WO2018227645A1 - 一种无醛添加的人造板胶粘剂及用其制造的无醛添加人造板 - Google Patents

一种无醛添加的人造板胶粘剂及用其制造的无醛添加人造板 Download PDF

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Publication number
WO2018227645A1
WO2018227645A1 PCT/CN2017/089126 CN2017089126W WO2018227645A1 WO 2018227645 A1 WO2018227645 A1 WO 2018227645A1 CN 2017089126 W CN2017089126 W CN 2017089126W WO 2018227645 A1 WO2018227645 A1 WO 2018227645A1
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Prior art keywords
agent
aldehyde
wood
aliphatic polyester
meth
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PCT/CN2017/089126
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English (en)
French (fr)
Inventor
涂松
齐旺顺
李厚义
孙卫华
张梓军
吕兵
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万华化学集团股份有限公司
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Application filed by 万华化学集团股份有限公司 filed Critical 万华化学集团股份有限公司
Priority to CA3065388A priority Critical patent/CA3065388C/en
Priority to US16/612,847 priority patent/US11806892B2/en
Publication of WO2018227645A1 publication Critical patent/WO2018227645A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/147—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
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    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
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    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • 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
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    • C—CHEMISTRY; METALLURGY
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
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    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
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    • C—CHEMISTRY; METALLURGY
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    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
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    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions

Definitions

  • the present invention relates to an adhesive for producing a wood-based panel, and more particularly to an isocyanate-based binary adhesive. Another aspect of the invention relates to a wood panel manufactured using the adhesive and a method of manufacturing the same.
  • isocyanate adhesives Due to environmental considerations, aldehyde-free isocyanate adhesives have become more and more widely used in recent years. In addition to formaldehyde, isocyanate has many advantages, such as high bonding strength, fast curing speed, less stringent requirements on wood/straw material moisture content, and excellent physical properties of the board. However, the use of isocyanates as binders in wood based panels also has disadvantages.
  • U.S. Patent No. 4,944,823 discloses the use of sucrose or starch in combination with isocyanates to reduce the amount of isocyanate added to 1% to achieve the required strength, but due to the use of bio-based binders, the subsequent mildew of the board The problem will be difficult to solve.
  • U.S. Patent No. 4,944,823 discloses the use of sucrose or starch in combination with isocyanates to reduce the amount of isocyanate added to 1% to achieve the required strength, but due to the use of bio-based binders, the subsequent mildew of the board The problem will be difficult to solve.
  • 8,895,643 B2 discloses a wood based panel adhesive formulation comprising a polyphenyl polyisocyanate and at least one aqueous dispersion, the slab made with the formulation having at least 85% urethane after pre-compression The initial tackiness, but the patent does not mention the effect of the aqueous dispersion on the mechanical properties, water resistance, processability, etc. of the sheet.
  • isocyanate as a wood-based board binder
  • isocyanide During the curing process, the acid ester forms a large amount of urea structure with a large hardness, which causes the processing parts of the saw to wear more seriously than the urea-formaldehyde glue in the process of sawing and cutting the plate, and the processing cost is greatly increased.
  • the life of a typical dicing saw will be reduced by 20-40%.
  • the waterproof performance (dimensional stability) of wood-based panels plays an important role in practical applications.
  • various water repellents such as paraffin wax are generally required to be added in the production process of the artificial board.
  • the chemical composition of paraffin is a saturated normal paraffin with almost no reactivity. It is an excellent hydrophobic substance and has long been regarded as the best waterproofing agent.
  • the patent CN 104559828 discloses an emulsified paraffin waterproofing agent for particleboard, which is mainly composed of paraffin wax, stearic acid and water, alkyl polyoxyethylene ether and polytrientyl ester as emulsifiers, and tripolyphosphate wax.
  • the catalyst sodium carboxymethyl cellulose
  • the catalyst is an adhesive which is formed by emulsification and saponification at a certain temperature, and has high solid content and good waterproof performance.
  • paraffin does not have any reactivity
  • the addition of water repellent paraffin also hinders the bonding fastness between wood material and wood material, especially when using isocyanate as binder, it will hinder the reaction of isocyanate with active hydrogen in wood. This leads to a decrease in bonding strength. Therefore, whether in the production of medium (high) density fiberboard and particleboard, adding paraffin or increasing the amount of paraffin will often affect the mechanical properties of the product, mainly to reduce the bonding strength of the product, which has been the theory and practice since the advent of wood-based panel production. Confirmed.
  • paraffin wax will sublime or evaporate at a high temperature of 180-240 ° C during hot pressing of a wood-based panel, which may cause problems such as potential fire, increased production cost, and the like.
  • the present invention provides an aldehyde-free added wood-based panel adhesive comprising an agent A and a agent B, wherein the agent A is an isocyanate binder, and the agent B is an aliphatic group.
  • the isocyanate binder as the agent A is polymethylene polyphenyl polyisocyanate and/or a derivative thereof, and the NCO value (that is, the mass percentage of the -NCO group in the compound) It is 20-33%, has a functionality of 2.1-3.3, and has a viscosity of 50-2000 cp (25 ° C).
  • the derivative of the polymethylene polyphenyl polyisocyanate is obtained by reacting a polymethylene polyphenyl polyisocyanate with a polyol, and a method for preparing an isocyanate derivative known to those skilled in the art can be employed.
  • Mixed polyols and aliphatics are disclosed, for example, in CN103396526A, CN1380346, and CN101522741, respectively.
  • Process for the preparation of isocyanate derivatives from isocyanates US 3,996,154 discloses a process for the preparation of isocyanate derivatives from polyoxyethylene ether polymers and polymethylene polyphenyl polyisocyanates.
  • a polyhydric alcohol is added to the polymethylene polyphenyl polyisocyanate, and the reaction is carried out at 60 to 80 ° C to prepare the polymethylene polyphenyl polyisocyanate derivative.
  • Suitable polymethylene polyphenyl polyisocyanates and their derivative binders are preferably selected from the Wannate series polyisocyanates of Wanhua Chemical Group Co., Ltd., including PM-100, PM-200, PM-400, PM-600. One or more of PM-700, CW20, CW30, PM300E, and 9132FC.
  • the aliphatic polyester type polyurethane in the aqueous dispersion of the aliphatic polyester type polyurethane as the agent B preferably has a number average molecular weight of 5 to 500,000 Daltons, and a glass transition temperature. Below 5 °C.
  • the aqueous dispersion of the aliphatic polyester polyurethane and/or its modified product as the agent B of the present invention has a solid content of 20 to 60% by weight, preferably 40 to 60% by weight.
  • the aqueous dispersion of the aliphatic polyester type polyurethane may be obtained by using an aliphatic diisocyanate, a polyester polyol, a chain extender containing a hydrophilic group, and optionally a chain extender containing no hydrophilic group.
  • the aliphatic polyester polyurethane obtained by polymerization of the raw materials is obtained by high-speed shear dispersion in water.
  • the preparation method of the aqueous dispersion of the aliphatic polyester type polyurethane is well known to those skilled in the art, such as the preparation method of the aqueous polyurethane dispersion disclosed in CN106243319A, CN106188465A, CN10431225.
  • the method for preparing an aqueous dispersion of an aliphatic polyester polyurethane as a B agent in the wood-based panel adhesive of the present invention may include the following steps:
  • Prepolymerization mixing the aliphatic diisocyanate, polyester polyol, and optionally a chain extender without a hydrophilic group and/or a chain extender containing a hydrophilic group, at 50-100 Polymerization occurs at ° C to obtain a prepolymer;
  • Chain extension a mixture of the chain extender containing a hydrophilic group, water and optionally a chain extender containing no hydrophilic group is added to the prepolymer dissolved in acetone, and then allowed to The polymerization is continued at 30-50 ° C to obtain an aliphatic polyester polyurethane dissolved in acetone;
  • Dispersion Water is slowly added under shear-dispersion conditions, acetone is removed, and an optional emulsifier is added to obtain an aqueous dispersion of the aliphatic polyester-type polyurethane.
  • An aliphatic diisocyanate used in the preparation of the aliphatic polyester polyurethane by polymerization The molar ratio of the NCO group to the sum of the hydroxyl group and the amino group in the polyester polyol, the chain extender containing a hydrophilic group, and optionally the chain extender component containing no hydrophilic group is 1: ( 0.8-1.4), preferably 1: (0.8-1.2).
  • the NCO group in the aliphatic diisocyanate used / the hydroxyl group in the polyester polyol / the chain extender containing a hydrophilic group is 1: (0.2 - 0.9): (0.02 - 0.3): (0 - 0.7).
  • the amount of the emulsifier is from 0.1 to 0.5% by weight of the aqueous dispersion of the aliphatic polyester polyurethane.
  • step (1) and (3) use a chain extender containing a hydrophilic group and/or both use a chain extender containing no hydrophilic group
  • step (1) The corresponding components in (3) and (3) may be the same or different.
  • the aliphatic diisocyanate is selected from the group consisting of hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone.
  • HDI hexamethylene diisocyanate
  • HMDI dicyclohexylmethane diisocyanate
  • IPDI diisocyanate
  • HXDI cyclohexane dimethylene diisocyanate
  • the polyester polyol is an adipic acid polyester diol, an aromatic polyester polyol or a polycaprolactone polyol.
  • the average molecular weight is 400-8000 Daltons; polybutylene adipate diol (PBA), polyethylene adipate diol (PEA), preferably having a number average molecular weight of 1000-5000 Daltons, Polypropylene glycol propylene glycol diol (PPA), poly(diethylene glycol adipate diol) (PDA), poly(p-hexane adipate) (PNA), polyethylene adipate One or more of alcohol ester diol (PEBA), polyethylene adipate glycol propylene glycol (PEPA), polyhexane adipate diol diol (PHA), polycaprolactone diol (PCL)kind.
  • the hydrophilic group in the chain extender containing a hydrophilic group is selected from the group consisting of a carboxyl group, a sulfonic acid group, an ethoxy group, and a propoxy group. Or one or more of ethoxypropoxy groups.
  • the chain extender containing a hydrophilic group is preferably dimethylolpropionic acid, dimethylolbutanoic acid, 1,2-dihydroxybutane-1-sulfonic acid, sodium ethylenediamine ethanesulfonate, One or two or more of sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid.
  • the chain extender containing no hydrophilic group is not necessarily used.
  • the hydrophilic group-free chain extender is selected from a polyol having a functionality of 2 to 3 carbon atoms of 2-3 and a functionality of 2 to 20 carbon atoms of 2-3.
  • One or more of the polyamines preferably ethylene glycol, 1,4-butanediol, hexanediol, ethylenediamine, propylenediamine, butyl
  • the emulsifier includes an anionic emulsifier such as sodium dodecyl sulfate, sodium lauryl sulfate, sodium tridecyl sulfate, sodium succinate sulfonate; or a nonionic emulsifier such as tridecyl Alcohol ethoxylate, oleic acid ethoxylate, phenol ethylene oxide-propylene oxide, ethylene oxide-propylene oxide, polyoxyethylene sorbitan fatty acid ester (Tween).
