Crosslinked copolymers containing repeating units of amide groups and carboxyl groups and / or their ammonium salts, and repeating units of α-monoolefins

Abstract

The present disclosure provides a polymerizable composition comprising: (i) at least one repeating unit having an amide group and a carboxy group and / or an ammonium salt thereof; (ii) a linear or branched C2-C 18 and (iii) at least one repeat unit derived from a monomer having at least two carbon-carbon unsaturated double bonds. The present disclosure also relates to an article of manufacture comprising a component formed from the adhesive of the present invention.

Description

[Technical Field]

[0001] The present disclosure provides a polymerizable composition comprising: (i) at least one repeating unit having an amide group and a carboxy group and / or an ammonium salt thereof; (ii) a linear or branched C2-C 18 The present disclosure relates to a copolymer A having (iii) at least one repeating unit derived from an α-monoolefin and at least one repeating unit derived from a monomer having at least two carbon-carbon unsaturated double bonds. The present disclosure also relates to an adhesive comprising copolymer A and an article of manufacture comprising a component formed from the adhesive of the present invention. [Background technology]

[0002] Among current adhesives, especially those used in the production of artificial boards, "three aldehyde adhesives" (urea-formaldehyde resin, phenol-formaldehyde resin, and melamine-formaldehyde resin) prepared using formaldehyde as a raw material account for a relatively large proportion, exceeding 80%. Although "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 posing a serious threat to the physical health of residents.

[0003] Several literature has proposed solutions to reduce formaldehyde emissions from "three-aldehyde adhesive" 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 adding formaldehyde scavengers. Chinese Utility Model No. 203344147 discloses adding activated carbon, bamboo charcoal, diatomaceous earth, etc. during board production to give the board a certain gas adsorption capacity. However, these methods do not fundamentally solve the problem, and formaldehyde emissions will still occur during use.

[0004] Adhesives made from biomass materials such as soy protein, tannin, starch, and gelatin do not use formaldehyde, but they do have the problem of rapid degradation of biomass materials, resulting in boards that are prone to aging. Although the addition of antioxidants can slow down the degradation to some extent, biomass-based adhesives still have relatively high costs and resource-related issues, which limits their practical use.

[0005] Furthermore, boards can also be produced using polymers such as polyvinyl chloride, high molecular weight polyethylene, and chloroprene rubber. However, these polymers are not water-soluble and cannot form aqueous adhesives. They can only be mixed with wood raw materials by hot melt or organic solvents, which still result in the disadvantages of high cost, energy consumption, and environmental unfriendliness.

[0006] Therefore, it is particularly important to develop copolymers that can be used in new formaldehyde-free adhesives, taking into consideration safety, environmental friendliness, low production costs, ease of application process, and durability of the finished product. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Chinese Patent Application Publication No. 107033309 [Patent Document 2] Chinese Utility Model No. 203344147 Summary of the Invention [Problem to be solved by the invention]

[0008] In view of the above-mentioned state of the art, the inventors of the present invention have conducted extensive and in-depth research into copolymers in the adhesive field in order to find a copolymer that can be used for an adhesive that does not emit formaldehyde, is low cost, is easy to apply, and has excellent performance. The inventors have discovered a specific copolymer A and an adhesive containing the specific copolymer A, and the adhesive not only does not emit formaldehyde, but is also low cost, easy to apply, and has excellent performance.

[0009] The present invention was completed based on the above findings.

[0010] An object of the present invention is to provide a copolymer A.

[0011] Another object of the present invention is to provide an adhesive containing copolymer A, which has the advantages of being safe, environmentally friendly, low cost, easy to apply, and excellent performance.

[0012] Another object of the present invention is to provide articles of manufacture containing components formed by the adhesives of the present invention. [Means for solving the problem]

[0013] The technical solutions to achieve the objectives of the present invention can be summarized as follows:

[0014] 1. (i) at least one repeating unit having an amide group and a carboxy group and / or an ammonium salt thereof; (ii) Linear or branched C2-C 18 at least one repeat unit derived from an α-monoolefin, and (iii) at least one repeat unit derived from a monomer having at least two carbon-carbon unsaturated double bonds; Copolymer A having the formula:

[0015] 2. The copolymer A according to item 1, wherein the amount of repeating unit (i) in the copolymer A is 10-80% by weight, preferably 20-80% by weight or 22-79% by weight, based on the total amount of repeating units of the copolymer A.

[0016] 3. The linear or branched C2-C 18 α-monoolefins are linear or branched C2-C 12 3. The adhesive according to item 1 or 2, which is an α-monoolefin, preferably a linear or branched C2-C8 α-monoolefin.

[0017] 4. The copolymer A according to any one of items 1 to 3, wherein the amount of repeating unit (ii) in the copolymer A is 10 to 75% by weight, preferably 15 to 74% by weight or 20 to 70% by weight, based on the total amount of repeating units of the copolymer A.

[0018] 5. Copolymer A according to any one of items 1 to 4, wherein the carbon-carbon unsaturated double bond in the monomer having at least two carbon-carbon unsaturated double bonds is selected from a (meth)acrylic acid ester group, a (meth)acrylamide group, a vinyl group, an allyl group, and a carbon-carbon double bond in an alkene or cycloalkene.

[0019] 6. The copolymer A according to any one of items 1 to 5, wherein the amount of repeating unit (iii) in the copolymer A is 0.1 to 70% by weight, preferably 0.1 to 30% by weight, based on the total amount of repeating units of the copolymer A.

[0020] 7. The copolymer A is derived from copolymer B, and the copolymer B is (i′) at least one repeating unit having an anhydride group; (ii) Linear or branched C2-C 18 at least one repeat unit derived from an α-monoolefin, and (iii) at least one repeat unit derived from a monomer having at least two carbon-carbon unsaturated double bonds; 7. The copolymer A according to any one of items 1 to 6,

[0021] 8. The copolymer A according to item 7, wherein the repeating unit (i') having an anhydride group in the copolymer B is derived from at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group.

[0022] 9. Copolymer A according to item 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, preferably maleic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride, more preferably maleic anhydride.

[0023] 10. The copolymer A according to any one of items 1 to 9, wherein the copolymer A is derived from the reaction of copolymer B with ammonia.

[0024] 11. An adhesive comprising copolymer A according to any one of items 1 to 10.

[0025] 12. The adhesive according to item 11, wherein the adhesive is a solid, preferably in powder form; or an aqueous composition, preferably in the form of an aqueous solution, and preferably the content of copolymer A is 2-40% by weight, in particular 5-30% by weight, based on the total weight of the aqueous composition.

