WO2022116364A1 - 交联的具有酰胺基团与羧基和/或其铵盐的重复单元和α-单烯烃的重复单元的共聚物 - Google Patents

交联的具有酰胺基团与羧基和/或其铵盐的重复单元和α-单烯烃的重复单元的共聚物 Download PDF

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WO2022116364A1
WO2022116364A1 PCT/CN2021/070698 CN2021070698W WO2022116364A1 WO 2022116364 A1 WO2022116364 A1 WO 2022116364A1 CN 2021070698 W CN2021070698 W CN 2021070698W WO 2022116364 A1 WO2022116364 A1 WO 2022116364A1
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copolymer
weight
carbon
parts
article
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PCT/CN2021/070698
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English (en)
French (fr)
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杨万泰
黄延宾
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清华大学
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Priority to JP2023533792A priority Critical patent/JP2023552988A/ja
Priority to MX2023006506A priority patent/MX2023006506A/es
Priority to CA3200291A priority patent/CA3200291A1/en
Priority to EP21899408.5A priority patent/EP4257655A1/en
Priority to US18/255,626 priority patent/US20240109993A1/en
Priority to KR1020237022234A priority patent/KR20230140560A/ko
Publication of WO2022116364A1 publication Critical patent/WO2022116364A1/zh
Priority to ZA2023/06760A priority patent/ZA202306760B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/36—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/24—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having ten or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J135/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition

Definitions

  • the present disclosure relates to a copolymer A having (i) at least one repeating unit bearing an amide group and a carboxyl group and/or an ammonium salt thereof, (ii) at least one C2 derived from linear or branched - repeating units of a C18 alpha-monoolefin, and (iii) at least one repeating unit derived from a monomer having at least two carbon-carbon unsaturated double bonds.
  • the present disclosure also relates to adhesives comprising Copolymer A and articles comprising components formed from the adhesives of the present invention.
  • the "trialdehyde glue” (urea-formaldehyde resin, phenolic resin and melamine-formaldehyde resin) prepared with formaldehyde as raw material occupies a large proportion, exceeding 80% %.
  • "Trialdehyde glue” is simple to prepare and cheap, but this kind of board will release free formaldehyde for a long time in the process of use, pollute the indoor environment, and seriously threaten the health of residents.
  • CN 107033309 A attempts to reduce formaldehyde by adjusting the ratio of raw materials and the pH value of each polymerization stage, adding formaldehyde scavengers, etc. freed.
  • CN 203344147 U discloses that, in the production of the board, activated carbon, bamboo charcoal, diatomaceous earth, etc. are mixed into the board to give the board a certain gas adsorption capacity.
  • the above-mentioned method does not fundamentally solve the problem, and formaldehyde is still released during the use of the board.
  • Adhesives prepared based on biomass raw materials such as soybean protein, tannin, starch, and gelatin do not involve the use of formaldehyde, but the degradation rate of biomass raw materials is fast, which brings the problem of easy aging of the board. Although the degradation can be delayed to a certain extent by adding anti-aging agents, biomass-based adhesives still have problems in terms of high cost and resources. This also limits its practical use.
  • polymers such as polyvinyl chloride, high molecular weight polyethylene, and neoprene for the production of sheets, but these polymers are not water-soluble and cannot form water-based adhesives. Solvents mix polymers with wood raw materials, and still have the disadvantages of high cost, energy consumption and environmental friendliness.
  • the inventors of the present invention have conducted extensive and in-depth research on copolymers in the field of adhesives, in order to find a formaldehyde-free, low-cost, easy-to-apply and excellent performance adhesive that can be used for adhesives.
  • agent copolymer The present inventors have discovered a specific copolymer A and an adhesive comprising the specific copolymer A, which is not only free of formaldehyde emission, low cost, easy to apply, and has excellent properties.
  • the present invention has been completed based on the above findings.
  • the object of the present invention is to provide a copolymer A.
  • Another object of the present invention is to provide an adhesive comprising the copolymer A, which has the advantages of safety and environmental protection, low cost, easy application and excellent performance.
  • Another object of the present invention is to provide an article comprising components formed from the adhesive of the present invention.
  • linear or branched C2- C18 alpha-monoolefin is a linear or branched C2 - C12 alpha-monoolefin, preferably a linear Chained or branched C2 - C8 alpha-monoolefins.
  • copolymer A according to any one of items 1 to 3, wherein in the copolymer A the amount of recurring units (ii) is 10-75% by weight, preferably 15-74% by weight or 20-70% by weight % by weight, based on the total amount of repeating units of Copolymer A.
  • copolymer A according to any one of items 1 to 5, wherein in the copolymer A the amount of repeating units (iii) is from 0.1 to 70% by weight, preferably from 0.1 to 30% by weight, based on the copolymer The total amount of repeating units of A.
  • Copolymer A according to any one of items 1 to 6, wherein said copolymer A is derived from copolymer B having:
  • the copolymer A according to item 8 wherein the monomer having a carbon-carbon unsaturated double bond and an acid anhydride group is selected from the group consisting of monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 8 carbon atoms, preferably a leic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride, more preferably maleic anhydride.
  • Copolymer A according to any of items 1 to 9, wherein said copolymer A is obtained from the reaction of copolymer B with ammonia.
  • An adhesive comprising the copolymer A of any of items 1-10.
