WO2022116362A1 - 包含具有酰胺基团与羧基和/或其铵盐的重复单元的共聚物的粘合剂和用其制备的人造板 - Google Patents

包含具有酰胺基团与羧基和/或其铵盐的重复单元的共聚物的粘合剂和用其制备的人造板 Download PDF

Info

Publication number
WO2022116362A1
WO2022116362A1 PCT/CN2021/070694 CN2021070694W WO2022116362A1 WO 2022116362 A1 WO2022116362 A1 WO 2022116362A1 CN 2021070694 W CN2021070694 W CN 2021070694W WO 2022116362 A1 WO2022116362 A1 WO 2022116362A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
copolymer
wood
groups
unsaturated double
Prior art date
Application number
PCT/CN2021/070694
Other languages
English (en)
French (fr)
Inventor
杨万泰
陈楚轩
赵长稳
徐灿
陈冬
马育红
Original Assignee
北京化工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 北京化工大学 filed Critical 北京化工大学
Priority to MX2023006508A priority Critical patent/MX2023006508A/es
Priority to CA3200575A priority patent/CA3200575A1/en
Priority to JP2023533787A priority patent/JP2023551554A/ja
Priority to KR1020237021846A priority patent/KR20230141757A/ko
Priority to US18/255,860 priority patent/US20240010887A1/en
Priority to EP21899406.9A priority patent/EP4257653A1/en
Publication of WO2022116362A1 publication Critical patent/WO2022116362A1/zh

Links

Images

Classifications

    • 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
    • C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J135/02—Homopolymers or copolymers of esters
    • 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
    • C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • B27N3/08—Moulding or pressing
    • B27N3/20—Moulding or pressing characterised by using platen-presses
    • B27N3/203—Moulding or pressing characterised by using platen-presses with heating or cooling means
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • 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
    • C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J135/06—Copolymers with vinyl aromatic monomers
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • B27N3/007—Manufacture of substantially flat articles, e.g. boards, from particles or fibres and at least partly composed of recycled material
    • 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
    • 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