[0026] 13. The adhesive according to item 11 or 12, wherein the adhesive does not contain an organic crosslinking agent capable of undergoing a covalent crosslinking reaction with the amide groups and / or carboxy groups of copolymer A.

[0027] 14. A product comprising a component formed from the adhesive according to any one of items 11-13.

[0028] 15. The product according to item 14, wherein the product is an artificial board, paper, fabric or paint.

[0029] 16. The product of item 15, wherein the product is an artificial board formed from lignocellulosic material and the adhesive.

[0030] 17. The product of item 16, wherein the adhesive is used as a matrix resin, and preferably the adhesive fills gaps between lignocellulosic materials.

[0031] 18. The product according to any one of items 14-17, wherein the dosage of adhesive on a solids basis is 1-45 wt.%, preferably 2-35 wt.%, more preferably 3-30 wt.%, based on the total weight of the product.

[0032] 19. The product according to any one of items 14-18, wherein the dosage of copolymer A as defined in any one of items 1-10 is 1-40% by weight, preferably 2-30% by weight, more preferably 3-25% by weight, based on the total weight of the product.

[0033] 20. Use of the adhesive according to any one of items 11-13 in the preparation of artificial boards, paper, fabrics or paints. [Brief explanation of the drawings]

[0034] [Figure 1] Infrared spectra of different polymers in Example 3. From bottom to top: 1. Infrared spectrum of crosslinked isobutylene-maleic anhydride copolymer; 2. Infrared spectrum of copolymer converted to amic acid; 3. Infrared spectrum of copolymer after hot pressing. DETAILED DESCRIPTION OF THE INVENTION

[0035] Specific values disclosed herein for the relevant characteristics (including the endpoints of the disclosed ranges) may be combined with each other to form new ranges.

[0036] Copolymer A

[0037] One aspect of the present invention is (i) at least one repeating unit having an amide group and a carboxy group and / or an ammonium salt thereof; (ii) Linear or branched C2-C 18 at least one repeat unit derived from an α-monoolefin, and (iii) at least one repeat unit derived from a monomer having at least two carbon-carbon unsaturated double bonds; The copolymer A has the formula:

[0038] According to the present invention, the repeating unit (i) in copolymer A is different from the repeating unit (ii) and the repeating unit (iii).

[0039] According to the present invention, a portion (for example, 1-10% by weight) of the carboxy groups in the repeating unit (i) of copolymer A may be in the form of their ammonium salts.

[0040] Those skilled in the art will appreciate that the term "derived from" also includes cases where the copolymer has a particular repeat unit, but the repeat unit is not directly formed by the corresponding monomer of the repeat unit. For example, a carboxyethylene repeat unit [ka] may be derived from the polymerization of acrylic acid or may be obtained by polymerizing an acrylate followed by hydrolysis.

[0041] In one embodiment of the present invention, the amount of repeating unit (i) may be 10-80% by weight, for example, 20-80% by weight, 22-79% by weight, 22-78% by weight, 25-75% by weight, 30-70% by weight, or 35-65% by weight, based on the total amount of repeating units of Copolymer A.

[0042] According to the present invention, the at least one repeating unit (ii) is a linear or branched C2-C 18 Derived from α-monoolefins.18 α-monoolefins are linear or branched C2-C 16 α-monoolefin or C4-C 16 α-monoolefins, linear or branched, C2-C 14 α-monoolefin or C4-C 14 α-monoolefins, linear or branched, C2-C 12 α-monoolefin or C4-C 12 α-monoolefins, linear or branched, C2-C 10 α-monoolefin or C4-C 10 It may be an α-monoolefin, preferably a linear or branched C2-C8 α-monoolefin or a C4-C8 α-monoolefin.

[0043] These linear or branched C2-C 18 Specific examples of α-monoolefins include ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

[0044] In the copolymer A, the amount of repeating unit (ii) may be 10-75 wt %, 15-74 wt %, 17-73 wt %, 20-70 wt %, 25-65 wt %, or 30-60 wt %, based on the total amount of repeating units of copolymer A.

[0045] According to the present invention, the at least one repeating unit (iii) is derived from a monomer having at least two carbon-carbon unsaturated double bonds. According to one embodiment of the present invention, the carbon-carbon unsaturated double bonds in the monomer having at least two (e.g., 2-4) carbon-carbon unsaturated double bonds are selected from a (meth)acrylic acid ester group, a (meth)acrylamide group, a vinyl group, an allyl group, and a carbon-carbon double bond in an alkene or cycloalkene.

[0046] The amount of the repeating unit (iii) may be 0.1-70% by weight, for example 0.1-30% by weight, 0.2-20% by weight, 0.2-10% by weight, or 0.5-5% by weight, based on the total amount of repeating units of copolymer A.

[0047] Copolymer A is generally crosslinked because it has at least one repeating unit (iii) derived from a monomer having at least two carbon-carbon unsaturated double bonds.

[0048] According to the present invention, copolymer A may optionally contain an auxiliary repeat unit, which may be selected from the repeat units derived from the following monomers:

[0049] Monoethylenically unsaturated C3-C8 monocarboxylic acids, C1-C of monoethylenically unsaturated C3-C8 monocarboxylic acids 10 Alkyl esters, amides of monoethylenically unsaturated C3-C8 monocarboxylic acids, vinyl alkyl ethers with C1-C8 alkyl groups, styrene, C4-C of non-α-monoolefins 22 Monoolefins, C1-C 12 Alkyl groups, C1-C 12 Styrene, C1-C substituted by one or more substituents selected from alkoxy groups and halogens 20 vinyl esters of carboxylic acids, vinylpyrrolidone, (meth)acrylonitrile, hydroxy group-containing ethylenically unsaturated monomers, N-vinylformamide, vinylimidazole, allylbenzene, indene, methylindene and furan ring-containing compounds, or The auxiliary repeat unit is derived from at least one monomer containing a carbon-carbon unsaturated double bond originating from a reaction feedstock of gasoline, a C4 fraction, a C5 fraction, a C8 fraction, a C9 fraction, or a light coal tar fraction.

[0050] Details regarding the monomers of these repeating units (i), (ii), (iii) and auxiliary repeating units, as well as the reactants, are detailed in the following text regarding Copolymer B.