  • binder according to item 11 wherein the binder is in the form of a solid, preferably a powder; or in the form of an aqueous composition, preferably in the form of an aqueous solution, preferably the content of the copolymer A is 2-40% by weight, Especially 5 to 30% by weight, based on the total weight of the aqueous composition.
  • An article comprising a component formed from the adhesive of any of items 11-13.
  • Figure 1 Infrared spectra of different polymers in Example 3, from bottom to top 1: Infrared spectra of cross-linked isobutylene-maleic anhydride copolymers; 2: Infrared spectra of copolymers converted to amic acid Fig. 3: Infrared spectrum of the copolymer after hot pressing.
  • One aspect of the present invention pertains to a copolymer A having
  • repeating unit (i) in copolymer A is different from repeating unit (ii) and repeating unit (iii).
  • a part (eg 1-10% by weight) of the carboxyl groups in the repeating unit (i) of the copolymer A may be in the form of its ammonium salt.
  • the expression “derived from” also includes the case where the copolymer has a certain repeating unit, but the repeating unit is not directly formed from the monomer corresponding to the repeating unit.
  • the repeating unit is not directly formed from the monomer corresponding to the repeating unit.
  • carboxyethylene repeating units It can be obtained from the polymerization of acrylic acid or by the polymerization of acrylates followed by hydrolysis.
  • the amount of repeating units (i) may be 10-80 wt%, such as 20-80 wt%, 22-79 wt%, 22-78 wt%, 25-75 wt%, 30 - 70% by weight or 35-65% by weight, based on the total amount of repeating units of copolymer A.
  • the at least one repeating unit (ii) is derived from a linear or branched C 2 -C 18 ⁇ -monoolefin.
  • the linear or branched C 2 -C 18 alpha-monoolefin may be a linear or branched C 2 -C 16 alpha-monoolefin or a C 4 -C 16 alpha-monoolefin, linear or branched C2 - C14 alpha-monoolefins or C4 - C14 alpha-monoolefins, linear or branched C2 - C12 alpha-monoolefins or C4 - C12 alpha-monoolefins, linear or Branched C 2 -C 10 alpha-monoolefins or C 4 -C 10 alpha-monoolefins, preferably linear or branched C 2 -C 8 alpha-monoolefins or C 4 -C 8 alpha-
  • linear or branched C 2 -C 18 ⁇ -monoolefins may be mentioned ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, 1- Decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene.
  • the amount of repeating units (ii) may be 10-75 wt %, 15-74 wt %, 17-73 wt %, 20-70 wt %, 25-65 wt % or 30-60 wt % % by weight, based on the total amount of repeating units of Copolymer A.
  • the at least one repeating unit (iii) is derived from a monomer having at least two carbon-carbon unsaturated double bonds.
  • the carbon-carbon unsaturated double bonds in the monomer having at least two (eg 2-4) carbon-carbon unsaturated double bonds are selected from (meth)acrylate groups , (meth)acrylamide groups, vinyl groups, allyl groups, and carbon-carbon double bonds in alkenes or cycloalkenes.
  • the amount of the repeating unit (iii) may be 0.1-70% by weight, for example 0.1-30%, 0.2-20%, 0.2-10% or 0.5-5% by weight, based on the repeating units of copolymer A. total.
  • the copolymer A has at least one repeating unit (iii) derived from a monomer having at least two carbon-carbon unsaturated double bonds, the copolymer A is generally cross-linked.
  • the copolymer A may optionally contain supplementary repeating units.
  • Said supplementary repeating unit may for example be selected from repeating units derived from the following monomers:
  • Monoethylenically unsaturated C3 - C8 monocarboxylic acids C1 - C10 alkyl esters of monoethylenically unsaturated C3 - C8 monocarboxylic acids, monoethylenically unsaturated C3 - C8 monocarboxylic acids amides, vinyl alkyl ethers with C 1 -C 8 alkyl groups, styrene, C 4 -C 22 monoolefins other than alpha-monoolefins, selected from one or more C 1 -C 12 alkyl groups, Substituents of C 1 -C 12 alkoxy and halogen substituted styrenes, vinyl esters of C 1 -C 20 carboxylic acids, vinyl pyrrolidones, (meth)acrylonitrile, ethylenically unsaturated monomers containing hydroxyl groups , N-vinylformamide, vinylimidazole, allylbenzene, in
  • the supplemental repeat unit is derived from at least one carbon-carbon unsaturated double bond-containing monomer derived from the reaction mass of gasoline, C4 , C5 , C8 , C9 , or coal tar light ends.
  • the copolymer A is derived from a copolymer B having:
  • the copolymer A is obtained from the reaction of the copolymer B with ammonia.
  • the repeating unit (i') with an acid anhydride group of the copolymer B is derived from at least one monomer having a carbon-carbon unsaturated double bond and an acid anhydride group.
  • the monomer having a carbon-carbon unsaturated double bond and an acid anhydride group may 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, more preferably maleic anhydride.
  • the amount of repeating units (i') may be 10-80% by weight, such as 20-80% by weight, 22-79% by weight, 22-78% by weight, 25-75% by weight, 30-70% by weight % by weight or 35-65% by weight, based on the total amount of repeating units of copolymer B.
  • Repeating units (ii) in copolymer B are as described above for copolymer (A).
  • the amount of repeating units (ii) may be 10-75 wt %, 15-74 wt %, 17-73 wt %, 20-70 wt %, 25-65 wt % or 30-60 wt % % by weight, based on the total amount of repeating units of Copolymer B.
  • the at least one repeating unit (iii) is derived from a monomer having at least two carbon-carbon unsaturated double bonds.