  • anionic emulsifier such as sodium dodecyl sulfate, sodium lauryl sulfate, sodium tridecyl sulfate, sodium succinate sulfonate
  • a nonionic emulsifier such as tridecyl Alcohol ethoxylate, oleic acid ethoxylate, phenol ethylene oxide-propylene oxide, ethylene oxide-propylene oxide, polyoxyethylene sorbitan fatty
  • the aliphatic polyester type polyurethane modified product of the present invention is preferably a vinyl polymerizable monomer polymer modified aliphatic polyester type polyurethane which is polymerized from an aliphatic polyester type polyurethane and a vinyl polymerizable monomer. The substance is obtained by chemical bonding.
  • the polymer portion of the vinyl polymerizable monomer accounts for 5 to 50% by weight of the aliphatic polyester type polyurethane.
  • the method for preparing an aqueous dispersion of the aliphatic polyester-type polyurethane modified product of the present invention comprises the following steps:
  • the aqueous dispersion of the aliphatic polyester polyurethane to be modified is prepared by the following steps:
  • Prepolymerization an aliphatic diisocyanate, a polyester polyol, a hydroxyl group- or amino group-containing vinyl polymerizable monomer, and optionally a hydrophilic group-free chain extender and/or a hydrophilic group
  • the chain extender is mixed and polymerized at 50-100 ° C to obtain a prepolymer
  • Chain extension a mixture of the chain extender containing a hydrophilic group, water and optionally a chain extender containing no hydrophilic group is added to the prepolymer dissolved in acetone, and then allowed to The polymerization reaction is continued at 30-50 ° C to obtain an aliphatic polyester polyurethane to be modified dissolved in acetone;
  • Dispersion water is slowly added under shear-dispersion conditions, acetone is removed, and an optional emulsifier is added to obtain an aqueous dispersion of the aliphatic polyester-type polyurethane to be described.
  • the method for preparing an aqueous dispersion of the aliphatic polyester type polyurethane to be modified The preparation method of the aqueous dispersion of the above aliphatic polyester type polyurethane is the same.
  • the number of moles of the hydroxyl group-containing vinyl polymerizable monomer used is 0.2-5 of the number of moles of the NCO group contained in the aliphatic diisocyanate. %.
  • the hydroxyl group- or amino group-containing vinyl polymerizable monomer includes hydroxyethyl (meth)acrylate, ⁇ -hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and (meth)acrylamide. One or more of them.
  • the initiator is selected from the group consisting of an azo compound initiator, a peroxide initiator, and a redox initiator.
  • an azo compound initiator such as azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, t-butyl hydroperoxide, dodecanoyl peroxide, One or more of t-butyl peroxypivalate and diisopropyl peroxydicarbonate.
  • the emulsifier used may be those defined above.
  • the vinyl polymerizable monomer is selected from the group consisting of methyl (meth)acrylate, butyl (meth)acrylate, phenyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid 2- One or more of ethylhexyl ester, benzyl (meth)acrylate, (meth)acrylic acid, (meth)acrylamide, styrene, ⁇ -alkylstyrene, (meth)acrylonitrile Preferred as one or two of methyl (meth)acrylate, butyl (meth)acrylate, phenyl (meth)acrylate, styrene, ⁇ -alkylstyrene, ethyl (meth)acrylate More than one species.
  • the vinyl polymerizable monomer polymer modified aliphatic polyester polyurethane is phenyl (meth) acrylate and methyl (meth) acrylate or styrene copolymer modified aliphatic poly
  • the total mass of the vinyl polymerizable monomer added is about 5-50% of the mass of the aliphatic polyester polyurethane to be modified.
  • the weight ratio of the A agent to the B agent in the aldehyde-free added wood-based panel adhesive of the present invention is 1-5:1.
  • the present invention provides a method for producing an aldehyde-free added wood-based panel, comprising the steps of:
  • the B agent an aqueous dispersion of an aliphatic polyester type polyurethane and/or a modified substance thereof) in the aldehyde-free added wood-based board adhesive of the present invention is diluted with water, and the weight ratio of the agent B to water is 0.5. -4:1 to obtain a diluted B agent having a viscosity of ⁇ 600 cp (25 ° C);
  • the pre-formed artificial board is hot pressed.
  • the total addition amount of the A agent and the B agent of the aldehyde-free added artificial board adhesive is wood and/or straw material. 1-6% by weight, preferably 2-5% by weight.
  • the agent A and the diluted agent B may be separately sizing to the wood and/or straw material in any order. in. More preferably, however, all or part of the A agent is mixed with all of the diluted B agent to obtain a mixture of the A agent and the B agent, and the mixture of the A agent and the B agent is sized to the wood and/or Or in the straw material; if there is an unmixed portion A agent, the unmixed portion A agent is sizing into the wood and/or straw material prior to or after the mixture of the agent A and the agent B.
  • the A agent for mixing with the diluted B agent accounts for 40-100% of the total weight of the A agent.
  • the mixing of all or part of the A agent and all of the B agent diluted with water can be carried out by mechanical agitation mixing or in-line static mixer mixing.
  • the method for preparing an aldehyde-free added artificial board according to the present invention is mixed in the above steps (1) and (2) using mechanical stirring mixing or an in-line static mixer, respectively.
  • the wood and/or straw material mixed with the aldehyde-free added artificial board adhesive of the present invention is heated to 40 before the pre-pressing. -75 ° C.
  • the hot pressing temperature is 170-240 °C.
  • the wood material is selected from one or more of poplar, pine, eucalyptus, apple wood, and beech;
  • the straw material is selected from the group consisting of corn stalks and straw One or more of wheat straw, sunflower straw, rape stalk, cotton stalk; wood material and straw material are mixed in any ratio.
  • the wood and/or straw material preferably has a moisture content of from 1 to 20%.
  • the wood and/or straw material can first be prepared into shavings or fibers.
  • the preparation of fibers or shavings is a technique well known to those skilled in the art.
  • the patent CN104290169A describes a method for preparing a wood fiber
  • CN104385424A discloses a method for preparing a crop straw shavings. It will be appreciated that the wood and/or straw material described below includes the form of shavings and/or fibers.
  • the present invention also provides an aldehyde-free added wood-based panel manufactured according to the above method.
  • the present invention provides an aldehyde-free added wood-based panel, the raw material of which comprises the following components: (1) wood and/or straw material; (2) 1-6 wt%, preferably of the wood and/or straw material 2-5 wt% of the aldehyde-free added wood-based panel adhesive of the present invention (sum of the agent A and the agent B).
  • the 24h water absorption thickness expansion ratio of the aldehyde-free artificial board is less than 12%, and more typically less than 10%;
  • the strength is greater than 0.5 MPa, and a more typical example is greater than 0.7 MPa (test method according to GB/T 17657-2013).
  • the mechanism of the aldehyde-free added wood-based panel adhesive of the invention to improve the mechanical properties, water resistance and sawability of the sheet is as follows:
  • the aqueous dispersion of the aliphatic polyester polyurethane and/or the modified product thereof contained in the aldehyde-free added wood-based panel adhesive of the present invention has good adhesion to wood.
  • a part of the isocyanate reacts with a reactive group such as a hydroxyl group or a carboxyl group on the structure of the aliphatic polyester type polyurethane and/or its modified product to form a network structure having excellent adhesion properties.
  • This network structure enhances the mechanical properties of the sheet on the one hand and the water resistance of the sheet on the other hand.
  • the aliphatic polyester polyurethane is modified with a vinyl monomer polymer
  • the vinyl monomer polymer is microphase-separated and filled in the adhesive in the adhesive system
  • the hardness of the adhesive is further lowered, and the saw blade is worn. decline.
  • water resistance is improved due to the hydrophobic property of the vinyl monomer polymer, which makes it difficult for moisture to penetrate into the adhesive.
  • the aqueous dispersion encapsulates and consumes the isocyanate, reducing the reaction of the isocyanate with water to form a hard Polyurea structure (the main reason for poor sawing performance).
  • the possibility of chemical bonding of the isocyanate to the wood is also reduced, so that the wear of the saw blade during sawing can be reduced.
  • the aldehyde-free added artificial board produced by using the aldehyde-free added wood-based board adhesive of the present invention has good mechanical properties, excellent water repellency, reduced adhesive cost, and markedly reduced wear on the saw during subsequent processing.
  • PCL polycaprolactone glycol, Japan Daicel Chemical Industry Co., Ltd.;
  • PEA polyethylene adipate glycol diol, Huada Chemical Co., Ltd.
  • HMDI dicyclohexylmethane diisocyanate, Wanhua Chemical Group Co., Ltd.;
  • IPDI isophorone diisocyanate, Wanhua Chemical Group Co., Ltd.;
  • HMDA 4,4'-diaminodicyclohexylmethane, Wanhua Chemical Group Co., Ltd.;
  • IPDA isophorone diamine, Wanhua Chemical Group Co., Ltd.;
  • DMPA dimethylolpropionic acid, Perstorp, Sweden
  • the number average molecular weight was measured by a gel chromatograph (Hewlett Packard, Inc. HP100 type), and the column was HP PL gel MIXED-B.
  • the standard sample is a narrow distribution polystyrene.
  • the sample was dissolved in mobile phase tetrahydrofuran to prepare a 1.5 g/L solution, which was filtered and injected.
  • the injection volume was 400 ⁇ L
  • the column pressure was 5.0 MPa
  • the flow rate was 1.5 ml/min.
  • the measurement of the glass transition temperature was measured by differential scanning calorimetry (DSC). Using METTLER TOLEDO's DSC3 differential scanning calorimeter, the test range is 100 ⁇ 30 ° C, the sample weighs 8 ⁇ 12mg, the sample is cooled to -100 ° C under liquid nitrogen protection, and then at 10 ° C / The heating rate of min was heated, and the DSC curve was tested to determine the glass transition temperature. The viscosity was measured using a Brookfield LV rotary viscometer according to the method specified in GB/T 2794.
  • the acetone was decanted under vacuum, and then 0.1 wt% Tween-20 emulsifier was added to obtain an aqueous dispersion of an aliphatic polyester polyurethane (B agent) having a solid content of 52.9 wt%, which was tested by gel chromatography and DSC.
  • the aliphatic polyester polyurethane in the aqueous dispersion was tested to have a number average molecular weight of 112,000 Daltons and a glass transition temperature of -20 °C.
  • Poplar shavings with a moisture content of 8-10% by weight were used as wood substrates for the platen test. 2000 g of surface poplar shavings was weighed into a blender. 20 g of the agent B prepared in this example was diluted with 10 g of deionized water, and the viscosity after dilution was 100 cp (25 ° C). Weigh 50g of polymethylene polyphenyl polyisocyanate PM-200 (A agent; Wanhua Chemical Group Co., Ltd.), and mix 20g of A agent with the above diluted B agent to obtain A and B agents. mixture.
