CN113388360A - Two-component polyurethane adhesive capable of being rapidly cured in long opening time - Google Patents
Two-component polyurethane adhesive capable of being rapidly cured in long opening time Download PDFInfo
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- CN113388360A CN113388360A CN202110728925.8A CN202110728925A CN113388360A CN 113388360 A CN113388360 A CN 113388360A CN 202110728925 A CN202110728925 A CN 202110728925A CN 113388360 A CN113388360 A CN 113388360A
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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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/679—Acetylenic compounds
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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
- C08G2170/00—Compositions for adhesives
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Abstract
The invention provides a two-component polyurethane adhesive capable of being rapidly cured in a long opening time, which comprises a component A and a component B in a volume ratio of 2-10: 1; the component A comprises, by weight, 30-50 parts of polyhydric alcohol, 1-10 parts of a small molecular diol chain extender, 1-10 parts of alkynol, 0.01-1 part of a metal catalyst, 0.2-2 parts of a silane coupling agent and 30-80 parts of a filler; the component B comprises 80-40 mass percent of diphenylmethane polyisocyanate and 20-60 mass percent of aliphatic polyisocyanate. The invention adopts the combined action of the metal catalyst and the alkynol to play a role in slowing down the initial reaction of the adhesive, and after the reaction of the alkynol and the isocyanate is finished, the reaction of the polyol and the isocyanate is formally started, so that the effect of quick reaction is achieved by depending on high catalyst content; the compounded polyisocyanate reduces the cross-linking point of the high-activity isocyanate and the alkynol in the initial reaction stage, further reduces the initial reaction speed and prolongs the operable time.
Description
Technical Field
The invention belongs to polyurethane adhesives, and particularly relates to a dual-component polyurethane adhesive with long opening time and rapid curing.
Background
The double-component polyurethane adhesive is a polyurethane adhesive material which takes isocyanate (NCO) group end-capped polymer as a main effective component, takes polyol containing hydroxyl (OH) groups as a curing agent, and is matched with a plasticizer, a filler, a catalyst and an auxiliary agent, has the advantages of high adhesive strength and good toughness, and can be used for bonding various profiled bars.
With the progress of the cross-linking reaction of the isocyanate and the polyol, the viscosity of the two-component polyurethane adhesive is gradually increased, and the strength of the two-component polyurethane adhesive is gradually increased. In the course of the streamlined industrial manufacturing, it is often desirable that the two-component polyurethane adhesive achieve a rapid curing strength in a short time in order to improve the efficiency of the process assembly. In the actual production process, the curing speed of the two-component polyurethane adhesive can be improved by increasing the content of the catalyst, external heating and the like. However, increasing the catalyst content often results in shortening the open time (operable time) of the two-component polyurethane adhesive, so that the construction of the adhesive cannot be guaranteed, and external heating often can only be applied in certain specific occasions. Therefore, the two-component polyurethane adhesive which can be cured under the conventional construction conditions (15-35 ℃) and has long opening time and fast curing is very competitive.
The hydroxyl component of the traditional two-component polyurethane adhesive generally takes polyether polyol, polyester polyol, castor oil, hydroxyl-terminated liquid polybutadiene polyol, polycarbonate polyol, polyacrylate polyol and the like as main raw materials, small-proportion aliphatic and aromatic micromolecule polyol is added, and aliphatic and aromatic micromolecule polyamine is taken as a chain extender to improve the strength of the product. These products are not exceptional and do not meet the requirements of both long open time and fast cure.
Disclosure of Invention
In view of the above, the present invention aims to provide a two-component polyurethane adhesive with long open time and fast curing, wherein the open time of the adhesive is long.
The invention provides a two-component polyurethane adhesive capable of being rapidly cured in a long opening time, which comprises the following components in percentage by volume of 2-10: 1, a component A and a component B;
the component A comprises the following components in parts by weight:
30-50 parts of polyol with the functionality of 2-4, 1-10 parts of small molecular diol chain extender, 1-10 parts of alkynol with the functionality of 1-4, 0.01-1 part of metal catalyst, 0.2-2 parts of silane coupling agent and 0-1 part of auxiliary agent;
the component B comprises 80-40 mass percent of diphenylmethane polyisocyanate and 20-60 mass percent of aliphatic polyisocyanate.
