WO2017177578A1 - 采用聚酰亚胺改性聚氨酯胶黏剂的重组木板及其制备方法 - Google Patents

采用聚酰亚胺改性聚氨酯胶黏剂的重组木板及其制备方法 Download PDF

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Publication number
WO2017177578A1
WO2017177578A1 PCT/CN2016/092776 CN2016092776W WO2017177578A1 WO 2017177578 A1 WO2017177578 A1 WO 2017177578A1 CN 2016092776 W CN2016092776 W CN 2016092776W WO 2017177578 A1 WO2017177578 A1 WO 2017177578A1
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Prior art keywords
parts
polyimide
modified polyurethane
polyurethane adhesive
board
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PCT/CN2016/092776
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English (en)
French (fr)
Inventor
孙龙祥
张恩玖
钱新民
王艳伟
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久盛地板有限公司
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Application filed by 久盛地板有限公司 filed Critical 久盛地板有限公司
Priority to KR1020177022805A priority Critical patent/KR102017033B1/ko
Priority to DE212016000047.0U priority patent/DE212016000047U1/de
Publication of WO2017177578A1 publication Critical patent/WO2017177578A1/zh

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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
    • 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
    • B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/0207—Pretreatment of wood before impregnation
    • B27K3/0214—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27M—WORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
    • B27M1/00—Working of wood not provided for in subclasses B27B - B27L, e.g. by stretching
    • B27M1/08—Working of wood not provided for in subclasses B27B - B27L, e.g. by stretching by multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27M—WORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
    • B27M3/00—Manufacture or reconditioning of specific semi-finished or finished articles
    • B27M3/0013—Manufacture or reconditioning of specific semi-finished or finished articles of composite or compound articles
    • B27M3/0086—Manufacture or reconditioning of specific semi-finished or finished articles of composite or compound articles characterised by connecting using glue
    • 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
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • 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
    • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from 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
    • 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
    • B27N7/00—After-treatment, e.g. reducing swelling or shrinkage, surfacing; Protecting the edges of boards against access of humidity
    • B27N7/005—Coating boards, e.g. with a finishing or decorating layer
    • 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
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
    • 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
    • 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
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C08G18/6438—Polyimides or polyesterimides
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to a recombinant wood board using a polyimide modified polyurethane adhesive and a preparation method thereof, and belongs to the technical field of production of wood floors, in particular, recombinant wood floors.
  • the invention can effectively reduce the waste of wood, save wood resources, and has superior economic benefits. Further, the present invention can effectively improve the viscosity and light transmittance of the wooden floor, and improve the joint strength between the floors.
  • a recombinant wood board using a polyimide modified polyurethane adhesive a composite wood core board which is adhered and pressed by an adhesive agent, and a surface of the reconstituted wooden core board is provided with paint
  • the side layer of the reconstituted wood core board is provided with side sills and side grooves; the adhesive is made of the following materials by weight:
  • Antioxidant 0.02-0.20 parts.
  • the adhesive is made of the following materials in parts by weight:
  • Antioxidant 0.05-0.1 parts.
  • the polyisocyanate is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, and six One or more of methylene diisocyanate or polyphenylpolymethylene polyisocyanate.
  • the polybasic acid anhydride is selected from the group consisting of pyromellitic dianhydride and 3,3',4,4'-benzophenone tetracarboxylic dianhydride. , 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride or 3,3',4,4'-biphenyl One or more of sulfone tetracarboxylic dianhydrides.
  • the polyol is selected from polytetrahydrofuran diol, polyoxypropylene diol, tetrahydrofuran-ethylene oxide copolymer diol having an average molecular weight of 1000-4000.
  • polytrimethylene ether glycol and polyethylene adipate glycol diol are examples of polytrimethylene ether glycol and polyethylene adipate glycol diol.
  • the plasticizer is selected from one of phthalic acid esters, terephthalic acid esters, and polyphenylene esters.
  • the catalyst is selected from one of triethanolamine, triethylenediamine, dibutyltin dilaurate, Dabco33-LV or zinc naphthenate. Or one or more; the antifoaming agent is selected from one or more of DF-520, DF-530, DF-899, DF-834, dimethicone; the water removing agent is selected from the original One or more of triethyl formate and p-toluenesulfonyl isocyanate.
