Adhesives and artificial boards prepared using them

Abstract

The present disclosure relates to an adhesive comprising at least one copolymer A described below. Copolymer A has at least one repeating unit having an amide group and a carboxy group and / or an ammonium salt thereof, and at least one other repeating unit different from the repeating unit having an amide group and a carboxy group and / or an ammonium salt thereof. The present disclosure also relates to an artificial board formed from the lignocellulosic material and the adhesive, and a method for producing the artificial board.

Description

[Technical Field] 【0001】 This disclosure relates to a type of adhesive, the adhesive comprising a copolymer having at least one repeating unit having an amide group and a carboxyl group and / or an ammonium salt thereof, and other repeating units. This disclosure also relates to a lignocellulose material and an artificial board formed from the adhesive, as well as a method for manufacturing the artificial board. [Background technology] 【0002】 In current artificial board production, "three aldehyde adhesives" (urea-formaldehyde resin, phenol-formaldehyde resin, and melamine-formaldehyde resin), prepared using artificial board and formaldehyde as raw materials, account for a relatively large proportion, exceeding 80%. While these "three aldehyde adhesives" are easy to prepare and inexpensive, this type of board can release free formaldehyde over the long term during use, polluting the indoor environment and seriously threatening the health of residents. 【0003】 Several documents have proposed solutions for reducing formaldehyde emissions from "three-aldehyde adhesive" type artificial boards. For example, Chinese Patent Application Publication No. 107033309 attempts to reduce formaldehyde emissions by adjusting the ratio of raw materials and the pH value at each polymerization stage, and by adding formaldehyde scavenging agents. Chinese Utility Model Publication No. 203344147 discloses incorporating activated carbon, bamboo charcoal, diatomaceous earth, etc., during board production to impart a certain gas adsorption capacity to the board. However, the above methods do not fundamentally solve the problem, and the boards still release formaldehyde during use. 【0004】 Adhesives prepared based on biomass raw materials such as soy protein, tannin, starch, and gelatin do not involve the use of formaldehyde, but they have the problem that the degradation rate of the biomass raw materials is fast and the board is prone to aging. Although the addition of anti-aging agents can delay the degradation to a certain extent, biomass-based adhesives still have relatively high costs and problems related to resources. Therefore, their practical use is also limited. 【0005】 Furthermore, for example, boards can also be produced using polymers such as polyvinyl chloride, high molecular weight polyethylene, and chloroprene rubber. However, all of these polymers do not have water solubility and cannot form aqueous adhesives. The polymers can only be mixed with wood raw materials by hot melt or organic solvents, and the disadvantages of high cost, energy consumption, and environmental unfriendliness still exist. 【0006】 Therefore, considering aspects such as safety, environmental friendliness, low production cost, simplicity of the coating process, and durability of the finished product, it is particularly important to develop a new formaldehyde-free artificial board adhesive. 【Prior Art Documents】 【Patent Documents】 【0007】 【Patent Document 1】 Specification of Chinese Patent Application Publication No. 107033309 【Patent Document 2】 Specification of Chinese Utility Model No. 203344147 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0008】 In view of the actual situation of the above prior art, the inventor of the present invention has conducted extensive and in-depth research on adhesives in the field of artificial boards in order to discover an adhesive that is used for artificial boards without formaldehyde emission, has low cost, is easy to apply, and has excellent performance. The inventor of the present invention has discovered that an adhesive containing at least one specific copolymer A not only has no formaldehyde emission, but also has low cost, is easy to apply, and has excellent performance. The copolymer A has at least one repeating unit having an amide group and a carboxyl group and / or its ammonium salt and other repeating units. 【0009】 The present invention has been completed based on the above findings. 【0010】 An object of the present invention is to provide an adhesive containing at least one copolymer A, the copolymer A having at least one repeating unit having an amide group and a carboxyl group and / or its ammonium salt and other repeating units, and the adhesive having the advantages of being safe, environmentally friendly, having low cost, being easy to apply, and having excellent performance. 【0011】 Another object of the present invention is to provide an artificial board formed from a lignocellulosic material and the adhesive of the present invention. 【0012】 A further object of the present invention is to provide a method for preparing an artificial board using the adhesive of the present invention. 【Means for Solving the Problems】 【0013】 The technical solution for realizing the object of the present invention can be summarized as follows. 【0014】 1. An adhesive, the adhesive containing at least one of the following-described copolymer A: The copolymer A comprises at least one repeating unit having an amide group and a carboxyl group and / or its ammonium salt, and at least one other repeating unit different from the one having the amide group and the carboxyl group and / or its ammonium salt. The aforementioned other repeating units are selected from repeating units derived from the following monomers: monoethylenically unsaturated C3-C8 monocarboxylic acids, C1-C of monoethylenically unsaturated C3-C8 monocarboxylic acids. 10 Alkyl esters, monoethylenically unsaturated C3-C8 monocarboxylic acid amides, C5-C 22 Monoolefin, C4-C 22 Conjugated dienes, vinyl alkyl ethers having C1-C8 alkyl groups, styrene, C1-C 20 Vinyl esters of carboxylic acids, vinylpyrrolidone, (meth)acrylonitrile, hydroxyl group-containing ethylenically unsaturated monomers, N-vinylformamide, vinylimidazole, allylbenzene, indene, methylindene and furan ring-containing compounds, or The aforementioned other repeating units are derived from at least one monomer containing a carbon-carbon unsaturated double bond, which is generated from the reaction material of the C4 or C5 fraction. 【0015】 2. The adhesive according to item 1, wherein the amount of repeating units having an amide and a carboxyl group and / or an ammonium salt thereof in copolymer A is 10-80% by weight or 30-70% by weight, based on the total amount of repeating units in copolymer A. 【0016】 3. The other repeating units of copolymer A are selected from repeating units derived from the following monomers: vinyl alkyl ethers having C1-C8 alkyl groups, C5-C 22 Monoolefin, C4-C 22 Conjugated dienes, C1-C 20 Vinyl esters of carboxylic acids and styrene, or The adhesive according to item 1 or 2, wherein the other repeating units of copolymer A are derived from at least one monomer containing a carbon-carbon unsaturated double bond resulting from a C4 fraction or C5 fraction of the reactant material. 【0017】 4. The adhesive according to any one of items 1-3, wherein the other repeating units of copolymer A are derived from at least one monomer containing a carbon-carbon unsaturated double bond resulting from a reaction material of a C4 fraction or a C5 fraction. 【0018】 5. The adhesive according to any one of items 1-4, wherein the copolymer A further comprises additional repeating units derived from at least one monomer having at least two 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)acrylic acid groups, (meth)acrylamide groups, vinyl groups, allyl groups, and non-conjugated carbon-carbon double bonds in alkenes or cycloalkenes. 