Definitions

  • the present disclosure relates to an adhesive comprising at least one copolymer having repeating units with amide groups and carboxyl groups and/or ammonium salts thereof and other repeating units.
  • the present disclosure also relates to wood-based panels formed from lignocellulosic materials and the binders and methods of making wood-based panels.
  • CN 107033309 A attempts to reduce formaldehyde by adjusting the ratio of raw materials and the pH value of each polymerization stage, adding formaldehyde scavengers, etc. freed.
  • CN 203344147 U discloses that, in the production of the board, activated carbon, bamboo charcoal, diatomaceous earth, etc. are mixed into the board to give the board a certain gas adsorption capacity.
  • the above-mentioned method does not fundamentally solve the problem, and formaldehyde is still released during the use of the board.
  • Adhesives prepared based on biomass raw materials such as soybean protein, tannin, starch, and gelatin do not involve the use of formaldehyde, but the degradation rate of biomass raw materials is fast, which brings the problem of easy aging of the board. Although the degradation can be delayed to a certain extent by adding anti-aging agents, biomass-based adhesives still have problems in terms of high cost and resources. This also limits its practical use.
  • polymers such as polyvinyl chloride, high molecular weight polyethylene, and neoprene for the production of sheets, but these polymers are not water-soluble and cannot form water-based adhesives. Solvents mix polymers with wood raw materials, and still have the disadvantages of high cost, energy consumption and environmental friendliness.
  • adhesive comprising at least one specific copolymer A having at least one compound bearing an amide group and a carboxyl group and a carboxyl group and and/or repeating units and other repeating units of its ammonium salts.
  • the present invention has been completed based on the above findings.
  • the adhesive has the advantages of safety and environmental protection, low cost, easy application and excellent performance.
  • Another object of the present invention is to provide a wood-based panel formed from a lignocellulosic material and the binder of the present invention.
  • Still another object of the present invention is to provide a method for producing wood-based panels using the adhesive of the present invention.
  • An adhesive comprising at least one of the following copolymers A:
  • the copolymer A has at least one repeating unit with an amide group and a carboxyl group and/or its ammonium salt and at least one other repeating unit different from the other repeating unit with an amide group and a carboxyl group and/or its ammonium salt ,
  • repeating units are selected from repeating units derived from the following monomers: monoethylenically unsaturated C3 - C8 monocarboxylic acids, C1 - C10 monoethylenically unsaturated C3 - C8 monocarboxylic acids Alkyl esters, amides of monoethylenically unsaturated C3 - C8 monocarboxylic acids, vinyl alkyl ethers with C1 - C8 alkyl groups, C4 - C22 conjugated dienes, compounded by one or more Substituent substituted styrenes selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy and halogen, vinyl esters of C 1 -C 20 carboxylic acids, vinylpyrrolidone, (meth)acrylonitrile , ethylenically unsaturated monomers containing hydroxyl groups, N-vinylformamide, vinylimidazole, allylbenzene, inden
  • Said other repeating units are derived from at least one carbon-carbon unsaturated double bond-containing monomer derived from the reaction mass of gasoline, C8 cut, C9 cut or coal tar light end.
  • the copolymer A further comprises additional Repeating units, preferably the non-conjugated carbon-carbon unsaturated double bonds in the monomer having at least two non-conjugated carbon-carbon unsaturated double bonds are selected from (meth)acrylate groups, (methyl) groups) acrylamide groups, vinyl groups, allyl groups, and non-conjugated carbon-carbon double bonds in alkenes or cycloalkenes.
  • the adhesive according to item 8 wherein the monomer having a carbon-carbon unsaturated double bond and an acid anhydride group is selected from monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 8 carbon atoms, preferably a leic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride, more preferably maleic anhydride.
  • copolymer B is composed of at least one monomer having a carbon-carbon unsaturated double bond and an acid anhydride group and at least one other carbon-containing - copolymers formed from monomers with carbon unsaturated double bonds
  • the at least one other carbon-carbon unsaturated double bond-containing monomer is selected from the group consisting of monoethylenically unsaturated C3 - C8 monocarboxylic acids, C1- C 10 alkyl esters, amides of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, vinyl alkyl ethers with C 1 -C 8 alkyl groups, C 4 -C 22 conjugated dienes, compounded by one or Multiple substituents selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy and halogen substituted styrene, vinyl ester of C 1 -C 20 carboxylic acid, vinylpyrrolidone, (methyl) Acrylonitrile, ethylenically unsaturated monomers containing hydroxyl groups, N-vinylformamide, vinylimidazole, allylbenzene, indene, formazan and compounds containing furan rings,
  • carbon-carbon unsaturated double bond-containing monomers are obtained from a reaction mass selected from gasoline, C8 cuts , C9 cuts, or coal tar light ends.
  • the copolymer B further comprises an additional amount derived from at least one monomer having at least two nonconjugated carbon-carbon unsaturated double bonds
  • the non-conjugated carbon-carbon unsaturated double bonds in the monomer having at least two non-conjugated carbon-carbon unsaturated double bonds are selected from (meth)acrylate groups, (methyl) groups) acrylamide groups, vinyl groups, allyl groups, and non-conjugated carbon-carbon double bonds in alkenes or cycloalkenes.
  • binder according to any one of items 1 to 11, wherein the binder is in the form of a solid, preferably in powder form; or in the form of an aqueous composition, preferably in the form of an aqueous solution, preferably the content of the copolymer A is 2-40% by weight, especially 5-30% by weight, based on the total weight of the aqueous composition.
  • a wood-based panel formed from a lignocellulosic material and a binder as in any of items 1-13.
  • wood-based panel according to any one of items 14-17, wherein the wood-based panel is particle board, plywood, MDF, fibreboard, straw board or finger-jointed board.
  • a method of making a wood-based panel comprising using an adhesive as defined in any of items 1-13.
  • One aspect of the present invention relates to an adhesive comprising at least one of the following copolymers A:
  • the copolymer A has at least one repeating unit with an amide group and a carboxyl group and/or its ammonium salt and at least one repeating unit different from the repeating unit with an amide group and a carboxyl group and/or its ammonium salt. other repeating units,
  • repeating units are selected from repeating units derived from the following monomers: monoethylenically unsaturated C3 - C8 monocarboxylic acids, C1 - C10 monoethylenically unsaturated C3 - C8 monocarboxylic acids Alkyl esters, amides of monoethylenically unsaturated C3 - C8 monocarboxylic acids, vinyl alkyl ethers with C1 - C8 alkyl groups, C4 - C22 conjugated dienes, compounded by one or more Substituent substituted styrenes selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy and halogen, vinyl esters of C 1 -C 20 carboxylic acids, vinylpyrrolidone, (meth)acrylonitrile , ethylenically unsaturated monomers containing hydroxyl groups, N-vinylformamide, vinylimidazole, allylbenzene, inden
  • Said other repeating units are derived from at least one carbon-carbon unsaturated double bond-containing monomer derived from the reaction mass of gasoline, C8 cut, C9 cut or coal tar light end.
  • a portion (eg, 1-10% by weight) of the carboxyl groups on the copolymer A may be in the form of its ammonium salt.
  • said other repeating units of copolymer A are selected from repeating units derived from the following monomers: monoethylenically unsaturated C3 - C8 monocarboxylic acids, with C1 -C8 alkanes vinyl alkyl ethers of C 1 -C 20 carboxylic acids, vinyl esters of C 1 -C 20 carboxylic acids and substituted with one or more substituents selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy and halogen Styrene.
  • the expression “derived from” also includes the case where the copolymer has a certain repeating unit, but the repeating unit is not directly formed from the monomer corresponding to the repeating unit.
  • the repeating unit is not directly formed from the monomer corresponding to the repeating unit.
  • carboxyethylene repeating units It can be obtained from the polymerization of acrylic acid or by the polymerization of acrylates followed by hydrolysis.
  • said other repeating units of copolymer A are derived from at least one carbon-carbon unsaturated bis of a reaction mass such as gasoline, C8 cut, C9 cut or coal tar light ends bond monomer.
  • a reaction mass such as gasoline, C8 cut, C9 cut or coal tar light ends bond monomer.
  • gasoline, C8 cuts , C9 cuts, and coal tar light fractions have carbon-carbon unsaturated double bond-containing monomers that, upon polymerization, can form copolymer A's repeating unit.
  • the copolymer A further comprises additional repeat units derived from at least one monomer having at least two non-conjugated carbon-carbon unsaturated double bonds, preferably the The non-conjugated carbon-carbon unsaturated double bond in the monomer of (eg 2-4) non-conjugated carbon-carbon unsaturated double bond is selected from (meth)acrylate group, (meth)propylene Amide groups, vinyl groups, allyl groups, and non-conjugated carbon-carbon double bonds in alkenes or cycloalkenes.
  • the amount of the additional repeat units derived from the at least one monomer having at least two non-conjugated carbon-carbon unsaturated double bonds may be 0.1-30 wt %, eg 0.5-20 wt % or 0.5-10 wt % %, based on the total amount of repeating units of Copolymer A.
  • the molecular weight of Copolymer A can be any molecular weight suitable for adhesive applications. According to one embodiment of the present invention, the molecular weight of the copolymer A may be at least 2000, eg at least 5000 or at least 8000.
  • the upper limit of the molecular weight of the copolymer A is not critical, for example, it can be 500,000, or 300,000. In the case where copolymer A has repeating units derived from C4 - C22 conjugated dienes and/or monomers having at least two non-conjugated carbon-carbon unsaturated double bonds, said copolymer A also Can be cross-linked.
  • the amount of repeating units bearing amide and carboxyl groups and/or their ammonium salts may be 10-80% by weight, for example 20-75% by weight, 30-70% by weight or 35-65% by weight, based on the copolymer The total amount of repeating units of A.
  • the copolymer A may optionally contain supplementary repeating units.
  • Said supplementary repeating units may for example be selected from repeating units derived from the following monomers: styrene and C2 - C22 monoolefins.
  • the copolymer A comprises repeating units bearing amide groups and carboxyl groups and/or ammonium salts thereof, said further repeating units and said supplementary repeating units.
  • the copolymer A comprises repeating units bearing amide groups and carboxyl groups and/or ammonium salts thereof, said further repeating units, said additional repeating units and said supplementary repeating units.
  • the copolymer A is derived from a copolymer B having at least one repeating unit bearing an anhydride group.
  • the copolymer A is obtained from the reaction of the copolymer B with ammonia.
  • the acid anhydride groups on the copolymer B are introduced into the copolymer B by the polymerization of at least one monomer having a carbon-carbon unsaturated double bond and an acid anhydride group.
  • the monomer with carbon-carbon unsaturated double bond and acid anhydride group can be selected from monoethylenic unsaturated dicarboxylic acid anhydrides with 4-8 carbon atoms, preferably maleic anhydride, itaconic anhydride, citraconic anhydride, Methylenemalonic anhydride and mixtures thereof, more preferably maleic anhydride.
  • the copolymer B is composed of at least one monomer having a carbon-carbon unsaturated double bond and an acid anhydride group and at least one other monomer having a carbon-carbon unsaturated double bond formed copolymers,
  • the at least one other carbon-carbon unsaturated double bond-containing monomer is selected from the group consisting of monoethylenically unsaturated C3 - C8 monocarboxylic acids, C1- C 10 alkyl esters, amides of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids, vinyl alkyl ethers with C 1 -C 8 alkyl groups, C 4 -C 22 conjugated dienes, compounded by one or Multiple substituents selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy and halogen substituted styrene, vinyl ester of C 1 -C 20 carboxylic acid, vinylpyrrolidone, (methyl) Acrylonitrile, ethylenically unsaturated monomers containing hydroxyl groups, N-vinylformamide, vinylimidazole, allylbenzene, indene, formazan and compounds containing furan rings,
  • carbon-carbon unsaturated double bond-containing monomers are obtained from a reaction mass selected from gasoline, C8 cuts , C9 cuts, or coal tar light ends.
  • monoethylenically unsaturated C 3 -C 8 monocarboxylic acids mention may be made of, for example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, preferably acrylic acid and methacrylic acid.
  • C 1 -C 10 -alkyl esters of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids mention may be made of C 1 -C 10 -alkyl alkyl (meth)acrylates, especially methyl methacrylate ester, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate or mixtures thereof.
  • vinyl alkyl ethers having C 1 -C 8 alkyl groups preference can be given to vinyl alkyl ethers having C 1 -C 4 alkyl groups, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether and 2-ethyl Hexyl vinyl ether.
  • vinyl alkyl ethers having C 1 -C 8 alkyl groups preference can be given to vinyl alkyl ethers having C 1 -C 4 alkyl groups, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether,
  • the C 4 -C 22 conjugated diene may for example be a C 4 -C 16 conjugated diene or a C 5 -C 16 conjugated diene, a C 4 -C 8 conjugated diene or a C 5 -C 8 conjugated diene ene.
  • these conjugated dienes may be mentioned 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, cyclopentadiene, methylcyclopentadiene And 1,3-cyclohexadiene and so on.
  • the alkyl or alkoxy group preferably has 1 to 10 carbon atoms , such as 1-4 carbon atoms; wherein the halogen is preferably chlorine and bromine.
  • vinyltoluene such as ⁇ -methylstyrene and p-methylstyrene
  • ⁇ -butylstyrene 4-n-butylstyrene
  • 4-n-decylstyrene 4-n-methoxy styrene
  • chlorostyrene and bromostyrene chlorostyrene and bromostyrene.
  • vinyl esters of C 1 -C 20 carboxylic acids may be mentioned vinyl laurate, vinyl stearate, vinyl propionate, vinyl neodecanoate and vinyl acetate.
  • Ethylenically unsaturated monomers containing hydroxyl groups include, for example, C 1 -C 10 hydroxyalkyl (meth)acrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxy acrylate Propyl, 2-hydroxypropyl methacrylate and 3-hydroxypropyl methacrylate.
  • C 1 -C 10 hydroxyalkyl (meth)acrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxy acrylate Propyl, 2-hydroxypropyl methacrylate and 3-hydroxypropyl methacrylate.
  • furan ring-containing compounds may mention monomers in which the furan ring is substituted with one or more (eg 2-4) substituents selected from C 1 -C 12 alkyl and C 1 -C 12 hydroxyalkyl groups, Like furfuryl alcohol, the furan ring can be further fused with a benzene ring, such as methylbenzofuran.
  • the reaction material containing the at least one carbon-carbon unsaturated double bond-containing monomer and saturated hydrocarbons, other impurities not participating in the polymerization such as gasoline, C 8 fraction, C 9 fraction, coal tar light fraction.
  • the copolymer B may be composed of at least one monomer having a carbon-carbon unsaturated double bond and an acid anhydride group and derived from, for example, gasoline, C8 cuts , C9 cuts, coal tar light ends A copolymer of at least one carbon-carbon unsaturated double bond-containing monomer of the reaction mass.
  • C 8 and C 9 fractions mainly come from steam cracking to ethylene process and naphtha platinum reforming process, and a part comes from toluene disproportionation or transalkylation products and coal tar.
  • the C8 cut typically contains 22-35% of monoolefins such as styrene, allylbenzene, vinyltoluene, indene, formazan. Other components in the C8 cut include 45-55% aromatics and about 20 % other unknown components.
  • the C8 cut can have the following specific composition:
  • the C9 cut usually contains 20-30% of monoolefins (eg styrene, allylbenzene, vinyltoluene, indene), 8-15% of dienes. Other components in the C9 cut include about 5% alkanes, 40-50% aromatics, and about 10% other unknown components.
  • the C9 cut can have the following specific composition:
  • the light oil components in coal tar mainly contain styrene, ⁇ -methylstyrene, alkylbenzene, vinyltoluene, dicyclopentadiene, benzofuran, indene, methylindene and methylbenzofuran.
  • Coal tar light ends may have the following specific composition:
  • the copolymer B further comprises additional repeat units derived from at least one monomer having at least two (eg 2-4) non-conjugated carbon-carbon unsaturated double bonds , preferably the non-conjugated carbon-carbon unsaturated double bonds in the monomer having at least two non-conjugated carbon-carbon unsaturated double bonds are selected from (meth)acrylate groups, (methyl) Acrylamide groups, vinyl groups, allyl groups, and non-conjugated carbon-carbon double bonds in alkenes or cycloalkenes.
  • the monomer having at least two non-conjugated carbon-carbon unsaturated double bonds can be selected, for example, from (meth)acrylates of alcohols having at least 2 hydroxyl groups, vinyl ethers of alcohols having at least 2 hydroxyl groups , Allyl ethers of alcohols having at least 2 hydroxyl groups, di(meth)acrylates of ethylene oxide and/or propylene oxide oligomers, vinyl (meth)acrylates, allyl (meth)acrylates , methylenebis(meth)acrylamides, aromatic compounds having at least two vinyl groups and C5 - C22 non-conjugated dienes.
  • the alcohol having at least two hydroxyl groups may, for example, have 2 to 6, preferably 2 to 4, hydroxyl groups.
  • These alcohols may be selected from glycols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butanediol, pentanediol and hexylene glycol, glycerol, trimethylolpropane and pentaerythritol, and the like.