[0051] According to one preferred embodiment of the present invention, the copolymer A is derived from a copolymer B, which is (i′) at least one repeating unit having an anhydride group; (ii) Linear or branched C2-C 18 at least one repeat unit derived from an α-olefin, and (iii) at least one repeat unit derived from a monomer having at least two carbon-carbon unsaturated double bonds; It has.

[0052] In one preferred embodiment, said copolymer A is derived from the reaction of said copolymer B with ammonia.

[0053] According to one preferred embodiment of the present invention, the repeating unit (i') having an anhydride group in the copolymer B is derived from at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group. According to the present invention, the monomer having a carbon-carbon unsaturated double bond and an anhydride group can be selected from monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 8 carbon atoms, preferably maleic anhydride, itaconic anhydride, citraconic anhydride, methylenemalonic anhydride and mixtures thereof, more preferably maleic anhydride.

[0054] In copolymer B, the amount of repeating unit (i') may be 10-80% by weight, for example, 20-80% by weight, 22-79% by weight, 22-78% by weight, 25-75% by weight, 30-70% by weight, or 35-65% by weight, based on the total amount of repeating units in copolymer B.

[0055] The repeating unit (ii) in copolymer B is as described above for copolymer (A). The amount of repeating unit (ii) in copolymer B may be 10-75 wt%, 15-74 wt%, 17-73 wt%, 20-70 wt%, 25-65 wt%, or 30-60 wt%, based on the total amount of repeating units in copolymer B.

[0056] According to the present invention, the at least one repeating unit (iii) is derived from a monomer having at least two carbon-carbon unsaturated double bonds. According to one embodiment of the present invention, the carbon-carbon unsaturated double bonds in the monomer having at least two (e.g., 2-4) carbon-carbon unsaturated double bonds are selected from a (meth)acrylic acid ester group, a (meth)acrylamide group, a vinyl group, an allyl group, and a carbon-carbon double bond in an alkene or cycloalkene.

[0057] Examples of the monomer having at least two carbon-carbon unsaturated double bonds include (meth)acrylates of alcohols having at least two hydroxy groups, vinyl ethers of alcohols having at least two hydroxy groups, allyl ethers of alcohols having at least two hydroxy groups, di(meth)acrylates of ethylene oxide and / or propylene oxide oligomers, vinyl (meth)acrylate, allyl (meth)acrylate, methylene bis(meth)acrylamide, aromatic compounds having at least two vinyl groups, and C4-C 22 dienes.

[0058] The alcohol having at least two hydroxy groups may have, for example, 2 to 6, preferably 2 to 4 hydroxy groups, and may be selected from diols having 2 to 6 carbon atoms, such as ethylene glycol, propanediol, butanediol, pentanediol, and hexanediol, glycerol, trimethylolpropane, and pentaerythritol.

[0059] Thus, the (meth)acrylate of an alcohol having at least two hydroxy groups may be a di(meth)acrylate of a diol containing 2 to 6 carbon atoms and may be selected from ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol di(meth)acrylates such as 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.

[0060] Illustrative examples of di(meth)acrylates of ethylene oxide and / or propylene oxide oligomers are diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and tetraethylene glycol dimethacrylate.

[0061] Illustrative examples of aromatic compounds having at least two vinyl groups include divinylbenzene, divinyltoluene, trivinylbenzene, and divinylnaphthalene.

[0062] C4-C 22 The diene may be an alkadiene or a cyclic diene. 22 The diene may be conjugated or non-conjugated. 22 Dienes can be, for example, conjugated or non-conjugated C4-C 16 or C5-C 16 Alkadienes or cyclic dienes, conjugated or non-conjugated C4-C 12 or C5-C 12Alkadienes or cyclic dienes, conjugated or non-conjugated C4-C8 or C5-C8 alkadienes or cyclic dienes; and bicyclic olefins having 8-20 carbon atoms, preferably 8-16 or 8-12 carbon atoms, such as dicyclopentadiene-based monomers, such as dicyclopentadiene, methyldicyclopentadiene (e.g., 2-methyldicyclopentadiene, 5-methyldicyclopentadiene), ethyldicyclopentadiene (e.g., 2-ethyldicyclopentadiene), and 5,5-dimethyldicyclopentadiene.

[0063] C4-C 22 Specific examples of alkadienes or cyclic dienes include 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, cyclopentadiene, methylcyclopentadiene, 1,3-cyclohexadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and the like.

[0064] Other specific examples of monomers having at least two (e.g., 2 to 4) carbon-carbon unsaturated double bonds include trimethylolpropane tri(meth)acrylate, butanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol triallyl ether, methylene bis(meth)acrylamide, and diallyl phthalate.

[0065] The amount of the repeating unit (iii) may be 0.1-70% by weight, for example 0.1-30% by weight, 0.2-20% by weight, 0.2-10% by weight, or 0.5-5% by weight, based on the total amount of repeating units of copolymer B.

[0066] According to the present invention, copolymer B may optionally contain auxiliary repeat units, which may be selected from repeat units derived from the following monomers:

[0067] Monoethylenically unsaturated C3-C8 monocarboxylic acids, C1-C of monoethylenically unsaturated C3-C8 monocarboxylic acids 10 Alkyl esters, amides of monoethylenically unsaturated C3-C8 monocarboxylic acids, vinyl alkyl ethers with C1-C8 alkyl groups, styrene, C4-C of non-α-monoolefins 22 Monoolefins, C1-C 12 Alkyl groups, C1-C 12 Styrene substituted with one or more substituents selected from alkoxy groups and halogens, C1-C 20 vinyl esters of carboxylic acids, vinylpyrrolidone, (meth)acrylonitrile, hydroxy group-containing ethylenically unsaturated monomers, N-vinylformamide, vinylimidazole, allylbenzene, indene, methylindene and furan ring-containing compounds, or The auxiliary repeat unit is derived from at least one monomer containing a carbon-carbon unsaturated double bond originating from a reaction feedstock of gasoline, a C4 fraction, a C5 fraction, a C8 fraction, a C9 fraction, or a light coal tar fraction.

[0068] Illustrative examples of monoethylenically unsaturated C3-C8 monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, preferably acrylic acid and methacrylic acid.

[0069] C1-C of monoethylenically unsaturated C3-C8 monocarboxylic acids 10 Examples of alkyl esters include C1-C 10 Mention may be made of alkyl (meth)acrylate esters of alkyl groups, in particular methyl methacrylate, methyl acrylate, N-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate or mixtures thereof.

[0070] As an example of an amide of a monoethylenically unsaturated C3-C8 monocarboxylic acid, mention may be made in particular of (meth)acrylamide.