【0019】 6. The adhesive according to any one of items 1-5, wherein copolymer A is derived from copolymer B, and copolymer B has at least one repeating unit having an anhydride group. 【0020】 7. The adhesive according to any one of items 1-6, wherein copolymer A is derived from the reaction of copolymer B with ammonia. 【0021】 8. The adhesive according to item 6 or 7, wherein the anhydride group on copolymer B is introduced into copolymer B by polymerization of at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group. 【0022】 9. The monomer having a carbon-carbon unsaturated double bond and an anhydride group is selected from monoethylenically unsaturated dicarboxylic anhydrides having 4 to 8 carbon atoms, preferably maleic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride, more preferably maleic anhydride, the adhesive according to item 8. 【0023】 10. The copolymer B is a copolymer formed from at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group, and at least one other monomer containing a carbon-carbon unsaturated double bond, The at least one other monomer containing a carbon-carbon unsaturated double bond is a monoethylenically unsaturated C3-C8 monocarboxylic acid, a C1-C 10 alkyl ester of a monoethylenically unsaturated C3-C8 monocarboxylic acid, an amide of a monoethylenically unsaturated C3-C8 monocarboxylic acid, C5-C 22 monoolefin, C4-C 22 conjugated diene, vinyl alkyl ether having a C1-C8 alkyl group, styrene, C1-C 20 vinyl ester of a carboxylic acid, vinyl pyrrolidone, (meth)acrylonitrile, a hydroxy group-containing ethylenically unsaturated monomer, N-vinylformamide, vinyl imidazole, allyl benzene, indene, methyl indene and furan ring-containing compounds, selected from or The other monomer containing a carbon-carbon unsaturated double bond is derived from a reaction material selected from a C4 fraction or a C5 fraction, The adhesive according to any one of items 6-9. 【0024】 11. The adhesive according to any one of items 6-10, wherein the copolymer B further comprises additional repeating units derived from at least one monomer having at least two 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)acrylic acid groups, (meth)acrylamide groups, vinyl groups, allyl groups, and non-conjugated carbon-carbon double bonds in alkenes or cycloalkenes. 【0025】 12. The adhesive according to any one of items 1-11, wherein the adhesive is a solid, preferably in powder form; or an aqueous composition, preferably in aqueous solution form, and preferably the content of copolymer A is 2-40% by weight, particularly 5-30% by weight, based on the total weight of the aqueous composition. 【0026】 13. The adhesive according to any one of items 1-12, wherein the adhesive does not contain an organic crosslinking agent capable of covalent crosslinking with the amide and / or carboxyl groups of copolymer A. 【0027】 14. A type of artificial board formed from a lignocellulose material and an adhesive as described in any one of items 1-13. 【0028】 15. The amount of solid-based adhesive is 1-45% by weight, preferably 2-35% by weight, more preferably 3-30% by weight, based on the total weight of the artificial board, as described in item 14. 【0029】 16. The amount of copolymer A specified by any one of items 1-12 is 1-40% by weight, preferably 2-30% by weight, more preferably 3-25% by weight, based on the total weight of the artificial board, as described in item 14 or 15. 【0030】 17. The artificial board according to any one of items 14-17, wherein the adhesive is used as a matrix resin, and preferably the adhesive fills the gaps between the lignocellulose materials. 【0031】 18. The artificial board is a particle board, plywood, density board, fiberboard, straw board, or finger-joint board, as described in any one of items 14-17. 【0032】 19. A method for preparing an artificial board, comprising using an adhesive specified by any one of items 1-13. 【0033】 20. The method according to item 19, comprising pressing a mixture of lignocellulose material and the adhesive at a temperature of 105-300°C and a pressure of 0.4-10 MPa, preferably for 2-60 minutes, and more preferably for 3-30 minutes. 【0034】 21. The method according to item 19 or 20, wherein the artificial board is an artificial board described in any one of items 14-18. 【0035】 22. Use of any one of the adhesives described in items 1-13 during the preparation of lignocellulose-based artificial boards. [Brief explanation of the drawing] 【0036】 [Figure 1] These are the infrared spectra of different polymers in Example 2: 1: C4-maleic anhydride copolymer; 2: C4-maleamic acid copolymer; 3: copolymer in an artificial board after hot pressing. [Modes for carrying out the invention] 【0037】 The specific values ​​disclosed herein for related features (including the endpoint values ​​of the disclosed ranges) can be combined to form new ranges. 【0038】 glue 【0039】 One aspect of the present invention relates to a type of adhesive, the adhesive comprising at least one copolymer A as described below: The copolymer A comprises at least one repeating unit having an amide group and a carboxyl group and / or an ammonium salt thereof, and at least one other repeating unit different from the repeating unit having an amide group and a carboxyl group and / or an ammonium salt thereof. The aforementioned other repeating units are selected from repeating units derived from the following monomers: monoethylenically unsaturated C3-C8 monocarboxylic acids, C1-C of monoethylenically unsaturated C3-C8 monocarboxylic acids. 10 Alkyl esters, monoethylenically unsaturated C3-C8 monocarboxylic acid amides, C5-C 22 Monoolefin, C4-C 22 Conjugated dienes, vinyl alkyl ethers having C1-C8 alkyl groups, styrene, C1-C 20 Vinyl esters of carboxylic acids, vinylpyrrolidone, (meth)acrylonitrile, hydroxyl group-containing ethylenically unsaturated monomers, N-vinylformamide, vinylimidazole, allylbenzene, indene, methylindene, and furan ring-containing compounds, preferably selected from repeating units derived from the following monomers: vinyl alkyl ethers having C1-C8 alkyl groups, C5-C 22 Monoolefin, C4-C 22 Conjugated dienes, C1-C 20 Vinyl esters of carboxylic acids and styrene, or The aforementioned other repeating units are derived from at least one monomer containing a carbon-carbon unsaturated double bond, which is generated from the reaction material of the C4 or C5 fraction. 【0040】 According to the present invention, a portion of the carboxyl groups of copolymer A (for example, 1-10% by weight) may be in the form of its ammonium salt. 【0041】 Those skilled in the art will understand that the expression "derived from" includes cases where the copolymer has a specific repeating unit, but that the repeating unit is not directly formed by the corresponding monomer of that repeating unit. For example, carboxyethylene repeating unit [ka] It may be derived from the polymerization of acrylic acid, or it may be obtained by polymerizing acrylate and then hydrolyzing it. 【0042】 According to one embodiment of the present invention, the other repeating units of copolymer A are selected from repeating units derived from the following monomers: vinyl alkyl ethers having C1-C8 alkyl groups, C5-C 22 Monoolefin, C4-C 22 Conjugated dienes, C1-C 20 Vinyl esters and styrenes of carboxylic acids. 【0043】 In one preferred embodiment of the present invention, the other repeating units of copolymer A are derived from, for example, at least one monomer containing a carbon-carbon unsaturated double bond in the reactant material of the C4 or C5 fraction. As described in detail with respect to copolymer B in the following document, the C4 or C5 fraction contains monomers containing a carbon-carbon unsaturated double bond, and these monomers can form repeating units of copolymer A after polymerization. 