CN111777759B - Catechol compound modified polyether, preparation method thereof and application thereof in improving adhesive strength of adhesive - Google Patents
Catechol compound modified polyether, preparation method thereof and application thereof in improving adhesive strength of adhesive Download PDFInfo
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- CN111777759B CN111777759B CN201910269406.2A CN201910269406A CN111777759B CN 111777759 B CN111777759 B CN 111777759B CN 201910269406 A CN201910269406 A CN 201910269406A CN 111777759 B CN111777759 B CN 111777759B
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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 adhesives. The catechol compound modified polyether is of a bionic modified structure, and the preparation method of the catechol compound modified polyether is characterized in that a tertiary butyl dimethylsilyl-protected catechol compound is prepared through a hydrosilylation reaction between 3,4 dihydroxybenzaldehyde and tertiary butyl dimethylsilyl chloride, and then the catechol compound modified polyether is prepared through an acetal reaction between aldehyde groups in the catechol compound and hydroxyl groups in polyether polyol. The adhesive prepared by using the catechol compound solves the problem of poor adhesiveness of the elastic adhesive in the prior art. The adhesive strength of the elastic adhesive on various base materials can be effectively improved, and meanwhile, the adhesive is endowed with good stability.
Description
Technical Field
The invention relates to an adhesive, in particular 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, and the curing crosslinking is completed by hydrolysis and polycondensation of siloxane bonds in the silane under the action of moisture, so that CO is not emitted 2 Therefore, the foam is not foamed in a high-temperature and high-humidity environment.
In order to improve the fluidity, reduce the hardness and adjust the modulus of the adhesive, a certain amount of plasticizer is usually added, but the amount of the plasticizer affects the sagging property and the mechanical property of the adhesive, and particularly affects the bonding strength of the adhesive and a substrate.
Along with the widening of application conditions of some high and new technology industries such as automobiles, electronic industries and the like, higher requirements are also put on the bonding strength of the adhesive. Especially for the middle-high strength adhesive (such as 100% modulus >1.5 MPa), the interfacial peeling and bonding failure are easy to occur.
Meanwhile, under certain use conditions, such as the joint of the outer wall of the residential industrialized precast slab, the adhesive performance of the adhesive is also required to be higher because the joint is in the conditions of outdoor ultraviolet irradiation, rain water leaching and the like for a long time. Therefore, the effective improvement of the adhesive force of the adhesive is one of the focus of attention.
Conventionally, a silane coupling agent is generally used as an adhesion promoter to improve 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 affected.
In addition to adding silane coupling agents, researchers have also attempted to improve the adhesive properties of adhesives by other methods: the patent document CN 106634768A improves the water resistance of the elastic colloid system by adding hydrophobic resin microspheres. Although the method improves the water-resistant bonding effect of the material, the introduction of the hydrophobic resin microspheres can reduce the bonding strength of the material and the base material to a certain extent; CN 102766431B improves the adhesion properties of adhesives to metal substrates by introducing sulfur-containing functional groups into the hydroxyl-terminated polysiloxane backbone, but the improvement in shear strength and bond strength of the material is limited.
Disclosure of Invention
The invention provides catechol compound modified polyether, a preparation method thereof and application thereof in improving the bonding strength of adhesives. The catechol compound modified polyether is a bionic modified structure, and solves the problem of poor adhesiveness of elastic adhesives in the prior art. The adhesive strength of the elastic adhesive on various base materials can be effectively improved, and meanwhile, the adhesive is endowed with good stability.
The catechol compound modified polyether has a structure shown in the specification, wherein the tertiary 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: the catechol compound modified polyether is prepared by first preparing a tertiary butyl dimethylsilyl-protected catechol compound by a hydrosilylation reaction between 3,4 dihydroxybenzaldehyde and tertiary butyl dimethylsilyl chloride, and then by an acetal reaction between aldehyde groups in the catechol compound and hydroxyl groups in a polyether polyol.
The polyether polyol is an oligomer with main chain containing ether bond (-R-O-R), terminal group or side group containing more than 2 hydroxyl groups (-OH), and is characterized in that the content of potassium ions and sodium ions is lower than 5ppm, the acid value is lower than 0.15mgKOH/g, and the hydroxyl value is 20-60 mgKOH/g. Commercially available products such as N220, N330, N240, N260, etc. manufactured by Shanghai high bridge petrochemical Co., ltd.
