CN111777759A - Catechol compound modified polyether, preparation method thereof and application thereof in improving adhesive bonding strength - Google Patents
Catechol compound modified polyether, preparation method thereof and application thereof in improving adhesive bonding strength Download PDFInfo
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- CN111777759A CN111777759A CN201910269406.2A CN201910269406A CN111777759A CN 111777759 A CN111777759 A CN 111777759A CN 201910269406 A CN201910269406 A CN 201910269406A CN 111777759 A CN111777759 A CN 111777759A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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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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- 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
- C09J11/08—Macromolecular additives
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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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses catechol compound modified polyether, a preparation method thereof and application thereof in improving the bonding strength of an adhesive. The catechol compound modified polyether is a bionic modified structure, and the preparation method of the catechol compound modified polyether is characterized in that firstly, a tert-butyldimethylsilyl group-protected catechol compound is prepared through hydrosilylation reaction between 3,4 dihydroxybenzaldehyde and tert-butyldimethylchlorosilane, and then the catechol compound modified polyether is prepared through acetal reaction between aldehyde groups in the catechol compound and hydroxyl groups in polyether polyol. The adhesive prepared by applying the catechol compound solves the problem of poor adhesive property of the elastic adhesive in the prior art. The adhesive can effectively improve the bonding strength of the elastic adhesive on various base materials, and simultaneously endows the adhesive with good stability.
Description
Technical Field
The invention relates to an adhesive, and in particular relates to catechol compound modified polyether, a preparation method thereof and application thereof in improving the bonding strength of the adhesive.
Background
The silane modified adhesive is prepared by taking silane-terminated polyether or silane-terminated polyurethane as base resin, has the advantages of low VOC, no plasticizer migration, no pollution and corrosion to a substrate and the like, is cured and crosslinked by hydrolyzing and polycondensing silicon-oxygen bonds in silane under the action of moisture, and does not emit CO2And thus does not foam in a high-temperature and high-humidity environment.
In order to improve the fluidity of the adhesive, reduce the hardness and adjust the modulus, a certain amount of plasticizer is usually added, but the dosage of the plasticizer influences the sagging property and the mechanical property of the adhesive, and especially influences the bonding strength of the adhesive and a base material.
With the widening of application conditions of high and new technology industries such as automobile industry, electronic industry and the like, higher requirements are also put forward on the bonding strength of the adhesive. Particularly, for medium and high strength adhesives (such as 100% modulus >1.5MPa), the phenomena of interface peeling and bonding failure are easy to occur.
Meanwhile, under certain use conditions, such as the joints of the outer walls of the industrial prefabricated panels of the houses, higher requirements are put forward on the adhesive property of the adhesive because the prefabricated panels are under the conditions of outdoor ultraviolet irradiation, rainwater immersion and the like for a long time. Therefore, it is one of the focuses of people to effectively improve the adhesive force of the adhesive.
Conventionally, a silane coupling agent is generally used as an adhesion promoter to improve the adhesion between a colloid and different base materials, and the silane adhesion promoter is crosslinked into an adhesive system when the adhesive is cured, so that the mechanical property and the adhesion property of the adhesive are greatly influenced.
In addition to the addition of silane coupling agents, researchers have attempted to improve the adhesive bonding performance of adhesives by other methods: in patent document CN 106634768A, hydrophobic resin microspheres are added to improve the water resistance of an elastic colloid system. Although the method improves the water-resistant bonding effect of the material, the introduction of the hydrophobic resin microspheres can reduce the bonding strength between the material and the base material to a certain extent; CN 102766431B introduces a sulfur-containing functional group into a hydroxyl-terminated polysiloxane main chain, so that the adhesive performance of the adhesive to a metal substrate is improved, but the shear strength and the bonding strength of the material are improved to a limited extent.
