CN112760075A - High-initial-strength hot-melt type two-component polyurethane structural adhesive and preparation method thereof - Google Patents

High-initial-strength hot-melt type two-component polyurethane structural adhesive and preparation method thereof Download PDF

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CN112760075A
CN112760075A CN202011561425.1A CN202011561425A CN112760075A CN 112760075 A CN112760075 A CN 112760075A CN 202011561425 A CN202011561425 A CN 202011561425A CN 112760075 A CN112760075 A CN 112760075A
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parts
component
diol
structural adhesive
strength hot
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韩红伟
王建斌
陈田安
解海华
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Yantai Darbond Technology Co Ltd
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Yantai Darbond Technology Co Ltd
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/48Polyethers
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
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    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2170/00Compositions for adhesives
    • C08G2170/20Compositions for hot melt adhesives

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Abstract

The invention discloses a high-initial-strength hot-melt type two-component polyurethane structural adhesive which comprises a component A and a component B, wherein the component A comprises the following substances in parts by weight: 25-45 parts of solid polyester polyol A, 15-45 parts of liquid polyester polyol, 20-50 parts of isocyanate, 0-45 parts of polyether polyol A, 0-20 parts of tackifying resin A and 0.1-3 parts of coupling agent; the component B comprises the following substances in parts by weight: 10-50 parts of hydroxyl-terminated polyurethane prepolymer, 30-60 parts of solid polyester polyol B, 20-50 parts of polyether polyol B, 10-30 parts of tackifying resin B and 0.01-0.5 part of catalyst. The invention has the beneficial effects that: the high-initial-strength hot-melt type two-component polyurethane structural adhesive has the characteristics of high initial strength, high post-curing speed, high final strength and the like, can replace acrylate structural adhesive, is used for structural bonding, and has the advantages of low odor, low shrinkage, low stress, environmental protection and the like.