  • the (meth)acrylates of alcohols having at least 2 hydroxyl groups may be di(meth)acrylates of dihydric alcohols containing 2 to 6 carbon atoms, which may be selected from ethylene glycol diacrylates, Ethylene glycol dimethacrylate, 1,2-propanediol diacrylate, 1,2-propanediol dimethacrylate, butanediol di(meth)acrylate, such as butane-1,4-diol Diacrylate, Butane-1,4-Diol Dimethacrylate, Hexylene Glycol Diacrylate, Hexylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Dimethacrylate Acrylates, 3-Methylpentanediol Diacrylate and 3-Methylpentanediol Dimethacrylate.
  • di(meth)acrylates of ethylene oxide and/or propylene oxide oligomers are diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethyl Acrylates, Tetraethylene Glycol Diacrylate and Tetraethylene Glycol Dimethacrylate.
  • aromatic compound having at least two vinyl groups divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene and the like can be mentioned.
  • C 5 -C 22 non-conjugated diene may be a alkadiene or a cyclic diene, and specific examples thereof may be mentioned 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene; and having 8-20 carbon atoms , preferably bicyclic alkenes with 8-16 or 8-12 carbon atoms, such as dicyclopentadiene-based monomers, such as dicyclopentadiene, methyl dicyclopentadiene (such as 2-methyl dicyclopentadiene, 5- methyl dicyclopentadiene), ethyl dicyclopentadiene (such as 2-ethyl dicyclopentadiene) and 5,5-dimethyl dicyclopentadiene, etc.
  • 1,4-pentadiene 1,4-hexadiene, 1,5-hexadiene, 1,4-cyclohex
  • monomers having at least two (eg 2-4) non-conjugated carbon-carbon unsaturated double bonds can be mentioned trimethylolpropane tri(meth)acrylate, butanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol triallyl ether, methylene bis(meth)acrylamide, diallyl phthalate, etc.
  • the amount of the additional repeat units derived from the at least one monomer having at least two non-conjugated carbon-carbon unsaturated double bonds may be 0.1-30 wt %, eg 0.5-20 wt % or 0.5-10 wt % %, based on the total amount of repeating units of Copolymer B.
  • the copolymer B may optionally contain supplementary repeating units.
  • Said supplementary repeating units may for example be selected from repeating units derived from the following monomers: styrene and C2 - C22 monoolefins.
  • copolymer B comprises repeating units bearing acid anhydride groups, said further repeating units and said supplementary repeating units.
  • copolymer B comprises repeating units bearing acid anhydride groups, said further repeating units, said additional repeating units and said supplementary repeating units.
  • the C2 - C22 monoolefins may be alkenes and cycloalkenes, for example having 2-20 or 5-20 carbon atoms, such as 2-12 or 5-12 carbon atoms, 2-8 or 5-8 carbon atoms alkenes such as ethylene, propylene, butene, 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene; with 5-20 carbon atoms, Preferably 5-12 or 5-8 carbon atoms cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene and other cycloalkenes; have 5-20 carbon atoms, preferably 5-16 or 8-12 carbon atoms Dihydrodicyclopentadiene, especially dihydrodicyclopentadiene (such as 2,3-dihydrodicyclopentadiene), dihydromethyldicyclopentadiene and dihydrodimethyldicyclopentad
  • the polymerization of monomers having carbon-carbon unsaturated double bonds and acid anhydride groups and other carbon-carbon unsaturated double bond-containing monomers to prepare copolymer B can be carried out using oil-soluble free radical initiators.
  • the oil-soluble free radical initiators include, for example, azo initiators or peroxide initiators.
  • the azo initiators include: azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, etc.; the peroxide initiators include: dibenzoyl peroxide , Dicumyl peroxide, bis(2,4-dichlorobenzoyl peroxide), di-tert-butyl peroxide, dodecanoyl peroxide, tert-butyl peroxybenzoate, diisoperoxydicarbonate propyl ester and dicyclohexyl peroxydicarbonate, etc.
  • the initiator is used in an amount of 0.05-10% by weight, preferably 0.5-6% by weight, based on the weight of the monomers.
  • the polymerization reaction can be carried out in the presence of a solvent.
  • the solvent may include aromatic hydrocarbons, mixtures of alkanes and ketones, carboxylic acid esters, mixtures of alkanes and aromatic hydrocarbons, mixtures of aromatic hydrocarbons and carboxylic acid esters, or mixtures of alkanes and carboxylic acid esters, or mixtures of alkanes, aromatic hydrocarbons and carboxylic acid esters.
  • aromatic hydrocarbons examples include toluene, xylene, ethylbenzene and the like.
  • Carboxylic acid esters may include C1 - C8 alkyl, phenyl or benzyl esters of C1- C6 carboxylic acids and C1 - C8 alkyl of aromatic carboxylic acids having 6-10 carbon atoms ester, specific examples may be mentioned ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, Phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, is
  • the ketone in the mixture of alkane and ketone can be selected from acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, and the alkane can be selected from n-pentane, n-hexane, cyclohexanone alkane, n-heptane, n-octane and isooctane, etc.
  • the ketones typically comprise 5-65% by volume.
  • the polymerization reaction can be carried out in the presence of an inert gas such as nitrogen.
  • the temperature of the polymerization reaction is usually 55-120°C, preferably 60-100°C; the time of the polymerization reaction is usually 1-12 hours, preferably 2-8 hours. After the polymerization reaction, the resulting copolymer B can be isolated and dried.
  • the polymerization reaction is carried out by precipitation polymerization.
  • the precipitation polymerization can be carried out by selecting a solvent capable of dissolving the monomers but not dissolving the resulting copolymer B.
  • the copolymer B can be obtained directly in powder form.
  • the unreacted alkane or aromatic hydrocarbon mixture after the reaction is completed can be separated simply by distillation, thereby obtaining various high added value solvents and industrial raw materials.
  • the copolymer B can be reacted with ammonia to give the copolymer A (described in further detail below).
  • the molecular weight of copolymer B generally corresponds to that of copolymer A.
  • Copolymer A can have any molecular weight suitable for adhesive applications.
  • the molecular weight of the copolymer B may be at least 2000, for example at least 5000 or at least 8000.
  • the upper limit of the molecular weight of the copolymer B is not critical, for example, it can be 500,000, or 300,000.
  • the copolymer B may are cross-linked.
  • the adhesive of the present invention may contain at least one additive, if necessary.
  • the additives may be one or more of the following: oxygen scavengers, emulsifiers, dyes, pigments, anti-migration aids, UV absorbers, biocides, defoamers, colorants, antistatic agents and antioxidants .
  • the adhesive of the present invention does not contain organic crosslinking agents capable of covalent crosslinking reaction with the amide groups and/or carboxyl groups of the copolymer A, such as polyols, polyamines, polyalkanolamines or their mixture.
  • the binder may be in the form of a solid, preferably in powder form; or in the form of an aqueous composition, preferably in the form of an aqueous solution.
  • the amount of Copolymer A may be 30-100% by weight, based on the total amount of the adhesive (if the adhesive is in a liquid state, such as an aqueous composition or aqueous solution, based on the solids content), such as 50-100 wt%, 60-100 wt%, 70-100 wt%, 80-100 wt%, or 50-98 wt%, or 60-90 wt%.
  • the binder is in the form of an aqueous composition, preferably an aqueous solution, the binder may have a solids content of 2-40% by weight, or 5-30% by weight, or 8-25% by weight.
  • One aspect of the present invention pertains to a method of preparing the adhesive of the present invention comprising reacting Copolymer B with ammonia in the presence or absence of a reaction medium such as water.
  • Copolymer B can form copolymer A by reaction with ammonia, ie, aminolysis.
  • the reaction generally involves reacting the copolymer B with ammonia in an aqueous medium with stirring at a temperature below 100°C, preferably 15-70°C, for example at room temperature.
  • the reaction time is usually 0.5 to 10 hours, preferably 1 to 6 hours.
  • the resulting reaction mixture is generally an aqueous composition, preferably in the form of an aqueous solution.
  • the resulting aqueous composition preferably an aqueous solution, can be used directly as a binder.
  • the reaction mixture can also be used as a binder after being mixed with at least one of the additives described above.
  • the copolymer B is in powder form prior to reaction with ammonia.
  • the copolymer B in powder form can be prepared by precipitation polymerization.
  • Copolymer B in powder form can also be obtained by grinding Copolymer B (eg in the form of a block) into powder form.
  • the average particle size of the copolymer B in powder form may be 0.01-10 ⁇ m, preferably 0.05-8 ⁇ m, more preferably 0.1-5 ⁇ m.
  • the average particle size of the copolymer A in powder form may be 0.01-10 ⁇ m, preferably 0.05-8 ⁇ m, more preferably 0.1-5 ⁇ m.
  • the reaction time of the copolymer B in solid form with ammonia is generally from 2 to 300 minutes, such as from 5 to 120 minutes.
  • the copolymer A in solid form can be dissolved in water, optionally mixed with at least one of the above-mentioned additives, and then applied.
  • the conversion of the anhydride groups of the copolymer B is generally over 90%, preferably over 95%, more preferably over 98%, such as 100%.
  • the carboxyl group can also form an ammonium salt with ammonia.
  • the wood-based panel of the present invention is to be understood in a broad sense, ie a board formed from any lignocellulosic material and the binder of the present invention.
  • the wood-based panels of the present invention are not limited to those formed of only wood, but may also include boards formed of materials such as bamboo and straw as described below.
  • the wood-based panel of the present invention may be various types of wood-based panels.
  • the wood-based panels include, but are not limited to, particleboard, plywood, fiberboard, MDF, straw board, and finger-jointed board.
  • Lignocellulosic materials can be obtained from a variety of lignocellulosic materials, such as wood, bamboo, bagasse, straw (eg, wheat straw), flax residue, nut shells, grain husks, etc., and mixtures thereof.
  • the wood includes various softwoods and/or hardwoods.
  • the lignocellulosic material can be in the form of sawdust, chips, wood chips, strands, flakes, fibers, sheets, wood chips, shavings, granules and the like, as well as in the form of combinations of these materials such as a combination of strands and sawdust.
  • Lignocellulosic material can be processed by various conventional techniques. Large lumber can be processed into wood chips in a log chipper. Large pieces of wood and leftovers can also be cut into pieces. Large lumber can also be flaked in a ring flaker. Large lumbers are usually peeled before flakes.
  • the size of the lignocellulosic material is generally not critical. Different sizes can be used for different types of wood-based panels.
  • the size of the lignocellulosic material may be 1-30 mesh, preferably 2-15 mesh.
  • the thickness of the sheet may be, for example, 0.5 mm to 5 cm, preferably 1 mm to 3 cm.
  • the amount of the binder in solid content is 1-45% by weight, preferably 2-40% by weight, more preferably 3-35% by weight or 4-30% by weight based on the total weight of the wood-based panel %, such as 5-25 wt%, 6-25 wt%, 7-25 wt%, 8-19 wt%.
  • the amount of copolymer A based on the total weight of the wood-based panel is 1-40% by weight, preferably 2-30% by weight, more preferably 3-25% by weight or 4-20% by weight, such as 5-20% by weight % by weight, 6-20% by weight or 7-18% by weight.
  • the binder is used as a matrix resin, and it is preferable that the binder fills the gaps between the lignocellulosic materials.
  • Another aspect of the present invention relates to a method of making a wood-based panel comprising using the adhesive of the present invention.
  • the method comprises compressing the mixture of lignocellulosic material and the binder of the invention at a temperature of 105-300° C. and a pressure of 0.4-10 MPa, preferably 2-60 MPa minutes, more preferably pressing for 3-30 minutes, such as 5-30 minutes.
  • a mixture of the lignocellulosic material for compression and the binder of the present invention can be prepared by mixing the lignocellulosic material with the binder of the present invention.
  • the binder When the binder is solid, the binder can be first dissolved in water and then mixed with the lignocellulosic material.
  • the removal of the water can be carried out by heating, for example, the heating temperature can be 50-90°C, preferably 60-80°C.
  • the pressing is carried out at a temperature of 120-220°C and/or at a pressure of 1-6 MPa.
  • the copolymer A has a carboxyl group in the form of its ammonium salt
  • the ammonium salt of the carboxyl group is decomposed into a carboxyl group again under the pressing conditions.
  • the present invention also relates to the use of the adhesive of the present invention in the preparation of lignocellulose-based wood-based panels.
  • the adhesive of the present invention is safe, environmentally friendly, has no release of toxic and harmful substances such as formaldehyde, is simple to apply and has low cost, and at the same time, the adhesive of the present invention has excellent performance, is particularly suitable for the manufacture of lignocellulose-based wood-based panels, and uses
  • the artificial board produced by the adhesive of the present invention has excellent mechanical properties and water resistance.
  • the adhesives of the present invention can also be prepared using gasoline, C8 and C9 fractions and coal tar light ends, which is of great significance for broadening the utilization of these industrial mixtures, and using the adhesives obtained from these industrial mixtures
  • the wood-based panels have more excellent mechanical properties and water resistance.
  • Source of chemicals used maleic anhydride (purity 98+%, Alfa Aesar (Tianjin) Chemical Co., Ltd.); dibenzoyl peroxide (purity 97%, Alfa Aesar (Tianjin) Chemical Co., Ltd.); Nitrogen (purity 98%, Shanghai Aladdin Biochemical Technology Co., Ltd.); ammonia water (concentration 20-25%, Beijing Inoke Technology Co., Ltd.); ammonia gas (purity 99.999%, Beijing Haipu Gas Co., Ltd.
  • the above premix is placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature is 180° C., the pressure is 0.4 MPa, and the hot pressing time is 10 minutes to obtain a particleboard with a thickness of 3 mm.
  • the characteristic peak of the acid anhydride group corresponding to the original C 8 -maleic anhydride copolymer basically disappeared;
  • Curve 3 is the infrared spectrum of the hot - pressed copolymer, the characteristic absorption of cyclic imide appears at 1770 cm -1 and 1710 cm -1 , and the characteristic absorption of CNC structure at 1350 cm -1 .
  • the above premix was placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature was 160° C., the pressure was 0.5 MPa, and the hot pressing time was 10 minutes to obtain a particleboard with a thickness of 3 mm.
  • the above premix is placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature is 180° C., the pressure is 0.4 MPa, and the hot pressing time is 10 minutes to obtain a particleboard with a thickness of 3 mm.
  • the viscous liquid is mixed with poplar wood shavings (water content 5%, 5-10 mesh), and the amount of the copolymer per 100 parts of shavings is 20 parts, and the mixture is uniform to obtain a premix.
  • the premix was dried at 70°C to remove water to 10% water content.
  • the above premix was placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature was 170° C., the pressure was 0.4 MPa, and the hot pressing time was 12 minutes to obtain a particleboard with a thickness of 3 mm.
  • coal tar light fraction 25 parts of maleic anhydride, 100 parts of isoamyl acetate and 2 parts of AIBN were mixed and dissolved, and the system was passed through nitrogen for 20 minutes and reacted at 70°C for 8 hours.
  • the product was centrifuged, washed, and dried to obtain a coal tar-maleic anhydride copolymer (weight average molecular weight 11,000) in the form of white powder, the yield was 90%, and the mass percentage of maleic anhydride monomer units in the copolymer was 42%.
  • the above premix was placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature was 160° C., the pressure was 0.4 MPa, and the hot pressing time was 10 minutes to obtain a particleboard with a thickness of 3 mm.
  • the above-mentioned premix was placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature was 180° C., the pressure was 1 MPa, and the hot pressing time was 10 minutes to obtain a particleboard with a thickness of 3 mm.
  • the above premix is placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature is 180° C., the pressure is 0.4 MPa, and the hot pressing time is 10 minutes to obtain a particleboard with a thickness of 3 mm.
  • the above premix is placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature is 170° C., the pressure is 0.4 MPa, and the hot pressing time is 10 minutes to obtain a particleboard with a thickness of 3 mm.
  • the C 8 -maleamic acid copolymer obtained in Example 1 was dissolved in water to obtain a viscous solution with a mass concentration of 10%.
  • the viscous liquid is evenly coated on a basswood veneer with a water content of 12% and a size of 160mm ⁇ 160mm ⁇ 1.5mm, with an average coating amount of 60g/m 2 , according to the horizontal grain-vertical grain-horizontal grain direction.
  • the embryos were assembled and pressed under a hot press, the hot pressing temperature was 180° C., the pressure was 1 MPa, and the hot pressing time was 10 minutes to obtain a three-layer plywood. According to GB/T 9846-2015, the internal bond strength of plywood is 1.16MPa.
  • Example 1-8 According to GB/T 4897-2015, the particleboard obtained in Example 1-8 is tested for internal bond strength, 24h water absorption thickness expansion ratio and moisture resistance (internal bond strength after boiling in water), and the results are listed in Table 4 below.
  • the amide group and the carboxyl group on the polymer in the adhesive of the present invention can be dehydrated to form an imide group under pressing conditions, and the carboxyl group can also be dehydrated to form an acid anhydride group, resulting in Anhydride groups can react with hydroxyl groups on lignocellulosic materials to form esters, which help improve the mechanical properties and water resistance of the resulting wood-based panels.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Forests & Forestry (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

