WO2024050653A1 - Composition et matériau adhésif combiné correspondant et panneau artificiel exempt de formaldéhyde et procédé pour sa préparation - Google Patents

Composition et matériau adhésif combiné correspondant et panneau artificiel exempt de formaldéhyde et procédé pour sa préparation Download PDF

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WO2024050653A1
WO2024050653A1 PCT/CN2022/116932 CN2022116932W WO2024050653A1 WO 2024050653 A1 WO2024050653 A1 WO 2024050653A1 CN 2022116932 W CN2022116932 W CN 2022116932W WO 2024050653 A1 WO2024050653 A1 WO 2024050653A1
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Prior art keywords
component
composition
group
adhesive composition
ethylene oxide
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PCT/CN2022/116932
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English (en)
Chinese (zh)
Inventor
王向硕
涂松
胡兵波
朱翰文
范丽颖
孙鹏
李鹏涛
尉晓丽
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万华化学集团股份有限公司
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Priority to PCT/CN2022/116932 priority Critical patent/WO2024050653A1/fr
Publication of WO2024050653A1 publication Critical patent/WO2024050653A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00—Pretreatment of moulding material
    • B27N1/02—Mixing the material with binding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing
    • B27N3/10—Moulding of mats
    • 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
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of adhesives for aldehyde-free artificial boards, and in particular relates to a composition and its adhesive combination, aldehyde-free artificial boards and a preparation method thereof.
  • Isocyanate adhesives represented by PMDI were the earliest adhesives used in panels. Because they do not contain formaldehyde and have extremely low volatility, they can greatly avoid harm to the human body caused by chemical substances during the production process.
  • the board produced by MDI adhesive is cured at high temperature to form stable chemical substances. It is an environmentally friendly adhesive board.
  • the Chinese patent with publication number CN1196374A discloses a preparation method of an adhesive for lignocellulose pressed boards.
  • the adhesive has good detachability during hot pressing and is suitable for the production of lignocellulosic pressed boards.
  • the adhesive The system is severely pre-cured, and a large amount of active ingredients in the adhesive have reacted before the board is formed, seriously affecting the improvement of board production efficiency.
  • the Chinese patent with publication number CN111958746A discloses an adhesive composition that uses polyurethane urea dispersion to improve the problem of poor initial viscosity of isocyanate adhesive in the preparation of ultra-thin high-density fiberboards, which leads to slab breakage.
  • the bonding The addition of additives has little effect on improving production efficiency and cannot solve the problem of improving fiberboard production efficiency.
  • the Chinese patent with publication number CN114181659A discloses an adhesive and its application.
  • the use of compositions including triethanolamine, diethanolamine, monoethanolamine and triethanolamine derivatives improves the production efficiency of isocyanate adhesives in the preparation of particleboards.
  • the hot pressing factor has been reduced from the conventional 6s/mm to 5s/mm; with the continuous promotion of the awareness of cost reduction and efficiency improvement, this technology can no longer meet the efficiency improvement requirements of plate companies, and there is an urgent need to further improve the production technology to obtain Lower heat pressure factor.
  • the object of the present invention is to provide a composition and an adhesive composition thereof in view of the shortcomings of the existing technology.
  • the adhesive composition can further improve the product while maintaining its excellent bonding performance and mechanical properties.
  • the production efficiency of artificial boards without formaldehyde addition for example, improving the production efficiency of hot pressing).
  • Another object of the present invention is to provide a formaldehyde-free artificial board prepared from the above-mentioned adhesive composition.
  • composition A for adhesive which composition includes A1 component and A2 component, wherein:
  • the A1 component includes metal ions and tertiary amine ethylene oxide derivatives; the metal ions are alkali metal ions; the structure of the tertiary amine ethylene oxide derivative is shown in formula (I):
  • the A2 component is a macrocyclic polyether containing multiple oxygen-methylene structural units, and its structure is as shown in formula (II):
  • n is a positive integer from 1 to 10 (for example, 2, 4, 6, 8, 9);
  • the weight percentage of component A1 is 95 to 99.99% (for example, 95.5%, 96%, 97%, 98.5%, 99%), preferably 98 to 99.99%;
  • the weight percentage of component A2 is 0.01% to 5% (for example, 0.02%, 0.04%, 0.08%, 0.1%, 0.5%, 1%, 2.5%, 4%), preferably 0.01% to 2%.
