WO2022007613A1 - Solvent-free single-component moisture-curing polyurethane adhesive for use on wood and preparation method therefor - Google Patents

Solvent-free single-component moisture-curing polyurethane adhesive for use on wood and preparation method therefor Download PDF

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Publication number
WO2022007613A1
WO2022007613A1 PCT/CN2021/100815 CN2021100815W WO2022007613A1 WO 2022007613 A1 WO2022007613 A1 WO 2022007613A1 CN 2021100815 W CN2021100815 W CN 2021100815W WO 2022007613 A1 WO2022007613 A1 WO 2022007613A1
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polyol
polyurethane adhesive
solvent
molecular weight
average molecular
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PCT/CN2021/100815
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French (fr)
Chinese (zh)
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陈由亮
江平
柳红毅
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旭川化学（苏州）有限公司
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Publication of WO2022007613A1 publication Critical patent/WO2022007613A1/en

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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
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C09J175/06—Polyurethanes from polyesters

Definitions

  • the invention belongs to the technical field of adhesives, and in particular relates to a solvent-free single-component moisture-curing polyurethane adhesive suitable for wood and a preparation method thereof.
  • synthetic resins used as wood adhesives generally refer to thermosetting resins.
  • Traditional wood adhesives include resorcinol-formaldehyde resin, phenol resorcinol-formaldehyde resin, melamine-urea-formaldehyde and other adhesives with formaldehyde as the main raw material.
  • such adhesives have higher shrinkage rates during curing.
  • the adhesive layer is prone to cracks and has poor water resistance; it contains free formaldehyde, which will emit formaldehyde gas to the surrounding environment during use and pollute the environment. After contact, it will cause multiple diseases such as bronchitis, asthma, dermatitis, and even malignant tumors after prolonged contact. .
  • polyurethane adhesives both It will not release toxic substances, and has the characteristics of fast curing speed, lighter color of cured product, high bonding strength, flexible structure design and convenient production and construction. According to the method of use, polyurethane adhesives can be divided into one-component and two-component.
  • One obvious advantage of one-component polyurethane adhesives over two-component polyurethane adhesives is that there is no need to perform chemical calculations or add other cross-linking agents when using them. It can be cured to produce bonding effect, which brings great convenience to construction, so it is widely used.
  • the one-component moisture-curable polyurethane adhesive used in industry is liquid, used at room temperature, and can bond to many non-wood substrates such as textile fibers, metals, plastics, rubber, etc.
  • the polyurethane adhesive includes polyol, diisocyanate, catalyst, coupling agent and chain extender, and by weight percentage, polyol 40-70 %, diisocyanate 30-55%, chain extender 0-5%, catalyst 0.1-0.5% and coupling agent 0-1%
  • the polyurethane adhesive is cured by the moisture in the air and the material, it is aimed at aluminum
  • the adhesive that can be bonded to aluminum is not necessarily suitable for use on wood, and the raw materials implemented from this patent are It can be seen from the above that only ordinary polyester polyols and polyether polyols are used, which may not
  • the present invention provides a solvent-free one-component moisture-curing polyurethane adhesive suitable for wood and a preparation method thereof.
  • a solvent-free one-component moisture-curing polyurethane adhesive in terms of mass percentage, the raw material formula of the polyurethane adhesive includes the following components:
  • the polyether polyol is a polypropylene oxide ether polyol with a functionality of 3 and a number average molecular weight of 5000-6000, a random copolymer of ethylene oxide and propylene oxide.
  • Alcohol a mixture of polytetrahydrofuran ether polyols with a functionality of 2 and a number average molecular weight of 1000-2000.
  • the polyether polyol is the random copolymerization polyether polyol of ethylene oxide and propylene oxide, the polypropylene oxide ether polyol, and the polytetrahydrofuran ether polyol in a mass ratio of 1 : 0.5 to 1: A combination of 0.5 to 3.
  • the number average molecular weight of the random copolymerized polyether polyol of ethylene oxide and propylene oxide is 2500-3500, and the molar ratio of ethylene oxide and propylene oxide is 6:3 ⁇ 5 with a functionality of 3.
  • the random copolymerized polyether polyol of ethylene oxide and propylene oxide is a polyether with a number average molecular weight of 3000, a functionality of 3, and a molar ratio of ethylene oxide to propylene oxide of 6:4 Triol. Specifically such as AD-3300E.
  • the polypropylene oxide ether polyol has a number-average molecular weight of 5000 and a degree of unsaturation of 0.005 mmol/g, a number-average molecular weight of 6000 and a degree of unsaturation of 0.005.
  • One or more of mmol/g polypropylene oxide ether polyols includes but is not limited to one or more of 330N and EP-3600.
  • the polyester polyol is a polycarbonate polyol having a functionality of 2 and a number-average molecular weight of 1000-2000, and adipic acid having a functionality of 2 and a number-average molecular weight of 1000-2000
  • adipic acid having a functionality of 2 and a number-average molecular weight of 1000-2000
  • One or more of the polyadipate-ester polyols synthesized with neopentyl glycol includes but is not limited to one or more of PCDL1000, AN-1000, and AN-2000.
  • the isocyanate is diphenylmethane diisocyanate (MDI-100), carbodiimide-modified diphenylmethane diisocyanate and mixtures thereof (liquefied MDI), 4,4' - One or more of the mixture of diphenylmethane diisocyanate and polyphenylmethane polyisocyanate (polymeric MDI).
  • the adjuvant is a surface activity modifier.
  • the auxiliary agent is one or more of organic chromium complexes, silane coupling agents, titanate coupling agents and aluminate compound coupling agents.
  • the catalyst is at least one of triethylenediamine, bismorpholine diethyl ether, N,N-dimethylcyclohexylamine, and bis(dimethylaminoethyl) ether kind.
  • Another technical solution adopted by the present invention is: the use of the above solvent-free single-component moisture-curing polyurethane adhesive in wood bonding.
  • the moisture content of the wood is a low moisture content of 8-15%.
  • Another technical solution adopted in the present invention is: the above-mentioned preparation method of solvent-free one-component moisture-curing polyurethane adhesive: reacting isocyanate, polyether polyol and polyester polyol at 70-80° C. to prepare A polyurethane prepolymer is obtained, the temperature is lowered to 50° C. or below, a catalyst and an auxiliary agent are added, and the NCO-terminated polyurethane adhesive is prepared by stirring uniformly.
  • the NCO% content of the polyurethane prepolymer is 10%-16%.
  • the present invention has the following advantages compared with the prior art:
  • the polyol in the formula is formulated with specific polyether polyol and polyester polyol, and the prepared polyurethane adhesive is used for bonding between wood and wood, and the The combined compressive shear strength is greater than 9.7MPa.
  • the single-component moisture-curable polyurethane adhesive of the present invention is used at room temperature, and is simply coated on the surface of wood, and can be cured only by using air or moisture of wood, resulting in a bonding effect, and the construction and operation are convenient.