Disclosure of Invention
The invention provides catechol compound modified polyether, a preparation method thereof and application thereof in improving the bonding strength of an adhesive. The catechol compound modified polyether is a bionic modified structure, and solves the problem of poor adhesion of an elastic adhesive in the prior art. The adhesive can effectively improve the bonding strength of the elastic adhesive on various base materials, and simultaneously endows the adhesive with good stability.
The structure of the catechol compound modified polyether is shown in the specification, wherein a tert-butyl dimethyl chlorosilane group structure is removed when the adhesive is used.
The preparation method of the catechol compound modified polyether comprises the following steps: firstly, preparing tert-butyldimethylsilyl protected catechol compound through hydrosilylation reaction between 3,4 dihydroxybenzaldehyde and tert-butyldimethylchlorosilane, and then preparing catechol compound modified polyether through acetal reaction between aldehyde group in the catechol compound and hydroxyl group in polyether polyol.
The polyether polyol is an oligomer with a main chain containing ether bonds (-R-O-R-) and terminal groups or side groups containing more than 2 hydroxyl groups (-OH), and is characterized in that the content of potassium ions and sodium ions is less than 5ppm, the acid value is less than 0.15mgKOH/g, and the hydroxyl value is 20-60 mgKOH/g. Commercially available products such as N220, N330, N240, N260, etc., produced by Shanghai Gaoqiao petrochemical Co.
The preparation method of the catechol compound modified polyether comprises the following steps:
(1) dissolving 5-10 parts of 3, 4-dihydroxybenzaldehyde and 30-40 parts of tert-butyldimethylchlorosilane in 100-200 parts of acetonitrile, cooling to 0-5 ℃, adding 30-40 parts of 1, 8-diazabicycloundecen-7-ene, and reacting at 0 ℃ for 12-24 hours;
(2) adding 50-150 parts of polyether polyol, slowly heating to 80-100 ℃, and reacting for 2.5-3 h; vacuum distilling, filtering to obtain catechol compound modified polyether.
The application of the catechol compound modified polyether is that the catechol compound modified polyether is added into an adhesive and is used for improving the adhesive property of the adhesive.
The application of the catechol compound modified polyether accounts for 1-30% of the weight of matrix resin of the adhesive, and the adhesive property of the adhesive can be remarkably improved.
The adhesive comprises silane modified resin, wherein the silane modified resin is silane modified polyurethane prepolymer or silane modified polyether prepolymer.
The silane modified polyurethane prepolymer is a silane-terminated prepolymer synthesized by isocyanate silane and polyether polyol in one step. Commercially available products such as product numbers XP2774, XP2636, XP2749, XP2458 and the like produced by Corsikong Polymer (China) Co.
The silane modified polyether prepolymer is a silane end-capped prepolymer synthesized by hydrosilicon and unsaturated bond end-capped polyether. Commercially available, such as those manufactured by Wake chemical (China) Ltd
XT50、
XT55、
XB502, and the like.
The adhesive comprises the following raw materials in parts by weight:
silane modified resin 100 parts
60-120 parts of a plasticizer,
0.5 to 1.5 parts of antioxidant,
1 to 5 parts of a water removing agent,
100-200 parts of a filler,
0 to 1 part of a light stabilizer,
0 to 2 parts of a light absorbing agent,
0.2 to 1.5 portions of catalyst
0.1-5 parts of cross-linking agent
1-30 parts of catechol compound modified polyether;
the plasticizer is one of diisononyl phthalate and diisooctyl phthalate;
the antioxidant is 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid isooctyl ester;
the water removing agent is vinyl siloxane;
the filler is one or more of nano calcium carbonate, light calcium carbonate, heavy calcium carbonate, titanium dioxide and carbon black;
the light stabilizer is one of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate and poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate;
the light absorbent is one of 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) benzotriazole and 2- (2' -hydroxy-3-dodecyl-5-methyl) benzotriazole;
the catalyst is one of dibutyltin dilaurate and stannous octoate;
the cross-linking agent is one or more of methyl triacetoxysilane, modified propyl acetoxy silane and ethyl triacetoxysilane.