[0071] Examples of vinyl alkyl ethers having a C1-C8 alkyl group include preferably 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.

[0072] Non-α-monoolefins C4-C 22 The monoolefins may be alkenes and cycloalkenes, such as alkenes or cycloalkenes having 4-20 or 5-20 carbon atoms, for example 4-16 or 5-16 carbon atoms, or 4-8 or 5-8 carbon atoms, such as 2-butene, 2-pentene, 2-methyl-2-butene, cyclopentene, cyclohexene, cycloheptene, etc.; dihydrobicycloalkenes having 5-20 carbon atoms, preferably 5-16 or 8-12 carbon atoms, in particular dihydrodicyclopentadiene (e.g. 2,3-dihydrodicyclopentadiene), dihydromethyldicyclopentadiene, and dihydrodimethyldicyclopentadiene, etc.

[0073] C1-C 12 Alkyl groups, C1-C 12 For styrene substituted with one or more substituents selected from alkoxy groups and halogens, the alkyl or alkoxy group preferably has 1-10 carbon atoms, for example, 1-4 carbon atoms; the halogens are preferably chlorine and bromine. Specific examples include vinyltoluenes (e.g., α-methylstyrene and p-methylstyrene), α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, p-methoxystyrene, chlorostyrene, and bromostyrene.

[0074] C1-C 20Illustrative examples of vinyl esters of carboxylic acids include vinyl laurate, vinyl stearate, vinyl propionate, vinyl neodecanoate, and vinyl acetate.

[0075] The hydroxyl group-containing ethylenically unsaturated monomers are, for example, C1-C 10 Hydroxyalkyl (meth)acrylates include, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl methacrylate.

[0076] Examples of furan ring-containing compounds include compounds in which the furan ring is C1-C 12 Alkyl groups and C1-C 12 Examples of suitable monomers include those substituted with one or more (e.g., 2-4) substituents selected from hydroxyalkyl groups, such as furfuryl alcohol, where the furan ring can be further condensed with a benzene ring, e.g., methylbenzofuran.

[0077] In one embodiment of the present invention, the reaction materials containing at least one monomer containing a carbon-carbon unsaturated double bond, saturated hydrocarbons, and other impurities not involved in polymerization, such as gasoline, C4 fraction, C5 fraction, C8 fraction, C9 fraction, and light coal tar fraction, can be used directly without separation to obtain auxiliary repeating units.When these reaction materials are used to form copolymer B (for example, by free radical polymerization), the components in these reaction materials other than the monomer containing a carbon-carbon unsaturated double bond can be used as solvents during the preparation process.When these fractions are used as reaction materials, the cost of the adhesive and artificial board of the present invention can be further reduced.

[0078] C4 fractions include by-products produced in petroleum cracking or catalytic cracking for the production of ethylene. They typically contain components such as isobutene, 1-butene-1,2-butene, and butane.

[0079] The C4 fraction may have the following specific composition: [Table 1]

[0080] C5 fraction is usually derived from petroleum cracking. It contains about 45-55% diolefins and 8-15% monoolefins. Other components in C5 fraction include 18-25% alkanes, around 1% alkynes, 10-20% C4, benzene, and other components.

[0081] The C5 fraction may have the following specific composition: [Table 2]

[0082] The C8 and C9 fractions are mainly derived from steam cracking processes for ethylene production and from naphtha platinum reforming processes, with some fractions also derived from toluene disproportionation or transalkylation products and coal tar, etc.

[0083] The C8 fraction typically contains 22-35% monoolefins such as styrene, allylbenzene, vinyltoluene, indene, and methylindene. Other components in the C8 fraction include 45-55% aromatic hydrocarbons and about 20% other unknown components.

[0084] The C8 fraction may have the following specific composition: [Table 3]

[0085] The C9 fraction typically contains 20-30% monoolefins (e.g., styrene, allylbenzene, vinyltoluene, indene), and 8-15% dienes. Other components in the C9 fraction include about 5% alkanes, 40-50% aromatic hydrocarbons, and around 10% other unknown components. The C9 fraction can have the following specific composition: [Table 4]

[0086] The light oil components in coal tar mainly include styrene, α-methylstyrene, alkylbenzene, vinyltoluene, dicyclopentadiene, benzofuran, indene, methylindene, and methylbenzofuran, and are currently mainly used as raw materials for dark-light coumarone resins. The specific composition of the coal tar light fraction can be as follows: [Table 5]

[0087] The polymerization to prepare copolymer B can be carried out using an oil-soluble free radical initiator. Examples of the oil-soluble free radical initiator include azo initiators or peroxide initiators. Examples of the azo initiator include azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobis(isobutyrate); examples of the peroxide initiator include benzoyl peroxide, dicumyl peroxide, bis(2,4-dichlorobenzoyl) peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate. The dosage of the initiator is 0.05-10% by weight, preferably 0.5-6% by weight, based on the weight of the monomers.

[0088] The polymerization reaction can be carried out in the presence of a solvent, which can include a mixture of an aromatic hydrocarbon, an alkane, and a ketone, a mixture of a carboxylic acid ester, an alkane, and an aromatic hydrocarbon, a mixture of an aromatic hydrocarbon and a carboxylic acid ester, a mixture of an alkane and a carboxylic acid ester, or a mixture of an alkane, an aromatic hydrocarbon, and a carboxylic acid ester.

[0089] Examples of aromatic hydrocarbons include toluene, xylene, and ethylbenzene.

[0090] The carboxylic acid ester may 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 to 10 carbon atoms. Specific examples include ester-based solvents such as ethyl formate, propyl formate, isobutyl formate, pentyl 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, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, and isoamyl phenylacetate.

[0091] 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, cyclohexane, n-heptane, n-octane, isooctane, etc. In the mixture of alkane and ketone, the ketone usually accounts for 5-65% by volume.

[0092] 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.

[0093] In one preferred embodiment, the polymerization reaction is carried out by precipitation polymerization. The precipitation polymerization can be carried out by selecting a solvent that can dissolve the monomers but cannot dissolve the resulting copolymer B. By precipitation polymerization, copolymer B can be directly obtained in powder form.

[0094] According to the present invention, if gasoline, C4 fraction, C5 fraction, C8 fraction, C9 fraction, or coal tar light fraction is used as the reaction material, after the reaction is completed, the unreacted alkane or aromatic hydrocarbon mixture can be separated by simple distillation, thereby obtaining various high-value-added solvents and industrial raw materials.