  • the solvent-free one-component moisture-curable polyurethane adhesive for wood provided in this example is prepared by reacting polyether polyol, polyester polyol and isocyanate to obtain prepolymer, and then adding catalyst and auxiliary agent to stir uniformly to prepare The obtained NCO-terminated polyurethane prepolymer, wherein,
  • Isocyanates are carbodiimide-modified diphenylmethane diisocyanates and their mixtures (liquefied MDI), combinations of 4,4'-diphenylmethane diisocyanate and mixtures of polyphenylmethane polyisocyanates (polymeric MDI) ;
  • the polyether polyol is a combination of polypropylene oxide ether triol, ethylene oxide and propylene oxide random copolymer polyether triol, and polytetrahydrofuran ether polyol, and the number average number of polypropylene oxide ether triol is used 330N with molecular weight of 5000 and degree of unsaturation of 0.005mmol/g; ethylene oxide and propylene oxide random copolymerization polyether triol, the molar ratio of ethylene oxide and propylene oxide is 6/4, and the number average molecular weight is 3000 AD-3300E (Asahikawa Chemical); polytetrahydrofuran ether polyol adopts PTMG-2000 with a functionality of 2 and a number average molecular weight of 2000;
  • Polyester polyol uses polycarbonate polyol PCDL1000 with functionality of 2 and number average molecular weight of 1000;
  • the catalyst is selected from triethylenediamine
  • the auxiliary uses organic chromium complex.
  • the specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
  • the polyurethane adhesive is specifically prepared by the following method:
  • polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100 ⁇ 110°C, pressure -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50°C, add polymerized MDI and liquefaction MDI, set the reaction temperature to 70-80°C, stir the reaction for 3 hours, cool down to 50°C, add catalyst and auxiliary agent, stir for 0.5 hour, detect NCO% as 10%, and discharge qualified.
  • the adhesive of this example is uniformly coated under the conditions of an air temperature of 24°C, an air humidity of 50%, and a wood moisture content of 8%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength is obtained after 48 hours. is 9.8MPa.
  • the solvent-free one-component moisture-curing polyurethane adhesive for wood provided in this example is different from Example 1 in that the polypropylene oxide ether triol in the polyether polyol adopts a number average molecular weight of 6000.
  • polyester polyol is a polyester polyol synthesized from adipic acid and neopentyl glycol with a functionality of 2 and a number average molecular weight of 1000 AN-1000 (Asahikawa Chemical)
  • the catalyst is selected from bismorpholine diethyl ether
  • the auxiliary agent is a silane coupling agent.
  • the specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
  • the polyurethane adhesive is specifically prepared by the following method:
  • polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100 ⁇ 110°C, pressure -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50°C, add polymerized MDI and liquefaction MDI, set the reaction temperature to 70-80°C, stir the reaction for 3 hours, cool down to 50°C, add catalyst and auxiliary agent, stir for 0.5 hour, detect NCO% as 12%, and discharge qualified.
  • the adhesive of this example is uniformly coated under the conditions of air temperature 24°C, air humidity 50%, and wood moisture content 10%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 10.6MPa.
  • the solvent-free one-component moisture-curing polyurethane adhesive for wood provided in this example is different from Example 2 in that: diphenylmethane diisocyanate (MDI-100) and liquefied MDI are selected as isocyanates; polyether The polytetrahydrofuran ether polyol in the polyol is PTMG-1000 with a functionality of 2 and a number average molecular weight of 1000; the polyester polyol is a polycarbonate polyol with a functionality of 2 and a number average molecular weight of 2000, PCDL2000; the catalyst is selected from N, N-dimethylcyclohexylamine; auxiliary agent adopts titanate coupling agent.
  • MDI-100 diphenylmethane diisocyanate
  • liquefied MDI are selected as isocyanates
  • polyether The polytetrahydrofuran ether polyol in the polyol is PTMG-1000 with a functionality of 2 and a number average molecular weight of
  • the specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
  • the polyurethane adhesive is specifically prepared by the following method:
  • polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100-110°C, pressure to -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50°C, add MDI-100 and Liquefy MDI, set the reaction temperature to 70-80°C, stir and react for 3 hours, cool down to 50°C, add catalyst and auxiliary agent, stir for 0.5 hours, detect NCO% as 14%, and discharge qualified.
  • the adhesive of this example is uniformly coated under the conditions of air temperature of 24 ° C, air humidity of 50%, and wood moisture content of 14%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 11.1MPa.
  • the solvent-free one-component moisture-curing polyurethane adhesive for wood provided in this example is different from Example 3 in that: the polypropylene oxide ether triol in the polyether polyol is 330N; polyester The polyol is a polyester polyol AN-2000 (Asahikawa Chemical) synthesized from adipic acid and neopentyl glycol with a functionality of 2 and a number average molecular weight of 2000; the catalyst is selected from bismorpholine diethyl ether; the auxiliary agent is aluminum Acid compound coupling agent.
  • the polypropylene oxide ether triol in the polyether polyol is 330N
  • polyester The polyol is a polyester polyol AN-2000 (Asahikawa Chemical) synthesized from adipic acid and neopentyl glycol with a functionality of 2 and a number average molecular weight of 2000
  • the catalyst is selected from bismorpholine diethyl ether
  • the auxiliary agent is aluminum Acid compound
  • the specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
  • the polyurethane adhesive is specifically prepared by the following method:
  • polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100-110°C, pressure to -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50°C, add MDI-100 and Liquefy MDI, set the reaction temperature to 70-80°C, stir and react for 3 hours, cool down to 50°C, add catalyst and auxiliary agent, stir for 0.5 hours, detect NCO% as 16%, and discharge qualified.
  • the adhesive of this example is uniformly coated under the conditions of air temperature of 24 ° C, air humidity of 50%, and wood moisture content of 15%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 12.3MPa.
  • the solvent-free one-component moisture-curing polyurethane adhesive provided in this comparative example differs from Example 4 in that AD-3300E is not used.
  • the specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
  • the polyurethane adhesive is specifically prepared by the following method:
  • polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100-110°C, pressure to -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50°C, add MDI-100 and Liquefy MDI, set the reaction temperature to 70-80°C, stir and react for 3 hours, cool down to 50°C, add catalyst and auxiliary, stir for 0.5 hours, and discharge.
  • the adhesive of this example is uniformly coated under the conditions of air temperature of 24 ° C, air humidity of 50%, and wood moisture content of 15%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 6.8MPa.
  • the solvent-free one-component moisture-curable polyurethane adhesive provided in this comparative example differs from Example 4 in that only AD-3300E is used for the polyether polyol.
  • the specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
  • the polyurethane adhesive is specifically prepared by the following method:
  • polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100-110°C, pressure to -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50°C, add MDI-100 and Liquefy MDI, set the reaction temperature to 70-80°C, stir and react for 3 hours, cool down to 50°C, add catalyst and auxiliary, stir for 0.5 hours, and discharge.
  • the adhesive of this example is uniformly coated under the conditions of air temperature of 24 ° C, air humidity of 50%, and wood moisture content of 15%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 7.9MPa.