The preparation method of the catechol compound modified polyether specifically comprises the following steps:
(1) 5 to 10 parts of 3,4 dihydroxybenzaldehyde and 30 to 40 parts of tert-butyl dimethyl chlorosilane are dissolved in 100 to 200 parts of acetonitrile, the temperature is reduced to 0 to 5 ℃, 30 to 40 parts of 1, 8-diazabicyclo undec-7-ene is added, and the mixture is reacted for 12 to 24 hours at the temperature of 0 ℃;
(2) 50-150 parts of polyether polyol is added, the temperature is slowly raised to 80-100 ℃ and the reaction is carried out for 2.5-3 hours; distilling under reduced pressure, and filtering to obtain catechol compound modified polyether.
The catechol compound modified polyether is added into an adhesive and is used for improving the adhesive property of the adhesive.
The catechol compound modified polyether accounts for 1-30% of the weight of the matrix resin of the adhesive, and can remarkably improve the adhesive property of the adhesive.
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 end-capped prepolymer synthesized by isocyanate silane and polyether polyol in one step. Commercially available products are, for example, those available under the trade designations XP2774, XP2636, XP2749, XP2458 from the company Kogyo Polymer (China).
The silane modified polyether prepolymer is silane end-capped prepolymer synthesized by hydrogen silicon and unsaturated bond end-capped polyether. Commercially available, e.g. from Wake chemical (China) Inc. under the trademark of
XT50、/>
XT55、
XB502, etc.
The adhesive comprises the following raw materials in parts by weight:
silane modified resin 100 parts
60-120 parts of plasticizer and the like,
0.5 to 1.5 parts of antioxidant,
1 to 5 parts of a water scavenger,
100-200 parts of filler,
0 to 1 part of light stabilizer,
0 to 2 parts of light absorber,
0.2 to 1.5 portions of catalyst
0.1 to 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 benzene propionic acid isooctyl ester;
the water scavenger is vinyl siloxane;
the filler is one or more of nano calcium carbonate, light calcium carbonate, heavy calcium carbonate, titanium pigment and carbon black;
the light stabilizer is one of bis (1, 2, 6-pentamethyl-4-piperidyl) sebacate and poly (1-hydroxyethyl-2, 6-tetramethyl-4-hydroxypiperidine) succinate;
the light absorber 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 dibutyl tin dilaurate and stannous octoate;
the cross-linking agent is one or more of methyl triacetoxy silane, modified propyl acetoxy silane and ethyl triacetoxy silane.
The preparation method of the adhesive comprises the following steps:
adding silane modified polymer, plasticizer, filler and catechol compound modified polyether into a double-planetary stirrer, stirring for 1-2 h at high speed in vacuum, adding antioxidant, water scavenger, light absorber, light stabilizer, catalyst and cross-linking agent, and stirring for 0.5-2 h in vacuum to obtain the adhesive.
The high speed stirring and vacuum stirring were performed in a double planetary stirrer.
The preferred preparation method is as follows:
adding silane modified polymer, plasticizer, filler and catechol compound modified polyether into a double-planetary stirrer, stirring for 1-2 h at a high speed under the conditions of 60-80 rpm of planetary revolution speed and 10-15 rpm of dispersion linear speed, then adding antioxidant, water remover, light absorber, light stabilizer, catalyst and cross-linking agent, and stirring for 0.5-2 h under the conditions of vacuum degree of 200mbar, 20-50 rpm of planetary revolution speed and 10-15 m/s of dispersion linear speed to obtain the adhesive.
According to the invention, catechol compound modified polyether is synthesized through bionic modification of the adhesion protein structure secreted by mussels. In order to prevent catechol group oxidation self-polymerization from affecting the storage stability of the adhesive, a tertiary butyl dimethyl chlorosilane structure is introduced, and simultaneously, cross-linking agents such as methyl triacetoxy silane, modified propyl acetoxy silane and the like are introduced into a formula, so that when the adhesive is used, the cross-linking agents react with moisture to remove acetic acid, and the tertiary butyl dimethyl chlorosilane structure can be removed under an acidic condition to form active catechol groups, thereby effectively improving the adhesiveness of the adhesive on various substrates without using a silane coupling agent to assist adhesion.