Preferably, the alkynol with the functionality of 1-4 is selected from one or more of propiolic alcohol, butynol and an isoderivative thereof, pentynol and an isoderivative thereof, hexynol and an isoderivative thereof, heptynol and an isoderivative thereof, octynol and an isoderivative thereof, nonynol and an isoderivative thereof, decynol and an isoderivative thereof, undecenol and an isoderivative thereof, butyndiol and a derivative thereof, hexyndiol and a derivative thereof, octyndiol and a derivative thereof, decynediol and a derivative thereof, and dodecenediol and a derivative thereof.
Preferably, the alkynol with functionality of 1-4 is selected from one or more of propargyl alcohol, butynol, pentynol, hexynol, heptynol, octynol, nonynol, decylenol, undecenol, methylbutynol, methylpentylenol, butynol, hexynol, octynol, decyndiol, dodecenyldiol, 2, 5-dimethyl-3-hexyne-2, 5-diol, 3, 6-dimethyl-4-octyne-3, 6-diol, ethyloctynol, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, and 2,5,8, 11-tetramethyl-6-dodecenyl-5, 8-diol.
Preferably, the molecular weight of the polyol with the functionality of 2-4 is 300-18000 g/mol;
the molecular weight of the micromolecular dihydric alcohol chain extender is lower than 300g/mol of aliphatic dihydric alcohol.
Preferably, the polyol with the functionality of 2-4 is selected from one or more of polyether polyol, polyester polyol, castor oil, polyether modified castor oil, hydroxyl terminated liquid polybutadiene polyol, polycarbonate polyol and polyacrylate polyol;
the chain extender of the micromolecular diol is selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 2-propanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 2-pentanediol, 2, 4-pentanediol, 2-methyl-1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 2-methyl-1, 5-pentanediol and 3-methyl-1, one or more of 5-pentanediol, 2-ethyl-1, 4-butanediol, 1, 2-octanediol, 3, 6-octanediol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 7-dimethyl-3, 6-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.
Preferably, the diphenylmethane polyisocyanate in the B component is selected from one or more of diphenylmethane diisocyanate, polymeric MDI, biuret group-modified MDI, isocyanurate group-modified MDI, urethane group-modified MDI, uretdione group-modified MDI, carbodiimide group-modified MDI and allophanate group-modified MDI;
the aliphatic polyisocyanate is selected from one or more of cyclohexane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalene-1, 5-diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, xylylene diisocyanate, tetramethyl m-xylylene diisocyanate and biuret bodies and trimers of the above types.
Preferably, the silane coupling agent is selected from one or more of epoxy silane, amino silane, mercapto silane, styrene silane, isobutylene silane, acryl silane and isocyanate silane.
Preferably, the filler is selected from one or more of calcium carbonate, talc, kaolin, clay, quartz, montmorillonite, organobentonite, hydrogenated castor oil, barium sulfate, fly ash, carbon black, fumed silica, aluminum hydroxide, magnesium hydroxide, antimony oxide, zinc borate, boron nitride, silicon carbide and melamine and derivatives thereof.
The invention provides a two-component polyurethane adhesive capable of being rapidly cured in a long opening time, which comprises the following components in percentage by volume of 2-10: 1, a component A and a component B; the component A comprises the following components in parts by weight: 30-50 parts of polyol with the functionality of 2-4, 1-10 parts of small molecular diol chain extender, 1-10 parts of alkynol with the functionality of 1-4, 0.01-1 part of metal catalyst, 0.2-2 parts of silane coupling agent and 30-80 parts of filler; the component B comprises 80-40 mass percent of diphenylmethane polyisocyanate and 20-60 mass percent of aliphatic polyisocyanate. The double-component polyurethane adhesive provided by the invention has the effect of slowing down the initial reaction of the double-component polyurethane adhesive by adopting the combined action of the metal catalyst and the alkynol with the functionality of 1-4, and after the reaction of the alkynol and the isocyanate is finished, the reaction of the polyol and the isocyanate is formally started, so that the effect of quick reaction is achieved by virtue of high catalyst content; the diphenylmethane polyisocyanate is used as the high-activity isocyanate to be compounded with the aliphatic polyisocyanate as the medium-low activity isocyanate, so that the crosslinking point of the high-activity isocyanate and the alkynol in the initial reaction stage is reduced, the initial reaction speed is further reduced, and the operable time is prolonged.