Abstract

A solvent-free single-component moisture-curing polyurethane adhesive for use on wood and a preparation method therefor. Calculating by mass percentage, the raw material formula of the polyurethane adhesive comprises the following components: an isocyanic acid 45.6-58%, a polyether polyol 18.7-30%, a polyester polyol 20-27%, a catalyst 0.1-0.3%, and an auxiliary 0.1-0.3%. The polyether polyol is a mixture of a propylene oxide polyether polyol having a functionality of 3 and a number average molecular weight of 5,000-6,000, a random copolymer polyether polyol of ethylene oxide and propylene oxide, and a polytetrahydrofuran ether polyol having a functionality of 2 and a number average molecular weight of 1,000-2,000. The polyol in the polyurethane adhesive utilizes a specific combination of a polyether polyol and a polyester polyol. The polyurethane adhesive obtained by the present preparation is used as an adhesive between pieces of wood, has a high compression shear strength, and allows for wood durability.

Description

一种适用于木材的无溶剂单组分湿气固化聚氨酯粘合剂及其制备方法A kind of solvent-free one-component moisture-curing polyurethane adhesive suitable for wood and preparation method thereof 技术领域technical field
本发明属于胶粘剂技术领域，具体涉及一种适用于木材的无溶剂单组分湿气固化聚氨酯粘合剂及其制备方法。The invention belongs to the technical field of adhesives, and in particular relates to a solvent-free single-component moisture-curing polyurethane adhesive suitable for wood and a preparation method thereof.
背景技术Background technique
随着世界性森林资源急剧减少和我国天然林资源保护工程的实施，小木材拼大板就要求胶黏剂粘接强度和耐久耐候等性能优于木材本身。胶黏剂用量的多少，已成为衡量木材工业技术发展水平的标志。With the sharp reduction of the world's forest resources and the implementation of my country's natural forest resources protection project, small wood panels require that the bonding strength and durability of the adhesive are better than those of the wood itself. The amount of adhesive used has become a symbol to measure the technical development level of the wood industry.
作为粘合剂在木材工业方面的应用，主要是在层积板材、指接、端接等方面。在合成粘合剂中，用作木材粘合剂的合成树脂一般是指热固型树脂。传统的木材粘合剂有间苯二酚-甲醛树脂、苯酚间苯二酚-甲醛树脂、三聚氰胺-尿素-甲醛等以甲醛为主要原料的胶粘剂，然而此类粘合剂存在固化时收缩率较大，胶层易产生裂缝，耐水性差；含有游离甲醛，使用期间会向周围散发甲醛气体而污染环境，接触后会引起多发性疾病如气管炎、哮喘、皮炎，长时间接触甚至会患恶性肿瘤。As an adhesive in the wood industry, it is mainly used in laminated boards, finger joints, terminations, etc. Among synthetic adhesives, synthetic resins used as wood adhesives generally refer to thermosetting resins. Traditional wood adhesives include resorcinol-formaldehyde resin, phenol resorcinol-formaldehyde resin, melamine-urea-formaldehyde and other adhesives with formaldehyde as the main raw material. However, such adhesives have higher shrinkage rates during curing. Large, the adhesive layer is prone to cracks and has poor water resistance; it contains free formaldehyde, which will emit formaldehyde gas to the surrounding environment during use and pollute the environment. After contact, it will cause multiple diseases such as bronchitis, asthma, dermatitis, and even malignant tumors after prolonged contact. .
随着人们生活水平的提高，环保问题日益成为各行各业的重中之重的问题，因此，木材加工行业开始将目光投向新型的环保粘合剂，如聚氨酯粘合剂，聚氨酯粘合剂既不会释放有毒物质，具有固化速度快、固化物颜色较浅、胶接强度高、结构设计灵活、生产施工方便的特点。按照使用方法来分，聚氨酯粘合剂可以分为单组份和双组份两种。单组份聚氨酯粘合剂较双组份聚氨酯粘合剂的一个明显的优点是使用时不需要进行化学计算，也不需要添加其他的交联剂，只需利用空气或基材表面的水分就可以固化，产生粘结作用，给施工带来了极大的方便，所以应用比较广泛。With the improvement of people's living standards, environmental protection issues have increasingly become the top priority of all walks of life. Therefore, the wood processing industry has begun to turn its attention to new environmentally friendly adhesives, such as polyurethane adhesives. Polyurethane adhesives both It will not release toxic substances, and has the characteristics of fast curing speed, lighter color of cured product, high bonding strength, flexible structure design and convenient production and construction. According to the method of use, polyurethane adhesives can be divided into one-component and two-component. One obvious advantage of one-component polyurethane adhesives over two-component polyurethane adhesives is that there is no need to perform chemical calculations or add other cross-linking agents when using them. It can be cured to produce bonding effect, which brings great convenience to construction, so it is widely used.
工业使用的单组分湿气固化聚氨酯粘合剂是液态的，在室温下使用，能和许多非木基材如纺织纤维、金属、塑料、橡胶等粘接。如中国专利CN101319129A公开的单组分无溶剂湿气固化聚氨酯胶粘剂及其制造方法，该聚氨酯胶粘剂包括多元醇、二异氰酸酯、催化剂、偶联剂和扩链剂，按重量百分比，多元醇40～70％、二异氰酸酯30～55％、扩链剂0～5％、催化剂0.1～0.5％和偶联剂0～1％，该聚氨酯胶粘剂通过空气中及材料中 的湿气固化，其针对的是铝材与铝材之间的粘结，但由于木材不管是含水率还是本身材质与铝材都不同，针对铝材可以粘合的胶粘剂用于木材上并不一定适用，且从该专利实施的原料中可以看出，所使用的只是普通的聚酯多元醇和聚醚多元醇，并不一定能够解决木材粘合剂所需要的初粘力问题。The one-component moisture-curable polyurethane adhesive used in industry is liquid, used at room temperature, and can bond to many non-wood substrates such as textile fibers, metals, plastics, rubber, etc. As disclosed in Chinese patent CN101319129A, the one-component solvent-free moisture-curing polyurethane adhesive and its manufacturing method, the polyurethane adhesive includes polyol, diisocyanate, catalyst, coupling agent and chain extender, and by weight percentage, polyol 40-70 %, diisocyanate 30-55%, chain extender 0-5%, catalyst 0.1-0.5% and coupling agent 0-1%, the polyurethane adhesive is cured by the moisture in the air and the material, it is aimed at aluminum However, since the moisture content of wood or its own material is different from that of aluminum, the adhesive that can be bonded to aluminum is not necessarily suitable for use on wood, and the raw materials implemented from this patent are It can be seen from the above that only ordinary polyester polyols and polyether polyols are used, which may not necessarily solve the problem of initial tack required by wood adhesives.
发明内容SUMMARY OF THE INVENTION
发明目的：为了解决现有技术存在的问题，本发明提供一种适用于木材的无溶剂单组分湿气固化聚氨酯粘合剂及其制备方法。Purpose of the invention: In order to solve the problems existing in the prior art, the present invention provides a solvent-free one-component moisture-curing polyurethane adhesive suitable for wood and a preparation method thereof.