本公开涉及一种粘合剂，所述粘合剂包含至少一种下述共聚物A：所述共聚物A具有至少一种带有酰胺基团与羧基和/或其铵盐的重复单元和至少一种不同于所述带有酰胺基团与羧基和/或其铵盐的其它重复单元。本公开还涉及由木素纤维素材料和所述粘合剂形成的人造板和制造人造板的方法。

Description

包含具有酰胺基团与羧基和/或其铵盐的重复单元的共聚物的粘合剂和用其制备的人造板 技术领域
本公开涉及一种粘合剂，所述粘合剂包含至少一种具有带有酰胺基团与羧基和/或其铵盐的重复单元和其他重复单元的共聚物。本公开还涉及由木素纤维素材料和所述粘合剂形成的人造板和制造人造板的方法。
背景技术
在目前的人造板生产中，以甲醛为原料制备的“三醛胶”(脲醛树脂、酚醛树脂和三聚氰胺甲醛树脂)占有较大的比重，超过80％。“三醛胶”制备简单，价格低廉，但这类板材在使用过程中会长期释放游离甲醛，污染室内环境，严重威胁居民的身体健康。
一些文献中对减少“三醛胶”型人造板的甲醛释放量提出过解决方案，例如CN 107033309 A试图通过调控原料的配比和各个聚合阶段的pH值，加入甲醛捕捉剂等方法来减少甲醛释放。CN 203344147 U公开了，在板材的生产中，混入活性炭，竹炭，硅藻土等，赋予板材一定的气体吸附能力。但是，上述的方法并没有从根本上解决问题，板材在使用过程中仍有甲醛释放。
以大豆蛋白、单宁、淀粉、明胶等生物质原料为基础制备的粘合剂不涉及甲醛的使用，但是生物质原料降解速度快，又带来了板材易老化的问题。虽然通过添加抗老化剂能在一定程度上延缓降解，但是生物质材类粘合剂仍然有成本较高和资源方面的问题。这也限制了其实际使用。
另外，也可以利用如聚氯乙烯，高分子量聚乙烯，氯丁橡胶等聚合物进行板材的生产，但是这些聚合物都不具有水溶性，不能形成水性粘合剂，只能通过热熔或者有机溶剂将聚合物与木材原料混合，仍然存在成本高、消耗能源和不环保的缺点。
因此，从安全环保、低生产成本、施加工艺简便性以及成品耐久性等 方面考虑，开发出一种新型无甲醛人造板粘合剂显得尤为重要。
发明内容
鉴于现有技术的上述状况，本发明的发明人对人造板领域的粘合剂进行了广泛而深入的研究，以期发现一种无甲醛释放、低成本、施加简便且性能优异的用于人造板的粘合剂。本发明人发现，包含至少一种特定共聚物A的粘合剂不仅无甲醛释放、成本低、施加简便且具有优异的性能，所述共聚物A具有至少一种带有酰胺基团与羧基和/或其铵盐的重复单元和其他重复单元。
本发明正是基于以上发现得以完成。
本发明的目的是提供一种包含至少一种共聚物A的粘合剂，所述共聚物A具有至少一种带有酰胺基团与羧基和/或其铵盐的重复单元和其他重复单元，所述粘合剂具有安全环保、低成本、施加简便和性能优异的优点。
本发明的另一目的是提供一种由木素纤维素材料和本发明粘合剂形成的人造板。
本发明的再一目的是提供使用本发明的粘合剂制备人造板的方法。
实现本发明目的的技术方案可以概括如下：
1.一种粘合剂，所述粘合剂包含至少一种下述共聚物A：
所述共聚物A具有至少一种带有酰胺基团与羧基和/或其铵盐的重复单元和至少一种不同于所述带有酰胺基团与羧基和/或其铵盐的其它重复单元，
其中所述其它重复单元选自得自如下单体的重复单元：单烯属不饱和C 3-C 8单羧酸、单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯、单烯属不饱和C 3-C 8单羧酸的酰胺、具有C 1-C 8烷基的乙烯基烷基醚、C 4-C 22共轭二烯、被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯、C 1-C 20羧酸的乙烯基酯、乙烯基吡咯烷酮、(甲基)丙烯腈、包含羟基的烯属不饱和单体、N-乙烯基甲酰胺、乙烯基咪唑、烯丙苯、茚、甲茚和含呋喃环的化合物，
或者
所述其它重复单元得自源自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。
2.根据第1项的粘合剂，其中在所述共聚物A中，带有酰胺与羧基和/或其铵盐的重复单元的量为10-80重量％，或30-70重量％，基于共聚物A的重复单元的总量。
3.根据第1或2项的粘合剂，其中共聚物A的所述其它重复单元选自得自如下单体的重复单元：单烯属不饱和C 3-C 8单羧酸、具有C 1-C 8烷基的乙烯基烷基醚、C 1-C 20羧酸的乙烯基酯和被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯，或者所述其它重复单元得自源自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。
4.根据第1-3项中任一项的粘合剂，其中共聚物A的所述其它重复单元得自源自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。
5.根据第1-4项中任一项的粘合剂，其中所述共聚物A进一步包含得自至少一种具有至少两个非共轭的碳-碳不饱和双键的单体的额外重复单元，优选所述具有至少两个非共轭的碳-碳不饱和双键的单体中的非共轭的碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的非共轭碳-碳双键。
6.根据第1-5项中任一项粘合剂，其中所述共聚物A衍生自共聚物B，该共聚物B具有至少一种带有酸酐基团的重复单元。
7.根据第1-6项中任一项的粘合剂，其中所述共聚物A得自共聚物B与氨的反应。
8.根据第6或7项的粘合剂，其中所述共聚物B上的酸酐基团通过至少一种具有碳-碳不饱和双键和酸酐基团的单体的聚合而引入所述共聚物B中。
9.根据第8项的粘合剂，其中所述具有碳-碳不饱和双键和酸酐基团的单体选自具有4-8个碳原子的单烯属不饱和二羧酸酐，优选马来酸酐、衣康酸酐、柠康酸酐和亚甲基丙二酸酐，更优选马来酸酐。
10.根据第6-9项中任一项的粘合剂，其中所述共聚物B为由至少一种具有碳-碳不饱和双键和酸酐基团的单体和至少一种其他含碳-碳不饱和双键的单体形成的共聚物，
所述至少一种其他含碳-碳不饱和双键的单体选自单烯属不饱和C 3-C 8单羧酸、单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯、单烯属不饱和C 3-C 8单羧酸的酰胺、具有C 1-C 8烷基的乙烯基烷基醚、C 4-C 22共轭二烯、被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯、C 1-C 20羧酸的乙烯基酯、乙烯基吡咯烷酮、(甲基)丙烯腈、包含羟基的烯属不饱和单体、N-乙烯基甲酰胺、乙烯基咪唑、烯丙苯、茚、甲茚和含呋喃环的化合物，
或者
其他含碳-碳不饱和双键的单体得自选自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料。
11.根据第6-10项中任一项的粘合剂，其中所述共聚物B进一步包含得自至少一种具有至少两个非共轭的碳-碳不饱和双键的单体的额外重复单元，优选所述具有至少两个非共轭的碳-碳不饱和双键的单体中的非共轭的碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的非共轭碳-碳双键。
12.根据第1-11项中任一项的粘合剂，其中所述粘合剂呈固体，优选粉末形式；或者呈含水组合物，优选呈水溶液形式，优选所述共聚物A的含量为2-40重量％，尤其是5-30重量％，基于含水组合物的总重量。
13.根据第1-12项中任一项的粘合剂，其中所述粘合剂不含能够与共聚物A的酰胺基团和/或羧基发生共价交联反应的有机交联剂。
14.一种人造板，其由木素纤维素材料和如第1-13项中任一项的粘合剂形成。
15.根据第14项的人造板，其中以固含量计的粘合剂用量基于人造板的总重量为1-45重量％，优选2-35重量％，更优选3-30重量％。
16.根据第14或15项的人造板，其中如第1-12项中任一项所定义的共聚物A的用量基于人造板的总重量为1-40重量％，优选2-30重量％，更 优选3-25重量％。
17.根据第14-16项中任一项的人造板，其中所述粘合剂用作基体树脂，优选所述粘合剂填充木素纤维素材料之间的缝隙。
18.根据第14-17项中任一项的人造板，其中所述人造板为刨花板、胶合板、密度板、纤维板、秸秆板或指接板。
19.一种制备人造板的方法，其包括使用如第1-13项中任一项所定义的粘合剂。
20.根据第19项的方法，其包括将木素纤维素材料和所述粘合剂的混合物在105-300℃温度下和在0.4-10MPa的压力下压制，优选压制2-60分钟，更优选压制3-30分钟。
21.根据第19或20项的方法，其中所述人造板为第14-18项中任一项的人造板。
22.如第1-13项中任一项的粘合剂在制备木素纤维素基人造板中的用途。
附图说明
图1.实施例1中不同聚合物的红外光谱图:1：C 8-马来酸酐共聚物；2：C 8-马来酰胺酸共聚物；3：热压后人造板中的共聚物。
具体实施方式
本文对相关特征公开具体值(包括所公开范围的端点值)可以相互结合成新的范围。
粘合剂
本发明的一个方面涉及一种粘合剂，所述粘合剂包含至少一种下述共聚物A：
所述共聚物A具有至少一种带有酰胺基团与羧基和/或其铵盐的重复单元和至少一种不同于所述带有酰胺基团与羧基和/或其铵盐的重复单元的其它重复单元，
其中所述其它重复单元选自得自如下单体的重复单元：单烯属不饱和C 3-C 8单羧酸、单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯、单烯属不饱和C 3-C 8单羧酸的酰胺、具有C 1-C 8烷基的乙烯基烷基醚、C 4-C 22共轭二烯、被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯、C 1-C 20羧酸的乙烯基酯、乙烯基吡咯烷酮、(甲基)丙烯腈、包含羟基的烯属不饱和单体、N-乙烯基甲酰胺、乙烯基咪唑、烯丙苯、茚、甲茚和含呋喃环的化合物，
或者
所述其它重复单元得自源自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。
根据本发明，共聚物A上的羧基的一部分(例如1-10重量％)可以呈其铵盐的形式。
根据本发明的一个实施方案，其中共聚物A的所述其它重复单元选自得自如下单体的重复单元：单烯属不饱和C 3-C 8单羧酸、具有C 1-C 8烷基的乙烯基烷基醚、C 1-C 20羧酸的乙烯基酯和被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯。
本领域技术人员可以理解，表述“得自”还包括共聚物具有某种重复单元，但是该重复单元并非直接由该重复单元对应的单体形成的情形。例如羧基亚乙基重复单元
Figure PCTCN2021070694-appb-000001
可以得自丙烯酸的聚合，也可通过将丙烯酸酯聚合，然后水解而得到。
在本发明的一个优选实施方案中，共聚物A的所述其它重复单元源自例如汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。如下文关于共聚物B所详细描述，汽油、C 8馏分、C 9馏分和煤焦油轻馏分中具有含碳-碳不饱和双键的单体，这些单体经聚合后可以形成共聚物A的重复单元。
根据本发明的一个实施方案，所述共聚物A进一步包含得自至少一种具有至少两个非共轭的碳-碳不饱和双键的单体的额外重复单元，优选所述具有至少两个(如2-4个)非共轭的碳-碳不饱和双键的单体中的非共轭的 碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的非共轭碳-碳双键。所述得自至少一种具有至少两个非共轭的碳-碳不饱和双键的单体的额外重复单元的量可以为0.1-30重量％，例如0.5-20重量％或0.5-10重量％，基于共聚物A的重复单元的总量。
共聚物A的分子量可以是适合粘合剂应用的任何分子量。根据本发明的一个实施方案，所述共聚物A的分子量可以为至少2000，例如至少5000或至少8000。共聚物A的分子量的上限并不关键，例如可以为500000，或300000。在共聚物A具有得自C 4-C 22共轭二烯和/或具有至少两个非共轭的碳-碳不饱和双键的单体的重复单元的情况下，所述共聚物A还可以是交联的。
根据本发明，带有酰胺与羧基和/或其铵盐的重复单元的量可以为10-80重量％，例如20-75重量％、30-70重量％或35-65重量％，基于共聚物A的重复单元的总量。
根据本发明，共聚物A可任选含有补充重复单元。所述补充重复单元例如可以选自得自如下单体的重复单元:苯乙烯和C 2-C 22单烯烃。
在本发明的一个实施方案中，共聚物A包含带有酰胺基团与羧基和/或其铵盐的重复单元、所述其它重复单元和所述补充重复单元。
在本发明的一个实施方案中，共聚物A包含带有酰胺基团与羧基和/或其铵盐的重复单元、所述其它重复单元、所述额外重复单元和所述补充重复单元。
关于这些其它重复单元的单体、以及额外重复单元的单体、补充重复单元的单体以及反应物料的细节在下文中如对共聚物B详细描述。
根据本发明的一个优选实施方案，所述共聚物A衍生自共聚物B，该共聚物B具有至少一种带有酸酐基团的重复单元。在一个优选实施方案中，所述共聚物A得自所述共聚物B与氨的反应。
根据本发明的一个优选实施方案，所述共聚物B上的酸酐基团通过至少一种具有碳-碳不饱和双键和酸酐基团的单体的聚合而引入所述共聚物B中。所述具有碳-碳不饱和双键和酸酐基团的单体可以选自具有4-8个碳原 子的单烯属不饱和二羧酸酐，优选马来酸酐、衣康酸酐、柠康酸酐、亚甲基丙二酸酐及其混合物，更优选马来酸酐。
根据本发明的一个优选实施方案，所述共聚物B为由至少一种具有碳-碳不饱和双键和酸酐基团的单体和至少一种其他含碳-碳不饱和双键的单体形成的共聚物，
所述至少一种其他含碳-碳不饱和双键的单体选自单烯属不饱和C 3-C 8单羧酸、单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯、单烯属不饱和C 3-C 8单羧酸的酰胺、具有C 1-C 8烷基的乙烯基烷基醚、C 4-C 22共轭二烯、被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯、C 1-C 20羧酸的乙烯基酯、乙烯基吡咯烷酮、(甲基)丙烯腈、包含羟基的烯属不饱和单体、N-乙烯基甲酰胺、乙烯基咪唑、烯丙苯、茚、甲茚和含呋喃环的化合物，
或者
其他含碳-碳不饱和双键的单体得自选自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料。