The preparation method of the adhesive comprises the following steps:
putting silane modified polymer, plasticizer, filler and catechol compound modified polyether into a double-planetary mixer, stirring at high speed for 1-2 h in vacuum, adding antioxidant, water removing agent, light absorbent, light stabilizer, catalyst and crosslinking agent, and stirring for 0.5-2 h in vacuum to obtain the adhesive.
The high-speed stirring and the vacuum stirring are carried out in a double planetary stirrer.
The preferred preparation method is as follows:
putting silane modified polymer, plasticizer, filler and catechol compound modified polyether into a double-planet stirrer, stirring for 1-2 h at a high vacuum speed under the conditions that the planet revolution speed is 60-80 rpm and the dispersion linear speed is 10-15 rpm, then adding antioxidant, water removing agent, light absorbent, light stabilizer, catalyst and crosslinking agent, and stirring for 0.5-2 h under the conditions that the vacuum degree is less than 200mbar, the planet revolution speed is 20-50 rpm and the dispersion linear speed is 10-15 m/s to obtain the adhesive.
The invention synthesizes catechol compound modified polyether by biomimetic modification of an adhesive protein structure secreted by mussels. In order to prevent catechol groups from oxidizing and self-polymerizing to influence the storage stability of the adhesive, a tert-butyldimethylsilyl chloride structure is introduced, and simultaneously a methyl triacetoxysilane, a modified propyl acetoxy silane and other crosslinking agents are introduced into the formula, so that when the adhesive is used, the crosslinking agents react with moisture to remove acetic acid, the tert-butyldimethylsilyl chloride structure can be removed under an acidic condition to form active catechol groups, and therefore, the adhesion of the adhesive on various base materials can be effectively improved under the condition that a silane coupling agent is not used for adhesion promotion.
The invention has the beneficial effects that:
(1) by introducing the combined action of the catechol compound modified polyether and the cross-linking agent, the adhesive strength of the elastic adhesive on various base materials can be effectively improved, the problems of interface peeling and adhesive failure when the medium-high modulus adhesive is in a large deformation state can be effectively solved, and meanwhile, the adhesive does not have adverse effects on other performances of the adhesive;
(2) by introducing a tert-butyldimethylsilyl chloride structure, the oxidation inactivation of catechol active groups can be prevented, and the stability of the elastic adhesive is improved.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The examples and comparative examples used the following main raw materials:
dibutyl tin dilaurate, Beijing Zhengheng chemical; stannous octoate, beijing orthodox chemical; nano calcium carbonate, Guangxi Huana; polyether polyol N220, Shanghai high bridge petrochemical; polyether polyol 330N, Shanghai high bridge petrochemical; dihydroxybenzaldehyde, tert-butyldimethylchlorosilane, acetonitrile, 1, 8-diazabicycloundec-7-ene, avastin reagent; STP-1, a silane-modified polyurethane prepolymer, scientific creation; STP-2 Wacker, a prepolymer of silane-modified polyether;
the other materials are all conventional industrial grade reagents.
Synthesis example 1:
preparing catechol compound modified polyether: 6 parts of 3, 4-dihydroxybenzaldehyde and 30 parts of tert-butyldimethylchlorosilane are dissolved in 130 parts of acetonitrile, the temperature is reduced to 0 ℃, 30 parts of 1, 8-diazabicycloundecen-7-ene are added, and the reaction is carried out for 12 hours at the temperature of 0 ℃; adding 60 parts of polyether polyol N220, slowly heating to 80 ℃, and reacting for 2.5 h; vacuum distilling, filtering to obtain catechol compound modified polyether CTCHPOL-1.