技术方案：为了解决上述技术问题，本发明采用如下技术方案：Technical scheme: in order to solve the above-mentioned technical problems, the present invention adopts the following technical scheme:
一种无溶剂单组分湿气固化聚氨酯粘合剂，按质量百分含量计，所述聚氨酯粘合剂的原料配方包括以下组分：A solvent-free one-component moisture-curing polyurethane adhesive, in terms of mass percentage, the raw material formula of the polyurethane adhesive includes the following components:
Figure PCTCN2021100815-appb-000001
Figure PCTCN2021100815-appb-000001
根据本发明的一些实施方面，所述聚醚多元醇为官能度为3、数均分子量5000～6000的聚环氧丙烷醚多元醇，环氧乙烷和环氧丙烷的无规共聚聚醚多元醇，官能度为2、数均分子量为1000～2000的聚四氢呋喃醚多元醇的混合物。According to some implementation aspects of the present invention, the polyether polyol is a polypropylene oxide ether polyol with a functionality of 3 and a number average molecular weight of 5000-6000, a random copolymer of ethylene oxide and propylene oxide. Alcohol, a mixture of polytetrahydrofuran ether polyols with a functionality of 2 and a number average molecular weight of 1000-2000.
优选地，所述聚醚多元醇为所述环氧乙烷和环氧丙烷的无规共聚聚醚多元醇、所述聚环氧丙烷醚多元醇、所述聚四氢呋喃醚多元醇按质量比1:0.5～1：0.5～3的组合。Preferably, the polyether polyol is the random copolymerization polyether polyol of ethylene oxide and propylene oxide, the polypropylene oxide ether polyol, and the polytetrahydrofuran ether polyol in a mass ratio of 1 : 0.5 to 1: A combination of 0.5 to 3.
根据本发明的一些实施例，所述环氧乙烷和环氧丙烷的无规共聚聚醚多元醇的数均分子量为2500～3500，环氧乙烷与环氧丙烷的摩尔比为6:3～5，官能度为3。优选地，所述环氧乙烷和环氧丙烷的无规共聚聚醚多元醇为数均分子量为3000，官能度为3，环氧乙烷与环氧丙烷的摩尔比为6:4的聚醚三元醇。具体如AD-3300E。According to some embodiments of the present invention, the number average molecular weight of the random copolymerized polyether polyol of ethylene oxide and propylene oxide is 2500-3500, and the molar ratio of ethylene oxide and propylene oxide is 6:3 ~5 with a functionality of 3. Preferably, the random copolymerized polyether polyol of ethylene oxide and propylene oxide is a polyether with a number average molecular weight of 3000, a functionality of 3, and a molar ratio of ethylene oxide to propylene oxide of 6:4 Triol. Specifically such as AD-3300E.
根据本发明的一些实施例，所述聚环氧丙烷醚多元醇的数均分子量为5000、不饱和度0.005mmol/g的聚环氧丙烷醚多元醇，数均分子量为6000、不饱和度0.005mmol/g的聚环氧丙烷醚多元醇中的一种或几种。具体包括但不限于330N、EP-3600中的一种或几种。According to some embodiments of the present invention, the polypropylene oxide ether polyol has a number-average molecular weight of 5000 and a degree of unsaturation of 0.005 mmol/g, a number-average molecular weight of 6000 and a degree of unsaturation of 0.005. One or more of mmol/g polypropylene oxide ether polyols. Specifically, it includes but is not limited to one or more of 330N and EP-3600.
根据本发明的一些实施方面，所述聚酯多元醇为官能度为2、数均分子量为 1000～2000的聚碳酸酯多元醇，官能度为2、数均分子量为1000～2000的由己二酸和新戊二醇合成的聚己二酸-酯多元醇中的一种或几种。具体包括但不限于PCDL1000、AN-1000、AN-2000中的一种或几种。According to some implementation aspects of the present invention, the polyester polyol is a polycarbonate polyol having a functionality of 2 and a number-average molecular weight of 1000-2000, and adipic acid having a functionality of 2 and a number-average molecular weight of 1000-2000 One or more of the polyadipate-ester polyols synthesized with neopentyl glycol. Specifically, it includes but is not limited to one or more of PCDL1000, AN-1000, and AN-2000.
根据本发明的一些实施方面，所述异氰酸酯为二苯基甲烷二异氰酸酯(MDI-100)、碳化二亚胺改性的二苯基甲烷二异氰酸酯以及它们的混合物(液化MDI)、4,4’-二苯基甲烷二异氰酸酯和多苯基甲烷多异氰酸酯的混合物(聚合MDI)中的一种或几种。According to some implementation aspects of the present invention, the isocyanate is diphenylmethane diisocyanate (MDI-100), carbodiimide-modified diphenylmethane diisocyanate and mixtures thereof (liquefied MDI), 4,4' - One or more of the mixture of diphenylmethane diisocyanate and polyphenylmethane polyisocyanate (polymeric MDI).
根据本发明的一些实施方面，所述助剂为表面活性改进剂。优选地，所述助剂为有机铬络合物、硅烷类偶联剂、钛酸酯类偶联剂和铝酸化合物偶联剂中的一种或几种。According to some implementing aspects of the present invention, the adjuvant is a surface activity modifier. Preferably, the auxiliary agent is one or more of organic chromium complexes, silane coupling agents, titanate coupling agents and aluminate compound coupling agents.
根据本发明的一些实施方面，所述催化剂为三乙烯二胺、双吗啉二乙基醚、N,N-二甲基环己胺、双(二甲胺基乙基)醚中的至少一种。According to some implementation aspects of the present invention, the catalyst is at least one of triethylenediamine, bismorpholine diethyl ether, N,N-dimethylcyclohexylamine, and bis(dimethylaminoethyl) ether kind.
本发明采取的又一技术方案为：上述无溶剂单组分湿气固化聚氨酯粘合剂在木材粘结上的用途。Another technical solution adopted by the present invention is: the use of the above solvent-free single-component moisture-curing polyurethane adhesive in wood bonding.
进一步地，所述木材的含水率为8～15％的低含水率。Further, the moisture content of the wood is a low moisture content of 8-15%.
本发明采取的另一技术方案为：上述所述的无溶剂单组分湿气固化聚氨酯粘合剂的制备方法：使异氰酸酯、聚醚多元醇和聚酯多元醇在70～80℃下反应，制得聚氨酯预聚体，降温至50℃或50℃以下，加入催化剂和助剂，搅拌均匀制得NCO封端的聚氨酯粘合剂。Another technical solution adopted in the present invention is: the above-mentioned preparation method of solvent-free one-component moisture-curing polyurethane adhesive: reacting isocyanate, polyether polyol and polyester polyol at 70-80° C. to prepare A polyurethane prepolymer is obtained, the temperature is lowered to 50° C. or below, a catalyst and an auxiliary agent are added, and the NCO-terminated polyurethane adhesive is prepared by stirring uniformly.
根据本发明的一些实施方面，所述聚氨酯预聚体的NCO％含量为10％～16％。According to some implementation aspects of the present invention, the NCO% content of the polyurethane prepolymer is 10%-16%.