Detailed Description
The invention provides a two-component polyurethane adhesive capable of being rapidly cured in a long opening time, which comprises a component A and a component B, wherein the volume ratio of the component A to the component B is 2-10: 1;
the component A comprises the following components in parts by weight:
30-50 parts of polyol with the functionality of 2-4, 1-10 parts of small molecular diol chain extender, 1-10 parts of alkynol with the functionality of 1-4, 0.01-1 part of metal catalyst, 0.2-2 parts of silane coupling agent and 30-80 parts of filler;
the component B comprises 80-40 mass percent of diphenylmethane polyisocyanate and 20-60 mass percent of aliphatic polyisocyanate.
The double-component polyurethane adhesive provided by the invention has the effect of slowing down the initial reaction of the double-component polyurethane adhesive by adopting the combined action of the metal catalyst and the alkynol with the functionality of 1-4, and after the reaction of the alkynol and the isocyanate is finished, the reaction of the polyol and the isocyanate is formally started, so that the effect of quick reaction is achieved by virtue of high catalyst content; the diphenylmethane polyisocyanate is used as the high-activity isocyanate to be compounded with the aliphatic polyisocyanate as the medium-low activity isocyanate, so that the crosslinking point of the high-activity isocyanate and the alkynol in the initial reaction stage is reduced, the initial reaction speed is further reduced, and the operable time is prolonged.
The two-component polyurethane adhesive provided by the invention comprises a component A and a component B with the volume of 2-10: 1, and preferably 3-5: 1.
The component A comprises 30-50 parts of polyhydric alcohol with the functionality of 2-4; the molecular weight of the polyhydric alcohol with the functionality of 2-4 is 300-18000 g/mol. The polyol is preferably selected from one or more of polyether polyol, polyester polyol, polyether modified castor oil, hydroxyl terminated liquid polybutadiene polyol, polycarbonate polyol and polyacrylate polyol, more preferably from polyether polyol and/or polyether modified castor oil. In particular embodiments, the polyol is selected from polyoxypropylene polyols; the polyoxypropylene polyol is specifically selected from the model Voranol 2471.
The component A comprises 1-10 parts of a micromolecular dihydric alcohol chain extender, and the molecular weight of the micromolecular dihydric alcohol chain extender is lower than that of aliphatic dihydric alcohol of 300 g/mol. The chain extender of the micromolecular diol is selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 2-propanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 2-pentanediol, 2, 4-pentanediol, 2-methyl-1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 2-methyl-1, 5-pentanediol and 3-methyl-1, one or more of 5-pentanediol, 2-ethyl-1, 4-butanediol, 1, 2-octanediol, 3, 6-octanediol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 7-dimethyl-3, 6-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol. The micromolecular diol chain extender is selected from 1, 4-butanediol.