  • the coupling agent is selected from the group consisting of ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane or One or more of ⁇ -(methacryloyloxy)propyltrimethoxysilane;
  • the antioxidant is selected from triethylene glycol bis-[3-(3-tert-butyl-4-hydroxy-5) -methylphenyl)propionic acid One or more of ester, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid octadecyl carbonate, and 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid isooctyl ester.
  • the preparation method of the adhesive includes the following steps:
  • the preparation method of the above-mentioned recombinant wood board using the polyimide modified polyurethane adhesive specifically includes the following steps;
  • the bundle of fiber strands is obtained by deconstructing the equipment, and the bundle fiber strands are dried;
  • the invention adopts fast-growing wood, irregular wood, and even edge material waste to process the fiber bundle, and then obtains the reconstituted wood board by pasting and hot pressing, thereby effectively reducing wood waste and saving wood resources.
  • the invention improves the formulation of the adhesive, and the adhesive of the invention introduces the polyimide segment into the polyurethane adhesive through reasonable components and ratios, thereby effectively improving the polyurethane adhesive. High temperature resistance, broadening the temperature range of use of polyurethane adhesives.
  • the invention not only can effectively regulate the content of polyimide in the adhesive, but also greatly simplifies the preparation process of the wooden floor using the polyimide modified polyurethane adhesive, and reduces the modification by the polyimide.
  • the production cost of the wood flooring of polyurethane adhesives has played an active role in promoting the industrial production of high-performance polyurethane adhesives and their wide application in the national industry.
  • the present invention also provides a method for preparing a polyimide-modified polyurethane adhesive and a heat treatment method for a wooden floor using the same.
  • the method directly adds the polybasic acid anhydride solid powder in the polyurethane prepolymerization process, and forms a polyimide by reacting between the isocyanate group and the polybasic acid anhydride, thereby realizing the formation and introduction of the polyimide in one step, greatly simplifying the use of the polyamido.
  • the preparation technology of the wood floor of the amine modified polyurethane adhesive can effectively control the polyimide content in the adhesive. Since the adhesive of the invention is improved, the mechanical properties are greatly improved, and the adhesive, the compressive strength, the tensile strength, the impermeability pressure and the like have superior effects, and the environment has good adaptability and long service life. .
  • Example 1 A reconstituted wood board using a polyimide-modified urethane adhesive, a fiber slab adhered by an adhesive, a pressed wood core board, and a surface of a reconstituted wood core board
  • the lacquer layer is provided, and the sides of the reconstituted wood core board are provided with side sills and side grooves
  • the adhesive is made of the following raw materials by weight: polytetrahydrofuran diol (molecular weight 2000) 40 parts, 4, 4'- 8.7 parts of diphenylmethane diisocyanate, 2.2 parts of pyromellitic dianhydride, 0.8 parts of dimethyl silicone oil, 0.06 parts of triethylene diamine, 20 parts of diisooctyl phthalate, p-toluene 0.05 parts of sulfonyl isocyanate, 0.05 parts of ⁇ -aminopropyltriethoxysilane, and 0.05 parts of 3,5-di-tert-butyl-4-hydroxy
  • the above method for producing a recombinant wooden wooden floor specifically includes the following steps;
  • the bundle of fiber strands is obtained by deconstructing the equipment, and the bundle fiber strands are dried;
  • the heat resistance temperature of the adhesive prepared by testing this example can be increased to about 180 degrees Celsius.
  • the temperature drop rate of 1 degree Celsius drops to 80 degrees Celsius, the temperature is 1 hour, the heating system is turned off, the temperature is naturally cooled to 40 degrees Celsius, the shutdown is performed, and the kiln is discharged.
  • Example 2 A reconstituted wood board using a polyimide-modified urethane adhesive, a composite wood core board obtained by sticking a fiber strip by an adhesive, and a surface of the reconstituted wood core board is provided with a lacquer layer.