作为单烯属不饱和C 3-C 8单羧酸的实例可以提及如丙烯酸、甲基丙烯酸、巴豆酸和乙烯基乙酸，优选丙烯酸和甲基丙烯酸。
单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯的实例可以提及C 1-C 10烷基的(甲基)丙烯酸烷基酯，尤其是甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸正丁酯、丙烯酸乙酯和丙烯酸2-乙基己酯或其混合物。
作为单烯属不饱和C 3-C 8单羧酸的酰胺的实例尤其可以提及(甲基)丙烯酰胺。
作为具有C 1-C 8烷基的乙烯基烷基醚，优选可以提及具有C 1-C 4烷基的乙烯基烷基醚，如甲基乙烯基醚、乙基乙烯基醚、异丁基乙烯基醚、正丁基乙烯基醚、叔丁基乙烯基醚、正戊基乙烯基醚、异戊基乙烯基醚、正己基乙烯基醚、正辛基乙烯基醚和2-乙基己基乙烯基醚。
C 4-C 22共轭二烯例如可以是C 4-C 16共轭二烯或C 5-C 16共轭二烯，C 4-C 8共轭二烯或C 5-C 8共轭二烯。这些共轭二烯的实例可以提及1,3-丁二烯、1,3-戊二烯、异戊二烯、1,3-己二烯、环戊二烯、甲基环戊二烯和1,3-环己二烯 等。
对于被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯，其中的烷基或烷氧基优选具有1-10个碳原子，如1-4个碳原子；其中的卤素优选为氯和溴。具体实例可以提及乙烯基甲苯(如α-甲基苯乙烯和对甲基苯乙烯)、α-丁基苯乙烯、4-正丁基苯乙烯、4-正癸基苯乙烯、对甲氧基苯乙烯、氯苯乙烯和溴苯乙烯。
C 1-C 20羧酸的乙烯基酯的实例可以提及月桂酸乙烯酯、硬脂酸乙烯酯、丙酸乙烯酯、新癸酸乙烯基酯和乙酸乙烯酯。
包含羟基的烯属不饱和单体例如包括(甲基)丙烯酸C 1-C 10羟烷基酯，例如丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸2-羟丙酯、丙烯酸3-羟丙酯、甲基丙烯酸2-羟丙酯和甲基丙烯酸3-羟丙酯。
含呋喃环的化合物的实例可以提及呋喃环被一个或多个(如2-4个)选自C 1-C 12烷基和C 1-C 12羟烷基的取代基取代的单体，如糠醇，所述呋喃环还可以进一步与苯环稠合，例如甲基苯并呋喃。
在本发明的一个优选实施方案中，可以不经过分离直接使用包含所述至少一种含碳-碳不饱和双键的单体以及饱和烃、不参与聚合的其他杂质的反应物料，例如汽油、C 8馏分、C 9馏分、煤焦油轻馏分。根据该优选实施方案，所述共聚物B可以为由至少一种具有碳-碳不饱和双键和酸酐基团的单体和源自例如汽油、C 8馏分、C 9馏分、煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体形成的共聚物。在使用这些反应物料形成共聚物B时(如经由自由基聚合)，这些反应物料中的含碳-碳不饱和双键的单体之外的成分可以用作制备过程中的溶剂。当使用这些馏分作为反应物料时，可以进一步降低本发明粘合剂和人造板的成本。
C 8和C 9馏分主要来源于蒸汽裂解制乙烯工艺和石脑油铂重整工艺，还有一部分来源于甲苯歧化或烷基转移产物及煤焦油等。
C 8馏分中通常包含22-35％的单烯烃，例如苯乙烯、烯丙苯、乙烯基甲苯、茚、甲茚。C 8馏分中的其他组分包括45-55％的芳烃以及约20％的其他未知组分。
C 8馏分可以具有如下具体组成：
表1
Figure PCTCN2021070694-appb-000002
C 9馏分中通常含有20-30％的单烯烃(如苯乙烯、烯丙苯、乙烯基甲苯、茚)、8-15％的二烯。C 9馏分中的其他组分包括约5％的烷烃、40-50％的芳烃以及10％左右的其他未知组分。C 9馏分可以具有如下具体组成：
表2
Figure PCTCN2021070694-appb-000003
煤焦油中的轻油组分主要含苯乙烯、α-甲基苯乙烯、烷基苯、乙烯基甲苯、双环戊二烯、苯并呋喃、茚、甲茚和甲基苯并呋喃等，目前主要作为深色-浅色的古马隆树脂原料。煤焦油轻馏分可以具有如下具体组成：
表3
组分 含量
苯乙烯 2％
α-甲基苯乙烯 1％
烷基苯 30％
乙烯基甲苯 4％
双环戊二烯 5％
苯并呋喃 7％
茚 48％
甲茚和甲基苯并呋喃 3％
在本发明的一个实施方案中，所述共聚物B进一步包含得自至少一种具有至少两个(如2-4个)非共轭的碳-碳不饱和双键的单体的额外重复单元，优选所述具有至少两个非共轭的碳-碳不饱和双键的单体中的非共轭的碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的非共轭碳-碳双键。
所述具有至少两个非共轭的碳-碳不饱和双键的单体例如可以选自具有至少2个羟基的醇的(甲基)丙烯酸酯、具有至少2个羟基的醇的乙烯基醚、具有至少2个羟基的醇的烯丙基醚、氧化乙烯和/氧化丙烯低聚物的二(甲基)丙烯酸酯、(甲基)丙烯酸酯乙烯酯、(甲基)丙烯酸酯烯丙酯、亚甲基二(甲基)丙烯酰胺、具有至少两个乙烯基的芳族化合物和C 5-C 22非共轭二烯。
所述具有至少两个羟基的醇例如可以具有2-6个，优选2-4个羟基。这些醇可以选自具有2-6个碳原子的二元醇如乙二醇、丙二醇、丁二醇、戊二醇和己二醇，甘油、三羟甲基丙烷和季戊四醇等。
因此，具有至少2个羟基的醇的(甲基)丙烯酸酯，可以为含有2-6个碳原子的二元醇的二(甲基)丙烯酸酯，其可选自乙二醇二丙烯酸酯，乙二醇二甲基丙烯酸酯，1,2-丙二醇二丙烯酸酯，1,2-丙二醇二甲基丙烯酸酯，丁二醇二(甲基)丙烯酸酯，如丁烷-1,4-二醇二丙烯酸酯，丁烷-1,4-二醇二甲基丙烯酸酯，己二醇二丙烯酸酯，己二醇二甲基丙烯酸酯，新戊二醇二丙烯酸酯，新戊二醇二甲基丙烯酸酯，3-甲基戊二醇二丙烯酸酯和3-甲基戊二醇二甲基丙烯酸酯。
氧化乙烯和/或氧化丙烯低聚物的二(甲基)丙烯酸酯的实例为二甘醇二丙烯酸酯、二甘醇二甲基丙烯酸酯、三甘醇二丙烯酸酯、三甘醇二甲基丙烯酸酯、四甘醇二丙烯酸酯和四甘醇二甲基丙烯酸酯。
具有至少两个乙烯基的芳族化合物的实例可以提及二乙烯基苯、二乙烯基甲苯、三乙烯基苯和二乙烯基萘等。
C 5-C 22非共轭二烯(如C 5-C 16非共轭二烯或C 5-C 8非共轭二烯)可以是链二烯或环二烯，其具体实例可以提及1,4-戊二烯、1,4-己二烯、1,5-己二烯、1,4-环己二烯、1,5-环辛二烯；以及具有8-20个碳原子，优选8-16或8-12个碳原子的双环烯，如双环戊二烯系单体，如双环戊二烯、甲基双环戊二烯(如2-甲基双环戊二烯、5-甲基双环戊二烯)、乙基双环戊二烯(如2-乙基双环戊二烯)和5,5-二甲基双环戊二烯等。
具有至少两个(如2-4个)非共轭的碳-碳不饱和双键的单体其他具体实例可以提及三羟甲基丙烷三(甲基)丙烯酸酯、丁二醇二乙烯基醚、三羟甲基丙烷三乙烯基醚、季戊四醇三烯丙基醚、亚甲基二(甲基)丙烯酰胺、邻苯二甲酸二烯丙基酯等。
所述得自至少一种具有至少两个非共轭的碳-碳不饱和双键的单体的额外重复单元的量可以为0.1-30重量％，例如0.5-20重量％或0.5-10重量％，基于共聚物B的重复单元的总量。
根据本发明，共聚物B可任选含有补充重复单元。所述补充重复单元例如可以选自得自如下单体的重复单元:苯乙烯和C 2-C 22单烯烃。
在本发明的一个实施方案中，共聚物B包含带有酸酐基团的重复单元、所述其它重复单元和所述补充重复单元。
在本发明的一个实施方案中，共聚物B包含带有酸酐基团的重复单元、所述其它重复单元、所述额外重复单元和所述补充重复单元。
C 2-C 22单烯烃可以是链烯和环烯，例如具有2-20或5-20个碳原子，如2-12或5-12个碳原子，2-8或5-8个碳原子的链烯，如乙烯、丙烯、丁烯、1-戊烯、2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯；具有5-20个碳原子，优选5-12或5-8个碳原子的环烯，如环戊烯、环己烯、环庚烯等环烯；具有5-20个碳原子，优选5-16或8-12个碳原子的二氢双环烯，特别是二氢双环戊二烯(如2,3-二氢双环戊二烯)、二氢甲基双环戊二烯和二氢二甲基双环戊二烯等。
制备共聚物B的具有碳-碳不饱和双键和酸酐基团的单体与其他含碳-碳不饱和双键的单体的聚合可以使用油溶性自由基引发剂进行。所述油溶性自由基引发剂例如包括偶氮类引发剂或者过氧化物引发剂。所述的偶氮 类引发剂包括：偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯等；所述过氧化物引发剂包括：过氧化二苯甲酰、过氧化二异丙苯、过氧化二(2,4-二氯苯甲酰)、过氧化二叔丁基、过氧化十二酰、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙基酯和过氧化二碳酸二环己酯等。所述引发剂的用量基于单体重量为0.05-10重量％，优选0.5-6重量％。
聚合反应可以在溶剂存在下进行。溶剂可以包括芳烃，烷烃与酮的混合物，羧酸酯，烷烃和芳烃等混合物，芳烃和羧酸酯的混合物，或者烷烃与羧酸酯的混合物，或者烷烃、芳烃和羧酸酯的混合物。
芳烃的实例可以提及甲苯、二甲苯和乙苯等。
羧酸酯可以包括C 1-C 6羧酸的C 1-C 8烷基酯、苯基酯或苄基酯以及具有6-10个碳原子的芳族羧酸的C 1-C 8烷基酯，具体实例可以提及甲酸乙酯、甲酸丙酯、甲酸异丁酯、甲酸戊酯、乙酸乙酯、乙酸丁酯、乙酸异丁酯、乙酸戊酯、乙酸异戊酯、乙酸苄酯、乙酸苯酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、丁酸异丁酯、丁酸异戊酯、异丁酸乙酯、异戊酸乙酯、异戊酸异戊酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯、苯甲酸异戊酯、苯乙酸甲酯、苯乙酸乙酯、苯乙酸丙酯、苯乙酸丁酯、苯乙酸异戊酯等酯类溶剂。
烷烃与酮的混合物中的酮可以选自丙酮、丁酮、环己酮、甲基异丁基酮、甲基异丙基酮，所述的烷烃可以选自正戊烷、正己烷、环己烷、正庚烷、正辛烷和异辛烷等。在烷烃与酮的混合物中，酮通常占5-65体积％。
聚合反应可以在惰性气体如氮气存在下进行。聚合反应的温度通常为55-120℃，优选60-100℃；聚合反应的时间通常为1-12小时，优选2-8小时。在聚合反应之后，可以将所得共聚物B分离和干燥。
在一个优选实施方案中，所述聚合反应通过沉淀聚合进行。所述沉淀聚合可以通过选择能够溶解单体但是不能溶解所得共聚物B的溶剂而进行。通过沉淀聚合，可以直接得到粉末形式的共聚物B。
根据本发明，如果使用汽油、C 8馏分、C 9馏分和煤焦油轻馏分作为反应物料的话，反应完成后未反应的烷烃或芳烃混合物只需简单蒸馏即可分离，进而得到各种高附加值的溶剂和工业原料。
根据本发明，所述共聚物B可以通过与氨反应而得到共聚物A(在下文中进一步详细描述)。
共聚物B的分子量通常与共聚物A对应。如上所述，共聚物A可以具有适合粘合剂应用的任何分子量。根据本发明的一个实施方案，所述共聚物B的分子量可以为至少2000，例如至少5000或至少8000。共聚物B的分子量的上限并不关键，例如可以为500000，或300000。在共聚物B具有得自C 4-C 22共轭二烯和/或具有至少两个非共轭的碳-碳不饱和双键的单体的重复单元的情况下，所述共聚物B可以是交联的。
在本发明的粘合剂中，除了共聚物A之外，需要的话，本发明的粘合剂还可以包含至少一种添加剂。所述添加剂可以是下面的一种或多种：除氧剂、乳化剂、染料、颜料、防迁移助剂、UV吸收剂、生物杀伤剂、消泡剂、着色剂、抗静电剂和抗氧化剂。
根据本发明，本发明的粘合剂不含能够与共聚物A的酰胺基团和/或羧基发生共价交联反应的有机交联剂，如多元醇，多胺，多链烷醇胺或它们的混合物。
根据本发明，所述粘合剂可以呈固体，优选粉末形式；或者呈含水组合物，优选呈水溶液形式。
在本发明的粘合剂中，共聚物A的量基于粘合剂的总量(如果粘合剂呈液态，如含水组合物或水溶液，则基于固含量)可以为30-100重量％，如50-100重量％，60-100重量％，70-100重量％，80-100重量％，或50-98重量％，或60-90重量％。
若所述粘合剂呈含水组合物，优选水溶液的形式，粘合剂的固含量可以为2-40重量％，或5-30重量％，或8-25重量％。
制备粘合剂的方法
本发明的一个方面涉及一种制备本发明的粘合剂的方法，其包括使共聚物B在反应介质(如水)存在或不存在下与氨反应。
共聚物B可以通过与氨反应，即氨解形成共聚物A。所述反应通常包括使共聚物B在低于100℃，优选15-70℃的温度下，例如在室温下在含水 介质中与氨在搅拌下反应。反应时间通常为0.5-10小时，优选1-6小时。
在反应之后，所得反应混合物通常为含水组合物，优选呈水溶液形式。所得含水组合物，优选水溶液可以直接用作粘合剂。也可将反应混合物与上述至少一种添加剂混合后用作粘合剂。
优选共聚物B与氨反应之前呈粉末的形式。优选所述粉末形式的共聚物B可以通过沉淀聚合制备。粉末形式的共聚物B也可通过将共聚物B(例如块状)研磨成粉末形式而得到。所述粉末形式的共聚物B的平均粒径可以为0.01-10μm，优选0.05-8μm，更优选0.1-5μm。所述粉末形式的共聚物A的平均粒径可以为0.01-10μm，优选0.05-8μm，更优选0.1-5μm。
固体形式的共聚物B与氨反应时间通常为2-300分钟，如5-120分钟。
在具体应用时，可以将固体形式的共聚物A溶于水中，任选与上述至少一种添加剂混合后再施加。
共聚物B的酸酐基团的转化率通常超过90％，优选超过95％，更优选超过98％，如100％。
在共聚物B与氨的反应中，羧基还可以与氨形成铵盐。
人造板
本发明的另一方面涉及一种人造板，其由木素纤维素材料和本发明的粘合剂形成。本发明的人造板应在宽的意义上理解，即由任何木素纤维素材料和本发明的粘合剂形成的板材。本发明的人造板并不局限于仅仅由木材形成的那些，还可以包括由竹子和秸秆等如下所述材料形成的板材。本发明的人造板可以是各种类型的人造板。在一个实施方案中，所述人造板包括但不限于刨花板、胶合板、纤维板、密度板、秸秆板和指接板。
木素纤维素材料可以得自各种木素纤维素材料，例如木材、竹子、甘蔗渣、秸秆(如麦秆)、亚麻残渣、坚果壳、谷粒壳等，以及它们的混合物。其中木材包括各种软木和/或硬木。
木素纤维素材料可以呈锯末、碎料、木片、条料、薄片、纤维、片材、木屑、刨花、颗粒和类似材料形式以及这些材料的组合的形式如条料和锯末的组合。
木素纤维素材料可以通过各种常规技术进行加工。可以将大木料在圆木刨片机中加工为木片。也可将大块木料和边角料切成碎料。还可将大木料在环形刨片机中刨片。通常在刨片之前将大木料去皮。
木素纤维素材料的尺寸通常并不关键。针对不同类型的人造板可以使用不同的尺寸。例如木素纤维素材料的尺寸可以为1-30目，优选2-15目。对于片材类的木素纤维素材料，片材的厚度可以例如为0.5mm-5cm，优选1mm-3cm。