[0095] According to the invention, copolymer A can be obtained by reacting said copolymer B with ammonia (as will be explained in more detail in the following documents).

[0096] glue

[0097] One aspect of the present invention relates to an adhesive comprising copolymer A of the present invention.

[0098] In addition to copolymer A, the adhesive of the present invention may also contain at least one additive, if necessary, which may be one or more of the following: oxygen scavengers, emulsifiers, dyes, pigments, antimigration aids, UV absorbers, biocides, antifoaming agents, colorants, antistatic agents, and antioxidants.

[0099] According to one embodiment, the adhesive of the present invention does not contain any organic crosslinking agent capable of undergoing a covalent crosslinking reaction with the amide groups and / or carboxy groups of copolymer A, such as a polyol, a polyamine, a polyalkanolamine or a mixture thereof.

[0100] According to the invention, the adhesive may be a solid, preferably in powder form; or an aqueous composition, preferably in the form of an aqueous solution.

[0101] In the adhesive of the present invention, the amount of copolymer A 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 the adhesive (based on the solids content if the adhesive is in liquid form, for example an aqueous composition or solution).

[0102] When the adhesive is in the form of an aqueous composition, preferably an aqueous solution, the solids content of the adhesive may be 2-40% by weight, or 5-30% by weight, or 8-25% by weight.

[0103] Adhesive Preparation Method

[0104] One aspect of the present invention relates to a method for preparing the adhesive of the present invention, which method comprises reacting Copolymer B with ammonia in the presence or absence of a reaction medium (e.g., water).

[0105] Copolymer B can be reacted with ammonia, i.e., by ammonolysis, to form copolymer A. The reaction typically involves reacting copolymer B with ammonia in an aqueous medium under stirring at a temperature below 100° C., preferably 15-70° C., e.g., at room temperature. The reaction time is typically 0.1-10 hours, preferably 0.5-6 hours.

[0106] After the reaction, the resulting reaction mixture is usually in the form of an aqueous composition, preferably an aqueous solution. The resulting aqueous composition, preferably an aqueous solution, can be used directly as an adhesive. Alternatively, the reaction mixture can be mixed with at least one of the above-mentioned additives and then used as an adhesive.

[0107] Preferably, copolymer B is in powder form before being reacted 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 a block form) into 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.

[0108] The reaction time between the solid copolymer B and ammonia is usually 2-300 minutes, for example 5-120 minutes.

[0109] In a specific application, the copolymer A in solid form can be dissolved in water and optionally mixed with at least one of the additives mentioned above before application.

[0110] The conversion of the anhydride groups in copolymer B is usually greater than 90%, preferably greater than 95%, more preferably greater than 98%, for example 100%.

[0111] In the reaction of Copolymer B with ammonia, the carboxyl group can also form an ammonium salt with the ammonia.

[0112] Articles containing components formed from the adhesives of the present invention

[0113] One aspect of the present invention relates to articles of manufacture that include components formed from the adhesives of the present invention.

[0114] According to the present invention, said product may be an artificial board, paper, fabric or paint.

[0115] In the product of the present invention, the dosage of adhesive on a solids basis may be 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, 8-19% by weight, based on the total weight of the product.

[0116] In the product of the present invention, the dosage of copolymer A may be 1-40 wt%, preferably 2-30 wt%, more preferably 3-25 wt% or 4-20 wt%, for example 5-20 wt%, 6-20 wt% or 7-18 wt%, based on the total weight of the product.

[0117] In one embodiment, the product is an artificial board formed from lignocellulosic material and the adhesive of the present invention. The artificial board of the present invention should be understood broadly, i.e., it is a board formed from any lignocellulosic material and the adhesive of the present invention. The artificial board of the present invention is not limited to boards formed only from wood, but can also include boards formed from materials described below, 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, particle board, plywood, fiber board, density board, straw board, and finger-joint board.

[0118] The lignocellulosic material may be derived from a variety of lignocellulosic materials, such as wood, bamboo, bagasse, straw (e.g., wheat straw), flax residues, nut shells, grain husks, etc., and mixtures thereof. Wood includes a variety of softwoods and / or hardwoods.

[0119] The lignocellulosic material may be in the form of sawdust, chips, wood chips, strips, flakes, fibers, sheets, wood flour, shavings, granules and similar forms of material and combinations of these materials, such as a combination of strips and sawdust.

[0120] Lignocellulosic materials can be processed by a variety of conventional techniques. Large pieces of wood can be processed into wood chips in a round wood chipper. Large pieces of wood and remnants can be cut into small pieces. Large pieces of wood can also be chipped in a ring chipper. Typically, large pieces of wood are debarked before being chipped.

[0121] The size of the lignocellulosic material is generally not critical. Different sizes can be used for different types of artificial boards. For example, the size of the lignocellulosic material can be 1-30 mesh, preferably 2-15 mesh. For sheet-type lignocellulosic material, the thickness of the sheet can be, for example, 0.5 mm-5 cm, preferably 1 mm-3 cm.

[0122] In the artificial board of the present invention, the adhesive is used as a matrix resin, and preferably the adhesive fills the gaps between the lignocellulosic materials.

[0123] Another aspect of the invention relates to a method for preparing the product of the invention, said method comprising using the adhesive of the invention.

[0124] According to the present invention, an artificial board can be prepared by the following method, which comprises pressing a mixture of lignocellulosic 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, for example for 5-30 minutes.

[0125] The mixture of lignocellulosic material and the adhesive of the present invention used in the press can be prepared by mixing the lignocellulosic material with the adhesive of the present invention. If the adhesive is a solid, it can be first dissolved in water and then mixed with the lignocellulosic material.

[0126] Prior to pressing, it is preferred to remove some of the moisture from the mixture of lignocellulosic material and adhesive, for example to reduce the moisture content of the mixture of lignocellulosic material and adhesive 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 typically greater than 5% by weight or greater than 8% by weight. The moisture removal can be achieved by heating, for example, at a heating temperature of 50-90°C, preferably 60-80°C.

[0127] In one preferred embodiment, the pressing is carried out at a temperature of 120-220° C. and / or under a pressure of 1-6 MPa.

[0128] When copolymer A has carboxy groups in the form of their ammonium salts, the ammonium salts of the carboxy groups decompose back into carboxy groups under the conditions of pressing.

[0129] Adhesive applications

[0130] Finally, the present invention also relates to the use of the adhesives of the invention in the preparation of artificial boards, paper, fabrics or paints.