  • the sides of the reconstituted wood core board are provided with side sills and side grooves, and the adhesive is made of the following raw materials by weight: tetrahydrofuran-ethylene oxide copolymer diol (molecular weight 3000) 35 parts, hexamethylene diisocyanate 12.2 5 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1.6 parts of dimethyl silicone oil, 0.12 parts of triethylenediamine, 35 parts of diisooctyl phthalate, 0.13 parts of triethyl orthoformate, 0.3 parts of ⁇ -(methacryloyloxy)propyltrimethoxysilane, and 0.08 parts of 3,5-di-tert
  • the above method for producing a recombinant wooden wooden floor specifically includes the following steps;
  • the bundle of fiber strands is obtained by deconstructing the equipment, and the bundle fiber strands are dried;
  • the heat resistance temperature of the adhesive prepared by testing this example can be increased to about 160 degrees Celsius.
  • the heat treatment method of the recombinant wood board using the polyimide modified polyurethane adhesive, the specification blank is introduced into the kiln, and the temperature is raised to 130 degrees Celsius at a heating rate of 1 degree Celsius per minute. At this time, the superheated saturated water vapor is introduced to control the oxygen content. 2%, constant temperature for one hour, then increase to 200 degrees Celsius at a rate of 1 degree Celsius per minute, constant temperature for 2 hours, to a temperature drop of 1 degree Celsius per minute to 130 degrees Celsius, turn off the superheated saturated water vapor, constant temperature for half an hour, At a temperature drop rate of 1 degree Celsius per minute to 80 degrees Celsius, constant temperature for 1 hour, turn off the heating system, naturally cool to 40 degrees Celsius, shut down, and exit the kiln.
  • Example 3 Adhesive strength comprehensive performance test.
  • Shear strength is determined according to GB7124-86;
  • Peel strength was measured according to GB/T7122-1996.
  • Example 1 and Example 2 are significantly better than that of the control group at 25 ° C.