  • the carbon-carbon unsaturated double bonds in the monomer having at least two (eg 2-4) carbon-carbon unsaturated double bonds are selected from (meth)acrylate groups , (meth)acrylamide groups, vinyl groups, allyl groups, and carbon-carbon double bonds in alkenes or cycloalkenes.
  • the monomer having at least two carbon-carbon unsaturated double bonds may be selected, for example, from (meth)acrylates of alcohols having at least 2 hydroxyl groups, vinyl ethers of alcohols having at least 2 Allyl ethers of alcohols with three hydroxyl groups, di(meth)acrylates of ethylene oxide and/or propylene oxide oligomers, vinyl (meth)acrylates, allyl (meth)acrylates, methylene Di(meth)acrylamides, aromatic compounds having at least two vinyl groups and C4 - C22 dienes.
  • the alcohol having at least two hydroxyl groups may, for example, have 2 to 6, preferably 2 to 4, hydroxyl groups.
  • These alcohols may be selected from glycols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butanediol, pentanediol and hexylene glycol, glycerol, trimethylolpropane and pentaerythritol, and the like.
  • the (meth)acrylates of alcohols having at least 2 hydroxyl groups may be di(meth)acrylates of dihydric alcohols containing 2 to 6 carbon atoms, which may be selected from ethylene glycol diacrylates, Ethylene glycol dimethacrylate, 1,2-propanediol diacrylate, 1,2-propanediol dimethacrylate, butanediol di(meth)acrylate, such as butane-1,4-diol Diacrylate, Butane-1,4-Diol Dimethacrylate, Hexylene Glycol Diacrylate, Hexylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate, Neopentyl Glycol Dimethacrylate Acrylates, 3-Methylpentanediol Diacrylate and 3-Methylpentanediol Dimethacrylate.
  • di(meth)acrylates of ethylene oxide and/or propylene oxide oligomers are diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethyl Acrylates, Tetraethylene Glycol Diacrylate and Tetraethylene Glycol Dimethacrylate.
  • aromatic compound having at least two vinyl groups divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene and the like can be mentioned.
  • the C 4 -C 22 dienes can be alkadienes or cyclic dienes.
  • the C4 - C22 dienes may be conjugated or non-conjugated.
  • the C 4 -C 22 dienes are, for example, conjugated or non-conjugated C 4 -C 16 or C 5 -C 16 alkadienes or cyclic dienes, conjugated or non-conjugated C 4 -C 12 or C 5 -C 12 alkadiene or cyclic diene, conjugated or non-conjugated C 4 -C 8 or C 5 -C 8 alkadiene or cyclic diene; and having 8-20 carbon atoms, preferably 8 - Bicycloalkenes of 16 or 8-12 carbon atoms, such as dicyclopentadiene-based monomers, such as dicyclopentadiene, methyldicyclopentadiene (such as 2-methyldicyclopentadiene, 5-methylbicyclopentadiene penta
  • C 4 -C 22 alkadienes or cyclodienes may be mentioned 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, cyclopentadiene alkene, methylcyclopentadiene, 1,3-cyclohexadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-cyclohexadiene , 1,5-cyclooctadiene, etc.
  • monomers having at least two (eg 2-4) carbon-carbon unsaturated double bonds can be mentioned trimethylolpropane tri(meth)acrylate, butanediol divinyl ether, trihydroxy Methyl propane trivinyl ether, pentaerythritol triallyl ether, methylene bis(meth)acrylamide, diallyl phthalate, etc.
  • the amount of the repeating units (iii) may be 0.1-70% by weight, for example 0.1-30%, 0.2-20%, 0.2-10% or 0.5-5% by weight, based on the repeating units of copolymer B. total.
  • the copolymer B may optionally contain supplementary repeating units.
  • Said supplementary repeating unit may for example be selected from repeating units derived from the following monomers:
  • Monoethylenically unsaturated C3 - C8 monocarboxylic acids C1 - C10 alkyl esters of monoethylenically unsaturated C3 - C8 monocarboxylic acids, monoethylenically unsaturated C3 - C8 monocarboxylic acids amides, vinyl alkyl ethers with C 1 -C 8 alkyl groups, styrene, C 4 -C 22 monoolefins other than alpha-monoolefins, selected from one or more C 1 -C 12 alkyl groups, Substituents of C 1 -C 12 alkoxy and halogen substituted styrenes, vinyl esters of C 1 -C 20 carboxylic acids, vinyl pyrrolidones, (meth)acrylonitrile, ethylenically unsaturated monomers containing hydroxyl groups , N-vinylformamide, vinylimidazole, allylbenzene, in
  • the supplemental repeat unit is derived from at least one carbon-carbon unsaturated double bond-containing monomer derived from the reaction mass of gasoline, C4 , C5 , C8 , C9 , or coal tar light ends.
  • monoethylenically unsaturated C 3 -C 8 monocarboxylic acids mention may be made of, for example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, preferably acrylic acid and methacrylic acid.
  • C 1 -C 10 -alkyl esters of monoethylenically unsaturated C 3 -C 8 monocarboxylic acids mention may be made of C 1 -C 10 -alkyl alkyl (meth)acrylates, especially methyl methacrylate ester, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate or mixtures thereof.
  • vinyl alkyl ethers having C 1 -C 8 alkyl groups preference can be given to vinyl alkyl ethers having C 1 -C 4 alkyl groups, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether and 2-ethyl Hexyl vinyl ether.