【0044】 According to one embodiment of the present invention, the copolymer A further comprises additional repeating units derived from at least one monomer having at least two non-conjugated carbon-carbon unsaturated double bonds, preferably the non-conjugated carbon-carbon unsaturated double bonds in the monomer having at least two (e.g., 2-4) non-conjugated carbon-carbon unsaturated double bonds are selected from (meth)acrylic acid groups, (meth)acrylamide groups, vinyl groups, allyl groups, and non-conjugated carbon-carbon double bonds in alkenes or cycloalkenes. The amount of additional repeating units derived from at least one monomer having at least two non-conjugated carbon-carbon unsaturated double bonds may be 0.1-30% by weight, for example, 0.5-20% by weight or 0.5-10% by weight, based on the total amount of repeating units of copolymer A. 【0045】 The molecular weight of copolymer A may be any molecular weight suitable for adhesive applications. According to one embodiment of the present invention, the molecular weight of copolymer A may be at least 2000, for example, at least 5000 or at least 8000. The upper limit of the molecular weight of copolymer A is not important and may be, for example, 500000 or 300000. Copolymer A is C4-C 22 In the case where the copolymer A has repeating units derived from a conjugated diene and / or a monomer having at least two non-conjugated carbon-carbon unsaturated double bonds, the copolymer A may also be crosslinked. 【0046】 According to the present invention, the amount of repeating units having an amide and a carboxyl group and / or its ammonium salt may be 10-80% by weight, for example, 20-75% by weight, 30-70% by weight, or 35-65% by weight, based on the total amount of repeating units of copolymer A. 【0047】 According to the present invention, copolymer A may optionally contain auxiliary repeating units. The auxiliary repeating units can be selected from, for example, repeating units derived from the following monomers: C2-C4 monoolefins. 【0048】 In one embodiment of the present invention, copolymer A comprises repeating units having an amide group and a carboxyl group and / or an ammonium salt thereof, the other repeating units and the auxiliary repeating units. 【0049】 In one embodiment of the present invention, copolymer A comprises repeating units having an amide group and a carboxyl group and / or an ammonium salt thereof, the other repeating units, the additional repeating units and the auxiliary repeating units. 【0050】 Details regarding these other repeating unit monomers, as well as additional repeating unit monomers, auxiliary repeating unit monomers, and reaction materials, are described in detail in the following document for copolymer B. 【0051】 According to one preferred embodiment of the present invention, copolymer A is derived from copolymer B, wherein copolymer B has at least one repeating unit having an anhydride group. In one preferred embodiment, copolymer A is derived from the reaction of copolymer B with ammonia. 【0052】 According to one preferred embodiment of the present invention, the anhydride group on copolymer B is introduced into copolymer B by polymerization of at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group. The monomer having a carbon-carbon unsaturated double bond and anhydride group can be selected from monoethylenically unsaturated dicarboxylic acid anhydrides having 4-8 carbon atoms, preferably maleic anhydride, itaconic anhydride, citraconic anhydride, methylenemalonic anhydride, and mixtures thereof, and more preferably maleic anhydride. 【0053】 According to one preferred embodiment of the present invention, copolymer B is a copolymer formed from at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group, and at least one other monomer containing a carbon-carbon unsaturated double bond. The at least one other monomer containing a carbon-carbon unsaturated double bond is a monoethylenically unsaturated C3-C8 monocarboxylic acid, or a C1-C of a monoethylenically unsaturated C3-C8 monocarboxylic acid. 10 Alkyl esters, monoethylenically unsaturated C3-C8 monocarboxylic acid amides, C5-C 22 Monoolefin, C4-C 22 Conjugated dienes, vinyl alkyl ethers having C1-C8 alkyl groups, styrene, C1-C 20 Selected from vinyl esters of carboxylic acids, vinylpyrrolidone, (meth)acrylonitrile, hydroxyl group-containing ethylenically unsaturated monomers, N-vinylformamide, vinylimidazole, allylbenzene, indene, methylindene, and furan ring-containing compounds, or Other monomers containing carbon-carbon unsaturated double bonds are derived from reaction materials selected from the C4 or C5 fraction. 【0054】 In one embodiment of the present invention, the at least one other monomer containing a carbon-carbon unsaturated double bond is a vinyl alkyl ether having a C1-C8 alkyl group, C5-C 22 Monoolefin, C4-C 22 Conjugated dienes, C1-C 20 The vinyl esters and styrenes of carboxylic acids can be selected. 【0055】 Examples of monoethylenically unsaturated C3-C8 monocarboxylic acids include, for example, acrylic acid, methacrylic acid, crotonic acid, and vinylacetic acid, preferably acrylic acid and methacrylic acid. 【0056】 C1-C of monoethylenically unsaturated C3-C8 monocarboxylic acids 10 Examples of alkyl esters include C1-C 10 Examples include alkyl (meth)acrylate esters of alkyl groups, particularly methyl methacrylate, methyl acrylate, N-butyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate, or mixtures thereof. 【0057】 As an example of a monoethylenically unsaturated C3-C8 monocarboxylic acid amide, (meth)acrylamide can be particularly cited. 【0058】 C5-C 22 The monoolefins may be alkenes and cycloalkenes, for example, alkenes having 5-20 carbon atoms, for example, 5-12 carbon atoms, or 5-8 carbon atoms, for example, 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene; cycloalkenes having 5-20 carbon atoms, preferably 5-12 or 5-8 carbon atoms, for example, cycloalkenes such as cyclopentene, cyclohexene, and cycloheptene; and dihydrobicycloalkenes having 8-20 carbon atoms, preferably 8-16 or 8-12 carbon atoms, particularly dihydrodicyclopentadiene (e.g., 2,3-dihydrodicyclopentadiene), dihydromethyldicyclopentadiene, and dihydrodimethyldicyclopentadiene. 【0059】 C4-C 22 Conjugated dienes are, for example, C4-C 16 Conjugated dienes or C5-C 16 These may be conjugated dienes, C4-C8 conjugated dienes, or C5-C8 conjugated dienes. Examples of these conjugated dienes include 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, cyclopentadiene, methylcyclopentadiene, and 1,3-cyclohexadiene. 【0060】 Examples of vinyl alkyl ethers having a C1-C8 alkyl group include vinyl alkyl ethers having a C1-C4 alkyl group, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, and 2-ethylhexyl vinyl ether. 【0061】 C1-C 20 Examples of vinyl esters of carboxylic acids include vinyl laurate, vinyl stearate, vinyl propionate, vinyl neodecanoate, and vinyl acetate. 【0062】 Examples of hydroxyl group-containing ethylenically unsaturated monomers are C1-C 10 This includes hydroxyalkyl (meth)acrylates, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl methacrylate. 【0063】 Examples of furan ring-containing compounds include those with a C1-C furan ring. 12 Alkyl and C1-C 12 Examples include monomers substituted with one or more (e.g., 2-4) substituents selected from hydroxyalkyl groups, such as furfuryl alcohol. The furan ring can be further condensed with a benzene ring, such as methylbenzofuran. 【0064】 In one preferred embodiment of the present invention, the reaction material, which includes at least one monomer containing a carbon-carbon unsaturated double bond and saturated hydrocarbons, and other impurities not involved in polymerization, such as a C4 fraction or a C5 fraction, can be used directly without separation. According to this preferred embodiment, copolymer B may be a copolymer formed from at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group, and at least one monomer containing a carbon-carbon unsaturated double bond resulting from the reaction material, for example, a C4 fraction or a C5 fraction. When forming copolymer B using these reaction materials (for example, by free radical polymerization), components in these reaction materials other than the monomer containing a carbon-carbon unsaturated double bond can be used as solvents in the preparation process. When these fractions are used as reaction materials, the cost of the adhesives and artificial boards of the present invention can be further reduced. 