在本发明的人造板中，其中以固含量计的粘合剂用量基于人造板的总重量为1-45重量％，优选2-40重量％，更优选3-35重量％或4-30重量％，如5-25重量％，6-25重量％，7-25重量％，8-19重量％。
在本发明的人造板中，共聚物A用量基于人造板的总重量为1-40重量％，优选2-30重量％，更优选3-25重量％或4-20重量％，如5-20重量％，6-20重量％或7-18重量％。
在本发明的人造板中，所述粘合剂用作基体树脂，优选所述粘合剂填充木素纤维素材料之间的缝隙。
人造板的制备方法
本发明的另一方面涉及一种制备人造板的方法，所述方法包括使用本发明的粘合剂。
根据本发明的一个实施方案，所述方法包括将木素纤维素材料和本发明的粘合剂的混合物在105-300℃的温度下和在0.4-10MPa的压力下压制，优选压制2-60分钟，更优选压制3-30分钟，例如5-30分钟。
用于压制的木素纤维素材料和本发明的粘合剂的混合物可以通过将木素纤维素材料与本发明的粘合剂混合而制备。当粘合剂为固体时，可以首先将粘合剂溶于水中后再与木素纤维素材料混合。
在压制之前，优选除去木素纤维素材料和粘合剂的混合物中的一部分水分，例如将木素纤维素材料和粘合剂的混合物的水份含量降至低于30重量％，优选低于25重量％，例如低于22重量％，或低于18重量％。所述混合物的水份含量通常高于5重量％或高于8重量％。所述水份的除去可 以通过加热进行，例如加热温度可以为50-90℃，优选60-80℃。
在一个优选实施方案中，所述压制在120-220℃的温度下和/或在1-6MPa的压力下进行。
当共聚物A具有呈其铵盐形式的羧基时，羧基的铵盐在压制条件下又分解为羧基。
粘合剂的用途
最后，本发明还涉及本发明的粘合剂在制备木素纤维素基人造板中的用途。
本发明的粘合剂安全、环保，没有甲醛等有毒有害物质的释放，施加简单且成本低，同时本发明的粘合剂性能优异，特别适用于木素纤维素基人造板的制造，并且用本发明的粘合剂制造的人造板具有优异的机械性能和耐水性。此外，本发明的粘合剂还可以采用汽油、C 8和C 9馏分以及煤焦油轻馏分制备，这为拓宽这些工业混合物的利用具有重要意义，并且采用由这些工业混合物得到的粘合剂制备的人造板具有更加优异的机械性能和耐水性。
实施例
以下结合本发明中的具体实施例，对本发明中的技术方案进一步描述，但不应将其理解为对本发明保护范围的限制。以下所描述的实施例仅是本发明一部分实施例，并非全部的实施例。基于本发明中所列举的实施例，本领域其他技术人员在没有采用创造性劳动的前提下所提出的其他实施例，均属于本发明保护的范围。除非另有说明，实施例中的百分数为重量百分数，实施例中的份数为质量份。
所用化学品来源：马来酸酐(纯度98+％，阿法埃莎(天津)化学有限公司)；过氧化二苯甲酰(纯度97％，阿法埃莎(天津)化学有限公司)；偶氮二异丁腈(纯度98％，上海阿拉丁生化科技股份有限公司)；氨水(浓度20-25％，北京伊诺凯科技有限公司)；氨气(纯度99.999％，北京海谱气体有限公司)；二乙烯基苯(纯度80％，阿法埃莎(天津)化学有限公司)； 醋酸乙烯酯(纯度99％，阿法埃莎(天津)化学有限公司)；丙烯酸(纯度99.5％，阿法埃莎(天津)化学有限公司)；α-甲基苯乙烯(纯度99％，阿法埃莎(天津)化学有限公司)；其他化学试剂均为分析纯，购自北京益利精细化工有限公司。C 8馏分组成如表1所示；C 9馏分组成如表2所示；煤焦油轻馏分组成如表3所示。
实施例1
按照质量份数，将100份C 8馏分，30份马来酸酐，100份二甲苯和2份过氧化二苯甲酰(BPO)混合溶解，体系通氮气20分钟后在70℃反应6小时，得到乳白色分散体系。将产物离心，用石油醚洗涤三次，干燥获得白色粉末形式的C 8-马来酸酐共聚物(重均分子量为45000)，收率为91％，共聚物中马来酸酐单体单元的质量百分数为46％。
将10份该C 8-马来酸酐共聚物，4份37％氨水，88份水在室温下搅拌4小时，获得质量浓度10％的C 8-马来酰胺酸共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)粘稠液。将该粘稠液与杨木刨花(5目-10目，含水量5％)混合，每100份刨花中共聚物用量8份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量15％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度180℃，压力0.4MPa，热压时间10分钟，获得厚度为3mm刨花板。
图1中曲线1为C 8-马来酸酐共聚物的红外谱图，1860cm -1，1780cm -1处为酸酐上两个羰基C＝O伸缩振动峰，940cm -1处为五元环酸酐特有的强吸收；
曲线2为C 8-马来酰胺酸共聚物的红外光谱图，3200cm -1处为-NH 2的不对称和对称伸缩振动峰，1650cm -1处为酰胺C＝O的伸缩振动峰。原来的C 8-马来酸酐共聚物对应的酸酐基团特征峰基本消失；
曲线3为经热压后的共聚物的红外光谱图，在1770cm - 1和1710cm - 1处出现了环状酰亚胺的特征吸收，1350cm -1处为C-N-C结构的特征吸收。
实施例2
按照质量份数，将120份C 9馏分，40份马来酸酐，100份二甲苯和4份偶氮二异丁腈(AIBN)混合溶解，体系通氮气20分钟后在70℃反应6小时，得到乳白色分散体系。将产物离心，用石油醚洗涤三次，干燥获得白色粉末形式的C 9-马来酸酐共聚物，收率为93％，共聚物中马来酸酐单体单元的质量百分数为46％。
将15份该C 9-马来酸酐共聚物，3份37％氨水，82份水在室温下搅拌4小时，获得质量浓度15％的C 9-马来酰胺酸共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为98％)粘稠液。将该粘稠液与杨木刨花(5目-10目，含水量5％)混合，每100份刨花中共聚物用量12份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量10％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度160℃，压力0.5MPa，热压时间10分钟，获得厚度为3mm刨花板。
实施例3
按照质量份数，将10份醋酸乙烯酯，11.5份马来酸酐，300份乙酸异戊酯和0.2份AIBN混合溶解，体系通氮气20分钟后在70℃反应6小时。将产物离心，洗涤，干燥获得白色粉末形式的醋酸乙烯酯-马来酸酐共聚物(重均分子量为19000)，收率为90％，共聚物中马来酸酐单体单元的质量百分数为52％。
将15份该醋酸乙烯酯-马来酸酐共聚物，5份37％氨水，80份水在室温下搅拌4小时，获得质量浓度15％的醋酸乙烯酯-马来酰胺酸共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)粘稠液。将该粘稠液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量10份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量15％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度180℃，压力0.4MPa，热压时间10分钟，获得厚度为3mm刨花板。
实施例4
将10份甲基乙烯基醚-马来酸酐共聚物(重均分子量为216000，购自上海阿拉丁生化科技股份有限公司，共聚物中马来酸酐单体单元的质量百分数为61％)置于圆底烧瓶中，通入10份氨气70℃反应2小时，得到甲基乙烯基醚-马来酰胺酸共聚物粉末。将甲基乙烯基醚-马来酰胺酸共聚物溶于水中，获得质量浓度10％的粘稠液。将该粘稠液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量20份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量10％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度170℃，压力0.4MPa，热压时间12分钟，获得厚度为3mm刨花板。
实施例5
按照质量份数，将100份煤焦油轻馏分，25份马来酸酐，100份乙酸异戊酯和2份AIBN混合溶解，体系通氮气20分钟后在70℃反应8小时。将产物离心，洗涤，干燥获得白色粉末形式的煤焦油-马来酸酐共聚物(重均分子量为11000)，收率为90％，共聚物中马来酸酐单体单元的质量百分数为42％。
将10份该煤焦油-马来酸酐共聚物，8份37％氨水，82份水在80℃下搅拌10分钟，获得质量浓度10％的煤焦油-马来酰胺酸共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)粘稠液。将该粘稠液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量10份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量10％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度160℃，压力0.4MPa，热压时间10分钟，获得厚度为3mm刨花板。
实施例6
按照质量份数，将100份苯乙烯，53份马来酸酐，24份丙烯酸，2000份二丙二醇二甲醚和2份过氧化二苯甲酰(BPO)混合溶解，体系通氮气20分钟后在80℃反应4小时，得到分散体系。将产物离心，用石油醚洗涤三次，干燥获得白色粉末形式的苯乙烯-丙烯酸-马来酸酐共聚物(比浓粘度25mL/g)，收率为82％，共聚物中马来酸酐单体单元的质量百分数为29％。
将10份该苯乙烯-丙烯酸-马来酸酐共聚物，5份37％氨水，85份水在室温下搅拌4小时，获得质量浓度10％的苯乙烯-丙烯酸-马来酰胺酸共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)粘稠液。将该粘稠液与杨木刨花(含水量5％，5目)混合，每100份刨花中共聚物用量10份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量15％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度180℃，压力1MPa，热压时间10分钟，获得厚度为3mm刨花板。
实施例7
按照质量份数，将10份α-甲基苯乙烯，9份马来酸酐，100份乙酸异戊酯和0.3份AIBN混合溶解，体系通氮气20分钟后在70℃反应6小时,得到乳白色分散体系。将产物离心，用乙酸异戊酯洗涤三次，干燥获得白色粉末形式的α-甲基苯乙烯-马来酸酐共聚物(重均分子量为27000)，收率为42％，共聚物中马来酸酐单体单元的质量百分数为45％。
将10份该α-甲基苯乙烯-马来酸酐共聚物，5份37％氨水，85份水在室温下搅拌4小时，获得质量浓度10％的α-甲基苯乙烯-马来酰胺酸共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)粘稠液。将该粘稠液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量10份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量15％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度180℃，压力0.4MPa，热压时间10分钟，获得厚度为3mm刨花板。
实施例8
按照质量份数，将8.5份醋酸乙烯酯，10份马来酸酐，0.3份二乙烯基苯，100份乙酸异戊酯和0.3份AIBN混合溶解，体系通氮气20分钟后在70℃反应6小时，得到乳白色分散体系。将产物离心，用乙酸异戊酯洗涤三次，干燥获得白色粉末形式的醋酸乙烯酯-马来酸酐-二乙烯基苯共聚物， 收率为92％，共聚物中马来酸酐单体单元的质量百分数为52％。
将10份该醋酸乙烯酯-马来酸酐-二乙烯基苯共聚物、4份37％氨水，86份水在室温下搅拌4小时，获得质量浓度10％的醋酸乙烯酯-马来酰胺酸-二乙烯基苯共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为100％)粘稠液。将该粘稠液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量9份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量15％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度170℃，压力0.4MPa，热压时间10分钟，获得厚度为3mm刨花板。
实施例9
将实施例1中得到的C 8-马来酰胺酸共聚物溶于水中，获得质量浓度10％的粘稠液。将该粘稠液均匀涂覆在含水量为12％，尺寸为160mm×160mm×1.5mm的椴木单板上，平均涂覆量为60g/m 2，按照横纹-竖纹-横纹方向进行组胚，置于热压机下进行压制，热压温度180℃，压力1MPa，热压时间10分钟，获得三层胶合板。根据GB/T 9846-2015测得胶合板的内结合强度为1.16MPa。
性能测试
根据GB/T 4897-2015对实施例1-8得到的刨花板进行内结合强度、24h吸水厚度膨胀率以及防潮性能(沸水煮后内结合强度)进行测试，结果列于下表4中。
表4：实施例1-8中的刨花板的性能数据
Figure PCTCN2021070694-appb-000004
Figure PCTCN2021070694-appb-000005
*表中的每个数据为6次测量的平均值。
实施例1-8中的刨花板的各项性能都优于国标中对于在潮湿状态下使用的家具型刨花板的性能要求。总体而言，使用C 8馏分的实施例1和使用C 9馏分的实施例2以及使用煤焦油轻馏分的实施例5中获得的人造板的性能要优于其他实施例获得的人造板的性能。
不希望受到任何理论的束缚，据信本发明粘合剂中的聚合物上的酰胺基团与羧基在压制条件下可以脱水生成酰亚胺基团，而羧基还可以脱水生成酸酐基团，所得酸酐基团可以与木素纤维素材料上的羟基发生反应形成酯，这有助于提高所得人造板的机械性能和耐水性。
以上所述仅仅为本发明的优选实施方式，需要指出的是，对于本技术领域的技术人员来说，在本发明原理的范围内，所作出的若干改进和修饰，这些改进和修饰也应被同样视为本发明的保护范围。