  • vinyl alkyl ethers having C 1 -C 8 alkyl groups preference can be given to vinyl alkyl ethers having C 1 -C 4 alkyl groups, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether,
  • C4 - C22 monoolefins other than alpha-monoolefins may be alkenes and cycloalkenes, for example having 4-20 or 5-20 carbon atoms, such as 4-16 or 5-16 carbon atoms, or 4-8 Or alkenes or cycloalkenes of 5-8 carbon atoms, such as 2-butene, 2-pentene, 2-methyl-2-butene, cyclopentene, cyclohexene, cycloheptene, etc.; with 5 -20 carbon atoms, preferably 5-16 or 8-12 carbon atoms, dihydrobicycloalkenes, especially dihydrobicyclopentadiene (eg 2,3-dihydrobicyclopentadiene), dihydromethylbicyclo Pentadiene and dihydrodimethyldicyclopentadiene, etc.
  • dihydrobicycloalkenes especially dihydrobicyclopentadiene (eg 2,3-dihydrobicyclopen
  • the alkyl or alkoxy group preferably has 1 to 10 carbon atoms , such as 1-4 carbon atoms; wherein the halogen is preferably chlorine and bromine.
  • vinyltoluene such as ⁇ -methylstyrene and p-methylstyrene
  • ⁇ -butylstyrene 4-n-butylstyrene
  • 4-n-decylstyrene 4-n-methoxy styrene
  • chlorostyrene and bromostyrene chlorostyrene and bromostyrene.
  • vinyl esters of C 1 -C 20 carboxylic acids may be mentioned vinyl laurate, vinyl stearate, vinyl propionate, vinyl neodecanoate and vinyl acetate.
  • Ethylenically unsaturated monomers containing hydroxyl groups include, for example, C 1 -C 10 hydroxyalkyl (meth)acrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxy acrylate Propyl, 2-hydroxypropyl methacrylate and 3-hydroxypropyl methacrylate.
  • C 1 -C 10 hydroxyalkyl (meth)acrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxy acrylate Propyl, 2-hydroxypropyl methacrylate and 3-hydroxypropyl methacrylate.
  • furan ring-containing compounds may mention monomers in which the furan ring is substituted with one or more (eg 2-4) substituents selected from C 1 -C 12 alkyl and C 1 -C 12 hydroxyalkyl groups, Like furfuryl alcohol, the furan ring can be further fused with a benzene ring, such as methylbenzofuran.
  • the reaction material containing the at least one carbon-carbon unsaturated double bond-containing monomer and saturated hydrocarbons, other impurities not participating in the polymerization can be used directly without separation, such as gasoline, C 4 -cut, C5 -cut, C8 -cut, C9 -cut, coal tar light-end to get supplementary repeat units.
  • these reaction masses to form Copolymer B eg, via free radical polymerization
  • components other than the carbon-carbon unsaturated double bond-containing monomers in these reaction masses can be used as solvents in the preparation process.
  • these fractions are used as reaction materials, the cost of the adhesives and wood-based panels of the present invention can be further reduced.
  • the C 4 fraction can be mentioned as a by-product of petroleum cracking or catalytic cracking to ethylene, which usually contains components such as isobutene, 1-butene-1, 2-butene and butane.
  • the C4 cut can have the following specific composition:
  • the C5 cut is generally the C5 cut from petroleum cracking.
  • the C5 cut contains about 45-55% diolefins and 8-15% monoolefins.
  • Other components in the C5 fraction include 18-25% alkanes, around 1% alkynes, 10-20% C4 , benzene and other components.
  • the C5 cut can have the following specific composition:
  • C 8 and C 9 fractions mainly come from steam cracking to ethylene process and naphtha platinum reforming process, and a part comes from toluene disproportionation or transalkylation products and coal tar.
  • the C8 cut typically contains 22-35% of monoolefins such as styrene, allylbenzene, vinyltoluene, indene, formazan. Other components in the C8 cut include 45-55% aromatics and about 20 % other unknown components.
  • the C8 cut can have the following specific composition:
  • the C9 cut usually contains 20-30% of monoolefins (eg styrene, allylbenzene, vinyltoluene, indene), 8-15% of dienes. Other components in the C9 cut include about 5% alkanes, 40-50% aromatics, and about 10% other unknown components.
  • the C9 cut can have the following specific composition:
  • the light oil components in coal tar mainly contain styrene, ⁇ -methylstyrene, alkylbenzene, vinyltoluene, dicyclopentadiene, benzofuran, indene, methylindene and methylbenzofuran.
  • Coal tar light ends may have the following specific composition:
  • the polymerization to prepare Copolymer B can be carried out using oil-soluble free radical initiators.
  • the oil-soluble free radical initiators include, for example, azo initiators or peroxide initiators.
  • the azo initiators include: azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, etc.;
  • the peroxide initiators include: dibenzoyl peroxide , Dicumyl peroxide, bis(2,4-dichlorobenzoyl peroxide), di-tert-butyl peroxide, dodecanoyl peroxide, tert-butyl peroxybenzoate, diisoperoxydicarbonate propyl ester and dicyclohexyl peroxydicarbonate, etc.
  • the initiator is used in an amount of 0.05-10% by weight, preferably 0.5-6% by weight, based on the weight of the monomers.
  • the polymerization reaction can be carried out in the presence of a solvent.