Description

High-initial-strength hot-melt type two-component polyurethane structural adhesive and preparation method thereof
Technical Field
The invention relates to a polyurethane adhesive, in particular to a high-initial-strength hot-melt type two-component polyurethane structural adhesive and a preparation method thereof.
Background
The moisture-curing Polyurethane (PUR) hot melt adhesive is a prepolymer with a certain molecular weight synthesized by taking isocyanate and polyol as main reaction raw materials under the conditions of a certain temperature, a certain pressure and a certain catalyst. The prepolymer mainly comprises a hard section and a soft section, wherein a carbamate bond and the like are used as the hard section, and a polyalcohol is used as the soft section, so that the advantages of impact resistance, tough adhesive film, good flexibility, high peeling strength, low temperature resistance, solvent resistance, fatigue resistance, wear resistance and the like of the PUR hot melt adhesive are determined by the structure. The PUR hot melt adhesive can be used for bonding polyurethane rubber and polyurethane sponge, bonding rubber and plastic, rubber and fabric, metal and ceramic, metal and rubber, metal, wood and leather and the like, the product types of the PUR hot melt adhesive are increasingly diversified, the application field is increasingly wide, the PUR hot melt adhesive has an indispensable important position in national economy and becomes one of the fastest adhesives developed in modern industry, however, the strength of the single-component PUR cannot meet the requirement of high-strength structure bonding, moisture is required for curing, and the single-component PUR hot melt adhesive cannot be used in closed occasions, so that the application is limited to a certain extent.
The acrylic structural adhesive is mainly used in the field of structural bonding, has the characteristics of rapid curing, high bonding strength and the like, can meet the needs of most structural bonding, and has the defects of large curing shrinkage, heavy smell and difficult industry overcoming. The double-component PUR has the characteristic of quick positioning of the single-component PUR, can meet the bonding requirement of a high-strength structure, and has no odor, environmental protection and low shrinkage. Can be widely applied to the bonding field of high-end structures such as consumer electronics, automobiles and the like.
Disclosure of Invention
The invention aims at the problems and provides a high-initial-strength hot-melt type two-component polyurethane structural adhesive which comprises a component A and a component B, wherein the component A comprises the following substances in parts by weight: 25-45 parts of solid polyester polyol A, 15-45 parts of liquid polyester polyol, 20-50 parts of isocyanate, 0-45 parts of polyether polyol A, 0-20 parts of tackifying resin A and 0.1-3 parts of coupling agent; the component B comprises the following substances in parts by weight: 10-50 parts of hydroxyl-terminated polyurethane prepolymer, 30-60 parts of solid polyester polyol B, 20-50 parts of polyether polyol B, 10-30 parts of tackifying resin B and 0.01-0.5 part of catalyst. The volume using ratio of the component A to the component B is (1-9): 1.
Specifically, the number average molecular weights of the solid polyester polyol A and the solid polyester polyol B are 2000-5000, and the solid polyester polyol A and the solid polyester polyol B are independently selected from one or more of butanediol adipate diol, hexanediol adipate diol, butanediol succinate diol, ethylene glycol oxalate diol, butanediol oxalate diol and the like or polycaprolactone diol; the liquid polyester polyol is selected from one or more of neopentyl glycol adipate diol, diethylene glycol adipate, dimethyl 2, 4-pentanediol adipate diol, dimer acid series diol ester diol or polycaprolactone diol; the isocyanate is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate or hexamethylene diisocyanate; the polyether polyol A and the polyether polyol B are independently selected from PPG and/or polytetrahydrofuran diol; the tackifying resin A and the tackifying resin B are independently selected from one or more of terpene resin, acrylic resin, polyester resin or polycaprolactone; the coupling agent is mercaptopropyl trimethoxysilane; the catalyst is one of nitrogen methyl morpholine, nitrogen methyl imidazole or double morpholinyl diethyl ether.
The preparation method of the high initial strength hot-melt type two-component polyurethane structural adhesive comprises the following steps:
A) preparation of component A
Weighing the substances in parts by weight, uniformly mixing solid polyester polyol, liquid polyester polyol, polyether polyol and tackifying resin, heating to 120 ℃ after the mixture is dehydrated for 1-2 hours, cooling to 80 ℃, adding isocyanate, heating to 90-110 ℃, reacting for 1-2 hours, adding micromolecule diol, continuing to react for 1-2 hours, measuring the NCO content, stopping the reaction when the R value is 1.3-2.5, and adding a coupling agent to obtain the modified polyether polyol;
B) preparation of component B
Weighing the components in parts by weight, mixing the substances except the catalyst, heating to 120 ℃ for dehydration for 1-2 hours, adding the catalyst, and uniformly stirring to obtain the catalyst.