Claims (22)

  1. 一种粘合剂，所述粘合剂包含至少一种下述共聚物A：
    所述共聚物A具有至少一种带有酰胺基团与羧基和/或其铵盐的重复单元和至少一种不同于所述带有酰胺基团与羧基和/或其铵盐的其它重复单元，
    其中所述其它重复单元选自得自如下单体的重复单元：单烯属不饱和C 3-C 8单羧酸、单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯、单烯属不饱和C 3-C 8单羧酸的酰胺、具有C 1-C 8烷基的乙烯基烷基醚、C 4-C 22共轭二烯、被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯、C 1-C 20羧酸的乙烯基酯、乙烯基吡咯烷酮、(甲基)丙烯腈、包含羟基的烯属不饱和单体、N-乙烯基甲酰胺、乙烯基咪唑、烯丙苯、茚、甲茚和含呋喃环的化合物，
    或者
    所述其它重复单元得自源自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。
  2. 根据权利要求1的粘合剂，其中在所述共聚物A中，带有酰胺与羧基和/或其铵盐的重复单元的量为10-80重量％，或30-70重量％，基于共聚物A的重复单元的总量。
  3. 根据权利要求1或2的粘合剂，其中共聚物A的所述其它重复单元选自得自如下单体的重复单元：单烯属不饱和C 3-C 8单羧酸、具有C 1-C 8烷基的乙烯基烷基醚、C 1-C 20羧酸的乙烯基酯和被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯，或者所述其它重复单元得自源自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。
  4. 根据权利要求1-3中任一项的粘合剂，其中共聚物A的所述其它重复单元得自源自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。
  5. 根据权利要求1-4中任一项的粘合剂，其中所述共聚物A进一步包 含得自至少一种具有至少两个非共轭的碳-碳不饱和双键的单体的额外重复单元，优选所述具有至少两个非共轭的碳-碳不饱和双键的单体中的非共轭的碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的非共轭碳-碳双键。
  6. 根据权利要求1-5中任一项粘合剂，其中所述共聚物A衍生自共聚物B，该共聚物B具有至少一种带有酸酐基团的重复单元。
  7. 根据权利要求1-6中任一项的粘合剂，其中所述共聚物A得自共聚物B与氨的反应。
  8. 根据权利要求6或7的粘合剂，其中所述共聚物B上的酸酐基团通过至少一种具有碳-碳不饱和双键和酸酐基团的单体的聚合而引入所述共聚物B中。
  9. 根据权利要求8的粘合剂，其中所述具有碳-碳不饱和双键和酸酐基团的单体选自具有4-8个碳原子的单烯属不饱和二羧酸酐，优选马来酸酐、衣康酸酐、柠康酸酐和亚甲基丙二酸酐，更优选马来酸酐。
  10. 根据权利要求6-9中任一项的粘合剂，其中所述共聚物B为由至少一种具有碳-碳不饱和双键和酸酐基团的单体和至少一种其他含碳-碳不饱和双键的单体形成的共聚物，
    所述至少一种其他含碳-碳不饱和双键的单体选自单烯属不饱和C 3-C 8单羧酸、单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯、单烯属不饱和C 3-C 8单羧酸的酰胺、具有C 1-C 8烷基的乙烯基烷基醚、C 4-C 22共轭二烯、被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯、C 1-C 20羧酸的乙烯基酯、乙烯基吡咯烷酮、(甲基)丙烯腈、包含羟基的烯属不饱和单体、N-乙烯基甲酰胺、乙烯基咪唑、烯丙苯、茚、甲茚和含呋喃环的化合物，
    或者
    其他含碳-碳不饱和双键的单体得自选自汽油、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料。
  11. 根据权利要求6-10中任一项的粘合剂，其中所述共聚物B进一步包含得自至少一种具有至少两个非共轭的碳-碳不饱和双键的单体的额外 重复单元，优选所述具有至少两个非共轭的碳-碳不饱和双键的单体中的非共轭的碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的非共轭碳-碳双键。
  12. 根据权利要求1-11中任一项的粘合剂，其中所述粘合剂呈固体，优选粉末形式；或者呈含水组合物，优选呈水溶液形式，优选所述共聚物A的含量为2-40重量％，尤其是5-30重量％，基于含水组合物的总重量。
  13. 根据权利要求1-12中任一项的粘合剂，其中所述粘合剂不含能够与共聚物A的酰胺基团和/或羧基发生共价交联反应的有机交联剂。
  14. 一种人造板，其由木素纤维素材料和如权利要求1-13中任一项的粘合剂形成。
  15. 根据权利要求14的人造板，其中以固含量计的粘合剂用量基于人造板的总重量为1-45重量％，优选2-35重量％，更优选3-30重量％。
  16. 根据权利要求14或15的人造板，其中如权利要求1-12中任一项所定义的共聚物A的用量基于人造板的总重量为1-40重量％，优选2-30重量％，更优选3-25重量％。
  17. 根据权利要求14-16中任一项的人造板，其中所述粘合剂用作基体树脂，优选所述粘合剂填充木素纤维素材料之间的缝隙。
  18. 根据权利要求14-17中任一项的人造板，其中所述人造板为刨花板、胶合板、密度板、纤维板、秸秆板或指接板。
  19. 一种制备人造板的方法，其包括使用如权利要求1-13中任一项所定义的粘合剂。
  20. 根据权利要求19的方法，其包括将木素纤维素材料和所述粘合剂的混合物在105-300℃温度下和在0.4-10MPa的压力下压制，优选压制2-60分钟，更优选压制3-30分钟。
  21. 根据权利要求19或20的方法，其中所述人造板为权利要求14-18中任一项的人造板。
  22. 如权利要求1-13中任一项的粘合剂在制备木素纤维素基人造板中的用途。
PCT/CN2021/070694 2020-12-02 2021-01-07 包含具有酰胺基团与羧基和/或其铵盐的重复单元的共聚物的粘合剂和用其制备的人造板 WO2022116362A1 (zh)