【0065】 Examples of C4 fractions include by-products generated in petroleum cracking or catalytic cracking for ethylene production. These typically contain components such as isobutene, 1-butene-1, 2-butene, and butane. 【0066】 The C4 fraction can have the following specific compositions. [Table 1] 【0067】 The C5 fraction is typically derived from petroleum cracking. It contains approximately 45-55% diolefins and 8-15% monoolefins. Other components in the C5 fraction include 18-25% alkanes, around 1% alkynes, and 10-20% C4, benzene, and other components. 【0068】 The C5 fraction can have the following specific compositions. [Table 2] 【0069】 In one embodiment of the present invention, the copolymer B further comprises at least one additional repeating unit derived from a monomer having at least two (e.g., 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)acrylic acid groups, (meth)acrylamide groups, vinyl groups, allyl groups, and non-conjugated carbon-carbon double bonds in alkenes or cycloalkenes. 【0070】 The monomers having at least two non-conjugated carbon-carbon unsaturated double bonds include, for example, (meth)acrylates of alcohols having at least two hydroxyl groups, vinyl ethers of alcohols having at least two hydroxyl groups, allyl ethers of alcohols having at least two 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-C 22 You can choose from non-conjugated dienes. 【0071】 The alcohol having at least two hydroxyl groups can, for example, have 2 to 6, preferably 2 to 4, hydroxyl groups. These alcohols can be selected from diols having 2 to 6 carbon atoms, such as ethylene glycol, propanediol, butanediol, pentanediol, and hexanediol, glycerol, trimethylolpropane, and pentaerythritol. 【0072】 Therefore, the (meth)acrylate of an alcohol having at least two hydroxyl groups may be a di(meth)acrylate of a diol containing 2-6 carbon atoms, and can be selected from ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol di(meth)acrylate, e.g., butane-1,4-diol diacrylate, butane-1,4-diol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate, and 3-methylpentanediol dimethacrylate. 【0073】 Examples of di(meth)acrylates of ethylene oxide and / or propylene oxide oligomers include diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol dimethacrylate. 【0074】 Examples of aromatic compounds having at least two vinyl groups include divinylbenzene, divinyltoluene, trivinylbenzene, and divinylnaphthalene. 【0075】 C5-C 22 Non-conjugated dienes (e.g., C5-C) 16 The non-conjugated diene (or C5-C8 non-conjugated diene) may be an alkadiene or a cyclic diene, specific examples of which include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene; and bicyclic olefins having 5-20 carbon atoms, preferably 5-16 or 8-12 carbon atoms, such as dicyclopentadiene monomers, such as dicyclopentadiene, methyldicyclopentadiene (e.g., 2-methyldicyclopentadiene, 5-methyldicyclopentadiene), ethyldicyclopentadiene (e.g., 2-ethyldicyclopentadiene), and 5,5-dimethyldicyclopentadiene. 【0076】 Other specific examples of monomers having at least two (e.g., 2-4) non-conjugated carbon-carbon unsaturated double bonds include trimethylolpropane tri(meth)acrylate, butanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol trialyl ether, methylenebis(meth)acrylamide, diallyl phthalate, and others. 【0077】 The amount of at least one additional repeating unit derived from the monomer having at least two non-conjugated carbon-carbon unsaturated double bonds may be 0.1-30% by weight, for example, 0.5-20% by weight or 0.5-10% by weight, based on the total amount of repeating units of copolymer B. 【0078】 According to the present invention, copolymer B may optionally contain auxiliary repeating units. The auxiliary repeating units can be selected from, for example, repeating units derived from the following monomers: C2-C4 monoolefins. 【0079】 In one embodiment of the present invention, copolymer B includes repeating units having anhydrous groups, the other repeating units, and the auxiliary repeating units. 【0080】 In one embodiment of the present invention, copolymer B includes repeating units having anhydrous groups, the other repeating units, the additional repeating units, and the auxiliary repeating units. 【0081】 According to the present invention, the C2-C4 monoolefin may be ethylene, propylene, and butene. 【0082】 Polymerization of copolymer B, which involves a monomer having a carbon-carbon unsaturated double bond and an anhydride group, with other monomers containing a carbon-carbon unsaturated double bond, can be carried out using an oil-soluble free radical initiator. The oil-soluble free radical initiator includes, for example, an azo initiator or a peroxide initiator. The azo initiator includes azobisisobutyronitrile, azobisisoheptonitrile, azobis(isobutyrate)dimethyl, etc.; the peroxide initiator includes benzoyl peroxide, dicumyl peroxide, bis(2,4-dichlorobenzoyl)peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate, etc. The dose of the initiator is 0.05-10% by weight, preferably 0.5-6% by weight, based on the weight of the monomer. 【0083】 Polymerization reactions can be carried out in the presence of a solvent. The solvent may include a mixture of aromatic hydrocarbons, alkanes and ketones, a mixture of carboxylic acid esters, alkanes and aromatic hydrocarbons, a mixture of aromatic hydrocarbons and carboxylic acid esters, or a mixture of alkanes and carboxylic acid esters, or a mixture of alkanes, aromatic hydrocarbons and carboxylic acid esters. 【0084】 Examples of aromatic hydrocarbons include toluene, xylene, and ethylbenzene. 【0085】 Carboxylic acid esters can include C1-C8 alkyl esters, phenyl esters, or benzyl esters of C1-C6 carboxylic acids and C1-C8 alkyl esters of aromatic carboxylic acids having 6-10 carbon atoms. Specific examples include ester solvents such as ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl 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 isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, and isoamyl phenylacetate. 【0086】 In a mixture of alkanes and ketones, the ketone can be selected from acetone, butanone, cyclohexanone, methyl isobutyl ketone, and methyl isopropyl ketone, and the alkane can be selected from n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, and isooctane, etc. In a mixture of alkanes and ketones, the ketone usually accounts for 5-65% by volume. 【0087】 The polymerization reaction can be carried out in the presence of an inert gas, such as nitrogen. The polymerization reaction temperature is usually 55-120°C, preferably 60-100°C; the polymerization reaction time is usually 1-12 hours, preferably 2-8 hours. After the polymerization reaction, the resulting copolymer B can be separated and dried. 【0088】 In one preferred embodiment, the polymerization reaction is carried out by precipitation polymerization. This precipitation polymerization can be carried out by selecting a solvent that can dissolve the monomers but not the resulting copolymer B. By precipitation polymerization, copolymer B can be obtained directly in powder form. 【0089】 According to the present invention, if a C4 fraction or a C5 fraction is used as the reactant, the unreacted alkane or aromatic hydrocarbon mixture can be separated by simple distillation after the reaction is complete, thereby yielding various high-value-added solvents and industrial raw materials. 【0090】 According to the present invention, copolymer A can be obtained by reacting copolymer B with ammonia. 【0091】 The molecular weight of copolymer B usually corresponds to that of copolymer A. As described above, copolymer A may have any molecular weight suitable for adhesive applications. According to one embodiment of the present invention, the molecular weight of copolymer B may be at least 2000, for example, at least 5000 or at least 8000. The upper limit of the molecular weight of copolymer B is not important and may be, for example, 500000 or 300000. Copolymer B is C4-C 22 The copolymer B may be crosslinked in a manner that has repeating units derived from a conjugated diene and / or a monomer having at least two non-conjugated carbon-carbon unsaturated double bonds. 