The beneficial effects of the invention are as follows:
(1) The catechol compound modified polyether and the cross-linking agent are introduced to act together, so that the bonding strength of the elastic adhesive on various base materials can be effectively improved, the problems of interface stripping and bonding failure when the medium-high modulus adhesive is in a large deformation state can be effectively solved, and other properties of the adhesive are not adversely affected;
(2) By introducing the tert-butyldimethyl chlorosilane structure, oxidation deactivation of catechol active groups can be prevented, and the stability of the elastic adhesive is improved.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
The following main raw materials were used in the examples and comparative examples:
dibutyl tin dilaurate, beijing constant chemical industry; stannous octoate, beijing, orthostatic; nano calcium carbonate, guangxi Huana; polyether polyol N220, shanghai Gao Qiao petrochemical; polyether polyol 330N, shanghai Gao Qiao petrochemical; dihydroxybenzaldehyde, tert-butyldimethylchlorosilane, acetonitrile, 1, 8-diazabicyclo undec-7-ene, ala Ding Shiji; silane modified polyurethane prepolymer STP-1, is scientifically created; silane modified polyether prepolymer STP-2, wake;
other materials are conventional industrial grade reagents.
Synthesis example 1:
preparation of catechol compound modified polyether: 6 parts of 3,4 dihydroxybenzaldehyde and 30 parts of tert-butyl dimethyl chlorosilane are dissolved in 130 parts of acetonitrile, the temperature is reduced to 0 ℃, 30 parts of 1, 8-diazabicyclo undec-7-ene is added for reaction for 12 hours at 0 ℃; 60 parts of polyether polyol N220 is added, the temperature is slowly increased to 80 ℃, and the reaction is carried out for 2.5 hours; vacuum distilling, and filtering to obtain catechol compound modified polyether CTCHPOL-1.
Synthesis example 2:
9 parts of 3,4 dihydroxybenzaldehyde and 38 parts of tert-butyldimethyl chlorosilane are dissolved in 185 parts of acetonitrile, the temperature is reduced to 3 ℃, 40 parts of 1, 8-diazabicyclo undec-7-ene are added for reaction at 2 ℃ for 24 hours; adding 90 parts of polyether polyol 330N, slowly heating to 90 ℃, and reacting for 3 hours; vacuum distilling, and filtering to obtain catechol compound modified polyether CTCHPOL-2.
Synthesis example 3:
10 parts of 3,4 dihydroxybenzaldehyde and 30 parts of tert-butyl dimethyl chlorosilane are dissolved in 170 parts of acetonitrile, the temperature is reduced to 0 ℃, 35 parts of 1, 8-diazabicyclo undec-7-ene is added for reaction 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, and filtering to obtain catechol compound modified polyether CTCHPOL-3.
Synthesis example 4:
dissolving 10 parts of 3,4 dihydroxybenzaldehyde and 30 parts of tert-butyldimethyl chlorosilane in 160 parts of acetonitrile, cooling to 0 ℃, adding 35 parts of 1, 8-diazabicyclo undec-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, and filtering to obtain catechol compound modified polyether CTCHPOL-4.
Synthesis example 5:
dissolving 10 parts of 3,4 dihydroxybenzaldehyde and 30 parts of tert-butyldimethyl chlorosilane in 180 parts of acetonitrile, cooling to 0 ℃, adding 35 parts of 1, 8-diazabicyclo undec-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, and filtering to obtain catechol compound modified polyether CTCHPOL-5.
Example 1
Preparation of elastic adhesive with excellent adhesive property:
100 parts of STP-1 are taken and added into a 5L planetary mixer, 80 parts of dioctyl phthalate, 100 light calcium carbonate and 10 parts of catechol compound modified polyether CTCGOL-1 are added, the mixture is stirred for 1.2 hours at a high speed under the conditions of a planetary revolution speed of 70rpm and a dispersion speed of 15m/s, then 1 part of vinylsilane and 0.5 part of isooctyl 3, 5-di-tert-butyl-4-hydroxybenzoate are added, 0.5 part of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 1 part of 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole, 0.5 part of dibutyltin dilaurate and 0.2 part of methyltriacetoxy silane are continuously stirred under vacuum (the vacuum degree is less than 200mbar, the planetary revolution linear speed is 45rpm, the dispersion linear speed is 15 m/s) for 1.5 hours, and the materials are discharged.