  • the solvent may include aromatic hydrocarbons, mixtures of alkanes and ketones, carboxylic acid esters, mixtures of alkanes and aromatic hydrocarbons, mixtures of aromatic hydrocarbons and carboxylic acid esters, or mixtures of alkanes and carboxylic acid esters, or mixtures of alkanes, aromatic hydrocarbons and carboxylic acid esters.
  • aromatic hydrocarbons examples include toluene, xylene, ethylbenzene and the like.
  • Carboxylic acid esters may include C1 - C8 alkyl, phenyl or benzyl esters of C1- C6 carboxylic acids and C1 - C8 alkyl of aromatic carboxylic acids having 6-10 carbon atoms ester, specific examples can be mentioned ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, Phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, is
  • the ketone in the mixture of alkane and ketone can be selected from acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, and the alkane can be selected from n-pentane, n-hexane, cyclohexanone alkane, n-heptane, n-octane and isooctane, etc.
  • the ketones typically comprise 5-65% by volume.
  • the polymerization reaction can be carried out in the presence of an inert gas such as nitrogen.
  • the temperature of the polymerization reaction is usually 55-120°C, preferably 60-100°C; the time of the polymerization reaction is usually 1-12 hours, preferably 2-8 hours. After the polymerization reaction, the resulting copolymer B can be isolated and dried.
  • the polymerization reaction is carried out by precipitation polymerization.
  • the precipitation polymerization can be carried out by selecting a solvent capable of dissolving the monomers but not dissolving the resulting copolymer B.
  • the copolymer B can be obtained directly in powder form.
  • the unreacted alkane or aromatic mixture after the reaction is completed can be separated by simple distillation , and then obtain various high value-added solvents and industrial raw materials.
  • the copolymer B can be reacted with ammonia to give the copolymer A (described in further detail below).
  • One aspect of the present invention pertains to adhesives comprising Copolymer A of the present invention.
  • the adhesive of the present invention may contain at least one additive, if necessary.
  • the additives may be one or more of the following: oxygen scavengers, emulsifiers, dyes, pigments, anti-migration aids, UV absorbers, biocides, defoamers, colorants, antistatic agents and antioxidants .
  • the adhesive of the present invention is free of organic crosslinking agents capable of covalent crosslinking reactions with the amide groups and/or carboxyl groups of the copolymer A, such as polyols, polyamines, polyalkanolamines or their mixtures.
  • the binder may be in the form of a solid, preferably in powder form; or in the form of an aqueous composition, preferably in the form of an aqueous solution.
  • the amount of Copolymer A may be 30-100% by weight, based on the total amount of the adhesive (if the adhesive is in a liquid state, such as an aqueous composition or aqueous solution, based on the solids content), such as 50-100 wt%, 60-100 wt%, 70-100 wt%, 80-100 wt%, or 50-98 wt%, or 60-90 wt%.
  • the binder is in the form of an aqueous composition, preferably an aqueous solution, the binder may have a solids content of 2-40% by weight, or 5-30% by weight, or 8-25% by weight.
  • One aspect of the present invention pertains to a method of preparing the adhesive of the present invention comprising reacting Copolymer B with ammonia in the presence or absence of a reaction medium such as water.
  • Copolymer B can form copolymer A by reaction with ammonia, ie, aminolysis.
  • the reaction generally involves reacting the copolymer B with ammonia with stirring at a temperature below 100°C, preferably 15-70°C, eg at room temperature, in an aqueous medium.
  • the reaction time is usually 0.1 to 10 hours, preferably 0.5 to 6 hours.
  • the resulting reaction mixture is generally an aqueous composition, preferably in the form of an aqueous solution.
  • the resulting aqueous composition preferably an aqueous solution, can be used directly as a binder.
  • the reaction mixture can also be used as a binder after being mixed with at least one of the additives described above.
  • the copolymer B is in powder form before being reacted with ammonia.
  • the copolymer B in powder form can be prepared by precipitation polymerization.
  • Copolymer B in powder form can also be obtained by grinding Copolymer B (eg in the form of a block) into powder form.
  • the average particle size of the copolymer B in powder form may be 0.01-10 ⁇ m, preferably 0.05-8 ⁇ m, more preferably 0.1-5 ⁇ m.
  • the average particle size of the copolymer A in powder form may be 0.01-10 ⁇ m, preferably 0.05-8 ⁇ m, more preferably 0.1-5 ⁇ m.
  • the reaction time of the copolymer B in solid form with ammonia is generally from 2 to 300 minutes, such as from 5 to 120 minutes.
  • the copolymer A in solid form can be dissolved in water, optionally mixed with at least one of the above-mentioned additives, and then applied.
  • the conversion of the anhydride groups of the copolymer B is generally over 90%, preferably over 95%, more preferably over 98%, such as 100%.
  • the carboxyl group can also form an ammonium salt with ammonia.
  • One aspect of the present invention pertains to articles comprising components formed from the adhesives of the present invention.
  • the article may be a wood-based panel, paper, cloth or paint.
  • the amount of binder in solids content may be 1-45% by weight, preferably 2-40% by weight, more preferably 3-35% by weight or 4-30% by weight, based on the total weight of the article , such as 5-25% by weight, 6-25% by weight, 7-25% by weight, 8-19% by weight.
  • the amount of copolymer A may be 1-40% by weight, preferably 2-30% by weight, more preferably 3-25% by weight or 4-20% by weight, such as 5-20% by weight, based on the total weight of the article %, 6-20 wt% or 7-18 wt%.
  • the article is a wood-based panel formed from lignocellulosic material and the binder of the present invention.