Synthesis example 2:
dissolving 9 parts of 3, 4-dihydroxybenzaldehyde and 38 parts of tert-butyldimethylchlorosilane in 185 parts of acetonitrile, cooling to 3 ℃, adding 40 parts of 1, 8-diazabicycloundec-7-ene, and reacting at 2 ℃ for 24 hours; adding 90 parts of polyether polyol 330N, slowly heating to 90 ℃, and reacting for 3 hours; vacuum distilling, filtering to obtain catechol compound modified polyether CTCHPOL-2.
Synthesis example 3:
dissolving 10 parts of 3, 4-dihydroxybenzaldehyde and 30 parts of tert-butyldimethylchlorosilane in 170 parts of acetonitrile, cooling to 0 ℃, adding 35 parts of 1, 8-diazabicycloundec-7-ene, and reacting at 1 ℃ for 24 hours; adding 40 parts of polyether polyol N220, adding 30 parts of polyether polyol 330N, slowly heating to 85 ℃, and reacting for 3 hours; vacuum distilling, filtering to obtain catechol compound modified polyether CTCHPOL-3.
Synthesis example 4:
dissolving 10 parts of 3, 4-dihydroxybenzaldehyde and 30 parts of tert-butyldimethylchlorosilane in 160 parts of acetonitrile, cooling to 0 ℃, adding 35 parts of 1, 8-diazabicycloundec-7-ene, and reacting at 1 ℃ for 24 hours; adding 40 parts of polyether polyol N220, adding 45 parts of polyether polyol 330N, slowly heating to 85 ℃, and reacting for 3 hours; vacuum distilling, filtering to obtain catechol compound modified polyether CTCHPOL-4.
Synthesis example 5:
dissolving 10 parts of 3, 4-dihydroxybenzaldehyde and 30 parts of tert-butyldimethylchlorosilane in 180 parts of acetonitrile, cooling to 0 ℃, adding 35 parts of 1, 8-diazabicycloundec-7-ene, and reacting at 1 ℃ for 24 hours; adding 40 parts of polyether polyol N220, adding 60 parts of polyether polyol 330N, slowly heating to 85 ℃, and reacting for 3 hours; vacuum distilling, filtering to obtain catechol compound modified polyether CTCHPOL-5.
Example 1
Preparing an elastic adhesive with excellent bonding performance:
adding 100 parts of STP-1 into a 5L planetary stirrer, adding 80 parts of dioctyl phthalate, 100 parts of light calcium carbonate and 10 parts of modified polyether CTCHPOL-1 of the tea phenol compound, stirring at a high vacuum speed for 1.2h under the conditions of 70rpm of planetary revolution speed and 15m/s of dispersion speed, then adding 1 part of vinyl silane, 0.5 part of 3, 5-di-tert-butyl-4-hydroxy-benzene propionic acid isooctyl ester, 0.5 part of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate), 1 part of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole, 0.5 part of dibutyltin dilaurate and 0.2 part of methyl triacetoxy silane, continuing to stir by vacuumizing for revolution (the vacuum degree is less than 200mbar, the planetary linear velocity is 45rpm, the dispersion linear velocity is 15m/s) for 1.5h, and (6) discharging.
Example 2
Preparing an elastic adhesive with excellent bonding performance:
adding 100 parts of STP-1 into a 5L planetary stirrer, adding 100 parts of dinonyl phthalate, 150 parts of nano calcium carbonate and 10 parts of modified polyether CTCHPOL-2 of a tea phenol compound, stirring at a planetary rotation speed of 80rpm and a dispersion speed of 12m/s for 1.5h at a high speed, then adding 2 parts of vinyl silane, 1.0 part of 3, 5-di-tert-butyl-4-hydroxy-benzenepropanoic acid isooctyl ester, 1 part of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, 2 parts of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole, 1 part of dibutyltin dilaurate, 2 parts of modified propyl acetoxy silane, and continuously vacuumizing and stirring (the vacuum degree is less than 200 revolutions, the planetary linear velocity is 50rpm, the dispersion linear velocity is 12m/s) for 2h, and (6) discharging.