  • the C1-C18 alkylene group is selected from methylene, ethylene, n-propylene, isopropylene, n-butylene and isopropylene.
  • the C1-C18 alkyleneoxy group is selected from the group consisting of methyleneoxy, ethyleneoxy, n-propyleneoxy, isopropyleneoxy, n-butyleneoxy and isobutyleneoxy. one or more of them.
  • the aryl group mentioned in the C6-C30 arylene group can be, for example, phenyl
  • the aralkyl group mentioned in the C6-C30 aralkylene group can be, for example, benzyl. group, phenethyl group
  • the aryloxy group mentioned in the C6-C18 aryleneoxy group may be, for example, a phenoxy group.
  • R 1 , R 2 , and R 3 are the same or different, and each is independently selected from C1-C18 alkylene and C1-C18 alkyleneoxy, preferably selected from C1- C8 alkylene group, C1-C8 alkylene group.
  • the molecular weight of the tertiary amine type ethylene oxide derivative is 150-4000g/mol (for example, 180g/mol, 200g/mol, 500g/mol, 800g/mol, 1000g/mol, 2000g/mol , 3000g/mol, 3500g/mol), preferably 400 to 1500g/mol.
  • the molecular weight of the tertiary amine type ethylene oxide derivative can be determined.
  • the synthesis process of component A1 can be achieved by conventional means in the art and will not be described again here.
  • the synthesis process of component A1 can be as follows: add the initiator into a stainless steel reactor, replace the reactor with nitrogen several times, add an alkali metal compound as a catalyst, and then add ethylene oxide at 60-100°C.
  • the polymerization reaction takes 1-10 hours; after the polymerization reaction is completed, excess monomers are removed by vacuuming to obtain the A1 component.
  • the metal ion accounts for 0.1 ppm to 0.1% of the mass of the A1 component.
  • the metal ion accounts for 0.01% to 0.1% of the mass of the A1 component (for example, 0.02%, 0.04%, 0.05%, 0.06%, 0.08%).
  • the metal ion is an alkali metal ion, such as sodium ion or potassium ion.
  • the macrocyclic polyether is selected from one of dioxane, 12-crown ether-4, 15-crown ether-5, 18-crown ether-6 and 24-crown ether-8 or Various.
  • composition A as described above in an adhesive composition is provided.
  • an adhesive composition including component A and component B, wherein,
  • composition A is composition A as described above;
  • the B component is polymethylene polyphenyl polyisocyanate and/or its derivatives, and the weight percentage of NCO contained therein is preferably 29-32.8% (for example, 30%, 31%, 32%), Its functionality is preferably 2.9-3.3 (for example, 3.0, 3.1, 3.2), and its viscosity is preferably 150-350cp (for example, 180cp, 200cp, 250cp, 300cp) (under 25°C conditions).
  • the adhesive composition provided by the present invention, in some embodiments, based on the total weight of the adhesive composition, wherein:
  • the weight percentage of the A component is 10 to 30% (for example, 12%, 15%, 22%, 25%), more preferably 10 to 20%;
  • the weight percentage of the B component is 70 to 90% (for example, 72%, 76%, 82%, 85%), and more preferably 80 to 90%.
  • a formaldehyde-free artificial board prepared by using the adhesive composition as described above is provided.
  • a method for preparing aldehyde-free artificial boards using the adhesive composition as described above including the following steps:
  • the control panel raw materials can be adjusted to the required moisture content through conventional methods in the art.
  • the range of moisture content is a conventional selection and can be determined according to different needs.
  • the moisture content required when preparing the aldehyde-free artificial board may be 1 to 20 wt%, for example, 2 wt%, 4 wt%, 8 wt%, 10 wt%, 15 wt%.