  • a spray gun is connected to the air compressor, and the unmixed 30 g of the A agent and the mixture of the above agent A and the agent B are sequentially sprayed by a spray gun into a stirrer under stirring to stir for 40-60 s.
  • the core shaving sizing is then carried out in accordance with the same process.
  • the sizing shavings are paved in a 350mm*350mm*100mm mold, and heated to 40 °C for pre-pressing, pre-pressing pressure 1Mpa, time 1min. Pressing the pre-pressed slab on a hot press to make the platen temperature 170 ° C, relative pressure 1.5-2MPa, hot pressing cycle 200s, plate thickness control is 18mm. After the completion of the pressing, the properties of the board are tested in accordance with the method specified in GB/T-17657-2013.
  • Pine wood shavings with a moisture content of 8-10% by weight were used as wood substrates for the pressboard test.
  • 40 g of the B agent prepared in this example was diluted with 20 g of deionized water to a viscosity of 550 cp (25 ° C).
  • a spray gun was connected to the air compressor, and the mixture of the above agent A and the agent B was stirred with unmixed 58 g of PM-200 and agitator which was sequentially sprayed by a spray gun into a stirring state for 40-60 s.
  • the core shaving sizing is then carried out in accordance with the same process.
  • the sizing shavings are paved in a 350mm*350mm*100mm mold, and the temperature is raised to 75 °C for pre-pressing, pre-pressing pressure. 1Mpa, time 1min.
  • the pre-pressed slab is pressed into a plate on a hot press, the platen temperature is 240 ° C, the relative pressure is 1.5-2 MPa, the hot pressing cycle is 200 s, and the plate thickness is controlled to be 18 mm.
  • the properties of the board are tested in accordance with the method specified in GB/T-17657-2013.
  • the reaction was started, and the reaction was carried out at 30 to 50 ° C for 10 minutes. While stirring 1500-2000 rpm, 400 g of deionized water was added under shear dispersion for 10 min. The acetone was decanted under vacuum, and then 0.1 wt% Tween-20 emulsifier was added to obtain an aqueous dispersion of an aliphatic polyester polyurethane having a solid content of 32.4% by weight (B agent), which was tested by gel chromatography and DSC. The aliphatic polyester polyurethane in the aqueous dispersion was tested to have a number average molecular weight of 325,000 Daltons and a glass transition temperature of -14 °C.
  • Poplar shavings with a moisture content of 8-10% by weight were used as wood substrates for the platen test. 2000 g of surface poplar shavings was weighed into a blender. 40 g of the agent B prepared in this example was diluted with 20 g of deionized water, and the viscosity after dilution was 80 cp (25 ° C). Weigh 80g of polymethylene polyphenyl polyisocyanate PM-200 (A agent; Wanhua Chemical Group Co., Ltd.), connect a spray gun to the air compressor, and spray the above 80g A agent and diluted B agent in sequence. The gun was sprayed into a mixer under stirring for 40-60 s. The core shaving sizing is then carried out in accordance with the same process.
  • PM-200 polymethylene polyphenyl polyisocyanate
  • the sizing shavings are paved in a 350mm*350mm*100mm mold, heated to 50 °C for pre-pressing, pre-pressing pressure 1Mpa, time 1min.
  • the pre-pressed slab is pressed into a plate on a hot press, the platen temperature is 240 ° C, the relative pressure is 1.5-2 MPa, the hot pressing cycle is 200 s, and the plate thickness is controlled to be 18 mm.
  • the properties of the board are tested in accordance with the method specified in GB/T-17657-2013.
  • the mixed fiber of eucalyptus and poplar with a water content of 8-10% by weight was used as a wood substrate for the platen test, and the mixing ratio was 1/1. 2000 g of the mixed fiber was weighed into a mixer. 20 g of the B agent prepared in this example was diluted with 10 g of deionized water, and the viscosity after dilution was 350 cp (25 ° C). 60 g of emulsifiable isocyanate PM300E (A agent; Wanhua Chemical Group Co., Ltd.) was weighed, and 40 g of the A agent and the diluted B agent were mixed and stirred to obtain a mixture of the A agent and the B agent.
  • PM300E emulsifiable isocyanate
  • a spray gun is connected to the air compressor, and the mixture of the unmixed 20 g of the A agent and the above-mentioned A agent and the B agent is sequentially sprayed by a spray gun into a stirrer under stirring to stir for 40-60 s.
  • the sized fiber was spread in a 350 mm*350 mm*100 mm mold, and the temperature was raised to 40 ° C for pre-pressing, and the pre-pressing pressure was 1 Mpa for 1 min.
  • the pre-pressed slab is pressed into a plate on a hot press, the platen temperature is 240 ° C, the relative pressure is 1.5-2 MPa, the hot pressing cycle is 200 s, and the plate thickness is controlled to be 18 mm.
  • the properties of the board are tested in accordance with the method specified in GB/T-17657-2013.
  • the aliphatic polyester urethane modified product in the aqueous dispersion had a number average molecular weight of 486,000 Daltons and a glass transition temperature of -2 ° C by gel chromatography test and DSC test.
  • the mixed fiber of eucalyptus and straw straw having a water content of 8-10% by weight was used as a wood substrate for the platen test, and the mixing ratio was 1/1. 2000 g of the mixed fiber was weighed into a mixer. 20 g of the B agent prepared in this example was diluted with 40 g of deionized water, and the viscosity after dilution was 5 cp (25 ° C). Weigh 50g of polyphenylpolymethylene polyisocyanate CW30 (A agent; Wanhua Chemical Group Co., Ltd.), and take 30g of the A agent and the diluted B agent and mix well to obtain a mixture of A and B. . A spray gun is connected to the air compressor, and the unmixed 10 g of the A agent and the mixture of the above agent A and the agent B are sequentially sprayed by a spray gun into a stirrer under stirring to stir for 40-60 s.
  • a spray gun is connected to the air compressor, and the unmixe
  • the sized fiber was spread in a 350 mm*350 mm*100 mm mold, and the temperature was raised to 40 ° C for pre-pressing, and the pre-pressing pressure was 1 Mpa for 1 min.
  • the pre-pressed slab is pressed into a plate on a hot press, the platen temperature is 240 ° C, the relative pressure is 1.5-2 MPa, the hot pressing cycle is 200 s, and the plate thickness is controlled to be 18 mm.
  • the properties of the board are tested in accordance with the method specified in GB/T-17657-2013.
  • the reaction was started for 10 minutes. While stirring 1500-2000 rpm, 500 g of deionized water was added under shear dispersion for 10 min. Acetone was decanted under vacuum, and then 0.1% by mass of Tween-20 emulsifier was added to obtain 874 g of an aqueous dispersion of the aliphatic polyester urethane to be modified having a solid content of 41.1% by weight.
  • the sized fiber was paved and pre-pressed in a 350 mm*350 mm*100 mm mold, and the pre-pressure was 1 Mpa for 1 min.
  • the pre-pressed slab is pressed into a plate on a hot press, the platen temperature is 240 ° C, the relative pressure is 1.5-2 MPa, the hot pressing cycle is 200 s, and the plate thickness is controlled to be 18 mm.
  • the properties of the board are tested in accordance with the method specified in GB/T-17657-2013.
  • Poplar shavings with a moisture content of 8-10% by weight were used as wood substrates for the platen test. 2000 g of surface poplar shavings was weighed into a blender. 50 g of polymethylene polyphenyl polyisocyanate PM-200 (Wanhua Chemical Group Co., Ltd.) was weighed. A spray gun is connected to the air compressor, and the PM-200 is sprayed by a spray gun into a stirrer under stirring to stir for 40-60 seconds. The core shaving sizing is then carried out in accordance with the same process.
  • the sizing shavings are paved in a 350mm*350mm*100mm mold, and heated to 40 °C for pre-pressing, pre-pressing pressure 1Mpa, time 1min.
  • the pre-pressed slab is pressed into a plate on a hot press, the platen temperature is 170 ° C, the relative pressure is 1.5-2 MPa, the hot pressing cycle is 200 s, and the plate thickness is controlled to be 18 mm.
  • the properties of the board are tested in accordance with the method specified in GB/T-17657-2013.
  • the mixed fiber of eucalyptus and poplar with a water content of 8-10% by weight was used as a wood substrate for the platen test, and the mixing ratio was 1/1.
  • 2000 g of the mixed fiber was weighed into a mixer, and 60 g of emulsifiable isocyanate PM300E (Wanhua Chemical Group Co., Ltd.) was weighed.
  • a spray gun is connected to the air compressor, and the PM300E is sprayed by a spray gun into a stirrer under stirring to stir for 40-60 seconds.
  • the sized fiber was spread in a 350 mm*350 mm*100 mm mold, and the temperature was raised to 40 ° C for pre-pressing, and the pre-pressing pressure was 1 Mpa for 1 min.
  • the pre-pressed slab is pressed into a plate on a hot press, the platen temperature is 240 ° C, the relative pressure is 1.5-2 MPa, the hot pressing cycle is 200 s, and the plate thickness is controlled to be 18 mm.
  • the properties of the board are tested in accordance with the method specified in GB/T-17657-2013.
  • the mixed fiber of eucalyptus and poplar with a water content of 8-10% by weight was used as a wood substrate for the platen test, and the mixing ratio was 1/1. 2000 g of the mixed fiber was weighed into a mixer. 20 g of the B' agent prepared in this comparative example was diluted with 10 g of deionized water, and the viscosity after dilution was 350 cp (25 ° C). 60 g of emulsifiable isocyanate PM300E (A agent; Wanhua Chemical Group Co., Ltd.) was weighed, and 40 g of the agent A and the diluted B' agent were mixed and stirred to obtain a mixture of the agent A and the agent B. A spray gun was connected to the air compressor, and the unmixed 20 g of the A agent and the mixture of the above agent A and the B' agent were sequentially sprayed by a spray gun into a stirrer under stirring to stir for 40-60 s.
  • the sized fiber was spread in a 350 mm*350 mm*100 mm mold, and the temperature was raised to 40 ° C for pre-pressing, and the pre-pressing pressure was 1 Mpa for 1 min.
  • the pre-pressed slab is pressed into a plate on a hot press, the platen temperature is 240 ° C, the relative pressure is 1.5-2 MPa, the hot pressing cycle is 200 s, and the plate thickness is controlled to be 18 mm.
  • the properties of the board are tested in accordance with the method specified in GB/T-17657-2013.
  • Example 1 and Example 5, and Example 4 and Example 6 it can be seen that the water-repellent property and the durability of the blade obtained by adding the aqueous dispersion of the aliphatic polyester-modified polyurethane modified with the vinyl monomer
  • the properties of the sheet which are higher than the aqueous dispersion of the unmodified aliphatic polyester polyurethane indicate that the modified addition of the modified aliphatic polyester polyurethane aqueous dispersion is more favorable for the comprehensive performance of the sheet.