  • the shear strength is much better than that of the control group at 150 ° C, and the effect is very remarkable.
  • the peel strengths of Example 1 and Example 2 were also much better than the comparative group.
  • the present invention not only has superior adhesion performance, but also effectively improves the high temperature resistance performance and broadens the use temperature range.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Forests & Forestry (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

一种采用聚酰亚胺改性聚氨酯胶黏剂的重组木板及其制备方法，属于木地板的生产技术领域。重组木芯板通过胶黏剂将纤维条粘贴，压制而成，重组木芯板的表面设有漆层，重组木芯板的侧面开设有侧榫和侧槽；所述胶黏剂按重量份由下列原料制成：多异氰酸酯5-20份，多元酸酐1-10份，多元醇30-50份，增塑剂20-50份，催化剂0.02-0.20份，消泡剂0.5-3份，除水剂0.02-0.20份，偶联剂0.02-0.5份，抗氧化剂0.02-0.20份。采用所述重组木板可以有效地减少木材的浪费，节约木材资源，同时具有优越的经济效益。此外，采用所述胶黏剂可有效地提高木地板的力学性能和耐高温性能。

Description

采用聚酰亚胺改性聚氨酯胶黏剂的重组木板及其制备方法 技术领域
本发明涉及一种采用聚酰亚胺改性聚氨酯胶黏剂的重组木板及其制备方法，属于木地板、特别是重组木地板的生产技术领域。
背景技术
随着经济快速发展，人民生活水平的逐步提高，木材的消耗进一步增加，造成了我国木质品价格的上涨，实木地板和以珍贵树种为木皮的多层实木地板价格节节攀升。为了缓解木地板市场的供需矛盾，也为了保护我国的珍贵树种，实现可持续发展，现在越来越多的地板行业者考虑在生产地板中充分利用木材，但是效果都不明显。
发明内容
本发明的目的在于，提供一种采用聚酰亚胺改性聚氨酯胶黏剂的重组木板及其制备方法。本发明可以有效地减少木材的浪费，节约木材资源，同时具有优越的经济效益。此外，本发明可有效地提高木地板的粘度和透光性，以及提高地板间的连接强度。
本发明的技术方案：一种采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，通过胶黏剂将纤维条粘贴，压制而成的重组木芯板，重组木芯板的表面设有漆层，重组木芯板的侧面开设有侧榫和侧槽；所述的胶黏剂按重量份由下列原料制成：
多异氰酸酯5-20份，
多元酸酐1-10份，
多元醇30-50份，
增塑剂20-50份，
催化剂0.02-0.20份，
消泡剂0.5-3份，
除水剂0.02-0.20份，
偶联剂0.02-0.5份，
抗氧化剂0.02-0.20份。
上述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板中，所述的胶黏剂按重量份由下列原料制成：
多异氰酸酯10-15份，
多元酸酐3-8份，
多元醇30-40份，
增塑剂30-50份，
催化剂0.1-0.2份，
消泡剂1-2份，
除水剂0.1-0.2份，
偶联剂0.1-0.5份，
抗氧化剂0.05-0.1份。
前述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板中，所述的多异氰酸酯选自4,4′-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六 亚甲基二异氰酸酯或多苯基多亚甲基多异氰酸酯中的一种或几种。
前述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板中，所述的多元酸酐选自均苯四酸二酐、3,3′,4,4′-二苯甲酮四酸二酐、3,3′,4,4′-联苯基四酸二酐、3,3′,4,4′-二苯醚四酸二酐或3,3′,4,4′-联苯基砜四羧酸二酐中的一种或几种。
前述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板中，所述的多元醇选自平均分子量在1000-4000的聚四氢呋喃二醇、聚氧化丙烯二醇、四氢呋喃-氧化乙烯共聚二醇、聚三亚甲基醚二醇、聚己二酸乙二醇酯二醇中的一种或几种。
前述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板中，所述的增塑剂选自邻苯二甲酸酯类、对苯二甲酸酯类、苯多酸酯类中的一种或几种。