由于上述技术方案运用，本发明与现有技术相比具有下列优点：Due to the application of the above-mentioned technical solutions, the present invention has the following advantages compared with the prior art:
本发明的单组分湿气固化聚氨酯粘合剂，配方中的多元醇采用特定聚醚多元醇和聚酯多元醇配合，制备得到的聚氨酯粘合剂用于木材与木材之间的粘合，贴合后压剪强度大于9.7MPa。且本发明的单组分湿气固化聚氨酯粘合剂在室温下使用，简单涂胶于木材表面，并只需利用空气或木材的水分就可以固化，产生粘结作用，施工操作方便。In the one-component moisture-curable polyurethane adhesive of the present invention, the polyol in the formula is formulated with specific polyether polyol and polyester polyol, and the prepared polyurethane adhesive is used for bonding between wood and wood, and the The combined compressive shear strength is greater than 9.7MPa. In addition, the single-component moisture-curable polyurethane adhesive of the present invention is used at room temperature, and is simply coated on the surface of wood, and can be cured only by using air or moisture of wood, resulting in a bonding effect, and the construction and operation are convenient.
具体实施方式detailed description
不需进一步详细说明，认为本领域熟练技术人员借助前面的描述，可以最大程度的利用本发明。因此，下面提供的实施例仅仅是进一步阐明本发明而已，并不意味着以任何方式限制本发明范围。Without further elaboration, it is believed that one skilled in the art can, with the help of the preceding description, utilize the present invention to its fullest extent. Accordingly, the examples provided below are merely to further illustrate the present invention and are not intended to limit the scope of the present invention in any way.
实施例1Example 1
本实施例提供的适用于木材的无溶剂单组分湿气固化聚氨酯粘合剂，其由聚醚多元醇、聚酯多元醇和异氰酸酯反应制得预聚体，然后加入催化剂和助剂搅拌均匀制得的NCO封端的聚氨酯预聚体，其中，The solvent-free one-component moisture-curable polyurethane adhesive for wood provided in this example is prepared by reacting polyether polyol, polyester polyol and isocyanate to obtain prepolymer, and then adding catalyst and auxiliary agent to stir uniformly to prepare The obtained NCO-terminated polyurethane prepolymer, wherein,
异氰酸酯为碳化二亚胺改性的二苯基甲烷二异氰酸酯以及它们的混合物(液化MDI)、4，4’-二苯基甲烷二异氰酸酯和多苯基甲烷多异氰酸酯的混合物(聚合MDI)的组合；Isocyanates are carbodiimide-modified diphenylmethane diisocyanates and their mixtures (liquefied MDI), combinations of 4,4'-diphenylmethane diisocyanate and mixtures of polyphenylmethane polyisocyanates (polymeric MDI) ;
聚醚多元醇为聚环氧丙烷醚三元醇、环氧乙烷和环氧丙烷无规共聚聚醚三元醇、聚四氢呋喃醚多元醇的组合，聚环氧丙烷醚三元醇使用数均分子量5000、不饱和度0.005mmol/g的330N；环氧乙烷和环氧丙烷无规共聚聚醚三元醇采用环氧乙烷和环氧丙烷的摩尔比为6/4，数均分子量3000的AD-3300E(旭川化学)；聚四氢呋喃醚多元醇采用官能度2、数均分子量2000的PTMG-2000；The polyether polyol is a combination of polypropylene oxide ether triol, ethylene oxide and propylene oxide random copolymer polyether triol, and polytetrahydrofuran ether polyol, and the number average number of polypropylene oxide ether triol is used 330N with molecular weight of 5000 and degree of unsaturation of 0.005mmol/g; ethylene oxide and propylene oxide random copolymerization polyether triol, the molar ratio of ethylene oxide and propylene oxide is 6/4, and the number average molecular weight is 3000 AD-3300E (Asahikawa Chemical); polytetrahydrofuran ether polyol adopts PTMG-2000 with a functionality of 2 and a number average molecular weight of 2000;
聚酯多元醇采用官能度为2、数均分子量为1000的聚碳酸酯多元醇PCDL1000；Polyester polyol uses polycarbonate polyol PCDL1000 with functionality of 2 and number average molecular weight of 1000;
催化剂采用选自三乙烯二胺；The catalyst is selected from triethylenediamine;
助剂采用有机铬络合物。The auxiliary uses organic chromium complex.
本例的聚氨酯粘合剂的具体的原料配方如下(以质量百分数计)：The specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
Figure PCTCN2021100815-appb-000002
Figure PCTCN2021100815-appb-000002
聚氨酯粘合剂具体通过以下方法制备得到：The polyurethane adhesive is specifically prepared by the following method:
按照配方，在反应釜中加入聚醚多元醇和聚酯多元醇，设置反应温度100～110℃、压强-0.095MPa，混合均匀并脱水至水分小于0.05％，降温至50℃，加入聚合MDI和液化MDI，设置反应温度70-80℃，搅拌反应3小时，降温到50℃，加入催化剂和助剂，搅拌0.5小时，检测NCO％为10％，合格出料。According to the formula, add polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100～110℃, pressure -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50℃, add polymerized MDI and liquefaction MDI, set the reaction temperature to 70-80°C, stir the reaction for 3 hours, cool down to 50°C, add catalyst and auxiliary agent, stir for 0.5 hour, detect NCO% as 10%, and discharge qualified.
将本例的粘合剂在空气温度24℃、空气湿度50％、木材含水率为8％的条件下均 匀涂胶，实施贴合保压7-10kg/平方厘米，最终48小时后压剪强度为9.8MPa。The adhesive of this example is uniformly coated under the conditions of an air temperature of 24°C, an air humidity of 50%, and a wood moisture content of 8%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength is obtained after 48 hours. is 9.8MPa.
实施例2Example 2
本实施例提供的适用于木材的无溶剂单组分湿气固化聚氨酯粘合剂与实施例1的不同之处在于：聚醚多元醇中的聚环氧丙烷醚三元醇采用数均分子量6000、不饱和度0.005mmol/g的聚环氧丙烷醚三元醇EP-3600；聚酯多元醇采用官能度2、数均分子量为1000的由己二酸、新戊二醇合成的聚酯多元醇AN-1000(旭川化学)；催化剂选自双吗啉二乙基醚；助剂采用硅烷类偶联剂。The solvent-free one-component moisture-curing polyurethane adhesive for wood provided in this example is different from Example 1 in that the polypropylene oxide ether triol in the polyether polyol adopts a number average molecular weight of 6000. , Polypropylene oxide ether triol EP-3600 with an unsaturation degree of 0.005mmol/g; polyester polyol is a polyester polyol synthesized from adipic acid and neopentyl glycol with a functionality of 2 and a number average molecular weight of 1000 AN-1000 (Asahikawa Chemical); the catalyst is selected from bismorpholine diethyl ether; the auxiliary agent is a silane coupling agent.
本例的聚氨酯粘合剂的具体的原料配方如下(以质量百分数计)：The specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
Figure PCTCN2021100815-appb-000003
Figure PCTCN2021100815-appb-000003
聚氨酯粘合剂具体通过以下方法制备得到：The polyurethane adhesive is specifically prepared by the following method:
按照配方，在反应釜中加入聚醚多元醇和聚酯多元醇，设置反应温度100～110℃、压强-0.095MPa，混合均匀并脱水至水分小于0.05％，降温至50℃，加入聚合MDI和液化MDI，设置反应温度70-80℃，搅拌反应3小时，降温到50℃，加入催化剂和助剂，搅拌0.5小时，检测NCO％为12％，合格出料。According to the formula, add polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100～110℃, pressure -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50℃, add polymerized MDI and liquefaction MDI, set the reaction temperature to 70-80°C, stir the reaction for 3 hours, cool down to 50°C, add catalyst and auxiliary agent, stir for 0.5 hour, detect NCO% as 12%, and discharge qualified.