The component A comprises 1-10 parts of alkynol with functionality of 1-4, and the alkynol with functionality of 1-4 is preferably selected from one or more of propiolic alcohol, butynol and its isocratic derivatives, pentynol and its isocratic derivatives, hexynol and its isocratic derivatives, heptynol and its isocratic derivatives, octynol and its isocratic derivatives, nonynol and its isocratic derivatives, decynylol and its isocratic derivatives, undenylol and its isocratic derivatives, butyndiol and its derivatives, hexyndiol and its derivatives, octyndiol and its derivatives, decynyldiol and its derivatives, and dodecenyldiol and its derivatives. The alkynol with the functionality of 1-4 is more preferably selected from one or more of propiolic alcohol, butynol and an isoderivative thereof, pentynol and an isoderivative thereof, hexynol and an isoderivative thereof, heptynol and an isoderivative thereof, octynol and an isoderivative thereof, nonynol and an isoderivative thereof, decynol and an isoderivative thereof, undecenol and an isoderivative thereof, butynol and a derivative thereof, hexynol and a derivative thereof, octynol and a derivative thereof, decynediol and a derivative thereof, and dodecenediol and a derivative thereof, and is more preferably selected from propiolic alcohol, butynol, pentynol, hexynol, heptynol, octynol, nonynol, decynediol, undecenol, methylbutynol, methylpentylol, butynol, hexynol, octyndiol, decynediol, 2, 5-dimethyl-3-hexyne-2, one or more of 5-diol, 3, 6-dimethyl-4-octyne-3, 6-diol, ethyloctyne alcohol, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, and 2,5,8, 11-tetramethyl-6-dodecenyl-5, 8-diol. In a specific embodiment, the alkynol with the functionality of 1-4 is selected from 2, 5-dimethyl-3-hexyne-2, 5-diol, 3, 6-dimethyl-4-octyne-3, 6-diol or 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol. In the present invention, alkynols of the above-mentioned kind form complexes with metal catalysts, hindering the initial catalytic effect of the metal catalysts, thereby prolonging the initial open time, and as the reaction of alkynol and polyisocyanate proceeds, active catalysts are released, thereby initiating a rapid reaction; the addition of the low reactivity polyisocyanate also reduces the reaction rate of the polyether component with the isocyanate component, thereby further extending the initial open time.
The component A comprises 0.01-1 part of metal catalyst; the metal catalyst is selected from one or more of an organic tin catalyst, an organic bismuth catalyst, an organic zinc catalyst and an organic zirconium catalyst; the organic tin catalyst is selected from one or more of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide, octyltin oxide, dibutyltin bis (dodecylthio) oxide and dibutyltin diacetate; the organic bismuth catalyst is selected from one or more of bismuth acetate, bismuth isooctanoate, bismuth neodecanoate, bismuth naphthenate, bismuth laurate and bismuth oleate; the organic zinc catalyst is selected from one or more of bismuth isooctanoate, zinc neodecanoate and zinc laurate; the organozirconium catalyst is selected from zirconium isooctanoate.
The component A comprises 0.2-2 parts of silane coupling agent; the silane coupling agent is preferably one or more selected from epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, styryl silane coupling agents, isobutylene silane coupling agents, acryl silane coupling agents and isocyanate silane coupling agents. The epoxy silane coupling agent is selected from one or more of beta- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, gamma-glycidyl ether propyl triethoxy silane and 3-glycidyl ether propyl methyl diethoxy silane; the aminosilane coupling agent is selected from one or more of bis- (gamma-trimethoxysilylpropyl) amine, N-phenyl-gamma-aminopropyltrimethoxysilane, N-phenyl-gamma-aminopropyltriethoxysilane, N-butyl-gamma-aminopropyltrimethoxysilane, N-butyl-gamma-aminopropyltriethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane and N-ethyl-3-aminopropyltriethoxysilane; the mercaptosilane coupling agent is selected from gamma-mercaptopropyltrimethoxysilane and/or gamma-mercaptopropyltriethoxysilane; the styrene silane coupling agent is selected from p-isobutylene trimethoxy silane; the isobutylene silane coupling agent is selected from 3-isobutylene propyl methyl dimethoxy silane and/or 3-isobutylene propyl triethoxy silane; the allyl silane coupling agent is selected from 3-allyl propyl trimethoxy silane; the isocyanate silane coupling agent is selected from gamma-isocyanate propyl triethoxy silane and/or gamma-isocyanate propyl trimethoxy silane. The silane coupling agent is more preferably selected from epoxy silane coupling agents and/or aminosilane coupling agents. In particular embodiments, the silane coupling agent is selected from Silquest A-187.