前述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板中，所述的催化剂选自三乙醇胺、三亚乙基二胺、二月桂酸二丁基锡、Dabco33-LV或环烷酸锌中的一种或几种；所述的消泡剂选自DF-520、DF-530、DF-899、DF-834、二甲基硅油中的一种或几种；所述的除水剂选自原甲酸三乙酯、对甲基苯磺酰异氰酸酯中的一种或几种。
前述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板中，所述的偶联剂选自γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷或γ-(甲基丙烯酰氧)丙基三甲氧基硅烷中的一种或几种；所述的抗氧化剂选自三甘醇双-[3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸 酯]、3,5-二叔丁基-4羟基苯基丙酸十八碳酸酯、3,5-二叔丁基-4羟基苯丙酸异辛酯中的一种或几种。
前述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板中，所述的胶粘剂的制备方法依次包括以下步骤：
1)多元醇脱水：按照重量比称取多元醇投入反应釜中，搅拌并加热至80-100℃，抽真空脱水处理3-4小时，再冷却至室温；
2)组合料配制：再加入消泡剂和多元酸酐，搅拌均匀，得到组合料；
3)预聚体制备：向组合料中加入多异氰酸酯，搅拌并加热至80-90℃，恒温反应至无气泡产生后再继续反应2-3小时，制得含有聚酰亚胺的预聚体；
4)胶黏剂制备：将增塑剂、除水剂加入预聚体中，在真空条件下搅拌1-2小时；随后向混合体系中加入抗氧化剂、偶联剂和催化剂，在真空条件下继续搅拌3小时；最后得到聚酰亚胺改性的聚氨酯胶黏剂。
前述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板的制备方法，具体包括以下步骤；
a、将木料去皮后，通过设备进行疏解得到束状纤维条，对束状纤维条进行干燥；
b、将胶粘剂倒入热压模具中，再倒入束状纤维条进行搅拌，浸胶30分钟；
c、对热压模具中的物料进行热压，固化，得到重组木芯板；
d、在重组木芯板上涂敷漆层，并在两侧开榫槽，得到成品。
与现有技术相比，本发明采用速生木、不规则木料、甚至是边料废料加工得到纤维束，再通过粘贴、热压得到重组木板，从而有效地减少了木材的浪费，节约木材资源，同时具有优越的经济效益。此外，本发明对胶粘剂的配方作了改进，本发明的胶黏剂通过合理的组分和配比，将聚酰亚胺链段引入到聚氨酯胶黏剂中，有效改善了聚氨酯胶黏剂的耐高温性能，拓宽了聚氨酯胶黏剂的使用温域。同时，本发明不但能够有效调控胶黏剂中聚酰亚胺的含量，而且大大简化了采用聚酰亚胺改性聚氨酯胶黏剂的木地板的制备工艺，降低了采用聚酰亚胺改性聚氨酯胶黏剂的木地板的生产成本，为高性能聚氨酯胶黏剂的工业化生产及其在国民工业中的广泛应用起到了积极的推动作用。此外，本发明还提供了一种聚酰亚胺改性聚氨酯胶黏剂的制备方法以及采用该胶黏剂的木地板的热处理方法。所述方法在聚氨酯预聚过程中直接加入多元酸酐固体粉末，依靠异氰酸酯基与多元酸酐间的反应形成聚酰亚胺，一步实现聚酰亚胺的生成与引入工作，大大简化了采用聚酰亚胺改性聚氨酯胶黏剂的木地板的制备技术，同能够有效控制胶黏剂中聚酰亚胺含量。由于本发明的胶黏剂作了改进，从而大大地提高力学性能，在粘度、抗压强度、抗拉强度、抗渗压力等方面，均具有优越的效果，而且环境适应性好，使用寿命长。
具体实施方式
实施例1：一种采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，通过胶黏剂将纤维条粘贴，压制而成的重组木芯板，重组木芯板的表面 设有漆层，重组木芯板的侧面开设有侧榫和侧槽，所述的胶黏剂由下列重量份的原料制成：聚四氢呋喃二醇(分子量2000)40份、4,4′-二苯基甲烷二异氰酸酯8.7份、均苯四酸二酐2.2份、二甲基硅油为0.8份、三亚乙基二胺为0.06份、邻苯二甲酸二异辛酯20份、对甲基苯磺酰异氰酸酯0.05份、γ-氨丙基三乙氧基硅烷0.05份、3,5-二叔丁基-4羟基苯基丙酸十八碳酸酯0.05份。
具体制备步骤为：
1)称取400g分子量为2000的聚四氢呋喃二醇投入到1L的反应釜中，搅拌并加热至100℃，抽真空脱水处理4小时；
2)向经脱水处理后冷却至室温的聚四氢呋喃二醇中依次投入8g二甲基硅油和22g均苯四酸二酐，机械搅拌均匀；
3)向上述混合料中加入87g4,4′-二苯基甲烷二异氰酸酯，搅拌并加热至90℃，恒温反应至无气泡产生后再继续反应2小时，制得含有聚酰亚胺的预聚体；