【0092】 In the adhesive of the present invention, in addition to copolymer A, the adhesive of the present invention may optionally also contain at least one additive. The additive may be one or more of the following: oxygen scavengers, emulsifiers, dyes, pigments, migration prevention aids, ultraviolet absorbers, biocides, defoamers, colorants, antistatic agents, and antioxidants. 【0093】 According to the present invention, the adhesive of the present invention does not contain an organic crosslinking agent capable of covalent crosslinking with the amide groups and / or carboxyl groups of copolymer A, such as a polyol, polyamine, polyalkanolamine, or a mixture thereof. 【0094】 According to the present invention, the adhesive may be a solid, preferably in powder form; or an aqueous composition, preferably in aqueous solution form. 【0095】 The amount of copolymer A in the adhesive of the present invention may be 30-100% by weight, for example, 50-100% by weight, 60-100% by weight, 70-100% by weight, 80-100% by weight, or 50-98% by weight, or 60-90% by weight, based on the total amount of adhesive (or based on the solid content if the adhesive is liquid, for example, an aqueous composition or aqueous solution). 【0096】 If the adhesive is in the form of an aqueous composition, preferably an aqueous solution, the solid content of the adhesive may be 2-40% by weight, 5-30% by weight, or 8-25% by weight. 【0097】 How to prepare adhesive 【0098】 One aspect of the present invention relates to a method for preparing an adhesive of the present invention, the method comprising reacting copolymer B with ammonia in or without the presence of a reaction medium (e.g., water). 【0099】 Copolymer B can be reacted with ammonia, i.e., by ammonia monolysis, to form copolymer A. The reaction typically involves reacting copolymer B with ammonia in an aqueous medium under stirring conditions at a temperature below 100°C, preferably 15-70°C, for example, at room temperature. The reaction time is typically 0.5-10 hours, preferably 1-6 hours. 【0100】 After the reaction, the resulting reaction mixture is usually an aqueous composition, preferably in aqueous solution form. The resulting aqueous composition, preferably aqueous solution, can be used directly as an adhesive. Alternatively, the reaction mixture can be mixed with at least one of the additives mentioned above before being used as an adhesive. 【0101】 Preferably, copolymer B is in powder form before reacting with ammonia. Preferably, copolymer B in powder form can be prepared by precipitation polymerization. Copolymer B in powder form can also be obtained by grinding copolymer B (e.g., in lump form) into a powder form. The average particle size of copolymer B in powder form may be 0.01-10 μm, preferably 0.05-8 μm, more preferably 0.1-5 μm. The average particle size of copolymer A in powder form may be 0.01-10 μm, preferably 0.05-8 μm, more preferably 0.1-5 μm. 【0102】 The reaction time between the solid copolymer B and ammonia is typically 2-300 minutes, preferably 5-120 minutes. 【0103】 In specific applications, copolymer A in solid form can be dissolved in water, optionally mixed with at least one of the above-mentioned additives, and then applied. 【0104】 The conversion rate of the anhydride group in copolymer B is usually over 90%, preferably over 95%, more preferably over 98%, and for example, 100%. 【0105】 In the reaction of copolymer B with ammonia, the carboxyl group can also form an ammonium salt with ammonia. 【0106】 Artificial board 【0107】 Another aspect of the present invention relates to a type of artificial board formed from a lignocellulose material and the adhesive of the present invention. The artificial board of the present invention should be understood in a broad sense, that is, a board formed from any lignocellulose material and the adhesive of the present invention. The artificial board of the present invention is not limited to being formed solely from wood, but may also include boards formed from materials described later, such as bamboo and straw. The artificial board of the present invention may be of various types. In one embodiment, the artificial board includes, but is not limited to, particleboard, plywood, fiberboard, density board, straw board and finger-joint board. 【0108】 The lignocellulose material may be derived from various lignocellulose materials, such as wood, bamboo, bagasse, straw (e.g., wheat straw), flax residue, nut shells, grain husks, and mixtures thereof. The wood includes various softwoods and / or hardwoods. 【0109】 Lignocellulose materials may be in the form of sawdust, flakes, wood chips, strips, flakes, fibers, sheets, wood powder, shavings, granules and similar material forms, or combinations of these materials, for example, a combination of strips and sawdust. 【0110】 Lignocellulose materials can be processed using various conventional techniques. Large pieces of wood can be processed into wood chips using a round wood chipper. Large pieces of wood and scraps can also be cut into smaller pieces. Large pieces of wood can also be chipped using a ring chipper. Typically, the bark of large pieces of wood is removed before chipping. 【0111】 The size of the lignocellulose material is usually not important. Different sizes can be used for different types of artificial boards. For example, the size of the lignocellulose material may be 1-30 mesh, preferably 2-15 mesh. For lignocellulose material sheets, the sheet thickness may be, for example, 0.5 mm-5 cm, preferably 1 mm-3 cm. 【0112】 In the artificial board of the present invention, the amount of solid-based adhesive is 1-45% by weight, preferably 2-40% by weight, more preferably 3-35% by weight or 4-30% by weight, for example 5-25% by weight, 6-25% by weight, 7-25% by weight, or 8-19% by weight, based on the total weight of the artificial board. 【0113】 In the artificial board of the present invention, the amount of copolymer A is 1-40% by weight, preferably 2-30% by weight, more preferably 3-25% by weight or 4-20% by weight, for example 5-20% by weight, 6-20% by weight or 7-18% by weight, based on the total weight of the artificial board. 【0114】 In the artificial board of the present invention, the adhesive is used as a matrix resin, preferably filling the gaps between lignocellulose materials. 【0115】 How to prepare an artificial board 【0116】 Another aspect of the present invention relates to a method for preparing an artificial board, the method comprising using the adhesive of the present invention. 【0117】 According to one embodiment of the present invention, the method comprises pressing a mixture of a lignocellulose material and the adhesive of the present invention at a temperature of 105-300°C and a pressure of 0.4-10 MPa, preferably for 2-60 minutes, more preferably for 3-30 minutes, and for example for 5-30 minutes. 【0118】 A mixture of lignocellulose material used in pressing and the adhesive of the present invention can be prepared by mixing the lignocellulose material and the adhesive of the present invention. If the adhesive is solid, the adhesive can first be dissolved in water and then mixed with the lignocellulose material. 【0119】 Before pressing, preferably some of the moisture in the mixture of lignocellulose material and adhesive is removed, reducing the moisture content of the mixture to less than 30% by weight, preferably less than 25% by weight, for example less than 22% by weight, or less than 18% by weight. The moisture content of the mixture is usually higher than 5% by weight or higher than 8% by weight. The removal of moisture can be carried out by heating, for example the heating temperature may be 50-90°C, preferably 60-80°C. 【0120】 In one preferred embodiment, the pressing is performed at a temperature of 120–220°C and / or at a pressure of 1–6 MPa. 【0121】 If copolymer A has carboxyl groups in the form of ammonium salts, the ammonium salts of the carboxyl groups decompose back into carboxyl groups under pressing conditions. 