[0131] The adhesive containing copolymer A of the present invention is safe, environmentally friendly, does not emit toxic and harmful substances such as formaldehyde, is easy to apply and is low cost, and at the same time, the adhesive of the present invention has excellent performance and is particularly suitable for the production of artificial boards, paper, cloth or paints, especially the production of lignocellulose-based artificial boards, and the products produced using the adhesive of the present invention have excellent mechanical properties and water resistance. [Example]

[0132] The technical solutions of the present invention will be further described below in conjunction with specific examples of the present invention, which should not be understood as limiting the scope of protection of the present invention. The examples described below are only a portion of the examples of the present invention, and are not all examples. Other examples proposed by those skilled in the art without creative work based on the examples described in the present invention shall fall within the scope of protection of the present invention. Unless otherwise specified, % in the examples means % by weight, and parts in the examples means parts by mass.

[0133] Example 1: Ethylene Copolymer System

[0134] Based on parts by weight, 5.8 parts of ethylene, 19.6 parts of maleic anhydride, 0.3 parts of crosslinker divinylbenzene, 300 parts of benzene and 0.5 parts of azobisisobutyronitrile were mixed and dissolved in an autoclave, and the mixture was heated to 70°C. o The temperature was raised to C and the reaction was continued for 6 hours. The product was separated by centrifugation, washed with benzene, and dried to obtain a powdery product, which was a crosslinked ethylene-maleic anhydride copolymer, of which the mass fraction of maleic anhydride units was approximately 78%.

[0135] 10 parts of the ethylene-maleic anhydride copolymer, 5 parts of 37% aqueous ammonia, and 85 parts of water were stirred at room temperature for 4 hours to obtain a 10% mass concentration ethylene-maleic anhydride copolymer suspension (the molar fraction of ammonolyzed maleic anhydride monomer units in the copolymer was 99%). The suspension was uniformly mixed with poplar wood shavings (5% moisture content, 5-10 mesh) to obtain a premix (8 parts of the copolymer per 100 parts of shavings). The premix was dried at 70°C to remove moisture to a moisture content of 15%.

[0136] The above premix was placed in a 25 cm x 25 cm x 2.5 cm press mold, the hot press temperature was 170°C, the pressure was 0.4 MPa, and the hot press time was 15 minutes to obtain a particle board with a thickness of 3 mm.

[0137] Example 2: (N-butene copolymer system)

[0138] Based on parts by weight, 11.2 parts of n-butene, 19.6 parts of maleic anhydride, 0.4 parts of crosslinker ethylene glycol dimethacrylate, 300 parts of isoamyl acetate and 0.7 parts of azobisisobutyronitrile were mixed and dissolved in an autoclave, and 70 o The temperature was raised to C and the reaction was continued for 6 hours. The product was separated by centrifugation, washed, and dried to obtain a powdery product, which was a crosslinked n-butene-maleic anhydride copolymer, of which the mass fraction of maleic anhydride units was approximately 64%.

[0139] 10 parts of the n-butene-maleic anhydride copolymer, 5 parts of 37% aqueous ammonia, and 85 parts of water were stirred at room temperature for 4 hours to obtain a 10% mass concentration n-butene-maleic anhydride copolymer suspension (the molar fraction of ammonolyzed maleic anhydride monomer units in the copolymer was 99%). The suspension was uniformly mixed with poplar wood shavings (5% moisture content, 5-10 mesh) to obtain a premix (8 parts of the copolymer per 100 parts of shavings). The premix was dried at 70°C to remove moisture to a moisture content of 10%.

[0140] The above premix was placed in a 25 cm x 25 cm x 2.5 cm press mold, the hot pressing temperature was 160°C, the pressure was 0.8 MPa, and the hot pressing time was 12 minutes to obtain a particle board with a thickness of 3 mm.

[0141] Example 3: (Isobutylene Copolymer System)

[0142] Based on parts by weight, 11.2 parts of isobutylene, 19.6 parts of maleic anhydride, 0.4 parts of crosslinker ethylene glycol dimethacrylate, 300 parts of isoamyl acetate and 0.6 parts of azobisisobutyronitrile were mixed and dissolved in an autoclave, and 70 oThe temperature was raised to C and the reaction was continued for 6 hours. The product was separated by centrifugation, washed, and dried to obtain a powdery product, which was a crosslinked isobutylene-maleic anhydride copolymer, of which the mass fraction of maleic anhydride units was approximately 64%.

[0143] 10 parts of the isobutylene-maleic anhydride copolymer, 5 parts of 37% aqueous ammonia, and 85 parts of water were stirred at room temperature for 4 hours to obtain a 10% mass concentration suspension of the isobutylene-maleic anhydride copolymer (the molar fraction of ammonolyzed maleic anhydride monomer units in the copolymer was 99%). The suspension was uniformly mixed with poplar wood shavings (5% moisture content, 5-10 mesh) to obtain a premix (8 parts of the copolymer per 100 parts of shavings). The premix was dried at 70°C to remove moisture to a moisture content of 15%.

[0144] The above premix was placed in a 25 cm x 25 cm x 2.5 cm press mold, the hot pressing temperature was 170°C, the pressure was 0.4 MPa, and the hot pressing time was 15 minutes to obtain a particle board with a thickness of 3 mm.

[0145] Figure 1 shows the infrared spectrum of the crosslinked isobutylene-maleic anhydride copolymer (1), the infrared spectrum of the copolymer converted to amic acid (2), and the infrared spectrum of the copolymer after hot pressing (3). Curve 1:1858cm -1 , 1778cm -1 are the C=O stretching vibration peaks of the two carbonyls on the anhydride, Curve 2: 1661cm -1 is the C=O stretching vibration peak of amide, and -1 The peaks are the C=O vibration peaks of the carboxylate salt, and the characteristic peaks of the original anhydride group have basically disappeared. Curve 3: 1778cm -1 , 1715cm -1 The peak at is a characteristic peak of cyclic imide.

[0146] Example 4: (1-pentene copolymer system)

[0147] Based on parts by mass, 14 parts of 1-pentene, 19.6 parts of maleic anhydride, 0.3 parts of the crosslinker divinylbenzene, 300 parts of isoamyl acetate, and 0.7 parts of azobisisobutyronitrile were mixed and dissolved, and the system was vented with nitrogen for 20 minutes, followed by reaction for 6 hours at 70° C. The product was centrifuged, washed, and dried to obtain a crosslinked 1-pentene-maleic anhydride copolymer in the form of a white powder, and the mass fraction of maleic anhydride monomer units in the copolymer was 58%.