  • the board-making raw materials can be conventional wood, including poplar, pine, eucalyptus, etc., which are crushed to produce wood particles and shavings, or can be wheat, rice, flax, bagasse, cotton stalks, reeds, etc. Wood pellets processed from wooden units.
  • the preparation method of board-making raw materials is a well-known technology in the industry.
  • the manufacturing process of wood fiber disclosed in Chinese patent application CN201811518932.
  • the sizing amount of the adhesive combination (based on the mass of the base material) is 10-30kg/m 3 (for example, 12kg/m 3 , 14kg/m 3 , 15kg/m 3 , 18kg/m 3 , 25kg/ m3 ).
  • the sizing method is a routine operation in the art; the mixing process can be performed in a glue mixing machine or through high-pressure injection through a discharge pipe. I won’t go into details here.
  • step S3 placing the mixture in a mold or on a carrier and paving and pre-pressing it according to a certain density or a specific assembly method are all routine operations in this field and will not be described again here. Heating methods such as microwave preheating and spray steaming can also be used in this operation process, but this is not a necessary process.
  • the suitable temperature for hot pressing when preparing the aldehyde-free artificial board is usually in the range of 100°C to 250°C, such as 120°C to 220°C, or 140°C to 210°C.
  • the suitable pressure for hot pressing to obtain the desired product size when preparing the aldehyde-free artificial board can be 10 bar to 300 bar, for example, 50 bar, 100 bar, 150 bar, 200 bar, 250 bar.
  • the time used for hot pressing when preparing the aldehyde-free artificial board will depend on the board type, thickness and density of the product to be produced.
  • non-limiting examples of the aldehyde-free artificial boards include oriented strand board (OSB), veneerable OSB, structural composite wood (SCL), fiberboard, blockboard, particleboard, plywood, and laminated veneer lumber. wait.
  • OSB oriented strand board
  • SCL structural composite wood
  • a method for preparing aldehyde-free artificial boards using the adhesive composition as described above includes the following steps:
  • S1 Use eucalyptus shavings as the base material, control the moisture content of the core layer of eucalyptus shavings at 2%-5%, and control the moisture content of the surface layer of eucalyptus shavings at 15-20%;
  • a macrocyclic polyether and a tertiary amine type ethylene oxide derivative by selecting a macrocyclic polyether and a tertiary amine type ethylene oxide derivative and using them in combination, not only can the degree of pre-curing be reduced before hot pressing, but the tertiary amine type ethylene oxide derivative can also be utilized
  • the catalytic effect of the polyether chain segment and the active tertiary amine group can build a micro-reaction zone inside the artificial board, and achieve further catalytic effects under the dual effects of interface interaction and activation. specifically:
  • the oxygen atoms in the macrocyclic polyether (such as crown ether) rings have unshared electron pairs, the ether ring is negatively charged, and at the same time, the tertiary amine group in the A1 component is positively charged, so before hot pressing Under the low temperature state, the macrocyclic polyether and the tertiary amine group limit the catalytic effect of the tertiary amine group through electrostatic attraction, thereby effectively curbing the curing catalytic reaction before hot pressing, which can reduce the transmission of the board after sizing.
  • the macrocyclic polyether and the tertiary amine group limit the catalytic effect of the tertiary amine group through electrostatic attraction, thereby effectively curbing the curing catalytic reaction before hot pressing, which can reduce the transmission of the board after sizing.
  • the degree of pre-curing caused during the paving and pre-pressing processes can also effectively reduce adhesion, clogging and other disadvantages to the production equipment, and ultimately ensure that more PMDI will participate in the subsequent hot-pressing process and affect the plate. Adhesion, thereby achieving better internal bonding strength to the board (which further ensures the excellent comprehensive mechanical properties of the board).
  • the mentioned pre-curing degree is reacted by the residual amount of isocyanate (NCO) in the glue solution PMDI.
  • reaction activity is further improved within the interface of the polyether segment, further improving the hot pressing production efficiency;
  • the macrocyclic polyether in the component can effectively limit the catalytic activity of the tertiary amine group, greatly reducing the early pre-curing reaction that may occur before hot pressing, thereby effectively reducing the
  • the pre-curing degree under the conditions can reduce the loss of glue used before hot pressing, which can ensure that more PMDI will participate in bonding the board during the hot pressing process, thereby achieving better internal bonding strength and excellent mechanics of the board. performance.
