular weight of the polyoxypropylene glycol is 2000 and the hydroxyl value is 114 mgKOH/g.
The component B is a modified polyurethane adhesive emulsion with 6% of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component B, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with a molar ratio of 0.5:1, and the active hydrogen compounds are epoxy modified polyoxypropylene triol and pentaerythritol polyoxypropylene tetraol with a molar ratio of 1:0.2, wherein the molecular weight of the modified polyoxypropylene triol is 4000, the hydroxyl value is 38mgKOH/g, the molecular weight of the pentaerythritol polyoxypropylene tetraol is 620, and the hydroxyl value is 1120 mgKOH/g; the modified polyoxypropylene triol was prepared as in example 1.
The composite fiber is prepared from the following components in a mass ratio of 1: 0.5: 0.3 of sepiolite fibers, alumina fibers and polyhydroxyalkanoate fiber composites. The functional assistant was the same as in example 1.
Example 4:
a polyurethane adhesive comprises the following components in parts by weight: 55 parts of polyurethane emulsion, 15 parts of organic silicon titanium modified epoxy resin, 2 parts of N- (4-hydroxyphenyl) maleimide, 2 parts of N-methyldiethanolamine, 3 parts of hydrogenated castor oil, 2 parts of composite fiber, 1 part of functional assistant and 5 parts of nano aluminum oxide. The particle size of the nano alumina is 130 nm.
The preparation method of the polyurethane adhesive is the same as that of example 1.
Wherein the polyurethane emulsion comprises a component A and a component B in a volume ratio of 1:1.
The component A is polyurethane adhesive emulsion with 5 percent of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component A, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with the molar ratio of 0.5:1, the active hydrogen compound is polyoxypropylene glycol, the molecular weight of the polyoxypropylene glycol is 2000, and the hydroxyl value is 112 mgKOH/g.
The component B is a modified polyurethane adhesive emulsion with 5% of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component B, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with a molar ratio of 0.5:1, and the active hydrogen compounds are epoxy modified polyoxypropylene triol and pentaerythritol polyoxypropylene tetraol with a molar ratio of 1:0.3, wherein the molecular weight of the modified polyoxypropylene triol is 4500, the hydroxyl value is 40mgKOH/g, the molecular weight of the pentaerythritol polyoxypropylene tetraol is 600, and the hydroxyl value is 1100 mgKOH/g; the modified polyoxypropylene triol was prepared as in example 1.
The composite fiber is prepared from the following components in a mass ratio of 1: 0.2: 0.3 of sepiolite fibers, alumina fibers and polyhydroxyalkanoate fiber composites. The functional assistant was the same as in example 1.
Example 5:
a polyurethane adhesive comprises the following components in parts by weight: 60 parts of polyurethane emulsion, 10 parts of organic silicon titanium modified epoxy resin, 2 parts of N- (4-hydroxyphenyl) maleimide, 3 parts of N-methyldiethanolamine, 1 part of hydrogenated castor oil, 0.5 part of composite fiber, 2 parts of functional assistant and 5.5 parts of nano aluminum oxide. The particle size of the nano alumina is 140 nm.
The preparation method of the polyurethane adhesive is the same as that of example 1.
Wherein the polyurethane emulsion comprises a component A and a component B in a volume ratio of 1: 1.5.
The component A is polyurethane adhesive emulsion with 6 percent of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component A, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with the molar ratio of 0.5:1, the active hydrogen compound is polyoxypropylene glycol, the molecular weight of the polyoxypropylene glycol is 1800, and the hydroxyl value is 120 mgKOH/g.
The component B is modified polyurethane adhesive emulsion with 6 percent of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component B, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with the molar ratio of 0.5:1, the active hydrogen compound is epoxy modified polyoxypropylene triol, the molecular weight of the modified polyoxypropylene triol is 3500, the hydroxyl value is 42mgKOH/g, and the preparation method of the modified polyoxypropylene triol is the same as that of the example 1.
The composite fiber is prepared from the following components in a mass ratio of 1: 0.2: 0.2 sepiolite fibers, alumina fibers, polyhydroxyalkanoate fiber composites. The functional assistant was the same as in example 1.
Example 6:
a polyurethane adhesive comprises the following components in parts by weight: 50 parts of polyurethane emulsion, 10 parts of organic silicon titanium modified epoxy resin, 2 parts of N- (4-hydroxyphenyl) maleimide, 3 parts of N-methyldiethanolamine, 1 part of hydrogenated castor oil, 1 part of composite fiber, 2 parts of functional assistant and 6 parts of nano aluminum oxide. The particle size of the nano alumina is 150 nm.
The preparation method of the polyurethane adhesive is the same as that of example 1.
Wherein the polyurethane emulsion comprises a component A and a component B in a volume ratio of 1:1.
The component A is polyurethane adhesive emulsion with 5.5 percent of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component A, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with the molar ratio of 0.5:1, the active hydrogen compound is polyoxypropylene glycol, the molecular weight of the polyoxypropylene glycol is 2000, and the hydroxyl value is 115 mgKOH/g.
The component B is a modified polyurethane adhesive emulsion with 5.6 percent of isocyanate group content, in the raw materials of the polyurethane adhesive emulsion of the component B, the isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with a molar ratio of 0.5:1, and the active hydrogen compounds are epoxy modified polyoxypropylene triol and pentaerythritol polyoxypropylene tetraol with a molar ratio of 1:0.2, wherein the molecular weight of the modified polyoxypropylene triol is 4000, the hydroxyl value is 39mgKOH/g, the molecular weight of the pentaerythritol polyoxypropylene tetraol is 580, and the hydroxyl value is 1100 mgKOH/g; the modified polyoxypropylene triol was prepared as in example 1.