The component A comprises 30-80 parts of filler; the filler is selected from one or more of calcium carbonate, talcum powder, kaolin, clay, quartz, montmorillonite, organic bentonite, hydrogenated castor oil, barium sulfate, fly ash, carbon black, fumed silica, aluminum hydroxide, magnesium hydroxide, antimony oxide, zinc borate, boron nitride, silicon carbide and melamine and derivatives thereof. In particular embodiments, the adjuvant is selected from the group consisting of aluminum hydroxide and melamine.
The component B comprises 80-40 mass percent of diphenylmethane polyisocyanate and 20-60 mass percent of aliphatic polyisocyanate. The diphenylmethane polyisocyanate is high-activity polyisocyanate; the diphenylmethane polyisocyanate is preferably selected from one or more of diphenylmethane diisocyanate, polymeric MDI, biuret group-modified MDI, isocyanurate group-modified MDI, urethane group-modified MDI, uretdione group-modified MDI, carbodiimide group-modified MDI and allophanate group-modified MDI. The aliphatic polyisocyanate is low-activity polyisocyanate; the aliphatic polyisocyanate is preferably one or more selected from cyclohexane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalene-1, 5-diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, xylylene diisocyanate, tetramethylm-xylylene diisocyanate, and biuret bodies and trimers of the above kind. In a specific embodiment, the component B comprises the following components in a mass ratio of 7: PM200 and N3300 of 3; or PM200 and N3300 at a mass ratio of 4: 6.
In a specific embodiment of the present invention, the two-component polyurethane adhesive with long open time and fast curing comprises:
the volume ratio is 100: 21 a component and B component; the component A comprises 45 parts of Voranol2471, 3 parts of 1, 4-butanediol, 1 part of 2, 5-dimethyl-3-hexyne-2, 5-diol, 35 parts of aluminum hydroxide, 15 parts of melamine, 0.5 part of Silquest A-187 and 0.1 part of Coscat 83; the component B comprises 70 parts of PM200 and 30 parts of N3300;
or the volume ratio is 100: 25 of a component and B component; the component A comprises 45 parts of Voranol2471, 3 parts of 1, 4-butanediol, 3 parts of 2, 5-dimethyl-3-hexyne-2, 5-diol, 35 parts of aluminum hydroxide, 15 parts of melamine, 0.5 part of Silquest A-187 and 0.1 part of Coscat 83; the component B comprises 70 parts of PM200 and 30 parts of N3300;
or the volume ratio is 100:30 of a component A and a component B; the component A comprises 45 parts of Voranol2471, 3 parts of 1, 4-butanediol, 5 parts of 2, 5-dimethyl-3-hexyne-2, 5-diol, 35 parts of aluminum hydroxide, 15 parts of melamine, 0.5 part of Silquest A-187 and 0.1 part of Coscat 83; the component B comprises 70 parts of PM200 and 30 parts of N3300;
or the volume ratio is 100:30 of a component A and a component B; the component A comprises 45 parts of Voranol2471, 3 parts of 1, 4-butanediol, 3 parts of 2, 5-dimethyl-3-hexyne-2, 5-diol, 35 parts of aluminum hydroxide, 15 parts of melamine, 0.5 part of Silquest A-187 and 0.1 part of Coscat 83; the component B comprises 40 parts of PM200 and 60 parts of N3300;
or a component A and a component B in a volume ratio of 100: 30; the component A comprises Voranol2471, 3 parts of 1, 4-butanediol, 5 parts of 3, 6-dimethyl-4-octyne-3, 6-diol, 35 parts of aluminum hydroxide, 15 parts of melamine, 0.5 part of Silquest A-187 and 0.5 part of Coscat 83; the component B comprises 70 parts of PM200 and 30 parts of N3300;
or a component A and a component B in a volume ratio of 100: 30; the component A comprises Voranol2471, 3 parts of 1, 4-butanediol, 5 parts of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 35 parts of aluminum hydroxide, 15 parts of melamine, 0.5 part of Silquest A-187 and 0.5 part of Coscat 83; the B component comprises 70 parts of PM200 and 30 parts of N3300.