  • CW20 a mixture of multifunctional isocyanate and diphenylmethane diisocyanate, NCO content is 31.0wt%, functionality is 3.1, viscosity at 25°C is 205cp, Wanhua Chemical Group Co., Ltd.;
  • CW30 a mixture of multifunctional isocyanate and diphenylmethane diisocyanate, NCO content is 30.5wt%, functionality is 3.1, viscosity at 25°C is 225cp, Wanhua Chemical Group Co., Ltd.;
  • 9132FC Multifunctional isocyanate derivative, NCO content is 29.7wt%, functionality is 2.9, viscosity at 25°C is 350cp, Wanhua Chemical Group Co., Ltd.;
  • PM300E multifunctional isocyanate derivative, NCO content is 30.0wt%, functionality is 3.0, viscosity at 25°C is 225cp, Wanhua Chemical Group Co., Ltd.;
  • Each tertiary amine type ethylene oxide derivative in component A1 is homemade; the sources of the main raw materials in the preparation process are as follows:
  • Triethanolamine purchased from Shanghai Aladdin, CAS number: 102-71-6;
  • Triisopropanolamine purchased from Shanghai Aladdin, CAS number 122-20-3;
  • Diisopropanolamine purchased from Beijing Bailingwei, CAS number: 110-97-4;
  • Diethanol monoisopropanolamine purchased from Sigma-Aldrich, CAS number 6712-98-7;
  • Ethylene oxide purchased from Wanhua Chemical, CAS number 75-21-8;
  • Potassium hydroxide purchased from Shanghai Aladdin, CAS number: 1310-58-3;
  • Macrocyclic polyethers are all commercially available products, including:
  • Dioxane purchased from Shanghai Aladdin, CAS number 123-91-1;
  • 12-Crown ether-4 purchased from Sigma-Aldrich, CAS number is 294-93-9;
  • 15-crown ether-5 purchased from Sigma-Aldrich, CAS number is 33100-27-5;
  • 18-crown ether-6 purchased from Shanghai Aladdin, CAS number: 17455-13-9;
  • 24-Crown ether-8 was purchased from Beijing Bailingwei, CAS number is 33089-37-1.
  • the main instrument used is: Dieffenbacher continuous hot press production line.
  • the internal bonding strength, static bending strength and elastic modulus of the plate are tested by the universal testing machine AI-7000S of Gaotie Testing Instrument Co., Ltd.;
  • the 2h water absorption thickness is tested through the DZKW-C Wolin double-row four-hole stainless steel water bath;
  • each component and its content is:
  • the A1 component content is 99.99%, including sodium ions and tertiary amine ethylene oxide derivatives
  • Component A2 is dioxane with a content of 0.01%
  • component A1 The synthesis process of component A1 is: add 15.804 parts by mass of the starter triethanolamine into a stainless steel reactor, replace the reactor with nitrogen 6-8 times, and add 0.03 parts by mass of catalyst sodium hydroxide (accounting for 10% of the mass of component A1 0.03%), then add 84.166 parts by mass of ethylene oxide and perform polymerization reaction at 80-90°C for 4 hours; after the polymerization reaction is completed, excess monomers are removed by vacuuming to obtain the A1 component.
  • Component B CW20.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 50-65bar; the temperature in the third zone is 140-160°C and the pressure is 100-120bar.
  • each component and its content is:
  • the A1 component content is 99.94%, including potassium ions and tertiary amine ethylene oxide derivatives
  • Component A2 is 12-crown ether-4, content 0.06%;
  • component A1 refers to Example 1. The difference is that the starting agent used is triisopropanolamine, and its added amount is 23.658 parts by mass; the catalyst is potassium hydroxide, and its added amount is 0.01 parts by mass; The added amount of ethylene oxide is 76.332 parts by mass.
  • Component B CW30.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-215°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 44-60bar; the temperature in the third zone is 145-160°C and the pressure is 120-140bar.