The composite fiber is prepared from the following components in a mass ratio of 1: 0.3: 0.3 of sepiolite fibers, alumina fibers and polyhydroxyalkanoate fiber composites. The functional assistant was the same as in example 1.
Comparative example 1: and (3) removing the composite fibers based on the embodiment 1, and obtaining the adhesive finished product under the unchanged other conditions.
Comparative example 2: based on the example 1, removing the organic silicon titanium modified epoxy resin and the composite fiber, and obtaining the adhesive finished product under the same other conditions.
Comparative example 3: the polyurethane adhesive component A of example 1 was taken.
Comparative example 4: the polyurethane adhesive component B of example 1 was taken.
Comparative example 5: comparative example 5 differs from example 1 in that the alumina used in comparative example 5 is a normal alumina, not a nano alumina.
Comparative example 6: comparative example 6 is different from example 1 in that the nano alumina used in comparative example 6 has a particle size of 160 nm.
The adhesives (dissolved in butanone) in the above examples and comparative examples were used for coating and bonding tetrafluoroethylene sheets, and cured under the same conditions, and the measured performance data were as follows:
TABLE 1
TABLE 2
As can be seen from the above tables 1-2, the polyurethane adhesive of the present application has an excellent performance improvement compared to the existing adhesive component (single component a or B), the component performance using nano alumina is also significantly better than that using ordinary alumina or not using alumina, and the shear strength, water and heat resistance, and weather resistance of the polyurethane adhesive are all significantly improved, so that the polyurethane adhesive has a stronger applicability, and is worthy of popularization and application.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (1)
1. The polyurethane adhesive is characterized by comprising the following preparation steps:
1) weighing raw materials in parts by weight, placing the composite fiber in an acetone-ethanol mixed solution, soaking at normal temperature for 3-5min, taking out, blending with N- (4-hydroxyphenyl) maleimide and organic silicon titanium modified epoxy resin, heating and blending at 80-90 ℃ for 5-10min, adding hydrogenated castor oil, continuously heating to 95 ℃, heating and blending for 3-5min to obtain a first mixture for later use;
2) blending the functional auxiliary agent, N-methyldiethanolamine and nano-alumina, then adding the mixture into the first mixture, firstly heating and stirring for 10min, then adding the mixture into polyurethane emulsion, and continuously stirring and mixing for 5-20min or carrying out ultrasonic treatment for 5-15min to obtain the polyurethane emulsion;
in the step 2), the temperature is raised and the stirring temperature is 45 ℃, the rotating speed is 300-500rpm, and the ultrasonic treatment frequency is 28-30 KHz;
the polyurethane adhesive comprises the following components in parts by weight: 50-60 parts of polyurethane emulsion, 10-15 parts of organic silicon titanium modified epoxy resin, 2-4 parts of N- (4-hydroxyphenyl) maleimide, 2-4 parts of N-methyldiethanolamine, 1-3 parts of hydrogenated castor oil, 0.5-2 parts of composite fiber, 0-3 parts of functional auxiliary agent and 4-6 parts of nano alumina;
the polyurethane emulsion comprises a component A and a component B in a volume ratio of 1:0.8-1.5, wherein the component A is a polyurethane adhesive emulsion with the isocyanate group content of 4.5-6%, and the component B is a modified polyurethane adhesive emulsion with the isocyanate group content of 5-8%;
in the component A, isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with the molar ratio of 0-0.5:1, the active hydrogen compound is polyoxypropylene glycol, the molecular weight of the polyoxypropylene glycol is 1500-;
in the component B, isocyanate groups are isophorone diisocyanate and polymethylene polyphenyl polyisocyanate with a molar ratio of 0.5:1, and the active hydrogen compounds are modified polyoxypropylene triol and pentaerythritol polyoxypropylene tetraol with a molar ratio of 1:0-0.3, wherein the molecular weight of the modified polyoxypropylene triol is 3500-5000, the hydroxyl value is 38-43mgKOH/g, the molecular weight of the pentaerythritol polyoxypropylene tetraol is 580-650, and the hydroxyl value is 1000-1200 mgKOH/g;
the preparation method of the modified polyoxypropylene triol comprises the steps of taking glycerol, bisphenol A and dimethylolbutyric acid as initial compounds, taking potassium hydroxide as a catalyst, heating to 90-100 ℃ in a reaction kettle in the atmosphere of nitrogen, then carrying out vacuum dehydration to remove water in the catalyst, adding epoxypropane and epoxyethane into the reaction kettle after dehydration, adjusting the internal pressure of the kettle to 0.25-0.3MPa and the temperature to 110-115 ℃ for reaction, carrying out reduced pressure distillation after the reaction is completed, and then sequentially carrying out neutralization, filtration and refining to obtain the modified polyoxypropylene triol;
the composite fiber is prepared from the following components in a mass ratio of 1: 0.2-0.5: 0.2-0.3 of sepiolite fiber, alumina fiber and polyhydroxyalkanoate fiber compound;
the functional auxiliary agent comprises a defoaming agent, a silane coupling agent and a surfactant, wherein the defoaming agent is a polysiloxane defoaming agent or a polyether modified organic silicon type defoaming agent, the silane coupling agent is vinyl tri-tert-butyl peroxide silane, and the surfactant is sodium dodecyl benzene sulfonate; the particle size of the nano alumina is 100-150 nm.
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