将本例的粘合剂在空气温度24℃、空气湿度50％、木材含水率为10％的条件下均匀涂胶，实施贴合保压7-10kg/平方厘米，最终48小时后压剪强度为10.6MPa。The adhesive of this example is uniformly coated under the conditions of air temperature 24°C, air humidity 50%, and wood moisture content 10%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 10.6MPa.
实施例3Example 3
本实施例提供的适用于木材的无溶剂单组分湿气固化聚氨酯粘合剂与实施例2的不同之处在于：异氰酸酯选用二苯基甲烷二异氰酸酯(MDI-100)和液化MDI；聚醚多元醇中的聚四氢呋喃醚多元醇采用官能度2、数均分子量1000的PTMG-1000；聚酯多元醇采用官能度2、数均分子量为2000的聚碳酸酯多元醇PCDL2000；催化剂选自N,N-二甲基环己胺；助剂采用钛酸酯类偶联剂。The solvent-free one-component moisture-curing polyurethane adhesive for wood provided in this example is different from Example 2 in that: diphenylmethane diisocyanate (MDI-100) and liquefied MDI are selected as isocyanates; polyether The polytetrahydrofuran ether polyol in the polyol is PTMG-1000 with a functionality of 2 and a number average molecular weight of 1000; the polyester polyol is a polycarbonate polyol with a functionality of 2 and a number average molecular weight of 2000, PCDL2000; the catalyst is selected from N, N-dimethylcyclohexylamine; auxiliary agent adopts titanate coupling agent.
本例的聚氨酯粘合剂的具体的原料配方如下(以质量百分数计)：The specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
Figure PCTCN2021100815-appb-000004
Figure PCTCN2021100815-appb-000004
聚氨酯粘合剂具体通过以下方法制备得到：The polyurethane adhesive is specifically prepared by the following method:
按照配方，在反应釜中加入聚醚多元醇和聚酯多元醇，设置反应温度100～110℃、压强-0.095MPa，混合均匀并脱水至水分小于0.05％，降温至50℃，加入MDI-100和液化MDI，设置反应温度70-80℃，搅拌反应3小时，降温到50℃，加入催化剂和助剂，搅拌0.5小时，检测NCO％为14％，合格出料。According to the recipe, add polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100-110℃, pressure to -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50℃, add MDI-100 and Liquefy MDI, set the reaction temperature to 70-80°C, stir and react for 3 hours, cool down to 50°C, add catalyst and auxiliary agent, stir for 0.5 hours, detect NCO% as 14%, and discharge qualified.
将本例的粘合剂在空气温度24℃、空气湿度50％、木材含水率为14％的条件下均匀涂胶，实施贴合保压7-10kg/平方厘米，最终48小时后压剪强度为11.1MPa。The adhesive of this example is uniformly coated under the conditions of air temperature of 24 ° C, air humidity of 50%, and wood moisture content of 14%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 11.1MPa.
实施例4Example 4
本实施例提供的适用于木材的无溶剂单组分湿气固化聚氨酯粘合剂与实施例3的不同之处在于：聚醚多元醇中的聚环氧丙烷醚三元醇采用330N；聚酯多元醇采用官能度2、数均分子量为2000的由己二酸、新戊二醇合成的聚酯多元醇AN-2000(旭川化学)；催化剂选自双吗啉二乙基醚；助剂采用铝酸化合物偶联剂。The solvent-free one-component moisture-curing polyurethane adhesive for wood provided in this example is different from Example 3 in that: the polypropylene oxide ether triol in the polyether polyol is 330N; polyester The polyol is a polyester polyol AN-2000 (Asahikawa Chemical) synthesized from adipic acid and neopentyl glycol with a functionality of 2 and a number average molecular weight of 2000; the catalyst is selected from bismorpholine diethyl ether; the auxiliary agent is aluminum Acid compound coupling agent.
本例的聚氨酯粘合剂的具体的原料配方如下(以质量百分数计)：The specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
Figure PCTCN2021100815-appb-000005
Figure PCTCN2021100815-appb-000005
Figure PCTCN2021100815-appb-000006
Figure PCTCN2021100815-appb-000006
聚氨酯粘合剂具体通过以下方法制备得到：The polyurethane adhesive is specifically prepared by the following method:
按照配方，在反应釜中加入聚醚多元醇和聚酯多元醇，设置反应温度100～110℃、压强-0.095MPa，混合均匀并脱水至水分小于0.05％，降温至50℃，加入MDI-100和液化MDI，设置反应温度70-80℃，搅拌反应3小时，降温到50℃，加入催化剂和助剂，搅拌0.5小时，检测NCO％为16％，合格出料。According to the recipe, add polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100-110℃, pressure to -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50℃, add MDI-100 and Liquefy MDI, set the reaction temperature to 70-80°C, stir and react for 3 hours, cool down to 50°C, add catalyst and auxiliary agent, stir for 0.5 hours, detect NCO% as 16%, and discharge qualified.
将本例的粘合剂在空气温度24℃、空气湿度50％、木材含水率为15％的条件下均匀涂胶，实施贴合保压7-10kg/平方厘米，最终48小时后压剪强度为12.3MPa。The adhesive of this example is uniformly coated under the conditions of air temperature of 24 ° C, air humidity of 50%, and wood moisture content of 15%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 12.3MPa.
对比例1Comparative Example 1
本对比例提供的无溶剂单组分湿气固化聚氨酯粘合剂，与实施例4的不同之处在于：不采用AD-3300E。The solvent-free one-component moisture-curing polyurethane adhesive provided in this comparative example differs from Example 4 in that AD-3300E is not used.
本例的聚氨酯粘合剂的具体的原料配方如下(以质量百分数计)：The specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
Figure PCTCN2021100815-appb-000007
Figure PCTCN2021100815-appb-000007
聚氨酯粘合剂具体通过以下方法制备得到：The polyurethane adhesive is specifically prepared by the following method:
按照配方，在反应釜中加入聚醚多元醇和聚酯多元醇，设置反应温度100～110℃、压强-0.095MPa，混合均匀并脱水至水分小于0.05％，降温至50℃，加入MDI-100和液化MDI，设置反应温度70-80℃，搅拌反应3小时，降温到50℃，加入催化剂和助剂，搅拌0.5小时，出料。According to the recipe, add polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100-110℃, pressure to -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50℃, add MDI-100 and Liquefy MDI, set the reaction temperature to 70-80°C, stir and react for 3 hours, cool down to 50°C, add catalyst and auxiliary, stir for 0.5 hours, and discharge.
将本例的粘合剂在空气温度24℃、空气湿度50％、木材含水率为15％的条件下均匀涂胶，实施贴合保压7-10kg/平方厘米，最终48小时后压剪强度为6.8MPa。The adhesive of this example is uniformly coated under the conditions of air temperature of 24 ° C, air humidity of 50%, and wood moisture content of 15%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 6.8MPa.