  • the wood-based panel of the present invention is to be understood in a broad sense, ie a board formed from any lignocellulosic material and the binder of the present invention.
  • the wood-based panels of the present invention are not limited to those formed of only wood, but may also include boards formed of materials such as bamboo and straw as described below.
  • the wood-based panel of the present invention may be various types of wood-based panels.
  • the wood-based panels include, but are not limited to, particleboard, plywood, fiberboard, MDF, straw board, and finger-jointed board.
  • Lignocellulosic materials can be obtained from a variety of lignocellulosic materials, such as wood, bamboo, bagasse, straw (eg, wheat straw), flax residue, nut shells, grain husks, etc., and mixtures thereof.
  • the wood includes various softwoods and/or hardwoods.
  • the lignocellulosic material can be in the form of sawdust, chips, wood chips, strands, flakes, fibers, sheets, wood chips, shavings, granules and the like, as well as in the form of combinations of these materials such as a combination of strands and sawdust.
  • Lignocellulosic material can be processed by various conventional techniques. Large lumber can be processed into wood chips in a log chipper. Large pieces of wood and leftovers can also be cut into pieces. Large lumber can also be flaked in a ring flaker. Large lumbers are usually peeled before flakes.
  • the size of the lignocellulosic material is generally not critical. Different sizes can be used for different types of wood-based panels.
  • the size of the lignocellulosic material may be 1-30 mesh, preferably 2-15 mesh.
  • the thickness of the sheet may be, for example, 0.5 mm to 5 cm, preferably 1 mm to 3 cm.
  • the binder is used as a matrix resin, and it is preferable that the binder fills the gaps between the lignocellulosic materials.
  • Another aspect of the present invention pertains to a method of making an article of the present invention, the method comprising using the adhesive of the present invention.
  • wood-based panels can be produced by a method comprising compressing a mixture of lignocellulosic material and the binder of the present invention at a temperature of 105-300° C. and a pressure of 0.4-10 MPa, preferably Compression is carried out for 2-60 minutes, more preferably for 3-30 minutes, eg 5-30 minutes.
  • a mixture of the lignocellulosic material for compression and the binder of the present invention can be prepared by mixing the lignocellulosic material with the binder of the present invention.
  • the binder When the binder is solid, the binder can be first dissolved in water and then mixed with the lignocellulosic material.
  • the moisture from the mixture of lignocellulosic material and binder Before pressing, it is preferred to remove a portion of the moisture from the mixture of lignocellulosic material and binder, for example to reduce the moisture content of the mixture of lignocellulosic material and binder to below 30% by weight, preferably below 25% by weight, for example less than 22% by weight, or less than 18% by weight.
  • the moisture content of the mixture is generally above 5% by weight or above 8% by weight.
  • the removal of the water content can be carried out by heating, for example, the heating temperature can be 50-90°C, preferably 60-80°C.
  • the pressing is carried out at a temperature of 120-220°C and/or at a pressure of 1-6 MPa.
  • the copolymer A has a carboxyl group in the form of its ammonium salt
  • the ammonium salt of the carboxyl group is decomposed into a carboxyl group again under the pressing conditions.
  • the present invention also relates to the use of the adhesives of the invention for the production of wood-based panels, paper, cloth or coatings.
  • the adhesive comprising the copolymer A of the present invention is safe, environmentally friendly, has no release of toxic and harmful substances such as formaldehyde, is simple to apply and has low cost, and at the same time, the adhesive of the present invention has excellent performance, and is especially suitable for wood-based panels, paper, cloth or coatings , especially the manufacture of lignocellulose-based wood-based panels, and the articles made with the adhesive of the present invention have excellent mechanical properties and water resistance.
  • the above-mentioned premix was placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature was 170° C., the pressure was 0.4 MPa, and the hot pressing time was 15 minutes to obtain a particleboard with a thickness of 3 mm.
  • n-butene-maleic anhydride copolymer stir 10 parts of the n-butene-maleic anhydride copolymer, 5 parts of 37% ammonia water, and 85 parts of water at room temperature for 4 hours to obtain a n-butene-maleamic acid copolymer (in the copolymer) with a mass concentration of 10%.
  • the mole percent of aminolyzed maleic anhydride monomer units is 99%) suspension.
  • the suspension is mixed with poplar shavings (water content 5%, 5-10 mesh) uniformly, and the amount of the copolymer in every 100 parts of shavings is 8 parts, and mixed uniformly to obtain a premix.
  • the premix was dried at 70°C to remove water to 10% water content.
  • the above premix is placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature is 160° C., the pressure is 0.8 MPa, and the hot pressing time is 12 minutes to obtain a particleboard with a thickness of 3 mm.
  • the above-mentioned premix was placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature was 170° C., the pressure was 0.4 MPa, and the hot pressing time was 15 minutes to obtain a particleboard with a thickness of 3 mm.
  • Curve 3 1778 cm -1 and 1715 cm -1 are characteristic peaks of cyclic imide.
  • the above-mentioned premix was placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature was 180° C., the pressure was 1 MPa, and the hot pressing time was 15 minutes to obtain a particleboard with a thickness of 3 mm.
  • the above-mentioned premix is placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature is 160° C., the pressure is 1 MPa, and the hot pressing time is 15 minutes to obtain a particleboard with a thickness of 3 mm.
  • the above premix is placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature is 170° C., the pressure is 0.5 MPa, and the hot pressing time is 15 minutes to obtain a particleboard with a thickness of 3 mm.