The invention has the beneficial effects that: the high-initial-strength hot-melt type two-component polyurethane structural adhesive has the characteristics of high initial strength, high post-curing speed, high final strength and the like, can replace acrylate structural adhesive, is used for structural bonding, and has the advantages of low odor, low shrinkage, low stress, environmental protection and the like.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Example 1
A preparation method of a high-initial-strength hot-melt type two-component polyurethane structural adhesive comprises the following steps:
the preparation process of the component A comprises the following steps: adipic acid hexanediol ester diol: 35 parts of: 30 parts of neopentyl glycol adipate glycol, 100020 parts of PPG and 10 parts of tackifying resin. After being mixed evenly, the mixture is heated to 110 ℃ for dehydration for 1.5 hours, then cooled to 80 ℃, added with 35 parts of diphenylmethane diisocyanate, heated to 90 ℃ for reaction for 2 hours, then added with 2 parts of ethylene glycol for continuous reaction for 1 hour. And measuring the NCO content. Wherein the R value is 2. After the reaction, 1 part of a coupling agent was added.
The preparation process of the component B comprises the following steps: the preparation process of the hydroxyl-terminated polyurethane prepolymer comprises the following steps:
44 parts of neopentyl glycol adipate diol, heating to 100 ℃ and 120 ℃, dehydrating for 1-2 hours, cooling to about 80 ℃, and adding 6 parts of diphenylmethane diisocyanate;
taking 50 parts of the prepared hydroxyl-terminated polyurethane prepolymer, 100030 parts of PPG and terpene resin: 20 portions, after being mixed evenly, the mixture is heated to 120 ℃ of 100 ℃, 0.01 to 0.5 portion of catalyst is added after 1 to 2 hours of dehydration, and the mixture is stirred evenly to obtain the component B;
the volume ratio of A to B is 1: 1.
Example 2
A preparation method of a high-initial-strength hot-melt type two-component polyurethane structural adhesive comprises the following steps:
the preparation process of the component A comprises the following steps: after uniformly mixing 35 parts of adipic acid hexanediol ester diol, 50 parts of liquid polyester polyol and 10 parts of terpene resin, heating to 110 ℃, dehydrating for 1.5 hours, cooling to 80 ℃, adding 35 parts of diphenylmethane diisocyanate, namely isocyanate, heating to 90 ℃, reacting for 2 hours, then adding 2 parts of ethylene glycol, continuing to react for 1 hour, measuring the NCO content, wherein the R value is 2, and after the reaction is finished, adding 1 part of a coupling agent;
the preparation process of the component B comprises the following steps: the preparation process of the hydroxyl-terminated polyurethane prepolymer comprises the following steps:
44 parts of adipic acid hexanediol ester diol and 6 parts of diphenylmethane diisocyanate, heating to 100 ℃ and 120 ℃, dehydrating for 1-2 hours, cooling to about 80 ℃, and adding isocyanate. The R value is 0.1-0.8;
taking 50 parts of the prepared hydroxyl-terminated polyurethane prepolymer, 30 parts of polyether polyol and terpene resin: 20 portions, after being mixed evenly, the mixture is heated to 120 ℃ of 100 ℃, 0.01 to 0.5 portion of catalyst is added after 1 to 2 hours of dehydration, and the mixture is stirred evenly to obtain the component B;
the volume ratio of A to B is 1: 1.
Example 3
A preparation method of a high-initial-strength hot-melt type two-component polyurethane structural adhesive comprises the following steps:
the preparation process of the component A comprises the following steps: 35 parts of adipic acid hexanediol ester diol, 50 parts of adipic acid neopentyl glycol ester diol and 10 parts of terpene resin. After uniform mixing, heating to 110 ℃, dehydrating for 1.5 hours, cooling to 80 ℃, adding 35 parts of diphenylmethane diisocyanate, isocyanate, heating to 90 ℃, reacting for 2 hours, then adding 2 parts of ethylene glycol, continuing to react for 1 hour, measuring the NCO content, wherein the R value is 2, and adding 1 part of a coupling agent after the reaction is finished;
the preparation process of the component B comprises the following steps: 10 parts of diethylene glycol, 10 parts of PPG 100010 parts and 80 parts of polycaprolactone, uniformly mixing, heating to 100 ℃, dehydrating for 1-2 hours, adding 0.01-0.5 part of catalyst, and uniformly stirring to obtain a component B;
the volume ratio of A to B is 2: 1.
Comparative example 1
A preparation method of the single-component PUR comprises the following steps: 35 parts of adipic acid hexanediol ester diol, 20 parts of adipic acid neopentyl glycol ester diol, 100030 parts of PPG: 10 parts of acrylate resin, uniformly mixing, heating to 110 ℃, dehydrating for 1.5 hours, cooling to 80 ℃, adding 35 parts of diphenylmethane diisocyanate, namely isocyanate, heating to 90 ℃, reacting for 2 hours, then adding 2 parts of ethylene glycol, continuing to react for 1 hour, measuring the NCO content, wherein the R value is 2, and adding 1 part of coupling agent after the reaction is finished.
Comparative example 2
Is a conventional acrylate structural adhesive.
The structural adhesives obtained in examples 1 to 3 and comparative examples 1 and 2 were subjected to a correlation performance test, as shown in table 1.
TABLE 1. examples 1-3 and comparative examples 1, 2 Performance of structural adhesives
Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Shear strength (MPa) 16 14 22 7 18
Tensile Strength (MPa) 18 11 19 5 13
Curing volume shrinkage% 0.1 0.5 0.5 1 10
Smell(s) Is free of Is free of Is free of Is free of Heavy load
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A high initial strength hot melt type double-component polyurethane structural adhesive comprises a component A and a component B and is characterized in that,
the component A consists of the following substances in parts by weight: 25-45 parts of solid polyester polyol A, 15-45 parts of liquid polyester polyol, 20-50 parts of isocyanate, 0-45 parts of polyether polyol A, 0-20 parts of tackifying resin A and 0.1-3 parts of coupling agent;
the component B comprises the following substances in parts by weight: 10-50 parts of hydroxyl-terminated polyurethane prepolymer, 30-60 parts of solid polyester polyol B, 20-50 parts of polyether polyol B, 10-30 parts of tackifying resin B and 0.01-0.5 part of catalyst.
2. The high initial strength hot melt two-component polyurethane structural adhesive according to claim 1, wherein the volume ratio of the component A to the component B is (1-9): 1.
3. The high initial strength hot melt type two-component polyurethane structural adhesive as claimed in claim 1, wherein the number average molecular weight of the solid polyester polyol A and the solid polyester polyol B is 2000-5000, and the solid polyester polyol A and the solid polyester polyol B are independently selected from one or more of butylene adipate diol, hexanediol adipate diol, butylene succinate diol, ethylene glycol oxalate diol, butylene glycol oxalate diol and the like or polycaprolactone diol.
4. The high initial strength hot melt two-component polyurethane structural adhesive of claim 1, wherein the liquid polyester polyol is selected from one or more of neopentyl glycol adipate diol, diethylene glycol adipate, dimethyl 2, 4-pentanediol adipate diol, dimer acid series diol esters diol, or polycaprolactone diol.
5. The high initial strength hot melt two-component polyurethane structural adhesive of claim 1, wherein the isocyanate is selected from one or more of diphenylmethane diisocyanate, toluene diisocyanate, or hexamethylene diisocyanate.
6. The high initial strength hot melt two component polyurethane structural adhesive of claim 1, wherein the polyether polyol a and polyether polyol B are independently selected from PPG and/or polytetrahydrofuran diol.
7. The high initial strength hot melt two-component polyurethane structural adhesive of claim 1, wherein the tackifying resin A and the tackifying resin B are independently selected from one or more of terpene resins, acrylic resins, polyester resins, or polycaprolactone.
8. The high initial strength hot melt two component polyurethane construction glue of claim 1, wherein the coupling agent is mercaptopropyl trimethoxysilane.
9. The high initial strength hot melt two component polyurethane structural adhesive of claim 1, wherein the catalyst is one of nitromethylmorpholine, nitromethylimidazole or dimorpholinyldiethylether.
10. A method for preparing the high initial strength hot melt type two-component polyurethane structural adhesive according to any one of claims 1 to 9, comprising the steps of:
A) preparation of component A
Weighing the substances in parts by weight, uniformly mixing solid polyester polyol, liquid polyester polyol, polyether polyol and tackifying resin, heating to 120 ℃ after the mixture is dehydrated for 1-2 hours, cooling to 80 ℃, adding isocyanate, heating to 90-110 ℃, reacting for 1-2 hours, adding micromolecule diol, continuing to react for 1-2 hours, measuring the NCO content, stopping the reaction when the R value is 1.3-2.5, and adding a coupling agent to obtain the modified polyether polyol;
B) preparation of component B
Weighing the components in parts by weight, mixing the substances except the catalyst, heating to 120 ℃ for dehydration for 1-2 hours, adding the catalyst, and uniformly stirring to obtain the catalyst.
CN202011561425.1A 2020-12-25 2020-12-25 High-initial-strength hot-melt type two-component polyurethane structural adhesive and preparation method thereof Pending CN112760075A (en)

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CN110229645A (en) * 2019-07-12 2019-09-13 重庆韩拓科技有限公司 High just allonge component moisture-curable reaction type polyurethane hot-melt adhesive and preparation method thereof
CN110669469A (en) * 2019-10-22 2020-01-10 格丽泰新材料科技(苏州)有限公司 Two-component polyurethane structural adhesive and preparation method and application thereof
CN111019585A (en) * 2019-12-17 2020-04-17 烟台德邦科技有限公司 Double-component reaction type polyurethane hot melt adhesive and preparation method thereof
CN111303819A (en) * 2020-03-05 2020-06-19 北京高盟新材料股份有限公司 Low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive and preparation method thereof
CN111849408A (en) * 2020-06-22 2020-10-30 上海回天新材料有限公司 Moisture-curing polyurethane hot melt adhesive with high initial adhesion strength and preparation method thereof
CN111808570A (en) * 2020-08-27 2020-10-23 格丽泰新材料科技(苏州)有限公司 Double-component polyurethane adhesive and application thereof

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CN114891473A (en) * 2022-06-15 2022-08-12 顶立新材料科技股份有限公司 Degradable single-component polyurethane structural adhesive for structural laminated wood and preparation method thereof

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