对比例2Comparative Example 2
本对比例提供的无溶剂单组分湿气固化聚氨酯粘合剂，与实施例4的不同之处在于：聚醚多元醇仅使用AD-3300E。The solvent-free one-component moisture-curable polyurethane adhesive provided in this comparative example differs from Example 4 in that only AD-3300E is used for the polyether polyol.
本例的聚氨酯粘合剂的具体的原料配方如下(以质量百分数计)：The specific raw material formula of the polyurethane adhesive of this example is as follows (in mass percent):
Figure PCTCN2021100815-appb-000008
Figure PCTCN2021100815-appb-000008
聚氨酯粘合剂具体通过以下方法制备得到：The polyurethane adhesive is specifically prepared by the following method:
按照配方，在反应釜中加入聚醚多元醇和聚酯多元醇，设置反应温度100～110℃、压强-0.095MPa，混合均匀并脱水至水分小于0.05％，降温至50℃，加入MDI-100和液化MDI，设置反应温度70-80℃，搅拌反应3小时，降温到50℃，加入催化剂和助剂，搅拌0.5小时，出料。According to the recipe, add polyether polyol and polyester polyol to the reaction kettle, set the reaction temperature to 100-110℃, pressure to -0.095MPa, mix well and dehydrate to less than 0.05% moisture, cool down to 50℃, add MDI-100 and Liquefy MDI, set the reaction temperature to 70-80°C, stir and react for 3 hours, cool down to 50°C, add catalyst and auxiliary, stir for 0.5 hours, and discharge.
将本例的粘合剂在空气温度24℃、空气湿度50％、木材含水率为15％的条件下均匀涂胶，实施贴合保压7-10kg/平方厘米，最终48小时后压剪强度为7.9MPa。The adhesive of this example is uniformly coated under the conditions of air temperature of 24 ° C, air humidity of 50%, and wood moisture content of 15%, and the bonding pressure is 7-10kg/square centimeter, and the final compressive shear strength after 48 hours is 7.9MPa.
上述测试中，压剪强度参考GBT 17517-1998标准测试。In the above test, the compressive shear strength is tested with reference to the GBT 17517-1998 standard.
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only intended to illustrate the technical concept and characteristics of the present invention, and the purpose thereof is to enable those who are familiar with the art to understand the content of the present invention and implement them accordingly, and cannot limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included within the protection scope of the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints of ranges and any values disclosed herein are not limited to the precise ranges or values, which are to be understood to encompass values proximate to those ranges or values. For ranges of values, the endpoints of each range, the endpoints of each range and the individual point values, and the individual point values can be combined with each other to yield one or more new ranges of values that Ranges should be considered as specifically disclosed herein.

Claims (15)

  1. 一种无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于，按质量百分含量计，所述聚氨酯粘合剂的原料配方包括以下组分：A solvent-free one-component moisture-curing polyurethane adhesive, characterized in that, in terms of mass percentage, the raw material formula of the polyurethane adhesive comprises the following components:
    Figure PCTCN2021100815-appb-100001
    Figure PCTCN2021100815-appb-100001
    所述聚醚多元醇为所述环氧乙烷和环氧丙烷的无规共聚聚醚多元醇、所述聚环氧丙烷醚多元醇、所述聚四氢呋喃醚多元醇按质量比1:0.5～1：0.5～3的组合；The polyether polyol is the random copolymerization polyether polyol of ethylene oxide and propylene oxide, the polypropylene oxide ether polyol, and the polytetrahydrofuran ether polyol in a mass ratio of 1:0.5～ 1: A combination of 0.5 to 3;
    所述环氧乙烷和环氧丙烷的无规共聚聚醚多元醇的数均分子量为2500～3500，环氧乙烷与环氧丙烷的摩尔比为6:3～5，官能度为3；The number-average molecular weight of the random copolymerized polyether polyol of ethylene oxide and propylene oxide is 2500-3500, the molar ratio of ethylene oxide and propylene oxide is 6:3-5, and the functionality is 3;
    所述聚环氧丙烷醚多元醇为数均分子量为5000、不饱和度0.005mmol/g的聚环氧丙烷醚多元醇，数均分子量为6000、不饱和度0.005mmol/g的聚环氧丙烷醚多元醇中的一种或几种；The polypropylene oxide ether polyol is a polypropylene oxide ether polyol with a number average molecular weight of 5000 and an unsaturation degree of 0.005mmol/g, and a number average molecular weight of 6000 and an unsaturation degree of 0.005mmol/g. Polypropylene oxide ether One or more of polyols;
    所述聚酯多元醇为官能度为2、数均分子量为1000～2000的聚碳酸酯多元醇，官能度为2、数均分子量为1000～2000的由己二酸和新戊二醇合成的聚酯多元醇中的一种或几种；The polyester polyol is a polycarbonate polyol with a functionality of 2 and a number-average molecular weight of 1000-2000, and a polymer with a functionality of 2 and a number-average molecular weight of 1000-2000 synthesized from adipic acid and neopentyl glycol. One or more of ester polyols;
    所述异氰酸酯为二苯基甲烷二异氰酸酯、碳化二亚胺改性的二苯基甲烷二异氰酸酯以及它们的混合物、4,4’-二苯基甲烷二异氰酸酯和多苯基甲烷多异氰酸酯的混合物中的一种或几种；The isocyanate is diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate and mixtures thereof, 4,4'-diphenylmethane diisocyanate and mixtures of polyphenylmethane polyisocyanates one or more of;
    所述助剂为有机铬络合物、硅烷类偶联剂、钛酸酯类偶联剂、铝酸化合物偶联剂中的一种或几种。The auxiliary agent is one or more of an organic chromium complex, a silane type coupling agent, a titanate type coupling agent, and an aluminate compound coupling agent.
  2. 一种无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于，按质量百分含量计，所述聚氨酯粘合剂的原料配方包括以下组分：A solvent-free one-component moisture-curing polyurethane adhesive, characterized in that, in terms of mass percentage, the raw material formula of the polyurethane adhesive comprises the following components:
    Figure PCTCN2021100815-appb-100002
    Figure PCTCN2021100815-appb-100002
    Figure PCTCN2021100815-appb-100003
    Figure PCTCN2021100815-appb-100003
    其中，所述聚醚多元醇为官能度为3、数均分子量5000～6000的聚环氧丙烷醚多元醇，环氧乙烷和环氧丙烷的无规共聚聚醚多元醇，官能度为2、数均分子量为1000～2000的聚四氢呋喃醚多元醇的混合物。Wherein, the polyether polyol is a polypropylene oxide ether polyol with a functionality of 3 and a number average molecular weight of 5000-6000, a random copolymerized polyether polyol of ethylene oxide and propylene oxide, and a functionality of 2 , a mixture of polytetrahydrofuran ether polyols with a number average molecular weight of 1000-2000.