4)向所制得的预聚体中依次加入邻苯二甲酸二异辛酯200g、对甲基苯磺酰异氰酸酯0.5g，在真空条件下搅拌2小时；随后向混合体系中加入三亚乙基二胺0.6g、γ-氨丙基三乙氧基硅烷0.5g、3,5-二叔丁基-4羟基苯基丙酸十八碳酸酯0.5g，在真空条件下继续搅拌3小时；最后得到采用聚酰亚胺改性聚氨酯胶黏剂的重组木板。
上述的重组木木制地板的生产方法，具体包括以下步骤；
a、将木料去皮后，通过设备进行疏解得到束状纤维条，对束状纤维条进行干燥；
b、将胶粘剂倒入热压模具中，再倒入束状纤维条进行搅拌，浸 胶30分钟；
c、对热压模具中的物料进行热压，固化，得到重组木芯板；
d、在重组木芯板上涂敷漆层，并在两侧开榫槽，得到成品。
经测试本实例所制备的胶黏剂耐热温度可提高到180摄氏度左右。
采用聚酰亚胺改性聚氨酯胶黏剂的重组木板的热处理方法，规格坯料进窑，以每分钟1摄氏度的升温速率升温至130摄氏度，此时通入过热饱和水蒸气，将氧含量控制在2％，恒温一小时，再以每分钟1摄氏度的升温速率升温至200摄氏度，恒温2小时，以每分钟1摄氏度的降温速率降至130摄氏度，关闭过热饱和水蒸气，恒温半小时，以每分钟1摄氏度的降温速率降至80摄氏度，恒温1小时，关闭加热系统，自然冷却至40摄氏度，关机，出窑。
实施例2：一种采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，通过胶黏剂将纤维条粘贴，压制而成的重组木芯板，重组木芯板的表面设有漆层，重组木芯板的侧面开设有侧榫和侧槽，所述的胶黏剂由下列重量份的原料制成：四氢呋喃-氧化乙烯共聚二醇(分子量3000)35份、六亚甲基二异氰酸酯12.2份、3,3′,4,4′-联苯基四酸二酐5份、二甲基硅油为1.6份、三亚乙基二胺为0.12份、邻苯二甲酸二异辛酯35份、原甲酸三乙酯0.13份、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷0.3份、3,5-二叔丁基-4羟基苯丙酸异辛酯0.08份。
具体制备步骤为：
1)称取350g分子量为3000的四氢呋喃-氧化乙烯共聚二醇投入到2L的反应釜中，搅拌并加热至95℃，抽真空脱水处理4小时；
2)向经脱水处理后冷却至室温的四氢呋喃-氧化乙烯共聚二醇中 依次投入16g二甲基硅油和50g3,3′,4,4′-联苯基四酸二酐，机械搅拌均匀；
3)向上述混合料中加入122g六亚甲基二异氰酸酯，搅拌并加热至90℃，恒温反应至无气泡产生后再继续反应2小时，制得预聚体；
4)向所制得的预聚体中依次加入邻苯二甲酸二异辛酯350g、原甲酸三乙酯1.3g，在真空条件下搅拌2小时；随后向混合体系中加入三亚乙基二胺1.2g、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷3g、3,5-二叔丁基-4羟基苯丙酸异辛酯0.8g，在真空条件下继续搅拌3小时；最后得到采用聚酰亚胺改性聚氨酯胶黏剂的重组木板。
上述的重组木木制地板的生产方法，具体包括以下步骤；
a、将木料去皮后，通过设备进行疏解得到束状纤维条，对束状纤维条进行干燥；
b、将胶粘剂倒入热压模具中，再倒入束状纤维条进行搅拌，浸胶30分钟；
c、对热压模具中的物料进行热压，固化，得到重组木芯板；
d、在重组木芯板上涂敷漆层，并在两侧开榫槽，得到成品。
经测试本实例所制备的胶黏剂耐热温度可提高到160摄氏度左右。
采用聚酰亚胺改性聚氨酯胶黏剂的重组木板的热处理方法，规格坯料进窑，以每分钟1摄氏度的升温速率升温至130摄氏度，此时通入过热饱和水蒸气，将氧含量控制在2％，恒温一小时，再以每分钟1摄氏度的升温速率升温至200摄氏度，恒温2小时，以每分钟1摄氏度的降温速率降至130摄氏度，关闭过热饱和水蒸气，恒温半小时， 以每分钟1摄氏度的降温速率降至80摄氏度，恒温1小时，关闭加热系统，自然冷却至40摄氏度，关机，出窑。
实施例3：胶黏力综合性能试验。
剪切强度按GB7124-86测定；
剥离强度按GB/T7122-1996测定。
取实施例1和2的木地板，再取行业内常用的聚氨酯胶黏剂制备的木地板作为对比组，分室温固化24小时、3天和10天测定其剪切强度和剥离强度，见表1。
表1木地板粘接性试验
Figure PCTCN2016092776-appb-000001
从表1可以看出，实施例1和实施例2在25℃环境下，剪切强度明显优于对比组，在150℃环境下剪切强度也大大优于对比组，效果非常显著。且实施例1和实施例2的剥离强度也大大优于对比组。由此可见，本发明不仅具有优越的粘贴性能，而且本发明有效改善了耐高温性能，拓宽了使用温域。

Claims (10)

  1. 采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，其特征在于：通过胶黏剂将纤维条粘贴，压制而成的重组木芯板，重组木芯板的表面设有漆层，重组木芯板的侧面开设有侧榫和侧槽；所述的胶黏剂按重量份由下列原料制成：
    多异氰酸酯 5-20份，
    多元酸酐 1-10份，