  • the above-mentioned premix is placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature is 160° C., the pressure is 1 MPa, and the hot pressing time is 15 minutes to obtain a particleboard with a thickness of 3 mm.
  • Example 8 (Mixed alpha-olefin copolymer system)
  • the above-mentioned premix was placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature was 180° C., the pressure was 1 MPa, and the hot pressing time was 15 minutes to obtain a particleboard with a thickness of 3 mm.
  • the above premix was placed in a 25cm ⁇ 25cm ⁇ 2.5cm die, the hot pressing temperature was 170° C., the pressure was 0.4 MPa, and the hot pressing time was 12 minutes to obtain a particleboard with a thickness of 3 mm.
  • the amide group and the carboxyl group on the polymer in the adhesive of the present invention can be dehydrated to form an imide group under pressing conditions, and the carboxyl group can also be dehydrated to form an acid anhydride group, resulting in Anhydride groups can react with hydroxyl groups on lignocellulosic materials to form esters, which help improve the mechanical properties and water resistance of the resulting wood-based panels.

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Abstract

本公开涉及一种共聚物A，其具有(i)至少一种带有酰胺基团与羧基和/或其铵盐的重复单元，(ii)至少一种得自直链或支化的C 2-C 18α-单烯烃的重复单元，和(iii)至少一种得自具有至少两个碳-碳不饱和双键的单体的重复单元。本公开还涉及包含由本发明粘合剂形成的组分的制品。

Description

交联的具有酰胺基团与羧基和/或其铵盐的重复单元和α-单烯烃的重复单元的共聚物 技术领域
本公开涉及一种共聚物A，其具有(i)至少一种带有酰胺基团与羧基和/或其铵盐的重复单元，(ii)至少一种得自直链或支化的C 2-C 18α-单烯烃的重复单元，和(iii)至少一种得自具有至少两个碳-碳不饱和双键的单体的重复单元。本公开还涉及包含共聚物A的粘合剂以及包含由本发明的粘合剂形成的组分的制品。
背景技术
在目前的粘合剂，特别是用于人造板生产的粘合剂中，以甲醛为原料制备的“三醛胶”(脲醛树脂、酚醛树脂和三聚氰胺甲醛树脂)占有较大的比重，超过80％。“三醛胶”制备简单，价格低廉，但这类板材在使用过程中会长期释放游离甲醛，污染室内环境，严重威胁居民的身体健康。
一些文献中对减少“三醛胶”型人造板的甲醛释放量提出过解决方案，例如CN 107033309 A试图通过调控原料的配比和各个聚合阶段的pH值，加入甲醛捕捉剂等方法来减少甲醛释放。CN 203344147 U公开了，在板材的生产中，混入活性炭，竹炭，硅藻土等，赋予板材一定的气体吸附能力。但是，上述的方法并没有从根本上解决问题，板材在使用过程中仍有甲醛释放。
以大豆蛋白、单宁、淀粉、明胶等生物质原料为基础制备的粘合剂不涉及甲醛的使用，但是生物质原料降解速度快，又带来了板材易老化的问题。虽然通过添加抗老化剂能在一定程度上延缓降解，但是生物质材类粘合剂仍然有成本较高和资源方面的问题。这也限制了其实际使用。
另外，也可以利用如聚氯乙烯，高分子量聚乙烯，氯丁橡胶等聚合物进行板材的生产，但是这些聚合物都不具有水溶性，不能形成水性粘合剂， 只能通过热熔或者有机溶剂将聚合物与木材原料混合，仍然存在成本高、消耗能源和不环保的缺点。
因此，从安全环保、低生产成本、施加工艺简便性以及成品耐久性等方面考虑，开发出一种新型无甲醛可用于粘合剂的共聚物显得尤为重要。
发明内容
鉴于现有技术的上述状况，本发明的发明人对粘合剂领域的共聚物进行了广泛而深入的研究，以期发现一种无甲醛释放、低成本、施加简便且性能优异的可用于粘合剂的共聚物。本发明人发现了一种特定的共聚物A和包含该特定共聚物A的粘合剂，所述粘合剂不仅无甲醛释放、成本低、施加简便且具有优异的性能。
本发明正是基于以上发现得以完成。
本发明的目的是提供一种共聚物A。
本发明的另一目的是提供一种包含共聚物A的粘合剂，所述粘合剂具有安全环保、低成本、施加简便和性能优异的优点。
本发明的另一目的是提供一种包含由本发明的粘合剂形成的组分的制品。
实现本发明目的的技术方案可以概括如下：
1.一种共聚物A，其具有