【0122】 Uses of adhesives 【0123】 Finally, the present invention further relates to the use of the adhesive of the present invention in the preparation of lignocellulose-based artificial boards. 【0124】 The adhesive of the present invention is safe, environmentally friendly, does not release toxic and harmful substances such as formaldehyde, is easy to apply and inexpensive, and at the same time exhibits excellent performance. It is particularly suitable for the manufacture of lignocellulose-based artificial boards, and artificial boards manufactured using the adhesive of the present invention have excellent mechanical properties and water resistance. In addition, the adhesive of the present invention can also be prepared using C4 and C5 fractions, which is of significant importance for expanding the use of these industrial mixtures, and artificial boards prepared using adhesives obtained from these industrial mixtures have even better mechanical properties and water resistance. 【0125】 Examples 【0126】 The technical solutions of the present invention will be further described below in conjunction with specific embodiments of the present invention, but these should not be understood as limiting the scope of protection of the present invention. The embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. Other embodiments proposed by those skilled in the art without creative work based on the embodiments described in the present invention shall be within the scope of protection of the present invention. Unless otherwise specified, % in embodiments refers to weight % and parts in embodiments refers to parts by mass. 【0127】 Source of chemicals used: Maleic anhydride (purity 98+%, AlphaAcer (Tianjin) Chemical Co., Ltd.); Benzoyl peroxide (purity 97%, AlphaAcer (Tianjin) Chemical Co., Ltd.); Azobisisobutyronitrile (purity 98%, Shanghai Aladdin Biochemical Technology Co., Ltd.); Ammonia water (concentration 20-25%, Beijing Yinuoka Technology Co., Ltd.); Ammonia gas (purity 99.999%, Beijing Haifu Gas Co., Ltd.); Styrene (purity 99%, AlphaAcer (Tianjin) Chemical Co., Ltd.); 1-Pentene (purity 98%, Bailingwei Technology Co., Ltd.); Ethylene glycol dimethacrylate (purity 98%, AlphaAcer (Tianjin) Chemical Co., Ltd.); Isobutene (purity 99.5%, Shanghai Aladdin Biochemical Technology Co., Ltd.); Vinyl acetate (purity 99%, AlphaAcer (Tianjin) Chemical Co., Ltd.); All other chemical reagents were analytical grade and purchased from Beijing Yili Fine Chemical Co., Ltd. The composition of the C4 fraction was as shown in Table 1; the composition of the C5 fraction was as shown in Table 2. 【0128】 reference Example 1 【0129】 Based on parts by mass, 13 parts styrene, 12.25 parts maleic anhydride, 300 parts ethyl acetate, and 0.2 parts AIBN were mixed and dissolved, the system was vented with nitrogen for 20 minutes, and then reacted at 70°C for 6 hours. The product was precipitated with 400 parts ethanol, centrifuged, washed three times with petroleum ether, and dried to obtain a styrene-maleic anhydride copolymer in the form of a white powder (weight-average molecular weight was 72,000) with a yield of 94% and a mass fraction of maleic anhydride monomer units in the copolymer of 44%. 【0130】 Twenty parts of the styrene-maleic anhydride copolymer, five parts of 37% aqueous ammonia, and 75 parts of water were stirred at room temperature for four hours to obtain a 20% by mass viscous liquid of the styrene-maleic anhydride copolymer (the mole fraction of ammonialated maleic anhydride monomer units in the copolymer was 99%). This viscous liquid was mixed with poplar wood shavings (5% moisture content, 5-10 mesh) at a dose of 15 parts of the copolymer per 100 parts of shavings, and the mixture was uniformly mixed to obtain a premix. The premix was dried at 70°C to remove moisture to a moisture content of 20%. 【0131】 The aforementioned premix was placed in a 25cm x 25cm x 2.5cm press mold, the hot press temperature was 180°C, the pressure was 1 MPa, and the hot press time was 15 minutes to obtain a particleboard with a thickness of 3 mm. 【0132】 Example 2 【0133】 Based on parts by mass, 100 parts of C4 fraction (composition as shown in Table 1), 30 parts of maleic anhydride, 100 parts of isoamyl acetate, and 2 parts of BPO were mixed and dissolved. The system was vented with nitrogen for 20 minutes, and then reacted at 70°C for 8 hours. The product was centrifuged, washed three times with petroleum ether, and dried to obtain a white powder-like C4-maleic anhydride copolymer (weight-average molecular weight was 20,000). The yield was 94%, and the mass fraction of maleic anhydride monomer units in the copolymer was 63%. 【0134】 Ten parts of the C4-maleic anhydride copolymer, five parts of 37% aqueous ammonia, and 85 parts of water were stirred at room temperature for four hours to obtain a viscous liquid of C4-maleic acid copolymer with a mass concentration of 10% (the mole fraction of ammonialated maleic anhydride monomer units in the copolymer was 99%). This viscous liquid was uniformly mixed with poplar wood shavings (moisture content 5%, 5-10 mesh) at a dose of 8 parts of the copolymer per 100 parts of shavings, and the mixture was uniformly mixed to obtain a premix. The premix was dried at 70°C to remove moisture to a moisture content of 15%. 【0135】 The aforementioned premix was placed in a 25cm x 25cm x 2.5cm press mold, the hot press temperature was 170°C, the pressure was 0.4 MPa, and the hot press time was 8 minutes, resulting in a particleboard with a thickness of 3 mm. 【0136】 Curve 1 in Figure 1 represents the infrared spectrum of the C4-maleic anhydride copolymer, at 1860 cm⁻¹. -1 , 1780cm -1 The peaks at 940 cm are the stretching vibration peaks of the two carbonyl C=O groups on the anhydrous material. -1 This is a characteristic strong absorption of five-membered ring anhydrous compounds; 【0137】 Curve 2 shows the infrared spectrum of the C4-maleamic acid copolymer at 3200 cm⁻¹. -1 The peaks at 1650 cm are the asymmetric and symmetric stretching vibration peaks of -NH2. -1 The peak at that point is the stretching vibration peak of the amide C=O. The characteristic peak of the anhydride group corresponding to the original C4-maleic anhydride copolymer has essentially disappeared. 【0138】 Curve 3 is the infrared spectrum of the copolymer after hot pressing, at 1770 cm⁻¹. -1 and 1710cm -1 At this point, characteristic absorption of cyclic imides appears, at 1350 cm². -1 This is a characteristic absorption of CNC. 【0139】 Example 3 【0140】 Based on parts by mass, 100 parts of C5 fraction (composition as shown in Table 2), 25 parts of maleic anhydride, 100 parts of isoamyl acetate, and 2 parts of AIBN were mixed and dissolved. The system was vented with nitrogen for 20 minutes, and then reacted at 70°C for 8 hours. The product was centrifuged, washed, and dried to obtain a white powder-like C5-maleic anhydride copolymer with a yield of 58% and a mass fraction of maleic anhydride monomer units in the copolymer of 63%. 【0141】 Ten parts of the C5-maleic anhydride copolymer, five parts of 37% aqueous ammonia, and 85 parts of water were stirred at room temperature for four hours to obtain a viscous liquid of C5-maleic anhydride copolymer with a mass concentration of 10% (the mole fraction of ammonialated maleic anhydride monomer units in the copolymer was 100%). This viscous liquid was uniformly mixed with poplar wood shavings (moisture content 5%, 5-10 mesh) at a dose of 9 parts of the copolymer per 100 parts of shavings, and the mixture was uniformly mixed to obtain a premix. The premix was dried at 70°C to remove moisture to a moisture content of 15%. 【0142】 The aforementioned premix was placed in a 25cm x 25cm x 2.5cm press mold, the hot press temperature was 180°C, the pressure was 1.5 MPa, and the hot press time was 8 minutes, resulting in a particleboard with a thickness of 3 mm. 