In the invention, the preparation method of the long-open-time fast-curing two-component polyurethane adhesive comprises the following steps:
heating polyhydric alcohol with functionality of 2-4, a small molecular diol chain extender, alkynol with functionality of 1-4 and a filler under stirring to 110-130 ℃ for dehydration, cooling to below 50 ℃, and adding a silane coupling agent and a metal catalyst to obtain a component A;
uniformly mixing diphenylmethane polyisocyanate and aliphatic polyisocyanate to obtain a component B;
and mixing the component A and the component B to obtain the double-component polyurethane adhesive.
The adhesive is tested for tensile strength, elongation at break and tensile shear strength by adopting the method in HG/T4363-. The flame retardancy test was carried out according to the method specified in UL-94. The open time supports a slow initial reaction and the 4h strength supports a fast curing.
For further illustration of the present invention, the following examples are provided to describe the two-component polyurethane adhesive with long open time and fast curing, but they should not be construed as limiting the scope of the present invention.
Examples 1 to 4
Heating polyhydric alcohol with the functionality of 2-4, a small molecular diol chain extender, alkynol with the functionality of 1-4 and a filler under the stirring condition to 110-130 ℃, dehydrating for 2 hours, cooling to below 50 ℃, and adding a silane coupling agent and a metal catalyst to obtain a component A;
uniformly mixing diphenylmethane polyisocyanate and aliphatic polyisocyanate to obtain a component B;
and mixing the component A and the component B to obtain the double-component polyurethane adhesive.
Table 1 test results of raw material usage and product performance of examples 1 to 4
Comparative examples 1 to 3
Preparing a two-component polyurethane adhesive according to the raw material dosage in the table 2 and the process steps of the example 1;
table 2 raw material amounts and product performance test results of comparative examples 1 to 3
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Component A | |||
| Voranol 2471 | 45 | 45 | 45 |
| 1, 4-butanediol | 3 | 3 | 3 |
| 2, 5-dimethyl-3-hexyne-2, 5-diols | 0 | 3 | 3 |
| Aluminum hydroxide | 35 | 35 | 35 |
| Melamine | 15 | 15 | 15 |
| Silquest A-187 | 0.5 | 0.5 | 0.5 |
| Coscat 83 | 0.3 | 0.3 | 0.3 |
| Component B | |||
| PM200 | 70 | 100 | |
| N3300 | 30 | 100 | |
| Volume ratio of component A/component B | 100/20 | 100/23 | 100/35 |
| Open time, min (15 ℃ C.) | 29 | 43 | 89 |
| Open time, min (23 ℃ C.) | 24 | 35 | 83 |
| Open time, min (35 ℃ C.) | 13 | 26 | 76 |
| Tensile shear strength, MPa (23 ℃,4h) | 4.7 | 6 | 3.6 |
| Tensile Strength, MPa (23 ℃,4h) | 5.2 | 6.5 | 3.7 |
| Tensile shear strength, MPa (23 ℃,7d) | 7.8 | 9.3 | 10.6 |
| Tensile Strength, MPa (23 ℃,7d) | 8.7 | 10.4 | 11.3 |
According to the embodiment, the two-component polyurethane adhesive provided by the invention has the effect of slowing down the initial reaction of the two-component polyurethane adhesive by adopting the combined action of the metal catalyst and the alkynol with the functionality of 1-4, the reaction of the polyol and the isocyanate is formally started after the reaction of the alkynol and the isocyanate is finished, and the effect of quick reaction is achieved by virtue of high catalyst content; the diphenylmethane polyisocyanate is used as the high-activity isocyanate to be compounded with the aliphatic polyisocyanate as the medium-low activity isocyanate, so that the crosslinking point of the high-activity isocyanate and the alkynol in the initial reaction stage is reduced, the initial reaction speed is further reduced, and the operable time is prolonged.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A two-component polyurethane adhesive capable of being rapidly cured in a long opening time comprises the following components in percentage by volume of 2-10: 1, a component A and a component B;
the component A comprises the following components in parts by weight:
30-50 parts of polyol with the functionality of 2-4, 1-10 parts of small molecular diol chain extender, 1-10 parts of alkynol with the functionality of 1-4, 0.01-1 part of metal catalyst, 0.2-2 parts of silane coupling agent and 30-80 parts of filler;
the component B comprises 80-40 mass percent of diphenylmethane polyisocyanate and 20-60 mass percent of aliphatic polyisocyanate.