  • Example 4 Comparative Example 2 and Comparative Example 3 that the mechanical properties and water resistance of the prepared sheet were obtained by using an aqueous dispersion containing an aromatic polyether polyurethane (Comparative Example 3) under the same plate making process conditions.
  • the water dispersibility is poor, even less than the addition of B agent (Comparative Example 2), which is mainly because the polyether segment has poor adhesion to wood/stalk, and the water dispersion of polyurethane after sizing
  • the body is evenly distributed on the shavings/fibers, blocking the adhesion of the isocyanate binder (agent A) to the wood/stalk surface.

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Abstract

公开了一种无醛添加的人造板胶粘剂、用其制造的无醛添加人造板及其制备方法。该无醛添加的人造板胶粘剂包括A剂和B剂，所述A剂为异氰酸酯基粘合剂，B剂为脂肪族聚酯型聚氨酯和/或其改性物的水分散体。所述无醛添加人造板由木质和/或秸秆材料与所述无醛添加的人造板胶粘剂混合后在热压下形成。使用该无醛添加的人造板胶粘剂制造的人造板材具有出色的防水性能和力学性能，同时降低了异氰酸酯用量从而节省了成本，且具有良好的可锯切性能。

Description

一种无醛添加的人造板胶粘剂及用其制造的无醛添加人造板 技术领域
本发明涉及用于制造人造板的胶粘剂，具体而言，涉及一种异氰酸酯类二元胶粘剂。本发明另一方面涉及使用所述胶粘剂制造的人造板及其制造方法。
背景技术
目前常用的人造板用合成胶粘剂为以甲醛为基础的胶粘剂，包括脲醛树脂(UF)、酚醛树脂(PF)、三聚氰胺-甲醛树脂等胶粘剂为代表的“三醛胶”。这三类胶粘剂均采用甲醛为合成原料，胶接制品在生产和使用过程中都有甲醛逸出,被视为室内空气污染的主要源头之一，污染周期长、难以根本去除，一直困扰着人造板行业的发展。
出于环境因素的考虑，无醛的异氰酸酯粘合剂近年来得到了越来越广泛的应用。除不含甲醛外，异氰酸酯还有许多优点，如胶接强度高，固化速度快，对木质/秸秆材料含水率要求不严格、优异的板材物理性能等。然而，在人造板中使用异氰酸酯作为粘合剂也具有劣势。
首先，异氰酸酯价格高昂，一般单价为普通脲醛树脂的8-15倍，即使达到板材性能要求所需的单方用量较普通脲醛树脂少，但综合应用成本仍居高不下，是人造板企业广泛应用的最大困难。美国专利US 6224800公开了一种将固态的尿素和/或三聚氰胺按3:1至7:1的比例配合异氰酸酯使用的方法，应用该方法可在降低的异氰酸酯用量下达到与在较高添加量异氰酸酯单独使用时的效果，但是该方法需要事先将固态尿素和/或三聚氰胺与异氰酸酯混合进行长时间研磨并筛分，大大增加了工艺难度与制造成本。美国专利US 4944823公开了一种将蔗糖或淀粉与异氰酸酯配合使用的方法，将异氰酸酯的添加量降至1％仍可达到满足标准要求的强度，但由于采用生物基粘合剂，板材后续的发霉问题将难以解决。美国专利8895643B2公开了一种木质人造板粘合剂配方，该配方包含多苯基多异氰酸酯和至少一种水性分散体，采用该配方所制得的板坯经预压后具有至少85％脲胶的初粘性，但是该专利并未提及水性分散体对板材力学性能、防水性能、加工性能等的作用。
其次，将异氰酸酯作为人造板粘合剂所制备的板材的另一缺点为，由于异氰 酸酯在固化过程中形成大量硬度较大的脲结构，造成在对板材进行锯切裁剪等工序时对锯等加工部件磨损较使用脲醛胶严重，加工费用大幅增加。例如，当用于切割以异氰酸酯为粘合剂的人造板时，典型切割锯的寿命将减少20-40％。
人造板的防水性能(尺寸稳定性)在实际应用中具有重要作用。为获得良好的防水性能，一般在人造板的生产过程中需要加入各种例如石蜡的防水剂。石蜡的化学成分是饱和正构烷烃，几乎没有任何反应活性，是优良的疏水物质，长期以来被视为最好的防水剂。如专利CN 104559828公开了一种刨花板用乳化石蜡防水剂，该防水剂以固体石蜡、硬脂酸和水为主要原料，烷基聚氧乙烯醚和聚三梨酯为乳化剂，三聚磷酸蜡为催化剂，羧甲基纤维素钠为胶黏剂，在一定温度下经分布乳化皂化反应而成，具有较高的固含量与良好的防水性能。但正是由于石蜡没有任何反应活性，防水剂石蜡添加也有碍于木质材料与木质材料之间的结合牢度，尤其在使用异氰酸酯为粘合剂时，会妨碍异氰酸酯与木材中活性氢的反应，导致结合强度降低。因此，无论是在中(高)密度纤维板和刨花板生产中,添加石蜡或增加石蜡用量往往会影响产品的力学性能,主要是降低产品的结合强度,这已经为人造板生产问世以来的理论与实践所证实。另外，在如人造板热压过程中的180-240℃高温下，石蜡将升华或蒸发，这将导致如潜在火灾，生产成本增加等问题。
因此，提供一种制备具有良好防水性能、较低生产成本、良好力学强度，较低切割锯磨损的人造板的制备方法具有重要意义。
发明内容
为了克服上述现有技术存在的问题，本发明提供一种无醛添加的人造板胶粘剂，其包括A剂和B剂，其中，所述A剂为异氰酸酯粘合剂，所述B剂为脂肪族聚酯型聚氨酯和/或其改性物的水分散体。
在本发明的人造板胶粘剂中，作为A剂的所述异氰酸酯粘合剂为多亚甲基多苯基多异氰酸酯和/或其衍生物，NCO值(即化合物中-NCO基团的质量百分数)为20-33％，官能度为2.1-3.3，粘度为50-2000cp(25℃)。
所述多亚甲基多苯基多异氰酸酯的衍生物由多亚甲基多苯基多异氰酸酯与多元醇反应得到，可采用本领域技术人员公知的异氰酸酯衍生物的制备方法。如CN103396526A，CN1380346，CN101522741中分别公开了混合多元醇与脂肪族 异氰酸酯制备异氰酸酯衍生物的方法，US3996154公开了一种以聚氧乙烯醚聚合物与多亚甲基多苯基多异氰酸酯制备异氰酸酯衍生物的方法。在本发明中，一般而言，在所述多亚甲基多苯基多异氰酸酯中加入多元醇，保持60-80℃进行反应来制备所述多亚甲基多苯基多异氰酸酯衍生物。
合适的多亚甲基多苯基多异氰酸酯及其衍生物粘合剂优选选自万华化学集团股份有限公司的Wannate系列多异氰酸酯，包括PM-100、PM-200、PM-400、PM-600、PM-700、CW20、CW30、PM300E、9132FC中的一种或多种。
在本发明的人造板胶粘剂中，作为B剂的所述脂肪族聚酯型聚氨酯的水分散体中的脂肪族聚酯型聚氨酯优选数均分子量为5-50万道尔顿，玻璃化转变温度低于5℃。
本发明的作为B剂的所述脂肪族聚酯型聚氨酯和/或其改性物的水分散体的固含量为20-60重量％，优选40-60重量％。
所述脂肪族聚酯型聚氨酯的水分散体可通过将包含脂肪族二异氰酸酯、聚酯多元醇、含有亲水基团的扩链剂以及任选的不含亲水基团的扩链剂的原料发生聚合反应得到的脂肪族聚酯型聚氨酯在水中经高速剪切分散得到。所述的脂肪族聚酯型聚氨酯的水分散体的制备方法是该领域内技术人员公知的，如CN106243319A，CN106188465A，CN10431225公布的聚氨酯水性分散体的制备方法。
具体地，本发明的人造板胶粘剂中作为B剂的脂肪族聚酯型聚氨酯的水分散体的制备方法可包括以下步骤：
(1)预聚：将所述脂肪族二异氰酸酯、聚酯多元醇以及任选的不含亲水基团的扩链剂和/或含有亲水基团的扩链剂混合，在50-100℃下发生聚合，得到预聚物；
(2)溶解：将得到的预聚物冷却后，与丙酮充分混合以使预聚体溶解；
(3)扩链：向溶于丙酮的预聚物中加入所述含有亲水基团的扩链剂、水和任选的不含亲水基团的扩链剂的混合物，然后使其在30-50℃下继续聚合得到溶于丙酮中的脂肪族聚酯型聚氨酯；
(4)分散：在剪切分散条件下缓慢加入水，脱除丙酮，再加入任选的乳化剂，得到所述脂肪族聚酯型聚氨酯的水分散体。
在通过聚合反应制备所述脂肪族聚酯型聚氨酯时，使用的脂肪族二异氰酸酯 中的NCO基团与聚酯多元醇、含有亲水基团的扩链剂、任选的不含亲水基团的扩链剂组分中的羟基与氨基之和的摩尔比为1:(0.8-1.4)，优选1:(0.8-1.2)。
作为一种优选的技术方案，制备所述脂肪族聚酯型聚氨酯时，使用的脂肪族二异氰酸酯中的NCO基团/聚酯多元醇中的羟基/含有亲水基团的扩链剂中的羟基和氨基之和/不含亲水基团的扩链剂中的羟基和氨基之和的摩尔比为1:(0.2-0.9)：(0.02-0.3)：(0-0.7)。
在所述步骤(4)中，所述乳化剂的量为所述脂肪族聚酯型聚氨酯的水分散体的0.1-0.5重量％。
在本发明的上述制备方法中，如果步骤(1)和(3)中均使用含有亲水基团的扩链剂和/或均使用不含亲水基团的扩链剂，则步骤(1)和(3)中相应的成分可以相同或不同。
在所述脂肪族聚酯型聚氨酯的水分散体的制备方法中，所述脂肪族二异氰酸酯选自六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)、环己烷二亚甲基二异氰酸酯(HXDI)中的一种或多种。