Priority Applications (6)

Application Number Priority Date Filing Date Title
MX2023006508A MX2023006508A (es) 2020-12-02 2021-01-07 Adhesivo que comprende un copolimero que tiene una unidad repetitiva que lleva un grupo amida y carboxilo y/o su sal de amonio y tabla artificial preparada con el mismo.
CA3200575A CA3200575A1 (en) 2020-12-02 2021-01-07 Adhesive comprising copolymer having repeating unit carrying amide group and carboxyl and/or its ammonium salt and artificial board prepared therewith
JP2023533787A JP2023551554A (ja) 2020-12-02 2021-01-07 アミド基とカルボキシ基および／またはそのアンモニウム塩との繰り返し単位を有する共重合体を含む接着剤およびそれを用いて調製した人工ボード
KR1020237021846A KR20230141757A (ko) 2020-12-02 2021-01-07 아미드기 및 카복실기 및/또는 이의 암모늄염의 반복단위를 갖는 공중합체를 포함하는 접착제, 및 이를 이용한 인조 판재
US18/255,860 US20240010887A1 (en) 2020-12-02 2021-01-07 Adhesive comprising copolymer having repeating unit carrying amide group and carboxyl and/or its ammonium salt and artificial board prepared therewith
EP21899406.9A EP4257653A1 (en) 2020-12-02 2021-01-07 Adhesive comprising copolymer having repeating unit of amide group and carboxyl group and/or ammonium salt thereof, and wood-based panel using same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011390257 2020-12-02
CN202011390257.4 2020-12-02

Publications (1)

Publication Number Publication Date
WO2022116362A1 true WO2022116362A1 (zh) 2022-06-09

Family

ID=76005025

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/070694 WO2022116362A1 (zh) 2020-12-02 2021-01-07 包含具有酰胺基团与羧基和/或其铵盐的重复单元的共聚物的粘合剂和用其制备的人造板

Country Status (9)

Country Link
US (1) US20240010887A1 (zh)
EP (1) EP4257653A1 (zh)
JP (1) JP2023551554A (zh)
KR (1) KR20230141757A (zh)
CN (2) CN112852356B (zh)
CA (1) CA3200575A1 (zh)
MX (1) MX2023006508A (zh)
TW (1) TW202222856A (zh)
WO (1) WO2022116362A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113801611B (zh) * 2021-10-29 2022-06-10 新元化学(山东)股份有限公司 工业化连续大规模生产无醛水性粘合剂的绿色安全环保工艺
CN114085631B (zh) * 2021-12-02 2023-02-28 北京化工大学 粘合剂组合物及其制造方法，使用该粘合剂组合物的制品
CN115652474A (zh) * 2022-09-28 2023-01-31 清华大学 由酰胺酸共聚物制备酰亚胺共聚物的纤维的方法和由其制备的纤维

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1363512A (en) * 1971-03-25 1974-08-14 Ethylene Plastique Sa Adhesives based on copolymer of ethylene and maleic anhydride
JPS49131243A (zh) * 1973-04-21 1974-12-16
JPS62235380A (ja) * 1986-04-04 1987-10-15 Idemitsu Petrochem Co Ltd 接着剤
CN100528503C (zh) * 2005-10-03 2009-08-19 罗门哈斯公司 复合材料及其制备方法
CN101555395A (zh) * 2009-05-22 2009-10-14 长春科龙节能墙体开发有限公司 一种聚苯板胶粘剂及其制备方法
CN203344147U (zh) 2013-04-19 2013-12-18 苏州佰家丽新材料科技有限公司 纤维板
CN104136540A (zh) * 2012-01-13 2014-11-05 佐治亚-太平洋化工品有限公司 粘合剂组合物及其制造与使用方法
US20160001506A1 (en) * 2014-07-02 2016-01-07 Seiko Epson Corporation Method of manufacturing three-dimensional structure, three-dimensional structure, and three-dimension formation composition
CN107033309A (zh) 2017-03-28 2017-08-11 曾华 一种纤维板胶黏剂的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0745649B2 (ja) * 1987-04-15 1995-05-17 出光石油化学株式会社 接着剤の製造方法
US20080274292A1 (en) * 2007-05-03 2008-11-06 Kiarash Alavi Shooshtari Binding of fibrous material utilizing a crosslinked polyamic acid
JP2009215473A (ja) * 2008-03-12 2009-09-24 Koyo Sangyo Co Ltd 耐水性接着剤組成物
CN108239496A (zh) * 2016-12-23 2018-07-03 张家港康得新光电材料有限公司 苯乙烯马来酸酐制备酰胺酸的制备方法、水性可剥胶组合物及水性可剥胶

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1363512A (en) * 1971-03-25 1974-08-14 Ethylene Plastique Sa Adhesives based on copolymer of ethylene and maleic anhydride
JPS49131243A (zh) * 1973-04-21 1974-12-16
JPS62235380A (ja) * 1986-04-04 1987-10-15 Idemitsu Petrochem Co Ltd 接着剤
CN100528503C (zh) * 2005-10-03 2009-08-19 罗门哈斯公司 复合材料及其制备方法
CN101555395A (zh) * 2009-05-22 2009-10-14 长春科龙节能墙体开发有限公司 一种聚苯板胶粘剂及其制备方法
CN104136540A (zh) * 2012-01-13 2014-11-05 佐治亚-太平洋化工品有限公司 粘合剂组合物及其制造与使用方法
CN203344147U (zh) 2013-04-19 2013-12-18 苏州佰家丽新材料科技有限公司 纤维板
US20160001506A1 (en) * 2014-07-02 2016-01-07 Seiko Epson Corporation Method of manufacturing three-dimensional structure, three-dimensional structure, and three-dimension formation composition
CN107033309A (zh) 2017-03-28 2017-08-11 曾华 一种纤维板胶黏剂的制备方法

Also Published As

Publication number Publication date
US20240010887A1 (en) 2024-01-11
TW202222856A (zh) 2022-06-16
EP4257653A1 (en) 2023-10-11
CN112852356A (zh) 2021-05-28
CN112852356B (zh) 2022-11-29
MX2023006508A (es) 2023-10-27
CN114891465A (zh) 2022-08-12
JP2023551554A (ja) 2023-12-08
KR20230141757A (ko) 2023-10-10
CA3200575A1 (en) 2022-06-09

Similar Documents

Publication Publication Date Title
WO2022116362A1 (zh) 包含具有酰胺基团与羧基和/或其铵盐的重复单元的共聚物的粘合剂和用其制备的人造板
WO2022116363A1 (zh) 粘合剂和用其制备的人造板
CN1293159C (zh) 一种木材用淀粉胶的制备方法
TW202231679A (zh) 交聯的具有醯胺基團與羧基和／或其銨鹽的重複單元和α－單烯烴的重複單元的共聚物
EP2163590B1 (en) Wood adhesives comprising protein and oxazoline polymer or resin
JP2000507279A (ja) 成形体用のホルムアルデヒド不含のバインダー
Thuraisingam et al. Novel natural rubber latex/lignin-based bio-adhesive: synthesis and its application on medium density fiber-board
CN114085631B (zh) 粘合剂组合物及其制造方法，使用该粘合剂组合物的制品
CN109401726B (zh) PEI-g-HBA预聚物植物蛋白复合改性胶黏剂及其制备方法与应用
Abdullayeva et al. Determining the properties of adhesives based on modified phenol-formaldehyde oligomer with amine-aromatic compound
US11214714B2 (en) Thermoplastic poly acrylated glycerol adhesives useful in cellulosic products
CN116376483A (zh) 一种粘合剂及其制备方法与应用
Tan et al. Properties of Acacia mangium wood particles and bioplastic binder
CN115637123A (zh) 高支化葡萄糖基耐水胶粘剂及其制备方法和应用
CN115595118A (zh) 一种易湿态涂布防霉阻燃大豆蛋白基胶黏剂及其制备方法
CN112679144A (zh) 一种高效吸附甲醛的饰面胶合板及其制备工艺
CN101563433A (zh) 生产木基产品的方法
Ngaini et al. INCORPORATION OF CYCLOTRIPHOSPHAZENES AS PENDANT GROUPS TO THE SAGO NETWORK

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21899406

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3200575

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2023533787

Country of ref document: JP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112023010762

Country of ref document: BR

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021899406

Country of ref document: EP

Effective date: 20230703

ENP Entry into the national phase

Ref document number: 112023010762

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20230601

WWE Wipo information: entry into national phase

Ref document number: 523441046

Country of ref document: SA