  • each component and its content is:
  • the A1 component content is 96.5%, including potassium ions and tertiary amine ethylene oxide derivatives;
  • Component A2 is 15-crown ether-5, with a content of 3.50%;
  • R1 and R2 are the same, each independently is an isopropoxy group, and R3 is an ethyleneoxy group;
  • component A1 The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is diisopropanolamine, and the added amount is 23.196 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.015 parts by mass; The mass parts of ethylene oxide are 76.789 parts by mass.
  • Component B 9132FC.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-220°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 45-65bar; the temperature in the third zone is 145-160°C and the pressure is 110-120bar.
  • each component and its content is:
  • the A1 component content is 95.190%, including potassium ions and tertiary amine ethylene oxide derivatives
  • Component A2 is a mixture of dioxane and 15-crown ether-5.
  • the dioxane content is 4.70%; the 15-crown ether-5 content is 0.11%;
  • R 1 and R 2 are the same, each independently an ethyleneoxy group, and R 3 is an isopropoxy group;
  • component A1 The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is diethanol monoisopropanolamine, and the added amount is 12.861 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.045 parts by mass. parts; the mass parts of ethylene oxide are 87.094 parts by mass.
  • Component B PM300E.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 48-60bar; the temperature in the third zone is 135-155°C and the pressure is 110-125bar.
  • each component and its content is:
  • the A1 component content is 99.938%, including potassium ions and tertiary amine ethylene oxide derivatives
  • Component A2 is 18-crown ether-6, with a content of 0.062%;
  • the synthesis process of A1 is as in Example 1. The difference is that the starting agent used is 2-amino-1-butanol, and the added amount is 10.633 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.075 parts by mass. ; The mass part of ethylene oxide is 89.292 parts by mass.
  • Component B CW30.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 205-215°C, and the pressure The temperature in the second zone is 165-185°C and the pressure is 45-65bar; the temperature in the third zone is 145-160°C and the pressure is 110-120bar.
  • each component and its content is:
  • the A1 component content is 95.0%, including sodium ions and tertiary amine ethylene oxide derivatives;
  • Component A2 is 24-crown ether-8, with a content of 5.0%;
  • component A1 The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is 2-amino-2-methyl-1-propanol, and the amount added is 13.454 parts by mass; the catalyst sodium hydroxide is added The amount is 0.01 parts by mass; the mass part of ethylene oxide is 86.536 parts by mass.
  • Component B CW20.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-215°C, and the pressure The temperature in the second zone is 180-195bar; the temperature in the second zone is 165-180°C, and the pressure is 51-65bar; the temperature in the third zone is 140-160°C, and the pressure is 112-121bar.
  • each component and its content is:
  • the A1 component content is 99.10%, including potassium ions and tertiary amine ethylene oxide derivatives
  • Component A2 is a mixture of 12-crown ether-4 and 15-crown ether-5; the content of 12-crown ether-4 is 0.42%; the content of 15-crown ether-5 is 0.48%;
  • R 1 and R 2 are the same, each independently an ethyleneoxy group, and R 3 is an isopropoxy group;
  • component A1 The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is isopropanolamine, and the added amount is 5.65 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.088 parts by mass; The mass parts of oxyethane are 94.262 parts by mass.
  • Component B CW20.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 203-214°C, and the pressure The temperature in the second zone is 163-180°C and the pressure is 42-65bar; the temperature in the third zone is 145-160°C and the pressure is 110-120bar.
  • each component and its content is:
  • the A1 component content is 99.34%, including potassium ions and tertiary amine ethylene oxide derivatives;
  • Component A2 is dioxane with a content of 0.66%
  • component A1 The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is triethanolamine, and the added amount is 17.415 parts by mass; the catalyst is potassium hydroxide, and the added amount is 0.053 parts by mass; ethylene oxide The mass parts of alkane are 82.532 parts by mass.
  • Component B CW30.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 203-210°C, and the pressure The temperature in the second zone is 163-180°C and the pressure is 50-65bar; the temperature in the third zone is 140-160°C and the pressure is 105-120bar.