在所述脂肪族聚酯型聚氨酯的水分散体的制备方法中，所述聚酯多元醇为己二酸系聚酯二醇、芳香族聚酯多元醇或聚己内酯型多元醇，数均分子量为400-8000道尔顿；优选数均分子量为1000-5000道尔顿的聚己二酸丁二醇酯二醇(PBA)、聚己二酸乙二醇酯二醇(PEA)、聚己二酸丙二醇酯二醇(PPA)、聚己二酸二甘醇酯二醇(PDA)、聚己二酸新戊二醇酯二醇(PNA)、聚己二酸乙二醇丁二醇酯二醇(PEBA)、聚己二酸乙二醇丙二醇(PEPA)、聚己二酸己二醇酯二醇(PHA)、聚己内酯二元醇(PCL)中的一种或多种。
在所述脂肪族聚酯型聚氨酯的水分散体的制备方法中，所述含有亲水基团的扩链剂中的亲水基团选自羧基、磺酸基、乙氧基、丙氧基或乙氧丙氧基中的一种或多种。所述含有亲水基团的扩链剂优选为二羟甲基丙酸、二羟甲基丁酸、1,2-二羟基丁烷-1-磺酸、乙二胺基乙磺酸钠、N-(2-氨基乙基)-2-氨基乙磺酸钠盐中的一种或者两种以上。
在所述脂肪族聚酯型聚氨酯的水分散体的制备方法中，所述不含亲水基团的扩链剂不是必需使用的。当使用时，所述不含亲水基团的扩链剂为选自含有2-20个碳原子的官能度为2-3的多元醇和含有2-20个碳原子的官能度为2-3的多元胺中的一种或两种以上，优选乙二醇、1,4-丁二醇、己二醇、乙二胺、丙二胺、丁 二胺、异佛尔酮二胺、1,4-环己烷二胺、4,4’-二氨基二环己基甲烷、二乙烯三胺中的一种或两种以上。
在所述脂肪族聚酯型聚氨酯的水分散体的制备方法中，使用的乳化剂可以为一种或多种。所述乳化剂包括阴离子型乳化剂，如十二烷基磺酸钠、十二烷基硫酸钠、十三烷基硫酸钠、琥珀酸磺酸钠；或非离子乳化剂，如十三烷基醇乙氧化物、油酸醇乙氧化物、苯酚氧化乙烯-氧化丙烯、氧化乙烯-氧化丙烯、聚氧乙烯失水山梨醇脂肪酸酯(吐温)。
本发明所述的脂肪族聚酯型聚氨酯改性物优选为乙烯基可聚合单体聚合物改性脂肪族聚酯型聚氨酯，其由脂肪族聚酯型聚氨酯与乙烯基可聚合单体的聚合物以化学键键合而得到。
在本发明所述的脂肪族聚酯型聚氨酯改性物中，所述乙烯基可聚合单体的聚合物部分占所述脂肪族聚酯型聚氨酯的重量百分比为5-50％。
优选地，本发明的所述脂肪族聚酯型聚氨酯改性物的水分散体的制备方法包括以下步骤：
(i)向100重量份的待改性的脂肪族聚酯型聚氨酯的水分散体中加入0.01-2重量份的乳化剂和占所述乙烯基可聚合单体总量的0.1-0.5％重量份的引发剂，以形成分散均匀的乳液，
(ii)将所述乳液加热至60-90℃，缓慢加入所述乙烯基可聚合单体，保温聚合直至反应完全；
(iii)再加入占所述乙烯基可聚合单体总量的0.1-0.5％重量份引发剂，在60-90℃下保温聚合直至反应完全，得到本发明的脂肪族聚酯型聚氨酯改性物的水分散体；
其中，所述待改性的脂肪族聚酯型聚氨酯的水分散体通过以下步骤制备得到：
(1)预聚：将脂肪族二异氰酸酯、聚酯多元醇、含羟基或氨基的乙烯基可聚合单体以及任选的不含亲水基团的扩链剂和/或含有亲水基团的扩链剂混合，在50-100℃下发生聚合，得到预聚物；
(2)溶解：将得到的预聚物冷却后，与丙酮充分混合以使预聚物溶解；
(3)扩链：向溶于丙酮的预聚物中加入所述含有亲水基团的扩链剂、水和任选的不含亲水基团的扩链剂的混合物，然后使其在30-50℃下继续进行聚合反应，得到溶于丙酮中的待改性的脂肪族聚酯型聚氨酯；
(4)分散：在剪切分散条件下缓慢加入水，脱除丙酮，再加入任选的乳化剂，得到所述待该性的脂肪族聚酯型聚氨酯的水分散体。
即，除了在步骤(1)中进一步使用含羟基或氨基的乙烯基可聚合单体参与聚合反应得到预聚物以外，所述待改性的脂肪族聚酯型聚氨酯的水分散体的制备方法与上述脂肪族聚酯型聚氨酯的水分散体的制备方法是相同的。
在一个优选的实施方案中，在所述步骤(1)中，使用的所述含有羟基或氨基的乙烯基可聚合单体摩尔数为脂肪族二异氰酸酯所含NCO基团摩尔数的0.2-5％。
所述含羟基或氨基的乙烯基可聚合单体包括(甲基)丙烯酸羟乙酯、(甲基)丙烯酸-β-羟丙酯、(甲基)丙烯酸羟丁酯、(甲基)丙烯酰胺中的一种或两种以上。
在本发明所述的脂肪族聚酯型聚氨酯改性物的水分散体的制备方法中，所述引发剂选自偶氮化合物引发剂、过氧化物引发剂和氧化还原引发剂的一种或多种，优选偶氮化合物引发剂和过氧化物引发剂，如偶氮二异丁腈，偶氮二异庚腈、过氧化苯甲酰、叔丁基过氧化氢、过氧化十二酰、过氧化叔戊酸叔丁酯、过氧化二碳酸二异丙酯中的一种或多种。
在本发明所述的脂肪族聚酯型聚氨酯改性物的水分散体的制备方法中，使用的乳化剂可以是上文中所定义的那些。
所述乙烯基可聚合单体选自(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸苯基酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸、(甲基)丙烯酰胺、苯乙烯、α-烷基苯乙烯、(甲基)丙烯腈中的一种或两种以上，优选(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸苯基酯、苯乙烯、α-烷基苯乙烯、(甲基)丙烯酸乙酯中的一种或两种以上。更优选的是，所述乙烯基可聚合单体聚合物改性脂肪族聚酯型聚氨酯为(甲基)丙烯酸苯基酯与(甲基)丙烯酸甲酯或苯乙烯共聚物改性脂肪族聚酯型聚氨酯，其中共聚物部分所含(甲基)丙烯酸苯基酯单体与(甲基)丙烯酸甲酯或苯乙烯单体的摩尔比为1-3:1。
优选地，在所述步骤(ii)中，加入的所述乙烯基可聚合单体的总质量约为所述待改性的脂肪族聚酯型聚氨酯质量的5-50％。
令人意外的是，通过以该乙烯基可聚合单体聚合物改性所述脂肪族聚酯型聚 氨酯，可提升所制备板材耐水性与可锯切性能。在一个优选实施方式中，本发明的无醛添加的人造板胶粘剂中A剂与B剂的重量比为1-5:1。
另一方面，本发明提供了一种无醛添加人造板的制造方法，包括以下步骤：
(1)将本发明的无醛添加的人造板胶粘剂中的B剂(脂肪族聚酯型聚氨酯和/或其改性物的水分散体)以水稀释，B剂与水的重量比为0.5-4:1，以得到粘度≤600cp(25℃)的稀释后的B剂；
(2)将本发明的无醛添加的人造板胶粘剂中的A剂(异氰酸酯粘合剂)与所述稀释后的B剂施胶到木质和/或秸秆材料中，然后，将木质和/或秸秆材料与所述无醛添加的人造板胶粘剂搅拌，使得木质和/或秸秆材料上均匀分布所述无醛添加的人造板胶粘剂；
(3)将混有所述无醛添加的人造板胶粘剂的木质和/或秸秆材料铺装并预压成型为人造板；
(4)将预压成型的人造板热压成型。
根据本发明提供的无醛添加人造板的制备方法，在所述步骤(2)中，所述无醛添加的人造板胶粘剂的A剂与B剂的总添加量为木质和/或秸秆材料的1-6重量％，优选2-5重量％。
根据本发明提供的无醛添加人造板的制备方法，在上述步骤(2)中，所述A剂与稀释后的B剂可以以任何顺序先后单独地施胶到所述木质和/或秸秆材料中。但是，更优选的是，将全部或部分的A剂与全部的稀释后的B剂混合得到A剂与B剂的混合物，将所述A剂和B剂的混合物施胶到所述木质和/或秸秆材料中；若存在未混合的部分A剂，则所述未混合的部分A剂先于或后于所述A剂与B剂的混合物施胶到所述木质和/或秸秆材料中。在此实施方式中，优选地，用于与稀释后的B剂混合的A剂占全部A剂重量的40-100％。所述全部或部分的A剂和全部的用水稀释后的B剂的混合可通过机械搅拌混合或在线静态混合器混合来进行。
根据本发明提供的无醛添加人造板的制备方法，在上述步骤(1)和(2)中，分别使用机械搅拌混合或在线静态混合器混合。
根据本发明提供的无醛添加人造板的制备方法，在上述步骤(3)中，在预压之前，将混合好本发明的无醛添加的人造板胶粘剂的木质和/或秸秆材料升温至40-75℃。
根据本发明提供的无醛添加人造板的制备方法，在上述步骤(4)中，热压温度为170-240℃。
在所述无醛添加的人造板的制造方法中，所述木质材料选自杨木、松木，桉木、苹果木、山毛榉中的一种或多种；所述秸秆材料选自玉米秸秆、稻草、麦秆、向日葵秸秆、油菜秆、棉花秆中的一种或多种；木质材料与秸秆材料按任意比例混合。所述木质和/或秸秆材料的含水率优选为1-20％。
根据所制备的板种，可首先将木质和/或秸秆材料制备成为刨花或纤维。纤维或刨花的制备是本领域技术人员公知的技术。如专利CN104290169A描述了一种木质纤维制备方法，CN104385424A公开一种农作物秸秆刨花的制备方法。可以理解的是，下文中所述木质和/或秸秆材料包括刨花和/或纤维的形式。
本发明还提供一种根据上述方法制造的无醛添加的人造板。特别地，本发明提供一种无醛添加人造板，其原料包含以下组分：(1)木质和/或秸秆材料；(2)所述木质和/或秸秆材料的1-6重量％、优选2-5重量％的本发明的无醛添加的人造板胶粘剂(A剂与B剂的总和)。
由于本发明的无醛添加的人造板胶粘剂存在于木质和/或秸秆材料之间，使该无醛添加人造板的24h吸水厚度膨胀率小于12％，更典型的例子为小于10％；内结合强度大于0.5MPa，更典型的例子为大于0.7MPa(依据GB/T 17657-2013所规定的测试方法)。
本发明的无醛添加的人造板胶粘剂提高板材力学性能、耐水性与可锯切性能的机理如下：
本发明的无醛添加的人造板胶粘剂中含有的脂肪族聚酯型聚氨酯和/或其改性物的水分散体本身对木材的粘接性能良好。在与异氰酸酯粘合剂混合的过程中，部分异氰酸酯与脂肪族聚酯型聚氨酯和/或其改性物结构上的羟基、羧基等活性基团反应，生成具有优异粘接性能的网络结构。此网络结构一方面增强板材的力学性能，另一方面增强板材的耐水性。尤其是当以乙烯基单体聚合物改性脂肪族聚酯型聚氨酯时，由于乙烯基单体聚合物在胶粘剂体系中形成微相分离填充于胶粘剂中，导致胶粘剂硬度进一步降低，对锯片磨损下降。同时，由于乙烯基单体聚合物的疏水性能，导致水分难以渗透入胶粘剂，因此耐水性提高。特别地，在将全部或部分异氰酸酯粘合剂与所述水分散体充分混合后再将该混合物施胶的情况下，所述水分散体包裹并消耗异氰酸酯，减少异氰酸酯与水反应生成坚硬的 聚脲结构(锯切性能差的主要原因)。同时，由于所述水分散体对木材表面的覆盖，也减少异氰酸酯与木材生成化学键合的可能性，因此可减少锯切时对锯片的磨损。