【0143】 reference Example 4 【0144】 Based on parts by mass, 13 parts styrene, 14.25 parts itaconic anhydride, 300 parts isoamyl acetate, and 0.2 parts AIBN were mixed and dissolved, the system was vented with nitrogen for 20 minutes, and then the mixture was reacted at 70°C for 6 hours. The product was centrifuged, washed, and dried to obtain a styrene-itaconic anhydride copolymer in the form of a white powder (with a weight-average molecular weight of 31,000) with a yield of 92% and a mass fraction of itaconic anhydride monomer units in the copolymer of 54%. 【0145】 Fifteen parts of the styrene-itaconic acid anhydride copolymer, ten parts of 37% aqueous ammonia, and seventy-five parts of water were stirred at 60°C for 10 minutes to obtain a 15% by mass styrene-itaconic acid anhydride copolymer viscous liquid (the mole fraction of ammoniaxified itaconic acid anhydride monomer units in the copolymer was 99%). This viscous liquid was uniformly mixed with poplar wood shavings (moisture content 5%, 5-10 mesh) at a dose of 15 parts of the copolymer per 100 parts of shavings, and the mixture was uniformly mixed to obtain a premix. The premix was dried at 70°C to remove moisture to a moisture content of 10%. 【0146】 The aforementioned premix was placed in a 25cm x 25cm x 2.5cm press mold, the hot press temperature was 170°C, the pressure was 1 MPa, and the hot press time was 15 minutes to obtain a particleboard with a thickness of 3 mm. 【0147】 reference Example 5 【0148】 Based on parts by mass, 10 parts vinyl acetate, 11.5 parts maleic anhydride, 300 parts isoamyl acetate, and 0.2 parts AIBN were mixed and dissolved, the system was vented with nitrogen for 20 minutes, and then the mixture was reacted at 70°C for 6 hours. The product was centrifuged, washed, and dried to obtain a vinyl acetate-maleic anhydride copolymer in the form of a white powder (weight-average molecular weight was 19000) with a yield of 90% and a mass fraction of maleic anhydride monomer units in the copolymer of 52%. 【0149】 Fifteen parts of the vinyl acetate-maleic anhydride copolymer, five parts of 37% aqueous ammonia, and eighty parts of water were stirred at room temperature for four hours to obtain a viscous liquid of vinyl acetate-maleic acid copolymer with a mass concentration of 15% (the mole fraction of ammonialated maleic anhydride monomer units in the copolymer was 99%). This viscous liquid was mixed with poplar wood shavings (moisture content 5%, 5-10 mesh) at a dose of 10 parts of the copolymer per 100 parts of shavings, and the mixture was uniformly mixed to obtain a premix. The premix was dried at 70°C to remove moisture to a moisture content of 15%. 【0150】 The aforementioned premix was placed in a 25cm x 25cm x 2.5cm press mold, the hot press temperature was 180°C, the pressure was 0.4 MPa, and the hot press time was 10 minutes to obtain a particleboard with a thickness of 3 mm. 【0151】 reference Example 6 【0152】 Ten parts of a methyl vinyl ether-maleic anhydride copolymer (weight-average molecular weight 216,000, purchased from Shanghai Alading Biochemical Technology Co., Ltd., with a mass fraction of maleic anhydride monomer units of 61%) were placed in a round-bottom flask, and 10 parts of ammonia gas were added and the mixture was reacted at 70°C for 2 hours to obtain a methyl vinyl ether-maleic acid copolymer powder. The methyl vinyl ether-maleic acid copolymer was dissolved in water to obtain a viscous liquid with a mass concentration of 10%. This viscous liquid was mixed with poplar wood shavings (moisture content 5%, 5-10 mesh), with a dosage of 20 parts of the copolymer per 100 parts of shavings, and the mixture was uniformly mixed to obtain a premix. The premix was dried at 70°C to remove moisture to a moisture content of 10%. 【0153】 The aforementioned premix was placed in a 25cm x 25cm x 2.5cm press mold, the hot press temperature was 170°C, the pressure was 0.4 MPa, and the hot press time was 12 minutes to obtain a particleboard with a thickness of 3 mm. 【0154】 reference Example 7 【0155】 Based on parts by mass, 14 parts 1-pentene, 19.6 parts maleic anhydride, 300 parts isoamyl acetate, and 0.7 parts AIBN were mixed and dissolved, the system was vented with nitrogen for 20 minutes, and then the mixture was reacted at 70°C for 6 hours. The product was centrifuged, washed, and dried to obtain a 1-pentene-maleic anhydride copolymer in the form of a white powder (weight-average molecular weight was 16000) with a yield of 90% and a mass fraction of maleic anhydride monomer units in the copolymer of 61%. 【0156】 Twenty parts of the 1-pentene-maleic anhydride copolymer, ten parts of 37% aqueous ammonia, and seventy parts of water were stirred at room temperature for four hours to obtain a 20% by mass viscous liquid of the 1-pentene-maleic anhydride copolymer (the mole fraction of ammonialated maleic anhydride monomer units in the copolymer was 99%). This viscous liquid was mixed with poplar wood shavings (moisture content 5%, 5-10 mesh) at a dose of 12 parts of the copolymer per 100 parts of shavings, and the mixture was uniformly mixed to obtain a premix. The premix was dried at 70°C to remove moisture to a moisture content of 20%. 【0157】 The aforementioned premix was placed in a 25cm x 25cm x 2.5cm press mold, the hot press temperature was 180°C, the pressure was 1 MPa, and the hot press time was 15 minutes to obtain a particleboard with a thickness of 3 mm. 【0158】 reference Example 8 【0159】 Based on parts by mass, 12.8 parts styrene, 12.25 parts maleic anhydride, 0.25 parts ethylene glycol dimethacrylate, 200 parts isoamyl acetate, and 0.2 parts AIBN were mixed and dissolved, the system was vented with nitrogen for 20 minutes, and then reacted at 70°C for 6 hours. The product was centrifuged, washed three times with petroleum ether, and dried to obtain a styrene-maleic anhydride-ethylene glycol dimethacrylate copolymer in the form of a white powder. The yield was 90%, and the mass fraction of maleic anhydride monomer units in the copolymer was 45%. 【0160】 Twenty parts of the styrene-maleic anhydride-ethylene glycol dimethacrylate copolymer, ten parts of 37% aqueous ammonia, and seventy parts of water were stirred at room temperature for four hours to obtain a 20% by mass viscous liquid of the styrene-maleic anhydride-ethylene glycol dimethacrylate copolymer (the mole fraction of ammonialated maleic anhydride monomer units in the copolymer was 99%). This viscous liquid was mixed with poplar wood shavings (moisture content 5%, 5-10 mesh) at a dose of 10 parts of the copolymer per 100 parts of shavings, and the mixture was uniformly mixed to obtain a premix. The premix was dried at 70°C to remove moisture to a moisture content of 15%. 【0161】 The aforementioned premix was placed in a 25cm x 25cm x 2.5cm press mold, the hot press temperature was 180°C, the pressure was 0.8 MPa, and the hot press time was 10 minutes to obtain a particleboard with a thickness of 3 mm. 【0162】 Example 9 【0163】 The C5-maleamic acid copolymer obtained in Example 3 was dissolved in water to obtain a viscous liquid with a mass concentration of 10%. This viscous liquid was uniformly applied to a linden veneer with a water content of 12% and dimensions of 160 mm × 160 mm × 1.5 mm, with an average application rate of 60 g / m². 2 The plywood was laid up according to the grain direction (horizontal-vertical-horizontal), placed under a hot press machine, and pressed. The hot press temperature was 180°C, the pressure was 1 MPa, and the hot press time was 10 minutes to obtain a three-layer plywood. The internal adhesive strength of the plywood, measured according to GB / T9846-2015, was 1.24 MPa. 【0164】 Comparative Example 10 【0165】 Based on parts by mass, 10 parts isobutene, 17.5 parts maleic anhydride, 100 parts isoamyl acetate, and 0.3 parts BPO were mixed and dissolved, the system was vented with nitrogen for 20 minutes, and then reacted at 70°C for 8 hours. The product was centrifuged, washed three times with petroleum ether, and dried to obtain an isobutene-maleic anhydride copolymer in the form of a white powder (weight-average molecular weight was 25,000), with a yield of 94% and a mass fraction of maleic anhydride monomer units in the copolymer of 63%. 