Example 2
Preparation of elastic adhesive with excellent adhesive property:
100 parts of STP-1 is taken and added into a 5L planetary mixer, 100 parts of dinonyl phthalate, 150 parts of nano calcium carbonate and 10 parts of catechol compound modified polyether CTCGOL-2 are added, the mixture is stirred at a high speed for 1.5h under the conditions of 80rpm of planetary revolution speed and 12m/s of dispersion speed, then 2 parts of vinylsilane and 1.0 part of isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate, 1 part of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 2 parts of 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole, 1 part of dibutyltin dilaurate and 2 parts of modified propylacetoxysilane are added, and the mixture is continuously vacuumized and stirred (the vacuum degree is less than 200mbar, the planetary revolution linear speed is 50rpm, the dispersion linear speed is 12 m/s) for 2h, and then the mixture is discharged.
Example 3
Preparation of elastic adhesive with excellent adhesive property:
100 parts of STP-1 is taken and added into a 5L planetary mixer, 100 parts of dinonyl phthalate, 150 parts of nano calcium carbonate and 10 parts of catechol compound modified polyether CTCGOL-3 are added, the mixture is stirred at a high speed for 1.5h under the conditions of 80rpm of planetary revolution speed and 12m/s of dispersion speed, then 2 parts of vinylsilane and 1.0 part of isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate, 1 part of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 2 parts of 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole, 1 part of dibutyltin dilaurate and 2 parts of modified propylacetoxysilane are added, and the mixture is continuously vacuumized and stirred (the vacuum degree is less than 200mbar, the planetary revolution linear speed is 50rpm, the dispersion linear speed is 12 m/s) for 2h, and then the mixture is discharged.
Example 4
Preparation of elastic adhesive with excellent adhesive property:
100 parts of STP-2 are taken and added into a 5L planetary mixer, 110 parts of dinonyl phthalate, 140 parts of light calcium carbonate, 40 parts of heavy calcium carbonate and 5 parts of catechol compound modified polyether CTCHPOL-3 are added, the mixture is stirred at a high speed for 1.5 hours under the conditions of 80rpm of planetary revolution and 15m/s of dispersion speed, then 4 parts of vinyl silane, 1.2 parts of isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate, 1 part of poly (1-hydroxyethyl-2, 6-tetramethyl-4-hydroxypiperidine) succinate, 2 parts of 2- (2' -hydroxy-3-dodecyl-5-methyl) benzotriazole, 1.5 parts of stannous octoate and 4.5 parts of ethyl triacetoxy silane are added, and the mixture is continuously subjected to vacuum stirring (vacuum degree is less than 200mbar, planetary revolution linear speed is 40rpm, and dispersion linear speed is 15 m/s) for 2 hours, and discharged.
Example 5
Preparation of elastic adhesive with excellent adhesive property:
100 parts of STP-2 are taken and added into a 5L planetary mixer, 110 parts of dinonyl phthalate, 140 parts of light calcium carbonate, 40 parts of heavy calcium carbonate and 10 parts of catechol compound modified polyether CTCHPOL-3 are added, the mixture is stirred at a high speed for 1.5 hours under the conditions of 80rpm of planetary revolution and 15m/s of dispersion speed, then 4 parts of vinyl silane, 1.2 parts of isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate, 1 part of poly (1-hydroxyethyl-2, 6-tetramethyl-4-hydroxypiperidine) succinate, 2 parts of 2- (2' -hydroxy-3-dodecyl-5-methyl) benzotriazole, 1.5 parts of stannous octoate and 4.5 parts of ethyl triacetoxy silane are added, and the mixture is continuously subjected to vacuum stirring (vacuum degree is less than 200mbar, planetary revolution linear speed is 40rpm, and dispersion linear speed is 15 m/s) for 2 hours, and discharged.