    多元醇 30-50份，
    增塑剂 20-50份，
    催化剂 0.02-0.20份，
    消泡剂 0.5-3份，
    除水剂 0.02-0.20份，
    偶联剂 0.02-0.5份，
    抗氧化剂 0.02-0.20份。
  2. 根据权利要求1所述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，其特征在于：所述的胶黏剂按重量份由下列原料制成：
    多异氰酸酯 10-15份，
    多元酸酐 3-8份，
    多元醇 30-40份，
    增塑剂 30-50份，
    催化剂 0.1-0.2份，
    消泡剂 1-2份，
    除水剂 0.1-0.2份，
    偶联剂 0.1-0.5份，
    抗氧化剂 0.05-0.1份。
  3. 根据权利要求1或2所述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，其特征在于：所述的多异氰酸酯选自4,4′-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯或多苯基多亚甲基多异氰酸酯中的一种或几种。
  4. 根据权利要求1或2所述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，其特征在于：所述的多元酸酐选自均苯四酸二酐、3,3′,4,4′-二苯甲酮四酸二酐、3,3′,4,4′-联苯基四酸二酐、3,3′,4,4′-二苯醚四酸二酐或3,3′,4,4′-联苯基砜四羧酸二酐中的一种或几种。
  5. 根据权利要求1或2所述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，其特征在于：所述的多元醇选自平均分子量在1000-4000的聚四氢呋喃二醇、聚氧化丙烯二醇、四氢呋喃-氧化乙烯共聚二醇、聚三亚甲基醚二醇、聚己二酸乙二醇酯二醇中的一种或几种。
  6. 根据权利要求1或2所述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，其特征在于：所述的增塑剂选自邻苯二甲酸酯类、对苯 二甲酸酯类、苯多酸酯类中的一种或几种。
  7. 根据权利要求1或2所述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，其特征在于：所述的催化剂选自三乙醇胺、三亚乙基二胺、二月桂酸二丁基锡、Dabco33-LV或环烷酸锌中的一种或几种；所述的消泡剂选自DF-520、DF-530、DF-899、DF-834、二甲基硅油中的一种或几种；所述的除水剂选自原甲酸三乙酯、对甲基苯磺酰异氰酸酯中的一种或几种。
  8. 根据权利要求1或2所述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，其特征在于：所述的偶联剂选自γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷或γ-(甲基丙烯酰氧)丙基三甲氧基硅烷中的一种或几种；所述的抗氧化剂选自三甘醇双-[3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]、3,5-二叔丁基-4羟基苯基丙酸十八碳酸酯、3,5-二叔丁基-4羟基苯丙酸异辛酯中的一种或几种。
  9. 根据权利要求1-8任一项所述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板，其特征在于：所述的胶粘剂的制备方法依次包括以下步骤：
    1)多元醇脱水：按照重量比称取多元醇投入反应釜中，搅拌并加热至80-100℃，抽真空脱水处理3-4小时，再冷却至室温；
    2)组合料配制：再加入消泡剂和多元酸酐，搅拌均匀，得到组合料；
    3)预聚体制备：向组合料中加入多异氰酸酯，搅拌并加热至80-90℃，恒温反应至无气泡产生后再继续反应2-3小时，制得含有聚酰亚胺的预聚体；
    4)胶黏剂制备：将增塑剂、除水剂加入预聚体中，在真空条件下搅拌1-2小时；随后向混合体系中加入抗氧化剂、偶联剂和催化剂，在真空条件下继续搅拌3小时；最后得到聚酰亚胺改性的聚氨酯胶黏剂。
  10. 根据权利要求1-9所述的采用聚酰亚胺改性聚氨酯胶黏剂的重组木板的制备方法，其特征在于：具体包括以下步骤；
    a、将木料去皮后，通过设备进行疏解得到束状纤维条，对束状纤维条进行干燥；
    b、将胶粘剂倒入热压模具中，再倒入束状纤维条进行搅拌，浸胶30分钟；
    c、对热压模具中的物料进行热压，固化，得到重组木芯板；
    d、在重组木芯板上涂敷漆层，并在两侧开榫槽，得到成品。
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