因此，使用本发明的无醛添加的人造板胶粘剂制造的无醛添加人造板力学性能良好，防水性能优异，胶粘剂成本降低，且在后续加工过程中对锯的磨损明显减少。
具体实施方式
下述例子是为了更好的说明本发明的无醛人造板制备方法的实施效果，以下所列的实施例中的组分、方法等具体选择并不限制本发明的范围。
实施例中使用的产品：
PCL，聚己内酯二元醇，日本大赛璐化学工业株式会社；
PBA，聚己二酸丁二醇酯二醇，华大化学有限公司；
PEA，聚己二酸乙二醇酯二醇，华大化学有限公司；
PHA,聚己二酸己二醇酯二醇，华大化学有限公司；
HDI，六亚甲基二异氰酸酯，万华化学集团股份有限公司；
HMDI，二环己基甲烷二异氰酸酯，万华化学集团股份有限公司；
IPDI，异佛尔酮二异氰酸酯，万华化学集团股份有限公司；
HXDI，环己烷二亚甲基二异氰酸酯，日本三井武田公司；
TDI，甲苯二异氰酸酯，博苏化学；
HMDA，4,4’-二氨基二环己基甲烷，万华化学集团股份有限公司；
IPDA，异佛尔酮二胺，万华化学集团股份有限公司；
DMPA，二羟甲基丙酸，瑞典Perstorp公司；
二羟甲基丁酸，金腾龙化工；
A95，N-(2-氨基乙基)-2-氨基乙磺酸钠盐，德国EVONIC公司；
PTMEG,聚四亚甲基醚二醇，韩国PTG公司。
数均分子量的测定采用凝胶色谱仪(Hewlett Packard公司HP100型)，色谱柱为HP PL gel MIXED-B。标准样品为窄分布聚苯乙烯。
将样品溶于流动相四氢呋喃，配成1.5g/L的溶液，过滤后进样。进样量为400μL，柱压5.0MPa，流速1.5ml/min。，
玻璃化转变温度的测定使用差示扫描量热法(DSC)测定。使用梅特勒-托利多公司的DSC3差式扫描量热仪，测试范围为100～30℃，试样重8～12mg，在液氮保护下样品被冷却到-100℃，然后以10℃/min的升温速率加热，测试其DSC曲线，确定玻璃化转变温度。粘度的测定使用Brookfield公司LV型旋转粘度计，按照国标GB/T 2794所规定的方法测试。
实施例1
(1)脂肪族聚酯型聚氨酯的水分散体的制备
将26.2g HMDI、16.8g HDI、170.0g PCL-2000(试剂后数字为该试剂的数均分子量，下同)、4.0g 1,4-丁二醇、1.0g DMPA加入到反应釜中，升温到70-80℃反应，待NCO值达到2.41％后，使预聚物冷却到40℃，加入350g丙酮稀释，维持温度40-45℃混合10min。将2.14g乙二胺和5.0g A95在15g去离子水中混合均匀，混合溶液在1分钟左右的时间内加入至反应釜中，混合液加入完成后开始计时，在30-50℃下反应10min。保持搅拌1500-2000转/min，加入0.34g三乙胺在搅拌下中和5min，以使pH为6-9。在剪切分散下加入185g去离子水，加入时间为10min。真空下，将丙酮脱出，然后再加入0.1重量％吐温-20乳化剂，得到固含量为52.9重量％的脂肪族聚酯型聚氨酯的水分散体(B剂)，以凝胶色谱测试和DSC测试，该水分散体中脂肪族聚酯型聚氨酯的数均分子量为11.2万道尔顿，玻璃化转变温度为-20℃。
(2)板材制备
以含水率为8-10wt％的杨木刨花作为压板试验的木材底物。称取表层杨木刨花2000g加入搅拌机中。将20g本实施例所制备的B剂以10g去离子水稀释，稀释后粘度为100cp(25℃)。称取50g多亚甲基多苯基多异氰酸酯PM-200(A剂；万华化学集团股份有限公司)，将其中20g A剂与上述稀释后的B剂混合搅拌均匀，得到A剂与B剂的混合物。将一喷枪连接空气压缩机，将未混合的30g A剂和上述A剂与B剂的混合物依次由喷漆枪喷入搅拌状态下的搅拌机中搅拌40-60s。之后按照同样的工艺进行芯层刨花施胶。
然后，按照360g表层刨花+980g芯层刨花+360g表层刨花的铺装比例，将施胶后的刨花于一350mm*350mm*100mm模具中进行铺装，升温至40℃进行预压，预压压力1Mpa，时间1min。将预压后的板坯于热压机上压制成板压板温度 170℃，相对压力1.5-2MPa，热压周期200s，板厚度控制为18mm。压制完成后，按照国标GB/T-17657-2013所规定的方法测试板材各性能。
实施例2
(1)脂肪族聚酯型聚氨酯的水分散体的制备
将10.0g IPDI、40.0g HDI、200.0g PBA-2000、8.0g 1,4-丁二醇加入到反应釜中，升温到70-80℃反应，待NCO值达到3.04％后，使预聚物冷却到40℃，加入300g丙酮稀释，维持温度40-45℃混合10min。将10g IPDA和5.0g A95在15g去离子水中混合均匀，混合溶液在1分钟左右的时间内加入至反应釜中，混合液加入完成后开始计时，在30-50℃下反应10min。保持搅拌1500-2000转/min，在剪切分散下加入385g去离子水，加入时间为10min。真空下，将丙酮脱出，然后再加入0.1重量％吐温-20乳化剂，得到固含量为40.6重量％的脂肪族聚酯型聚氨酯的水分散体(B剂)，以凝胶色谱测试和DSC测试，该水分散体中脂肪族聚酯型聚氨酯的数均分子量为48.5万道尔顿，玻璃化转变温度为-30℃。
(2)板材制备
以含水率为8-10wt％的松木刨花作为压板试验的木材底物。称取表层松木刨花2000g加入搅拌机中。将40g本实施例所制备的B剂以20g去离子水稀释至粘度为550cp(25℃)。称取80g多亚甲基多苯基多异氰酸酯PM-200(A剂；万华化学集团股份有限公司)，将其中32g A剂与上述稀释后的B剂混合搅拌均匀，得到A剂与B剂的混合物。将一喷枪连接空气压缩机，将上述A剂与B剂的混合物与未混合的58g PM-200和依次由喷漆枪喷入搅拌状态下的搅拌机中搅拌40-60s。之后按照同样的工艺进行芯层刨花施胶。
然后，按照360g表层刨花+980g芯层刨花+360g表层刨花的铺装比例，将施胶后的刨花于一350mm*350mm*100mm模具中进行铺装，升温至75℃进行预压，预压压力1Mpa，时间1min。将预压后的板坯于热压机上压制成板，压板温度240℃，相对压力1.5-2MPa，热压周期200s，板厚度控制为18mm。压制完成后，按照国标GB/T-17657-2013所规定的方法测试板材各性能。
实施例3
(1)脂肪族聚酯型聚氨酯的水分散体的制备
将80g HXDI、100.0g PEA-400、8.0g 1,4-丁二醇，2.0g DMPA加入到反应釜中，升温到70-80℃反应，待NCO值达到2.13％后，使预聚物冷却到40℃， 加入300g丙酮稀释，维持温度40-45℃混合10min。将4g IPDA和5.0g A95在15g去离子水中混合均匀，混合溶液在1分钟左右的时间内加入至反应釜中，混合液加入完成后开始计时，在30-50℃下反应10min。保持搅拌1500-2000转/min，在剪切分散下加入400g去离子水，加入时间为10min。真空下，将丙酮脱出，然后再加入0.1重量％吐温-20乳化剂，得到固含量为32.4重量％的脂肪族聚酯型聚氨酯的水分散体(B剂)，以凝胶色谱测试和DSC测试，该水分散体中脂肪族聚酯型聚氨酯的数均分子量为32.5万道尔顿，玻璃化转变温度为-14℃。
(2)板材制备
以含水率为8-10wt％的杨木刨花作为压板试验的木材底物。称取表层杨木刨花2000g加入搅拌机中。将40g本实施例所制备的B剂以20g去离子水稀释，稀释后粘度为80cp(25℃)。称取80g多亚甲基多苯基多异氰酸酯PM-200(A剂；万华化学集团股份有限公司)，将一喷枪连接空气压缩机，将上述80g A剂和稀释后的B剂依次由喷漆枪喷入搅拌状态下的搅拌机中搅拌40-60s。之后按照同样的工艺进行芯层刨花施胶。
然后，按照360g表层刨花+980g芯层刨花+360g表层刨花的铺装比例，将施胶后的刨花于一350mm*350mm*100mm模具中进行铺装，升温至50℃进行预压，预压压力1Mpa，时间1min。将预压后的板坯于热压机上压制成板，压板温度240℃，相对压力1.5-2MPa，热压周期200s，板厚度控制为18mm。压制完成后，按照国标GB/T-17657-2013所规定的方法测试板材各性能。
实施例4
(1)脂肪族聚酯型聚氨酯的水分散体的制备
将50.0g HDI、105.0g PBA-500、50.0g PHA-5000、4.0g 1,4-丁二醇、1.0g DMPA加入到反应釜中，升温到70-80℃反应，待NCO值达到1.98％后，使预聚物冷却到40℃，加入300g丙酮稀释，维持温度40-45℃混合10min。将6.0g HMDA和2.0g二羟甲基丁酸在15g去离子水中混合均匀，混合溶液在1分钟左右的时间内加入至反应釜中，混合液加入完成后开始计时，在30-50℃下反应10min。保持搅拌1500-2000转/min，在剪切分散下加入400g去离子水，加入时间为10min。真空下，将丙酮脱出，然后再加入0.1重量％吐温-20乳化剂，得到固含量为34.4重量％的脂肪族聚酯型聚氨酯的水分散体(B剂)，以凝胶色谱测试和DSC测试，，该水分散体中脂肪族聚酯型聚氨酯的数均分子量为22.4万道尔顿， 玻璃化转变温度为-25℃。
(2)板材制备
以含水率为8-10wt％的桉木与杨木的混合纤维，作为压板试验的木材底物，混合重量比1/1。称取混合纤维2000g加入搅拌机中。将20g本实施例所制备的B剂以10g去离子水稀释，稀释后粘度为350cp(25℃)。称取60g可乳化异氰酸酯PM300E(A剂；万华化学集团股份有限公司)，将其中40g A剂与上述稀释后的B剂混合搅拌均匀，得到A剂和B剂的混合物。将一喷枪连接空气压缩机，将未混合的20g A剂与上述A剂和B剂的混合物依次由喷漆枪喷入搅拌状态下的搅拌机中搅拌40-60s。