Example 6
Preparation of elastic adhesive with excellent adhesive property:
100 parts of STP-2 are taken and added into a 5L planetary mixer, 110 parts of dinonyl phthalate, 140 parts of light calcium carbonate, 40 parts of heavy calcium carbonate and 15 parts of the polyether CTCHPOL-3 modified by the tea phenol compound are added, the mixture is stirred at a high speed for 1.5 hours under the conditions of 80rpm of planetary revolution speed and 15m/s of dispersion speed, then 4 parts of vinyl silane, 1.2 parts of isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate, 1 part of poly (1-hydroxyethyl-2, 6-tetramethyl-4-hydroxypiperidine) succinate, 2 parts of 2- (2' -hydroxy-3-dodecyl-5-methyl) benzotriazole, 1.5 parts of stannous octoate and 4.5 parts of ethyl triacetoxy silane are added, and the mixture is continuously vacuumized and stirred (vacuum degree is less than 200mbar, planetary revolution linear speed is 40rpm, and dispersion linear speed is 15 m/s) for 2 hours.
Example 7
Preparation of elastic adhesive with excellent adhesive property:
100 parts of STP-2 are taken and added into a 5L planetary mixer, 100 parts of dioctyl phthalate, 160 parts of nano calcium carbonate, 1 part of carbon black and 20 parts of catechol compound modified polyether CTCHPOL-3 are added, and are stirred for 2 hours at a high speed under the conditions of 70rpm of planetary revolution and 12m/s of dispersion speed, then 4 parts of vinylsilane, 1.5 parts of isooctyl 3, 5-di-tert-butyl-4-hydroxy benzene propionate, 1 part of poly (1-hydroxyethyl-2, 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 methyltriacetoxy silane are added, and the vacuum stirring is continued (vacuum degree is less than 200mbar, planetary revolution linear speed is 50rpm, and dispersion linear speed is 15 m/s) for 2 hours, and the materials are discharged.
Comparative example 1
Preparation of elastic adhesive:
100 parts of STP-1 is taken and added into a 5L planetary mixer, 100 parts of dinonyl phthalate and 150 parts of nano calcium carbonate are added, the mixture is stirred for 1.2 hours at a high speed under the conditions of 80rpm of planetary revolution speed and 10m/s of dispersion speed, then 2 parts of vinyl silane, 1.0 part of isooctyl 3, 5-di-tert-butyl-4-hydroxy benzene propionate, 1 part of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 2 parts of 2- (2 ' -hydroxy-3 ',5' -di-tert-butylphenyl) benzotriazole, 1 part of stannous octoate and 0.5 part of methyltriacetoxysilane are added, and the mixture is continuously vacuumized and stirred (vacuum degree is less than 200mbar, planetary revolution linear speed is 50rpm, and dispersion linear speed is 12 m/s) for 2 hours, and discharged.
Comparative example 2
Preparation of elastic adhesive:
100 parts of STP-2 is taken and added into a 5L planetary mixer, 80 parts of dioctyl phthalate and 100 parts of modified nano calcium carbonate are added, the mixture is stirred for 1.5 hours at a high speed under the conditions of 70rpm of planetary revolution speed and 12m/s of dispersion speed, then 1 part of vinylsilane and 0.5 part of isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate, 0.5 part of bis (1, 2, 6-pentamethyl-4-piperidinyl) 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 acetoxysilane are added, and the mixture is continuously vacuumized and stirred (vacuum degree is less than 200mbar, planetary revolution linear speed is 45rpm, and dispersion linear speed is 15 m/s) for 1.5 hours, and then discharged.
The elastic adhesives prepared in examples 1 to 7 and comparative examples 1 to 2 were tested according to the criteria shown in Table 1, and the test results obtained are shown in Table 2.
As can be seen from table 2, the present invention was modified by introducing a biomimetic modified polymer: the catechol compound modified polyether can obtain the elastic adhesive with excellent adhesive property.