Example 3
Preparing an elastic adhesive with excellent bonding performance:
adding 100 parts of STP-1 into a 5L planetary stirrer, adding 100 parts of dinonyl phthalate, 150 parts of nano calcium carbonate and 10 parts of modified polyether CTCHPOL-3 of a tea phenol compound, stirring at a planetary rotation speed of 80rpm and a dispersion speed of 12m/s for 1.5h at a high speed, then adding 2 parts of vinyl silane, 1.0 part of 3, 5-di-tert-butyl-4-hydroxy-benzene propionic acid isooctyl ester, 1 part of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, 2 parts of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole, 1 part of dibutyltin dilaurate, 2 parts of modified propyl acetoxy silane, continuously vacuumizing and stirring (revolution degree <200mbar, planetary linear velocity of 50rpm and dispersion linear velocity of 12m/s) for 2h, and (6) discharging.
Example 4
Preparing an elastic adhesive with excellent bonding performance:
adding 100 parts of STP-2 into a 5L planetary stirrer, adding 110 parts of dinonyl phthalate, 140 parts of light calcium carbonate, 40 parts of heavy calcium carbonate and 5 parts of modified polyether CTCHPOL-3 of a tea phenol compound, stirring for 1.5h at a high vacuum speed under the conditions that the planetary revolution speed is 80rpm and the dispersion speed is 15m/s, then adding 4 parts of vinyl silane, 1.2 parts of 3, 5-di-tert-butyl-4-hydroxy-iso-octyl phenylpropionate, 1 part of poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxy-piperidine) succinate, 2 parts of 2- (2' -hydroxy-3-dodecyl-5-methyl) benzotriazole, 1.5 parts of stannous octoate and 4.5 parts of ethyl triacetoxysilane, continuously vacuumizing and stirring (the vacuum degree is less than 200mbar, planetary revolution linear speed of 40rpm, dispersion linear speed of 15m/s)2h, and discharging.
Example 5
Preparing an elastic adhesive with excellent bonding performance:
adding 100 parts of STP-2 into a 5L planetary stirrer, adding 110 parts of dinonyl phthalate, 140 parts of light calcium carbonate, 40 parts of heavy calcium carbonate and 10 parts of tea phenol compound modified polyether CTCHPOL-3, stirring at a planetary rotation speed of 80rpm and a dispersion speed of 15m/s for 1.5h at a high speed in vacuum, then adding 4 parts of vinyl silane, 1.2 parts of 3, 5-di-tert-butyl-4-hydroxy-iso-octyl phenylpropionate, 1 part of poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxy-piperidine) succinate, 2 parts of 2- (2' -hydroxy-3-dodecyl-5-methyl) benzotriazole, 1.5 parts of stannous octoate and 4.5 parts of ethyl triacetoxysilane, continuously vacuumizing and stirring (the vacuum degree is less than 200mbar, planetary revolution linear speed of 40rpm, dispersion linear speed of 15m/s)2h, and discharging.
Example 6
Preparing an elastic adhesive with excellent bonding performance:
adding 100 parts of STP-2 into a 5L planetary stirrer, adding 110 parts of dinonyl phthalate, 140 parts of light calcium carbonate, 40 parts of heavy calcium carbonate and 15 parts of modified polyether CTCHPOL-3 of a tea phenol compound, stirring for 1.5h at a high vacuum speed under the conditions that the planetary revolution speed is 80rpm and the dispersion speed is 15m/s, then adding 4 parts of vinyl silane, 1.2 parts of 3, 5-di-tert-butyl-4-hydroxy-iso-octyl phenylpropionate, 1 part of poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxy-piperidine) succinate, 2 parts of 2- (2' -hydroxy-3-dodecyl-5-methyl) benzotriazole, 1.5 parts of stannous octoate and 4.5 parts of ethyl triacetoxysilane, continuously vacuumizing and stirring (the vacuum degree is less than 200mbar, planetary revolution linear speed of 40rpm, dispersion linear speed of 15m/s)2h, and discharging.