2. The polyurethane adhesive of claim 1, wherein the alkynol with functionality of 1-4 is selected from one or more of propargyl alcohol, butynol and its derivatives, pentynol and its derivatives, hexynol and its derivatives, heptynol and its derivatives, octynol and its derivatives, nonynol and its derivatives, decynol and its derivatives, undecenol and its derivatives, butynol and its derivatives, hexynol and its derivatives, octynol and its derivatives, decynediol and its derivatives, and dodecenediol and its derivatives.
3. The polyurethane adhesive of claim 1, the alkynol with the functionality of 1-4 is selected from one or more of propiolic alcohol, butynol, pentynol, hexynol, heptynol, octynol, nonynol, decylenol, undecenol, methylbutynol, methylpentylenol, butynol, hexynol, octynol, decynediol, dodecaacetylenediol, 2, 5-dimethyl-3-hexyne-2, 5-diol, 3, 6-dimethyl-4-octyne-3, 6-diol, ethyloctynol, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 2,5,8, 11-tetramethyl-6-dodecayne-5, 8-diol.
4. The polyurethane adhesive of claim 1, wherein the polyol having a functionality of 2 to 4 has a molecular weight of 300 to 18000 g/mol;
the molecular weight of the micromolecular dihydric alcohol chain extender is lower than 300g/mol of aliphatic dihydric alcohol.
5. The polyurethane adhesive of claim 4, wherein the polyol having a functionality of 2 to 4 is selected from one or more of polyether polyol, polyester polyol, castor oil, polyether modified castor oil, hydroxyl terminated liquid polybutadiene polyol, polycarbonate polyol, and polyacrylate polyol;
the chain extender of the micromolecular diol is selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 2-propanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 2-pentanediol, 2, 4-pentanediol, 2-methyl-1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2-hexanediol, 1, 3-hexanediol, 1, 4-hexanediol, 2-methyl-1, 5-pentanediol and 3-methyl-1, one or more of 5-pentanediol, 2-ethyl-1, 4-butanediol, 1, 2-octanediol, 3, 6-octanediol, 2-ethyl-1, 3-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 7-dimethyl-3, 6-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.
6. The polyurethane adhesive of claim 1, wherein the diphenylmethane polyisocyanate of the B component is selected from one or more of diphenylmethane diisocyanate, polymeric MDI, biuret group-modified MDI, isocyanurate group-modified MDI, urethane group-modified MDI, uretdione group-modified MDI, carbodiimide group-modified MDI, and allophanate group-modified MDI;
the aliphatic polyisocyanate is selected from one or more of cyclohexane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, naphthalene-1, 5-diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, xylylene diisocyanate, tetramethyl m-xylylene diisocyanate and biuret bodies and trimers of the above types.
7. The polyurethane adhesive of claim 1, wherein the silane coupling agent is selected from one or more of the group consisting of epoxy silanes, amino silanes, mercapto silanes, styrene silanes, isobutylene silanes, acryl silanes, and isocyanate silanes.
8. The polyurethane adhesive of claim 1, wherein the filler is selected from one or more of calcium carbonate, talc, kaolin, clay, quartz, montmorillonite, organobentonite, hydrogenated castor oil, barium sulfate, fly ash, carbon black, fumed silica, aluminum hydroxide, magnesium hydroxide, antimony oxide, zinc borate, boron nitride, silicon carbide, and melamine and derivatives thereof.
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