  • each component and its content is:
  • the A1 component content is 98.760%, including potassium ions and tertiary amine ethylene oxide derivatives;
  • Component A2 is a mixture of dioxane and 18-crown ether-6.
  • the dioxane content is 0.78% and the 18-crown ether-6 content is 0.46%;
  • component A1 The synthesis process of component A1 is as in Example 1. The difference is that the starting agent used is 2-amino-2-methyl-1-propanol, and the added amount is 15.507 parts by mass; the catalyst is potassium hydroxide. The added amount is 0.025 parts by mass; the mass part of ethylene oxide is 84.468 parts by mass.
  • Component B 9132FC.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 210-220°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 55-68bar; the temperature in the third zone is 140-160°C and the pressure is 110-118bar.
  • component A is not added
  • Component B CW20;
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 50-65bar; the temperature in the third zone is 140-160°C and the pressure is 100-120bar.
  • component A is not added
  • Component B CW30;
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C and the pressure is 180-200bar; the temperature in the second zone is 160-180°C, and the pressure is 50-65bar; the temperature in the third zone is 140-160°C, and the pressure is 100-120bar.
  • Component A only contains component A1 and does not contain component A2;
  • the A1 component content is 100%, including sodium ions and tertiary amine ethylene oxide derivatives
  • Component B CW20;
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C, and the pressure The temperature in the second zone is 160-180°C and the pressure is 50-65bar; the temperature in the third zone is 140-160°C and the pressure is 100-120bar.
  • each component and its content is:
  • the A1 component content is 92%, including sodium ions and tertiary amine ethylene oxide derivatives
  • Component A2 is dioxane with a content of 8%
  • Example 1 For the synthesis process of component A1 and the structural formula of the tertiary amine type ethylene oxide derivative in component A1, refer to Example 1.
  • Component B CW20.
  • each frame for hot pressing is divided into three zones: the temperature in the first zone is 200-210°C and the pressure is 180-200bar; the temperature in the second zone is 160-180°C, and the pressure is 50-65bar; the temperature in the third zone is 140-160°C, and the pressure is 100-120bar.
  • the hot pressing factor can be used to judge the hot pressing efficiency
  • the pre-curing degree can be used to judge the loss of glue before entering the press
  • the internal bonding strength can be used to judge the bonding strength of the board
  • static bending strength can be used to judge the bonding strength of the board
  • elastic modulus can be used to judge the bonding strength of the board
  • Thickness expansion rate can be used to assist in judging mechanical properties.
  • the lowest hot-pressure factor of the adhesive composition with added component A is Significantly reduced, indicating that the hot-pressing time is effectively reduced and the hot-pressing efficiency is significantly improved (for example, compared with Comparative Example 1, the hot-pressing factor of Example 3 is reduced by 1.2s/mm, and the hot-pressing efficiency is increased by 20%).
  • various physical and chemical factors The performance can meet the requirements of the standard, indicating that the adhesive added with component A can effectively improve the production efficiency of the board while ensuring comprehensive performance.
  • the pre-curing degree of the adhesive with the A2 component is greatly reduced, indicating that the pre-curing degree of the adhesive with the A2 component can be effectively reduced. Due to the high degree of pre-curing caused by the use of the A1 component, the minimum pre-curing degree can be reduced to close to the situation without adding the A1 component, that is, the curing agent can be prevented from reacting with the isocyanate in advance before hot pressing; in addition, the use of After the A2 component is added, the internal bonding strength is greatly increased while reducing the pre-curing degree. This shows that the A2 component effectively prevents the A1 component from pre-curing with the PMDI glue before hot pressing, making more glue The liquid participates in the subsequent hot pressing reaction, thereby forming a higher bonding strength.
  • Comparative Example 3 Compared with Examples 1-6, the adhesives of Comparative Example 3 (without using A2 component) and Comparative Example 4 cannot effectively balance the pre-curing degree and hot pressing efficiency: only adding A1 component without adding A2 component will The degree of pre-curing cannot be significantly reduced, indicating that the use of component A1 alone cannot ensure bonding strength; if the amount of component A2 added is too large, the hot-pressing factor will not be significantly reduced. Although the degree of pre-curing can be reduced, it cannot simultaneously improve the hot-pressing efficiency. .