【0166】 Ten parts of isobutene-maleic anhydride copolymer were placed in a round-bottom flask, and two parts of ammonia gas were added. The mixture was reacted at room temperature for 10 minutes to obtain isobutene-maleic acid copolymer powder. The isobutene-maleic acid copolymer was dissolved in water to obtain a viscous liquid with a mass concentration of 10%. This viscous liquid was mixed with poplar wood shavings (moisture content 5%, 5-10 mesh) at a dose of 20 parts of the copolymer per 100 parts of shavings. The mixture was uniformly mixed to obtain a premix. The premix was dried at 70°C to remove moisture to a moisture content of 10%. 【0167】 The aforementioned premix was placed in a 25cm x 25cm x 2.5cm press mold, the hot press temperature was 170°C, the pressure was 0.4 MPa, and the hot press time was 12 minutes to obtain a particleboard with a thickness of 3 mm. 【0168】 Performance testing 【0169】 Examples according to GB / T4897-2015 2-3, Reference example 1 、4 The particleboard obtained in -8 was tested for internal adhesive strength, 24-hour water absorption and thickness expansion coefficient, and moisture resistance (internal adhesive strength after boiling in boiling water), and the results are listed in Table 3 below. [Table 3] 【0170】 Examples and reference examplesThe performance of each component of the particleboard was all better than the performance requirements for furniture-type particleboard used in humid conditions in the national standard. The 24h water absorption thickness expansion rate, internal adhesive strength, and internal adhesive strength after boiling water test of the artificial boards obtained in Example 2 using the C4 fraction and Example 3 using the C5 fraction were all better than those of other reference The performance of the artificial board obtained in the example is higher than that of the artificial board obtained in the example. In Comparative Example 10, an adhesive was prepared using isobutene as a copolymer monomer, and the 24h water absorption thickness expansion rate, internal adhesive strength, and internal adhesive strength after boiling water experiment of the artificial board prepared from the adhesive are higher than those of the other examples. and reference examples It was worse. 【0171】 While we do not wish to be bound by any theory, it is believed that the amide and carboxyl groups on the polymer in the adhesive of the present invention can be dehydrated under press conditions to produce imide groups, and the carboxyl groups can also be dehydrated to produce anhydride groups. These anhydride groups can then react with hydroxyl groups on the lignocellulose material to form esters, which is thought to help improve the mechanical properties and water resistance of the resulting artificial board. 【0172】 The above are merely preferred embodiments of the present invention. Those skilled in the art will point out that several improvements and modifications made within the scope of the principles of the present invention should also be considered within the scope of protection of the present invention.

Claims

[Claim 1] An adhesive comprising at least one copolymer A as described below, The copolymer A has at least one repeating unit having an amide group and a carboxyl group and / or an ammonium salt thereof, and at least one other repeating unit different from the one having an amide group and a carboxyl group and / or an ammonium salt thereof. The other repeating units mentioned above are C ４ Distillate or C ５ It originates from at least one monomer containing a carbon-carbon unsaturated double bond, which is generated from the reaction materials of the fraction. The preparation of copolymer A includes a polymerization reaction in which the C4 fraction or C5 fraction is used directly without separation. glue. [Claim 2] The adhesive according to claim 1, wherein the amount of repeating units having an amide and a carboxyl group and / or an ammonium salt thereof in the copolymer A is 10-80% by weight, based on the total amount of repeating units in copolymer A. [Claim 3] The adhesive according to claim 2, wherein the amount of repeating units having an amide and a carboxyl group and / or an ammonium salt thereof in the copolymer A is 30-70% by weight, based on the total amount of repeating units in copolymer A. [Claim 4] The adhesive according to any one of claims 1 to 3, wherein the copolymer A further comprises additional repeating units derived from at least one monomer having at least two non-conjugated carbon-carbon unsaturated double bonds. [Claim 5] The adhesive according to claim 4, wherein 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)acrylic acid groups, (meth)acrylamide groups, vinyl groups, allyl groups, and non-conjugated carbon-carbon double bonds in alkenes or cycloalkenes. [Claim 6] The adhesive according to any one of claims 1 to 5, wherein the copolymer A is derived from copolymer B, and copolymer B has at least one repeating unit having an anhydride group. [Claim 7] The adhesive according to claim 6, wherein the copolymer A is derived from the reaction of copolymer B with ammonia. [Claim 8] The adhesive according to claim 6 or 7, wherein the anhydride group on the copolymer B is introduced into the copolymer B by polymerization of at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group. [Claim 9] The adhesive according to claim 8, wherein the monomer having a carbon-carbon unsaturated double bond and an anhydride group is selected from monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 8 carbon atoms. [Claim 10] The adhesive according to claim 9, wherein the monomer having a carbon-carbon unsaturated double bond and an anhydride group is selected from maleic anhydride, itaconic anhydride, citraconic anhydride, and methylenemalonic anhydride. [Claim 11] The copolymer B is a copolymer formed from at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group, and at least one other monomer containing a carbon-carbon unsaturated double bond. Other monomers containing carbon-carbon unsaturated double bonds include C ４ Distillate or C ５ Derived from reaction materials selected from the fraction, The adhesive according to any one of claims 6 to 10. [Claim 12] The adhesive according to any one of claims 6 to 11, wherein the copolymer B further comprises additional repeating units derived from at least one monomer having at least two non-conjugated carbon-carbon unsaturated double bonds. [Claim 13] The adhesive according to any one of claims 1 to 12, wherein the adhesive is in solid form; or in aqueous composition form. [Claim 14] The adhesive according to any one of claims 1 to 13, wherein the adhesive does not contain an organic crosslinking agent capable of covalently crosslinking with the amide group and / or carboxyl group of copolymer A. [Claim 15] An artificial board formed from a lignocellulose material and an adhesive according to any one of claims 1 to 14. [Claim 16] The artificial board according to claim 15, wherein the amount of solid-based adhesive is 1-45% by weight, based on the total weight of the artificial board. [Claim 17] The artificial board according to claim 15 or 16, wherein the amount of copolymer A specified by any one of claims 1 to 13 is 1 to 40% by weight, based on the total weight of the artificial board. [Claim 18] The artificial board according to any one of claims 15 to 17, wherein the adhesive is used as a matrix resin. [Claim 19] The artificial board according to any one of claims 15 to 18, wherein the artificial board is particleboard, plywood, density board, fiberboard, straw board, or finger joint board. [Claim 20] A method for preparing an artificial board, comprising using an adhesive specified by any one of claims 1 to 14. [Claim 21] The method according to claim 20, comprising pressing a mixture of lignocellulose material and the adhesive at a temperature of 105–300°C and a pressure of 0.4–10 MPa. [Claim 22] The method according to claim 20 or 21, wherein the artificial board is the artificial board described in any one of claims 15 to 19. [Claim 23] Uses of the adhesive according to any one of claims 1 to 14 in the preparation of a lignocellulose-based artificial board.

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