[0148] 20 parts of the 1-pentene-maleic anhydride copolymer, 10 parts of 37% aqueous ammonia, and 70 parts of water were stirred at room temperature for 4 hours to obtain a 20% mass concentration suspension of the 1-pentene-maleic anhydride copolymer (the molar fraction of ammonolyzed maleic anhydride monomer units in the copolymer was 99%). The suspension was mixed with poplar wood shavings (5% moisture content, 5-10 mesh) to obtain a homogeneous mixture of 12 parts of the copolymer per 100 parts of the shavings. The premix was dried at 70°C to remove the moisture until the moisture content reached 20%.

[0149] The above premix was placed in a 25 cm x 25 cm x 2.5 cm press mold, the hot pressing temperature was 180°C, the pressure was 1 MPa, and the hot pressing time was 15 minutes to obtain a particle board with a thickness of 3 mm.

[0150] Example 5: (1-decene copolymer system)

[0151] 28 parts by mass of 1-decene, 19.6 parts by mass of maleic anhydride, 0.3 parts by mass of the crosslinking agent divinylbenzene, 300 parts by mass of isoamyl acetate, and 0.7 parts by mass of azobisisobutyronitrile were mixed and dissolved, and the system was vented with nitrogen for 20 minutes, followed by reaction for 6 hours at 70° C. The product was centrifuged, washed, and dried to obtain a crosslinked 1-decene-maleic anhydride copolymer in the form of a white powder, and the mass fraction of maleic anhydride monomer units in the copolymer was 41%.

[0152] 20 parts of the 1-decene-maleic anhydride copolymer, 10 parts of 37% aqueous ammonia, and 70 parts of water were stirred at room temperature for 4 hours to obtain a 20% mass concentration suspension of the 1-decene-maleic anhydride copolymer (the molar fraction of ammonolyzed maleic anhydride monomer units in the copolymer was 99%). The suspension was mixed with poplar wood shavings (5% moisture content, 5-10 mesh) to obtain a homogeneous premix, with 12 parts of the copolymer per 100 parts of shavings. The premix was dried at 70°C to remove moisture to a moisture content of 10%.

[0153] The above premix was placed in a 25 cm x 25 cm x 2.5 cm press mold, the hot pressing temperature was 160°C, the pressure was 1 MPa, and the hot pressing time was 15 minutes to obtain a particle board with a thickness of 3 mm.

[0154] Example 6: (1-Tetradecene Copolymer System)

[0155] Based on parts by mass, 39.2 parts of 1-tetradecene, 19.6 parts of maleic anhydride, 0.4 parts of the crosslinking agent ethylene glycol dimethacrylate, 300 parts of isoamyl acetate, and 0.7 parts of azobisisobutyronitrile were mixed and dissolved, and the system was vented with nitrogen for 20 minutes, followed by reaction for 6 hours at 70° C. The product was centrifuged, washed, and dried to obtain a crosslinked 1-tetradecene-maleic anhydride copolymer in the form of a white powder, and the mass fraction of maleic anhydride monomer units in the copolymer was 33%.

[0156] 20 parts of the 1-tetradecene-maleic anhydride copolymer, 10 parts of 37% aqueous ammonia, and 70 parts of water were stirred at room temperature for 4 hours to obtain a 20% mass concentration suspension of the 1-tetradecene-maleic anhydride copolymer (the molar fraction of ammonolyzed maleic anhydride monomer units in the copolymer was 99%). The suspension was mixed with poplar wood shavings (5% moisture content, 5-10 mesh) to obtain a homogeneous premix, with 12 parts of the copolymer per 100 parts of the shavings. The premix was dried at 70°C to remove moisture to a moisture content of 20%.

[0157] The above premix was placed in a 25 cm x 25 cm x 2.5 cm press mold, the hot pressing temperature was 170°C, the pressure was 0.5 MPa, and the hot pressing time was 15 minutes to obtain a particle board with a thickness of 3 mm.

[0158] Example 7: (1-octadecene copolymer system)

[0159] Based on parts by mass, 50.4 parts of 1-octadecene, 19.6 parts of maleic anhydride, 0.3 parts of the crosslinker divinylbenzene, 300 parts of isoamyl acetate, and 0.7 parts of azobisisobutyronitrile were mixed and dissolved, and the system was vented with nitrogen for 20 minutes, followed by reaction at 70°C for 6 hours. The product was centrifuged, washed, and dried to obtain a crosslinked 1-octadecene-maleic anhydride copolymer in the form of a white powder, with the mass fraction of maleic anhydride monomer units in the copolymer being 28%.

[0160] 20 parts of the 1-octadecene-maleic anhydride copolymer, 10 parts of 37% aqueous ammonia, and 70 parts of water were stirred at room temperature for 4 hours to obtain a 20% mass concentration suspension of the 1-octadecene-maleic anhydride copolymer (the molar fraction of ammonolyzed maleic anhydride monomer units in the copolymer was 99%). The suspension was mixed with poplar wood shavings (5% moisture content, 5-10 mesh) to obtain a homogeneous premix, with 12 parts of the copolymer per 100 parts of shavings. The premix was dried at 70°C to remove moisture to a moisture content of 15%.

[0161] The above premix was placed in a 25 cm x 25 cm x 2.5 cm press mold, the hot pressing temperature was 160°C, the pressure was 1 MPa, and the hot pressing time was 15 minutes to obtain a particle board with a thickness of 3 mm.

[0162] Example 8: (Mixed α-olefin copolymer system)

[0163] Based on parts by mass, 4.7 parts of 1-pentene, 9.3 parts of 1-decene, 14.9 parts of 1-hexadecene, 0.3 parts of the crosslinker divinylbenzene, 19.6 parts of maleic anhydride, 300 parts of isoamyl acetate, and 0.7 parts of azobisisobutyronitrile 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, and dried to obtain a mixed olefin-maleic anhydride copolymer in the form of a white powder. The mass fraction of maleic anhydride monomer units in the copolymer was 43%.

[0164] 20 parts of the mixed olefin-maleic anhydride copolymer, 10 parts of 37% aqueous ammonia, and 70 parts of water were stirred at room temperature for 4 hours to obtain a 20% mass concentration mixed olefin-maleic anhydride copolymer suspension (the molar fraction of ammonolyzed maleic anhydride monomer units in the copolymer was 99%). The suspension was mixed with poplar wood shavings (5% moisture content, 5-10 mesh) to obtain a homogeneous premix, with 12 parts of the copolymer per 100 parts of shavings. The premix was dried at 70°C to remove moisture to a moisture content of 20%.