Example 7
Preparing an elastic adhesive with excellent bonding performance:
adding 100 parts of STP-2 into a 5L planetary stirrer, adding 100 parts of dioctyl phthalate, 160 parts of nano calcium carbonate, 1 part of carbon black, 20 parts of modified polyether CTCHPOL-3 of the tea phenol compound, stirring for 2 hours at a high speed in vacuum under the conditions that the revolution speed of the planet is 70rpm and the dispersion speed is 12m/s, then adding 4 parts of vinyl silane, 1.5 parts of 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid isooctyl ester, 1 part of poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxy piperidine) succinate, 2 parts of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole, 1.0 part of dibutyltin dilaurate and 4.5 parts of methyltriacetoxysilane, continuously vacuumizing and stirring (the vacuum degree is less than 200mbar, planetary revolution linear speed is 50rpm, dispersion linear speed is 15m/s)2h, and discharging is carried out.
Comparative example 1
Preparing an elastic adhesive:
100 parts of STP-1 are taken and added into a 5L planetary stirrer, 100 parts of dinonyl phthalate and 150 parts of nano calcium carbonate are added, the mixture is stirred at a high speed for 1.2h under the conditions of planetary revolution speed of 80rpm and dispersion speed of 10m/s, then 2 parts of vinyl silane, 1.0 part of 3, 5-di-tert-butyl-4-hydroxy-isooctyl phenylpropionate, 1 part of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, 2 parts of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole, 1 part of stannous octoate and 0.5 part of methyl triacetoxysilane are added, the mixture is continuously vacuumized and stirred (the vacuum degree is less than 200mbar, the planetary revolution linear speed is 50rpm, and the dispersion linear speed is 12m/s) for 2h, and the material is discharged.
Comparative example 2
Preparing an elastic adhesive:
100 parts of STP-2 are taken and added into a 5L planetary stirrer, 80 parts of dioctyl phthalate and 100 parts of modified nano calcium carbonate are added, the mixture is stirred at a high speed for 1.5h under the conditions of 70rpm of planetary revolution speed and 12m/s of dispersion speed, then 1 part of vinyl silane, 0.5 part of 3, 5-di-tert-butyl-4-hydroxy-isooctyl phenylpropionate, 0.5 part of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate), 1 part of 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) benzotriazole, 0.5 part of dibutyltin dilaurate and 2 parts of modified propyl acetoxy silane are added, the mixture is continuously vacuumized and stirred (the vacuum degree is less than 200mbar, the planetary revolution linear speed is 45rpm, the dispersion linear speed is 15m/s) for 1.5h, and the material is discharged.
The elastic adhesives with excellent bonding performance prepared in examples 1-7 and comparative examples 1-2 were tested according to the standards shown in table 1, and the test results are shown in table 2.
As can be seen from table 2, the present invention is obtained by introducing a biomimetic modified polymer: the catechol compound modified polyether can be used for obtaining the elastic adhesive with excellent bonding performance.
Table 1 adhesive test standards
Table 2 elastic adhesive test results
Claims (9)
1. A catechol compound-modified polyether is characterized in that the structure is shown as follows,
2. The method for producing a catechol compound-modified polyether according to claim 1, wherein a tert-butyldimethylsilyl group-protected catechol compound is first produced by a hydrosilylation reaction between 3,4 dihydroxybenzaldehyde and tert-butyldimethylchlorosilane, and then a catechol compound-modified polyether is produced by an aldol reaction between an aldehyde group in the catechol compound and a hydroxyl group in a polyether polyol;
the polyether polyol is an oligomer which contains ether bonds (-R-O-R-) in the main chain and contains more than 2 hydroxyl groups (-OH) in the terminal group or the side group, the content of potassium ions and sodium ions is less than 5ppm, the acid value is less than 0.15mgKOH/g, and the hydroxyl value is 20-60 mgKOH/g.