  3. 根据权利要求2所述的无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于：所述聚醚多元醇为所述环氧乙烷和环氧丙烷的无规共聚聚醚多元醇、所述聚环氧丙烷醚多元醇、所述聚四氢呋喃醚多元醇按质量比1:0.5～1：0.5～3的组合。The solvent-free one-component moisture-curing polyurethane adhesive according to claim 2, wherein the polyether polyol is the random copolymerized polyether polyol of ethylene oxide and propylene oxide, A combination of the polypropylene oxide ether polyol and the polytetrahydrofuran ether polyol in a mass ratio of 1:0.5-1:0.5-3.
  4. 根据权利要求2所述的无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于：所述环氧乙烷和环氧丙烷的无规共聚聚醚多元醇的数均分子量为2500～3500，环氧乙烷与环氧丙烷的摩尔比为6:3～5，官能度为3。The solvent-free one-component moisture-curable polyurethane adhesive according to claim 2, wherein the number-average molecular weight of the random copolymerized polyether polyol of ethylene oxide and propylene oxide is 2500-3500 , the molar ratio of ethylene oxide to propylene oxide is 6:3 to 5, and the functionality is 3.
  5. 根据权利要求4所述的无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于：所述环氧乙烷和环氧丙烷的无规共聚聚醚多元醇的数均分子量为3000，官能度为3，环氧乙烷与环氧丙烷的摩尔比为6:4的聚醚三元醇。The solvent-free one-component moisture-curable polyurethane adhesive according to claim 4, wherein the number-average molecular weight of the random copolymerized polyether polyol of ethylene oxide and propylene oxide is 3000, and the functional Polyether triol with a degree of 3 and a molar ratio of ethylene oxide to propylene oxide of 6:4.
  6. 根据权利要求2所述的无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于：所述聚环氧丙烷醚多元醇为数均分子量为5000、不饱和度0.005mmol/g的聚环氧丙烷醚多元醇，数均分子量为6000、不饱和度0.005mmol/g的聚环氧丙烷醚多元醇中的一种或几种。The solvent-free one-component moisture-curable polyurethane adhesive according to claim 2, wherein the polypropylene oxide ether polyol is a polyepoxy polyol with a number average molecular weight of 5000 and an unsaturation degree of 0.005 mmol/g Propane ether polyol, one or more of polypropylene oxide ether polyols with a number-average molecular weight of 6000 and an unsaturation of 0.005 mmol/g.
  7. 根据权利要求2所述的无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于：所述聚酯多元醇为官能度为2、数均分子量为1000～2000的聚碳酸酯多元醇，官能度为2、数均分子量为1000～2000的由己二酸和新戊二醇合成的聚酯多元醇中的一种或几种。The solvent-free one-component moisture-curing polyurethane adhesive according to claim 2, wherein the polyester polyol is a polycarbonate polyol with a functionality of 2 and a number average molecular weight of 1000-2000, One or more of polyester polyols synthesized from adipic acid and neopentyl glycol with a functionality of 2 and a number average molecular weight of 1000-2000.
  8. 根据权利要求2所述的无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于：所述异氰酸酯为二苯基甲烷二异氰酸酯、碳化二亚胺改性的二苯基甲烷二异氰酸酯以及它们的混合物、4,4’-二苯基甲烷二异氰酸酯和多苯基甲烷多异氰酸酯的混合物中的一种或几种。The solvent-free one-component moisture-curing polyurethane adhesive according to claim 2, wherein the isocyanate is diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate and their One or more of the mixture of 4,4'-diphenylmethane diisocyanate and polyphenylmethane polyisocyanate.
  9. 根据权利要求2所述的无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于：所述助剂为表面活性改性剂。The solvent-free one-component moisture-curable polyurethane adhesive according to claim 2, wherein the auxiliary agent is a surface active modifier.
  10. 根据权利要求9所述的无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于：所述助剂为有机铬络合物、硅烷类偶联剂、钛酸酯类偶联剂和铝酸化合物偶联剂中的 一种或几种。The solvent-free one-component moisture-curing polyurethane adhesive according to claim 9, wherein the auxiliary agent is an organic chromium complex, a silane coupling agent, a titanate coupling agent and aluminum One or more of acid compound coupling agents.
  11. 根据权利要求2所述的无溶剂单组分湿气固化聚氨酯粘合剂，其特征在于：所述催化剂为三乙烯二胺、双吗啉二乙基醚、N,N-二甲基环己胺、双(二甲胺基乙基)醚中的至少一种。The solvent-free one-component moisture-curing polyurethane adhesive according to claim 2, wherein the catalyst is triethylenediamine, bismorpholine diethyl ether, N,N-dimethylcyclohexane At least one of amine and bis(dimethylaminoethyl) ether.
  12. 权利要求2～11中任一项权利要求所述的无溶剂单组分湿气固化聚氨酯粘合剂在木材粘结上的用途。Use of the solvent-free one-component moisture-curing polyurethane adhesive according to any one of claims 2 to 11 on wood bonding.
  13. 根据权利要求12所述的用途，其特征在于：所述木材的含水率为8～15％。The use according to claim 12, wherein the moisture content of the wood is 8-15%.
  14. 权利要求2～11中任一项权利要求所述的无溶剂单组分湿气固化聚氨酯粘合剂的制备方法，其特征在于：使异氰酸酯、聚醚多元醇和聚酯多元醇在70～80℃下反应，制得聚氨酯预聚体，降温至50℃以下，加入催化剂和助剂，搅拌均匀制得NCO封端的聚氨酯粘合剂。The preparation method of the solvent-free one-component moisture-curable polyurethane adhesive according to any one of claims 2 to 11, characterized in that: the isocyanate, polyether polyol and polyester polyol are heated at 70 to 80° C. Under the reaction, a polyurethane prepolymer is prepared, the temperature is lowered to below 50 DEG C, a catalyst and an auxiliary agent are added, and the NCO-terminated polyurethane adhesive is prepared by stirring uniformly.
  15. 根据权利要求14所述的无溶剂单组分湿气固化聚氨酯粘合剂的制备方法，其特征在于：所述聚氨酯预聚体的NCO％含量为10％～16％。The method for preparing a solvent-free one-component moisture-curable polyurethane adhesive according to claim 14, wherein the NCO% content of the polyurethane prepolymer is 10% to 16%.
PCT/CN2021/100815 2020-07-09 2021-06-18 Solvent-free single-component moisture-curing polyurethane adhesive for use on wood and preparation method therefor WO2022007613A1 (en)

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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
CN115322725A (en) * 2022-08-22 2022-11-11 哈尔滨工业大学无锡新材料研究院 Epoxy resin modified single-component moisture-cured polyurethane adhesive and preparation method thereof
CN116855221A (en) * 2023-07-12 2023-10-10 韦尔通科技股份有限公司 UV (ultraviolet) delay curing polyurethane adhesive and preparation method thereof

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CN112143435A (en) * 2020-09-25 2020-12-29 烟台斯普瑞电子材料有限公司 Hot-melt reaction type polyurethane adhesive for compounding electronic nylon film
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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
CN115322725A (en) * 2022-08-22 2022-11-11 哈尔滨工业大学无锡新材料研究院 Epoxy resin modified single-component moisture-cured polyurethane adhesive and preparation method thereof
CN116855221A (en) * 2023-07-12 2023-10-10 韦尔通科技股份有限公司 UV (ultraviolet) delay curing polyurethane adhesive and preparation method thereof

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