  • the adhesives in various embodiments of the present invention can improve the hot pressing efficiency while also ensuring excellent bonding strength and mechanical properties, which benefit from the joint action of the A1 component and the A2 component.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention appartient au domaine technique des adhésifs pour des panneaux artificiels exempts de formaldéhyde et concerne en particulier une composition et un matériau adhésif combiné correspondant et un panneau artificiel exempt de formaldéhyde et un procédé pour sa préparation. Le matériau adhésif combiné comprend une composition A et une composition B, la composition A comprenant un constituant A1 et un constituant A2, le constituant A1 comprenant des ions métalliques et un dérivé d'oxyde d'éthylène de type amine tertiaire et le constituant A2 étant un polyéther macrocyclique contenant une pluralité de motifs structuraux d'oxyméthylène. Dans la présente invention, un panneau artificiel exempt de formaldéhyde est préparé à partir du matériau adhésif combiné, de telle sorte que l'efficacité de production du panneau artificiel exempt de formaldéhyde peut être encore améliorée tout en conservant de bonnes propriétés adhésives et de bonnes propriétés mécaniques.
PCT/CN2022/116932 2022-09-05 2022-09-05 Composition et matériau adhésif combiné correspondant et panneau artificiel exempt de formaldéhyde et procédé pour sa préparation WO2024050653A1 (fr)

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US4555531A (en) * 1985-01-14 1985-11-26 Basf Wyandotte Corporation Rigid polyurethane foams employing alkylene oxide adducts of alkanolamines
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WO2009124680A1 (fr) * 2008-04-10 2009-10-15 Bayer Materialscience Ag Mélanges de polyisocyanates
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CN107057051A (zh) * 2017-01-23 2017-08-18 山东诺威新材料有限公司 高活性硬泡聚醚多元醇及其制备方法
CN107674195A (zh) * 2017-08-18 2018-02-09 佳化化学（茂名）有限公司 一种聚氧化乙烯类聚合物的合成催化剂及其合成方法
CN109415479A (zh) * 2016-05-10 2019-03-01 陶氏环球技术有限责任公司 包含胺引发的多元醇的双组分无溶剂粘合剂组合物
CN114106315A (zh) * 2020-09-01 2022-03-01 万华化学集团股份有限公司 一种新型窄分布三乙醇胺嵌段聚醚的制备方法、嵌段聚醚及其应用
CN114181659A (zh) * 2021-12-17 2022-03-15 万华化学集团股份有限公司 一种胶黏剂及其应用

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555531A (en) * 1985-01-14 1985-11-26 Basf Wyandotte Corporation Rigid polyurethane foams employing alkylene oxide adducts of alkanolamines
CN101240062A (zh) * 2007-12-21 2008-08-13 王伟松 三乙醇胺嵌段聚醚的合成方法
WO2009124680A1 (fr) * 2008-04-10 2009-10-15 Bayer Materialscience Ag Mélanges de polyisocyanates
JP2017031275A (ja) * 2015-07-30 2017-02-09 パナソニックＩｐマネジメント株式会社 熱硬化性樹脂組成物の硬化方法および熱硬化性樹脂組成物
CN109415479A (zh) * 2016-05-10 2019-03-01 陶氏环球技术有限责任公司 包含胺引发的多元醇的双组分无溶剂粘合剂组合物
CN107057051A (zh) * 2017-01-23 2017-08-18 山东诺威新材料有限公司 高活性硬泡聚醚多元醇及其制备方法
CN107674195A (zh) * 2017-08-18 2018-02-09 佳化化学（茂名）有限公司 一种聚氧化乙烯类聚合物的合成催化剂及其合成方法
CN114106315A (zh) * 2020-09-01 2022-03-01 万华化学集团股份有限公司 一种新型窄分布三乙醇胺嵌段聚醚的制备方法、嵌段聚醚及其应用
CN114181659A (zh) * 2021-12-17 2022-03-15 万华化学集团股份有限公司 一种胶黏剂及其应用

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