然后，将施胶后的纤维于一350mm*350mm*100mm模具中进行铺装，升温至40℃进行预压，预压压力1Mpa，时间1min。将预压后的板坯于热压机上压制成板，压板温度240℃，相对压力1.5-2MPa，热压周期200s，板厚度控制为18mm。压制完成后，按照国标GB/T-17657-2013所规定的方法测试板材各性能。
实施例5
(1)脂肪族聚酯型聚氨酯改性物的水分散体的制备
将30.0g HDI、225.0g PHA-3000、6.0g 1,6-己二醇、2.0g DMPA、0.25g甲基丙烯酸羟乙酯加入到反应釜中，升温到70-80℃反应，待NCO值达到7.65％后，使预聚物冷却到40℃，加入300g丙酮稀释，维持温度40-45℃混合10min。将10g HMDA和5.0g A95在15g去离子水中混合均匀，混合溶液在1分钟左右的时间内加入至反应釜中，混合液加入完成后开始计时，在30-50℃下反应10min。保持搅拌1500-2000转/min，在剪切分散下加入600g去离子水，加入时间为10min。真空下，将丙酮脱出，然后再加入0.1重量％吐温-20乳化剂，得到固含量为31.2重量％的待改性的脂肪族聚酯型聚氨酯的水分散体894g。
然后，向得到的上述894g水分散体中加入1.5g十二烷基磺酸钠，逐渐升温至60℃，加入过硫酸铵0.15g作为聚合引发剂，同时在3h内均匀缓慢地滴入甲基丙烯酸苯基酯84g，甲基丙烯酸甲酯42g，80℃反应2h，再加入过硫酸铵0.15g，升温至85℃继续反应1h，降温至50℃出料，得到固含量为39.7％的脂肪族聚酯型聚氨酯改性物的水分散体(B剂)。以凝胶色谱测试和DSC测试，该水分散体中脂肪族聚酯型聚氨酯改性物的数均分子量为48.6万道尔顿，玻璃化转变温度为-2℃。
(2)板材制备
以含水率为8-10wt％的桉木与稻草秸秆的混合纤维，作为压板试验的木材底物，混合重量比1/1。称取混合纤维2000g加入搅拌机中。将20g本实施例所制备的B剂以40g去离子水稀释，稀释后粘度为5cp(25℃)。称取50g多苯基多亚甲基多异氰酸酯CW30(A剂；万华化学集团股份有限公司)，取其中30g A剂与上述稀释后的B剂混合搅拌均匀，得到A剂与B剂的混合物。将一喷枪连接空气压缩机，将未混合的10g A剂和上述A剂与B剂的混合物依次由喷漆枪喷入搅拌状态下的搅拌机中搅拌40-60s。
然后，将施胶后的纤维于一350mm*350mm*100mm模具中进行铺装，升温至40℃进行预压，预压压力1Mpa，时间1min。将预压后的板坯于热压机上压制成板，压板温度240℃，相对压力1.5-2MPa，热压周期200s，板厚度控制为18mm。压制完成后，按照国标GB/T-17657-2013所规定的方法测试板材各性能。
实施例6
(1)脂肪族聚酯型聚氨酯改性物的水分散体的制备
将20.0g HMDI、18.0g IPDI、300.0g PBA-4000，6.0g 1,6-己二醇、2.0g DMPA、0.5g甲基丙烯酸羟乙酯加入到反应釜中，升温到70-80℃反应，待NCO值达到2.35％后，使预聚物冷却到40℃，加入300g丙酮稀释，维持温度40-45℃混合10min。将10g HMDA和2.0g A95在15g去离子水中混合均匀，混合溶液在1分钟左右的时间内加入至反应釜中，混合液加入完成后开始计时，反应10min。保持搅拌1500-2000转/min，在剪切分散下加入500g去离子水，加入时间为10min。真空下，将丙酮脱出，然后再加入0.1质量％吐温-20乳化剂，得到固含量为41.1重量％的待改性的脂肪族聚酯型聚氨酯的水分散体874g。
然后，向上述得到的水分散体874g中加入1.5g十二烷基磺酸钠，逐渐升温至60℃，加入过硫酸铵0.04g，同时缓慢在3h内均匀滴入甲基丙烯酸苯基酯18.0g，苯乙烯13.0g，80℃反应2h，再加入过硫酸铵0.04g，升温至85℃继续反应1h，降温至50℃出料，得到固含量约43.1重量％的脂肪族聚酯型聚氨酯改性物的水分散体(B剂)。以凝胶色谱测试和DSC测试，该水分散体中脂肪族聚酯型聚氨酯改性物的数均分子量为22.0万道尔顿，玻璃化转变温度为-18℃。
(2)板材制备
以含水率为8-10wt％的桉木与稻草秸秆的混合纤维，作为压板试验的木材底 物，混合重量比1/1。称取混合纤维2000g加入搅拌机中。将20g本实施例所制备的B剂以40g去离子水稀释，稀释后粘度为50cp(25℃)。称取60g多苯基多亚甲基多异氰酸酯CW20(A剂；万华化学集团股份有限公司)，取其中30g A剂与上述稀释后的B剂混合搅拌均匀，得到A剂与B剂的混合物。将一喷枪连接空气压缩机，将未混合的30g A剂和上述A剂与B剂的混合物依次由喷漆枪喷入搅拌状态下的搅拌机中搅拌40-60s。
然后，将施胶后的纤维于一350mm*350mm*100mm模具中进行铺装并预压，预压压力1Mpa，时间1min。将预压后的板坯于热压机上压制成板，压板温度240℃，相对压力1.5-2MPa，热压周期200s，板厚度控制为18mm。压制完成后，按照国标GB/T-17657-2013所规定的方法测试板材各性能。
对比例1
以含水率为8-10wt％的杨木刨花作为压板试验的木材底物。称取表层杨木刨花2000g加入搅拌机中。称取50g多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)。将一喷枪连接空气压缩机，将上述PM-200由喷漆枪喷入搅拌状态下的搅拌机中搅拌40-60s。之后按照同样的工艺进行芯层刨花施胶。
然后，按照360g表层刨花+980g芯层刨花+360g表层刨花的铺装比例，将施胶后的刨花于一350mm*350mm*100mm模具中进行铺装，升温至40℃进行预压，预压压力1Mpa，时间1min。将预压后的板坯于热压机上压制成板，压板温度170℃，相对压力1.5-2MPa，热压周期200s，板厚度控制为18mm。压制完成后，按照国标GB/T-17657-2013所规定的方法测试板材各性能。
对比例2
以含水率为8-10wt％的桉木与杨木的混合纤维，作为压板试验的木材底物，混合重量比1/1。称取混合纤维2000g加入搅拌机中，称取60g可乳化异氰酸酯PM300E(万华化学集团股份有限公司)。将一喷枪连接空气压缩机，将上述PM300E由喷漆枪喷入搅拌状态下的搅拌机中搅拌40-60s。
然后，将施胶后的纤维于一350mm*350mm*100mm模具中进行铺装，升温至40℃进行预压，预压压力1Mpa，时间1min。将预压后的板坯于热压机上压制成板，压板温度240℃，相对压力1.5-2MPa，热压周期200s，板厚度控制为18mm。压制完成后，按照国标GB/T-17657-2013所规定的方法测试板材各性能。
对比例3
(1)芳香族聚醚型聚氨酯的水分散体的制备
将40.0g TDI、300.0g PTMEG-3000、4.0g 1,4-丁二醇、1.0g DMPA加入到反应釜中，升温到70-80℃反应，待NCO值达到2.89％后，使预聚物冷却到40℃，加入300g丙酮稀释，维持温度40-45℃混合10min。将6g HMDA和2.0g二羟甲基丁酸在15g去离子水中混合均匀，混合溶液在1分钟左右的时间内加入至反应釜中，混合液加入完成后开始计时，在30-50℃下反应10min。保持搅拌1500-2000转/min，在剪切分散下加入280g去离子水，加入时间为10min。真空下，将丙酮脱出，然后再加入0.1质量％吐温-20乳化剂，得到固含量为54.5质量％的芳香族聚醚型聚氨酯的水分散体(B’剂)，以凝胶色谱测试，该水分散体中芳香族聚醚型聚氨酯的数均分子量为33.4万道尔顿。
(2)板材制备
以含水率为8-10wt％的桉木与杨木的混合纤维，作为压板试验的木材底物，混合重量比1/1。称取混合纤维2000g加入搅拌机中。将20g本对比例所制备的B’剂以10g去离子水稀释，稀释后粘度为350cp(25℃)。称取60g可乳化异氰酸酯PM300E(A剂；万华化学集团股份有限公司)，将其中40g A剂与上述稀释后的B’剂混合搅拌均匀，得到A剂与B’剂的混合物。将一喷枪连接空气压缩机，将未混合的20g A剂和上述A剂与B’剂的混合物依次由喷漆枪喷入搅拌状态下的搅拌机中搅拌40-60s。
然后，将施胶后的纤维于一350mm*350mm*100mm模具中进行铺装，升温至40℃进行预压，预压压力1Mpa，时间1min。将预压后的板坯于热压机上压制成板，压板温度240℃，相对压力1.5-2MPa，热压周期200s，板厚度控制为18mm。压制完成后，按照国标GB/T-17657-2013所规定的方法测试板材各性能。
表1.板材性能对比
Figure PCTCN2017089126-appb-000001
Figure PCTCN2017089126-appb-000002
Figure PCTCN2017089126-appb-000003
*锯片耐用度测试依据标准JB-T9951-1999木工硬质合金圆锯片耐用度试验进行，耐用度以锯片顶刃后面磨损平均VB值达到0.5mm时，切削板材总长度表示。
对比以上板材性能可以看出，实施例1与对比例1相比，异氰酸酯粘合剂施胶量相当(2.5％)，由于添加了脂肪族聚酯型聚氨酯的水分散体，实施例1所制板材的力学性能、防水性能与锯片耐用度均提升。表明脂肪族聚酯型聚氨酯的水分散体的添加有助于提升板材力学性能、防水性能与可锯切性。纤维板中仍可看到同样的趋势(实施例4与对比例2)。对比实施例1和实施例5，以及实施例4与实施例6可以看出，添加经乙烯基单体改性的脂肪族聚酯型聚氨酯的水分散体所得板材的防水性能与锯片耐用度均高于未改性脂肪族聚酯型聚氨酯的水分散体的板材性能，表明改性添加改性脂肪族聚酯型聚氨酯水分散体更有利于板材综合性能提高。