3. The method according to claim 2, wherein the method for preparing the catechol compound-modified polyether specifically comprises the following steps:
(1) dissolving 5-10 parts of 3, 4-dihydroxybenzaldehyde and 30-40 parts of tert-butyldimethylchlorosilane in 100-200 parts of acetonitrile, cooling to 0-5 ℃, adding 30-40 parts of 1, 8-diazabicycloundecen-7-ene, and reacting at 0 ℃ for 12-24 hours;
(2) adding 50-150 parts of polyether polyol, slowly heating to 80-100 ℃, and reacting for 2.5-3 h; vacuum distilling, filtering to obtain catechol compound modified polyether.
4. The use of the catechol compound-modified polyether of claim 1, wherein the catechol compound-modified polyether is added to an adhesive to improve the adhesive property of the adhesive.
5. The use according to claim 4, wherein the catechol compound-modified polyether is present in an amount of 1-30% by weight of the matrix resin of the adhesive.
6. The use according to claim 5, wherein the composition further comprises a silane-modified resin, wherein the silane-modified resin is a silane-modified polyurethane prepolymer or a silane-modified polyether prepolymer;
the silane modified polyurethane prepolymer is a silane-terminated prepolymer synthesized by isocyanate silane and polyether polyol in one step;
the silane modified polyether prepolymer is a silane end-capped prepolymer synthesized by hydrosilicon and unsaturated bond end-capped polyether.
7. The adhesive is characterized by comprising the following raw materials in parts by weight:
100 parts of silane modified resin, namely 100 parts of silane modified resin,
60-120 parts of a plasticizer,
0.5 to 1.5 parts of antioxidant,
1 to 5 parts of a water removing agent,
100-200 parts of a filler,
0 to 1 part of a light stabilizer,
0 to 2 parts of a light absorbing agent,
0.2 to 1.5 parts of catalyst,
0.1 to 5 parts of a crosslinking agent,
1-30 parts of catechol compound modified polyether;
the plasticizer is one of diisononyl phthalate and diisooctyl phthalate;
the antioxidant is 3, 5-di-tert-butyl-4-hydroxy-phenylpropionic acid isooctyl ester;
the water removing agent is vinyl siloxane;
the filler is one or more of nano calcium carbonate, light calcium carbonate, heavy calcium carbonate, titanium dioxide and carbon black;
the light stabilizer is one of bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate and poly (1-hydroxyethyl-2, 2,6, 6-tetramethyl-4-hydroxypiperidine) succinate;
the light absorbent is one of 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) benzotriazole and 2- (2' -hydroxy-3-dodecyl-5-methyl) benzotriazole;
the catalyst is one of dibutyltin dilaurate and stannous octoate;
the cross-linking agent is one or more of methyl triacetoxysilane, modified propyl acetoxy silane and ethyl triacetoxysilane.
8. The method for preparing the adhesive according to claim 7, characterized by comprising the following steps:
putting silane modified polymer, plasticizer, filler and catechol compound modified polyether into a double-planetary mixer, stirring at high speed for 1-2 h in vacuum, adding antioxidant, water removing agent, light absorbent, light stabilizer, catalyst and crosslinking agent, and stirring for 0.5-2 h in vacuum to obtain the adhesive;
the high-speed stirring and the vacuum stirring are carried out in a double planetary stirrer.
9. The method according to claim 8, wherein the adhesive is prepared by putting silane modified polymer, plasticizer, filler and catechol compound modified polyether into a double planetary mixer, stirring at a planetary revolution speed of 60-80 rpm and a dispersion linear speed of 10-15 rpm for 1-2 h under vacuum high speed, adding antioxidant, water removing agent, light absorbent, light stabilizer, catalyst and crosslinking agent, and stirring at a vacuum degree of less than 200mbar, a planetary revolution speed of 20-50 rpm and a dispersion linear speed of 10-15 m/s under vacuum for 0.5-2 h.
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