[0165] The above premix was placed in a 25 cm x 25 cm x 2.5 cm press mold, the hot pressing temperature was 180°C, the pressure was 1 MPa, and the hot pressing time was 15 minutes to obtain a particle board with a thickness of 3 mm.

[0166] Comparative Example 1

[0167] 10 parts by mass of isobutylene, 17.5 parts by mass of maleic anhydride, 100 parts by mass of isoamyl acetate, and 0.3 parts by mass of BPO were mixed and dissolved, and the system was vented with nitrogen for 20 minutes, followed by reaction for 8 hours at 70° C. The product was centrifuged, washed three times with petroleum ether, and dried to obtain an isobutylene-maleic anhydride copolymer in the form of a white powder, and the mass fraction of maleic anhydride monomer units in the copolymer was 63%.

[0168] 10 parts of isobutylene-maleic anhydride copolymer, 10 parts of 37% aqueous ammonia, and 80 parts of water were stirred at room temperature for 4 hours to obtain a viscous liquid with a mass concentration of 10%. The viscous liquid was mixed with poplar wood shavings (5% moisture content, 5-10 mesh) to obtain a premix with a uniform mixing ratio of 20 parts of the copolymer to 100 parts of the shavings. The premix was dried at 70°C to remove moisture to a moisture content of 10%.

[0169] The above premix was placed in a 25 cm x 25 cm x 2.5 cm press mold, the hot pressing temperature was 170°C, the pressure was 0.4 MPa, and the hot pressing time was 12 minutes to obtain a particle board with a thickness of 3 mm.

[0170] Performance Test

[0171] According to GB / T4897-2015, the particle boards obtained in Examples 1-8 and Comparative Example 1 were tested for internal adhesive strength, 24-hour water absorption thickness swelling rate, and moisture resistance (internal adhesive strength after boiling in boiling water), and the results are listed in Table 6 below.

[0172] [Table 6]

[0173] The performance of each item of the particleboards in Examples 1-8 was better than the performance required for furniture-type particleboards used under wet conditions in the national standards, and was also better than the performance of the particleboard in Comparative Example 1.

[0174] Without wishing to be bound by any theory, it is believed that under pressing conditions, the amide and carboxy groups on the polymers in the adhesives of the present invention can dehydrate to form imide groups, and the carboxy groups can also dehydrate to form anhydride groups, which can react with hydroxy groups on the lignocellulosic material to form esters, which help improve the mechanical properties and water resistance of the resulting engineered board.

[0175] The above is only a preferred embodiment of the present invention. It is pointed out that for those skilled in the art, some improvements and modifications made within the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. (i) at least one repeating unit having an amide group and a carboxy group and / or an ammonium salt thereof; (ii) Linear or branched C ２ -C １８ at least one repeat unit derived from an α-monoolefin, and (iii) at least one repeat unit derived from a monomer having at least two carbon-carbon unsaturated double bonds; Copolymer A having the formula:

2. 2. The copolymer A according to claim 1, wherein the amount of the repeating unit (i) in the copolymer A is 10-80% by weight, preferably 20-80% by weight or 22-79% by weight, based on the total amount of repeating units in the copolymer A.

3. The linear or branched C ２ -C １８ The α-monoolefin is a linear or branched C ２ -C １２ α-monoolefins, preferably linear or branched C ２ -C ８ 3. The copolymer A according to claim 1, which is an α-monoolefin.

4. The copolymer A according to any one of claims 1 to 3, wherein the amount of the repeating unit (ii) in the copolymer A is 10 to 75% by weight, preferably 15 to 74% by weight or 20 to 70% by weight, based on the total amount of repeating units in the copolymer A.

5. The copolymer A according to any one of claims 1 to 4, wherein the carbon-carbon unsaturated double bonds in the monomer having at least two carbon-carbon unsaturated double bonds are selected from a (meth)acrylic acid ester group, a (meth)acrylamide group, a vinyl group, an allyl group, and a carbon-carbon double bond in an alkene or cycloalkene.

6. The copolymer A according to any one of claims 1 to 5, wherein the amount of the repeating unit (iii) in the copolymer A is 0.1 to 70% by weight, preferably 0.1 to 30% by weight, based on the total amount of repeating units in the copolymer A.

7. The copolymer A is derived from the copolymer B, (i') at least one repeating unit having an anhydride group; (ii) Linear or branched C ２ -C １８ at least one repeat unit derived from an α-monoolefin, and (iii) at least one repeat unit derived from a monomer having at least two carbon-carbon unsaturated double bonds; The copolymer A according to any one of claims 1 to 6, having the formula:

8. The copolymer A according to claim 7, wherein the repeating unit (i') having an anhydride group in the copolymer B is derived from at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group.

9. 9. Copolymer A 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, preferably maleic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride, more preferably maleic anhydride.

10. The copolymer A according to any one of claims 7 to 9, wherein the copolymer A is derived from a reaction between copolymer B and ammonia.

11. An adhesive comprising the copolymer A according to any one of claims 1 to 10.

12. The adhesive according to claim 11, wherein the adhesive is a solid, preferably in powder form; or an aqueous composition, preferably in the form of an aqueous solution, and preferably the content of copolymer A is 2-40% by weight, in particular 5-30% by weight, based on the total weight of the aqueous composition.

13. The adhesive according to claim 11 or 12, wherein the adhesive does not contain an organic crosslinking agent capable of undergoing a covalent crosslinking reaction with the amide groups and / or carboxy groups of Copolymer A.

14. An article of manufacture comprising a component formed from the adhesive of any one of claims 11 to 13.

15. 15. The product of claim 14, wherein the product is an artificial board, paper, fabric, or paint.

16. 16. The article of manufacture of claim 15, wherein the article is an engineered board formed from lignocellulosic material and the adhesive.

17. 17. The product of claim 16, wherein the adhesive is used as a matrix resin, preferably the adhesive fills gaps between lignocellulosic materials.

18. A product according to any one of claims 14 to 17, wherein the adhesive dosage on a solids basis is 1-45 wt%, preferably 2-35 wt%, more preferably 3-30 wt%, based on the total weight of the product.

19. The product according to any one of claims 14 to 18, wherein the dosage of copolymer A as specified by any one of claims 1 to 10 is 1-40 wt%, preferably 2-30 wt%, more preferably 3-25 wt%, based on the total weight of the product.

20. Use of an adhesive according to any one of claims 11 to 13 in the preparation of artificial boards, papers, fabrics or paints.

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