由实施例2和3对比可以看出，在较高异氰酸酯粘合剂添加量下，采用混合后施胶的锯片耐用度较分别施胶好。这是因为混合施胶使得异氰酸酯与脂肪族聚酯型聚氨酯反应，较少生成难以锯切的聚脲结构，使得锯片耐用度提升。
由实施例4、对比例2和对比例3可以看出，在相同的制板工艺条件下，采用添加芳香族聚醚型聚氨酯的水分散体(对比例3)，所制板材力学性能与耐水性较添加脂肪族聚酯型聚氨酯的水分散性差，甚至较不添加B剂(对比例2)差，这主要是因为聚醚链段与木材/秸秆粘附性差，施胶后聚氨酯的水分散体均匀分布在刨花/纤维上，阻隔异氰酸酯粘合剂(A剂)与木材/秸秆表面的粘接所致。

Claims (18)

  1. 一种无醛添加的人造板胶粘剂，包括A剂和B剂，其中，所述A剂为异氰酸酯粘合剂，所述B剂为脂肪族聚酯型聚氨酯和/或其改性物的水分散体，优选地，所述A剂与B剂的重量比为1-5:1。
  2. 根据权利要求1所述的无醛添加的人造板胶粘剂，其中，作为A剂的所述异氰酸酯粘合剂为多亚甲基多苯基多异氰酸酯和/或其衍生物，NCO值为20-33％，官能度为2.1-3.3，粘度为50-2000cp(25℃)；所述多亚甲基多苯基多异氰酸酯的衍生物由多亚甲基多苯基多异氰酸酯与多元醇反应得到。
  3. 根据权利要求1所述的无醛添加的人造板胶粘剂，其中，作为B剂的所述脂肪族聚酯型聚氨酯的水分散体中所述脂肪族聚酯型聚氨酯的数均分子量为5-50万道尔顿，玻璃化转变温度低于5℃。
  4. 根据权利要求1所述的无醛添加的人造板胶粘剂，其中，作为B剂的所述脂肪族聚酯型聚氨酯和/或其改性物的水分散体的固含量为20-60重量％，优选40-60重量％。
  5. 根据权利要求1所述的无醛添加的人造板胶粘剂，其中，所述B剂为所述脂肪族聚酯型聚氨酯的水分散体，其通过包含脂肪族二异氰酸酯、聚酯多元醇、含有亲水基团的扩链剂以及任选的不含亲水基团的扩链剂的原料发生聚合反应得到的脂肪族聚酯型聚氨酯在水中经高速剪切分散得到。
  6. 根据权利要求5所述的无醛添加的人造板胶粘剂，其中，所述脂肪族二异氰酸酯中的NCO基团/聚酯多元醇中的羟基/含有亲水基团的扩链剂中的羟基和氨基之和/不含亲水基团的扩链剂中的羟基和氨基之和的摩尔比为1:(0.2-0.9)：(0.02-0.3)：(0-0.7)。
  7. 根据权利要求5所述的无醛添加的人造板胶粘剂，其中，所述脂肪族二异氰酸酯选自六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、环己烷二亚甲基二异氰酸酯中的一种或多种；
    所述聚酯多元醇为己二酸系聚酯二醇、芳香族聚酯多元醇或聚己内酯型多元醇，数均分子量为400-8000道尔顿；优选数均分子量为1000-5000道尔顿的聚己二酸丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚己二酸丙二醇酯二醇、聚己二酸二甘醇酯二醇、聚己二酸新戊二醇酯二醇、聚己二酸乙二醇丁二醇酯二醇、 聚己二酸乙二醇丙二醇、聚己二酸己二醇酯二醇、聚己内酯二元醇中的一种或多种；
    所述含有亲水基团的扩链剂中的亲水基团选自羧基、磺酸基、乙氧基、丙氧基或乙氧丙氧基中的一种或多种；所述含有亲水基团的扩链剂优选为二羟甲基丙酸、二羟甲基丁酸、1,2-二羟基丁烷-1-磺酸、乙二胺基乙磺酸钠、N-(2-氨基乙基)-2-氨基乙磺酸钠盐中的一种或者两种以上；
    所述任选的不含亲水基团的扩链剂为选自含有2-20个碳原子的官能度为2-3的多元醇和含有2-20个碳原子的官能度为2-3的多元胺中的一种或两种以上，优选乙二醇、1,4-丁二醇、己二醇、乙二胺、丙二胺、丁二胺、异佛尔酮二胺、1,4-环己烷二胺、4,4’-二氨基二环己基甲烷、二乙烯三胺中的一种或两种以上。
  8. 根据权利要求1所述的无醛添加的人造板胶粘剂，其中，所述B剂为所述脂肪族聚酯型聚氨酯改性物的水分散体，其中，所述脂肪族聚酯型聚氨酯改性物为乙烯基可聚合单体聚合物改性脂肪族聚酯型聚氨酯，其由脂肪族聚酯型聚氨酯与乙烯基可聚合单体的聚合物以化学键键合而得到。
  9. 根据权利要求8所述的无醛添加的人造板胶粘剂，其中，所述乙烯基可聚合单体的聚合物部分占所述脂肪族聚酯型聚氨酯的重量百分比为5-50％。
  10. 根据权利要求9所述的无醛添加的人造板胶粘剂，其中，所述脂肪族聚酯型聚氨酯改性物的水分散体的制备方法包括以下步骤：
    (i)向100重量份的待改性的脂肪族聚酯型聚氨酯的水分散体中加入0.01-2重量份的乳化剂和占所述乙烯基可聚合单体总量的0.1-0.5％重量份的引发剂，以形成分散均匀的乳液，
    (ii)将所述乳液加热至60-90℃，缓慢加入所述乙烯基可聚合单体，保温聚合直至反应完全；
    (iii)再加入占所述乙烯基可聚合单体总量的0.1-0.5％重量份的引发剂，在60-90℃下保温聚合直至反应完全，得到所述脂肪族聚酯型聚氨酯改性物的水分散体；
    其中，在步骤(i)中所使用的待改性的脂肪族聚酯型聚氨酯的水分散体通过以下步骤制备得到：
    (1)预聚：将所述脂肪族二异氰酸酯、聚酯多元醇、含羟基或氨基的乙烯 基可聚合单体以及任选的不含亲水基团的扩链剂和/或含有亲水基团的扩链剂混合，在50-100℃下发生聚合反应，得到预聚物；
    (2)溶解：将得到的预聚物冷却后，与丙酮充分混合以使预聚物溶解；
    (3)扩链：向溶于丙酮的预聚物中加入所述含有亲水基团的扩链剂、水和任选的不含亲水基团的扩链剂的混合物，然后使其在30-50℃下继续进行聚合反应，得到溶于丙酮中的待改性的脂肪族聚酯型聚氨酯；
    (4)分散：在剪切分散条件下缓慢加入水，脱除丙酮，再加入任选的乳化剂，得到所述待该性的脂肪族聚酯型聚氨酯的水分散体。
  11. 根据权利要求10所述的无醛添加的人造板胶粘剂，其中，在所述步骤(1)中，使用的所述含有羟基或氨基的乙烯基可聚合单体摩尔数为脂肪族二异氰酸酯所含NCO基团摩尔数的0.2-5％；
    在所述步骤(4)中，所述乳化剂的量为所述待改性的脂肪族聚酯型聚氨酯的水分散体的0.1-0.5重量％；
    在所述步骤(ii)中，加入的所述乙烯基可聚合单体的总质量约为所述待改性的脂肪族聚酯型聚氨酯质量的5-50％。
  12. 根据权利要求11所述的无醛添加的人造板胶粘剂，其中，所述含羟基或氨基的乙烯基可聚合单体包括(甲基)丙烯酸羟乙酯、(甲基)丙烯酸-β-羟丙酯、(甲基)丙烯酸羟丁酯、(甲基)丙烯酰胺中的一种或两种以上；
    所述乙烯基可聚合单体选自(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸苯基酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸、(甲基)丙烯酰胺、苯乙烯、α-烷基苯乙烯、(甲基)丙烯腈中的一种或两种以上，优选(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸苯基酯、苯乙烯、α-烷基苯乙烯、(甲基)丙烯酸乙酯中的一种或两种以上；更优选的是，所述乙烯基可聚合单体聚合物改性脂肪族聚酯型聚氨酯为(甲基)丙烯酸苯基酯与(甲基)丙烯酸甲酯或苯乙烯共聚物改性脂肪族聚酯型聚氨酯，其中共聚物部分所含(甲基)丙烯酸苯基酯单体与(甲基)丙烯酸甲酯或苯乙烯单体的摩尔比为1-3:1。
  13. 一种无醛添加人造板的制造方法，使用如权利要求1所述的无醛添加的人造板胶粘剂，所述制造方法包括以下步骤：
    (1)将所述无醛添加的人造板胶粘剂中的B剂以水稀释，B剂与水的重量比为0.5-4:1，以得到粘度≤600cp(25℃)的稀释后的B剂；
    (2)将所述无醛添加的人造板胶粘剂中的A剂与所述稀释后的B剂施胶到木质和/或秸秆材料中，然后，将木质和/或秸秆材料与所述无醛添加的人造板胶粘剂搅拌，使得木质和/或秸秆材料上均匀分布所述无醛添加的人造板胶粘剂；
    (3)将混有所述无醛添加的人造板胶粘剂的木质和/或秸秆材料铺装并预压成型为人造板；
    (4)将预压成型的人造板热压成型。
  14. 根据权利要求13所述的制造方法，其中，在所述步骤(2)中，所述无醛添加的人造板胶粘剂的A剂与B剂的总添加量为木质和/或秸秆材料的1-6重量％，优选2-5重量％。
  15. 根据权利要求14所述的制造方法，其中，在上述步骤(2)中，所述A剂与稀释后的B剂以任何顺序先后单独地施胶到所述木质和/或秸秆材料中，或，
    将全部或部分的A剂与全部的稀释后的B剂混合得到A剂与B剂的混合物，将所述A剂和B剂的混合物施胶到所述木质和/或秸秆材料中；若存在未混合的部分A剂，则所述未混合的部分A剂先于或后于所述A剂与B剂的混合物施胶到所述木质和/或秸秆材料中。
  16. 根据权利要求15所述的制造方法，其中，在所述步骤(2)中，用于与稀释后的B剂混合的部分A剂占全部A剂重量的40-100％。
  17. 根据权利要求13所述的制造方法，其中，在所述步骤(3)中，在预压之前，将混合好所述无醛添加的人造板胶粘剂的木质和/或秸秆材料升温至40-75℃；在所述步骤(4)中，热压温度为170-240℃。
  18. 一种无醛添加人造板，其原料包含以下组分：(1)木质和/或秸秆材料；(2)所述木质和/或秸秆材料的1-6重量％、优选2-5重量％的根据权利要求1-12中任一项所述的无醛添加的人造板胶粘剂。
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