TABLE 1 adhesive test criteria
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 preparing catechol compound-modified polyether of claim 1, wherein the catechol compound-modified polyether is prepared by first preparing a tert-butyldimethylsilyl-protected catechol compound by a reaction between 3, 4-dihydroxybenzaldehyde and tert-butyldimethylsilyl chloride, and then preparing the catechol compound-modified polyether by an acetal reaction between an aldehyde group in the catechol compound and a hydroxyl group in a polyether polyol;
the polyether polyol is an oligomer with main chain containing ether bond, terminal group or side group containing more than 2 hydroxyl groups, the content of potassium ions and sodium ions is 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, characterized in that 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-butyl dimethyl chlorosilane in 100-200 parts of acetonitrile, cooling to 0-5 ℃, adding 30-40 parts of 1, 8-diazabicyclo undec-7-ene, and reacting for 12-24 hours at 0 ℃;
(2) 50-150 parts of polyether polyol is added, the temperature is slowly raised to 80-100 ℃ and the reaction is carried out for 2.5-3 hours; distilling under reduced pressure, and filtering to obtain catechol compound modified polyether.
4. The use of a catechol-modified polyether of claim 1, wherein the catechol-modified polyether is added to an adhesive for improving the adhesive properties 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 adhesive composition further comprises a silane modified resin, the silane modified resin being a silane modified polyurethane prepolymer or a silane modified polyether prepolymer;
the silane modified polyurethane prepolymer is a silane end-capped prepolymer synthesized by isocyanate silane and polyether polyol in one step;
the silane modified polyether prepolymer is silane end-capped prepolymer synthesized by hydrogen silicon and unsaturated bond end-capped polyether.
7. The adhesive is characterized by comprising the following raw materials in parts by weight:
100 parts of a silane-modified resin,
60-120 parts of plasticizer and the like,
0.5 to 1.5 parts of antioxidant,
1 to 5 parts of a water scavenger,
100-200 parts of filler,
0 to 1 part of light stabilizer,
0 to 2 parts of light absorber,
0.2 to 1.5 portions of catalyst,
0.1 to 5 parts of cross-linking agent,
1-30 parts of catechol compound-modified polyether as claimed in claim 1;
the plasticizer is one of diisononyl phthalate and diisooctyl phthalate;
the antioxidant is 3, 5-di-tert-butyl-4-hydroxy benzene propionic acid isooctyl ester;
the water scavenger is vinyl siloxane;
the filler is one or more of nano calcium carbonate, light calcium carbonate, heavy calcium carbonate, titanium pigment and carbon black;
the light stabilizer is one of bis (1, 2, 6-pentamethyl-4-piperidyl) sebacate and poly (1-hydroxyethyl-2, 6-tetramethyl-4-hydroxypiperidine) succinate;
the light absorber 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 dibutyl tin dilaurate and stannous octoate;
the cross-linking agent is one or two of methyl triacetoxy silane and ethyl triacetoxy silane; the silane modified resin is silane modified polyurethane prepolymer or silane modified polyether prepolymer;
the silane modified polyurethane prepolymer is a silane end-capped prepolymer synthesized by isocyanate silane and polyether polyol in one step;
the silane modified polyether prepolymer is silane end-capped prepolymer synthesized by hydrogen silicon and unsaturated bond end-capped polyether.
8. The method for preparing the adhesive according to claim 7, wherein the following steps are adopted:
adding silane modified resin, plasticizer, filler and catechol compound modified polyether into a double-planetary stirrer, stirring for 1-2 hours at high speed in vacuum, adding antioxidant, water scavenger, light absorber, light stabilizer, catalyst and cross-linking agent, and stirring for 0.5-2 hours in vacuum to obtain the adhesive;
the high speed stirring and vacuum stirring were performed in a double planetary stirrer.
9. The method according to claim 8, wherein silane modified resin, plasticizer, filler and catechol compound modified polyether are put into a double planetary mixer, stirred for 1-2 hours at a high vacuum speed under the conditions of a planetary revolution speed of 60-80 rpm and a dispersion speed of 10-15 m/s, then antioxidant, water scavenger, light absorber, light stabilizer, catalyst and cross-linking agent are added, and the adhesive is obtained by vacuum stirring for 0.5-2 hours under the conditions of a vacuum degree of <200mbar, a planetary revolution speed of 20-50 rpm and a dispersion speed of 10-15 m/s.
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| CN112409974B (en) * | 2020-11-19 | 2021-12-21 | 江南大学 | Amphiphilic bio-based degradable underwater adhesive and preparation method and application thereof |
| CN113980629B (en) * | 2021-10-25 | 2023-10-03 | 珠海冠宇电池股份有限公司 | Adhesive and lithium ion battery containing same |
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