(i)至少一种带有酰胺基团与羧基和/或其铵盐的重复单元，
(ii)至少一种得自直链或支化的C 2-C 18α-单烯烃的重复单元，和
(iii)至少一种得自具有至少两个碳-碳不饱和双键的单体的重复单元。
2.根据第1项的共聚物A，其中在所述共聚物A中，重复单元(i)的量为10-80重量％，优选20-80重量％或22-79重量％，基于共聚物A的重复单元的总量。
3.根据第1或2项的粘合剂，其中所述直链或支化的C 2-C 18α-单烯烃为直链或支化的C 2-C 12α-单烯烃，优选直链或支化的C 2-C 8α-单烯烃。
4.根据第1-3项中任一项的共聚物A，其中在所述共聚物A中，重复单元(ii)的量为10-75重量％，优选15-74重量％或20-70重量％，基于共聚 物A的重复单元的总量。
5.根据第1-4项中任一项的共聚物A，其中所述具有至少两个碳-碳不饱和双键的单体中的碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的碳-碳双键。
6.根据第1-5项中任一项的共聚物A，其中在所述共聚物A中，重复单元(iii)的量为0.1-70重量％，优选0.1-30重量％，基于共聚物A的重复单元的总量。
7.根据第1-6项中任一项共聚物A，其中所述共聚物A衍生自共聚物B，该共聚物B具有：
(i’)至少一种带有酸酐基团的重复单元，
(ii)至少一种得自直链或支化的C 2-C 18α-单烯烃的重复单元，和
(iii)至少一种得自具有至少两个碳-碳不饱和双键的单体的重复单元。
8.根据第7项的共聚物A，其中所述共聚物B的带有酸酐基团的重复单元(i’)得自至少一种具有碳-碳不饱和双键和酸酐基团的单体。
9.根据第8项的共聚物A，其中所述具有碳-碳不饱和双键和酸酐基团的单体选自具有4-8个碳原子的单烯属不饱和二羧酸酐，优选马来酸酐、衣康酸酐、柠康酸酐和亚甲基丙二酸酐，更优选马来酸酐。
10.根据第1-9项中任一项的共聚物A，其中所述共聚物A得自共聚物B与氨的反应。
11.一种包含第1-10项中任一项的共聚物A的粘合剂。
12.根据第11项的粘合剂，其中所述粘合剂呈固体，优选粉末形式；或者呈含水组合物，优选呈水溶液形式，优选所述共聚物A的含量为2-40重量％，尤其是5-30重量％，基于含水组合物的总重量。
13.根据第11或12项的粘合剂，其中所述粘合剂不含能够与共聚物A的酰胺基团和/或羧基发生共价交联反应的有机交联剂。
14.一种包含由第11-13项中任一项的粘合剂形成的组分的制品。
15.根据第14项的制品，其中所述制品为人造板、纸张、布或涂料。
16.根据第15项的制品，其中所述制品为由木素纤维素材料和所述粘合剂形成的人造板。
17.根据第16项的制品，其中所述粘合剂用作基体树脂，优选所述粘合剂填充木素纤维素材料之间的缝隙。
18.根据第14-17项中任一项的制品，其中以固含量计的粘合剂用量基于制品的总重量为1-45重量％，优选2-35重量％，更优选3-30重量％。
19.根据第14-18项中任一项的制品，其中如第1-10项中任一项所定义的共聚物A的用量基于制品的总重量为1-40重量％，优选2-30重量％，更优选3-25重量％。
20.如第11-13项中任一项的粘合剂在制备人造板、纸张、布或涂料中的用途。
附图说明
图1.实施例3中不同聚合物的红外谱图，由下往上分别为1：交联的异丁烯-马来酸酐共聚物的红外谱图；2：转化为酰胺酸的共聚物的红外谱图；3：热压后的共聚物的红外谱图。
具体实施方式
本文对相关特征公开具体值(包括所公开范围的端点值)可以相互结合成新的范围。
共聚物A
本发明的一个方面涉及一种共聚物A，其具有
(i)至少一种带有酰胺基团与羧基和/或其铵盐的重复单元，
(ii)至少一种得自直链或支化的C 2-C 18α-单烯烃的重复单元，和
(iii)至少一种得自具有至少两个碳-碳不饱和双键的单体的重复单元。
根据本发明，共聚物A中的重复单元(i)不同于重复单元(ii)和重复单元(iii)。
根据本发明，共聚物A的重复单元(i)中的的羧基的一部分(例如1-10重量％)可以呈其铵盐的形式。
本领域技术人员可以理解，表述“得自”还包括共聚物具有某种重复 单元，但是该重复单元并非直接由该重复单元对应的单体形成的情形。例如羧基亚乙基重复单元
Figure PCTCN2021070698-appb-000001
可以得自丙烯酸的聚合，也可通过将丙烯酸酯聚合，然后水解而得到。
在本发明的一个实施方案中，重复单元(i)的量可以为10-80重量％，例如20-80重量％、22-79重量％、22-78重量％、25-75重量％、30-70重量％或35-65重量％，基于共聚物A的重复单元的总量。
根据本发明，所述至少一种重复单元(ii)得自直链或支化的C 2-C 18α-单烯烃。所述直链或支化的C 2-C 18α-单烯烃可以为直链或支化的C 2-C 16α-单烯烃或C 4-C 16α-单烯烃，直链或支化的C 2-C 14α-单烯烃或C 4-C 14α-单烯烃，直链或支化的C 2-C 12α-单烯烃或C 4-C 12α-单烯烃，直链或支化的C 2-C 10α-单烯烃或C 4-C 10α-单烯烃，优选直链或支化的C 2-C 8α-单烯烃或C 4-C 8α-单烯烃。
这些直链或支化的C 2-C 18α-单烯烃的具体实例可以提及乙烯、丙烯、1-丁烯、异丁烯、1-戊烯、1-己烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯和1-十八碳烯。
在所述共聚物A中，重复单元(ii)的量可以为10-75重量％、15-74重量％、17-73重量％、20-70重量％、25-65重量％或30-60重量％，基于共聚物A的重复单元的总量。
根据本发明，所述至少一种重复单元(iii)得自具有至少两个碳-碳不饱和双键的单体。根据本发明的一个实施方案，所述具有至少两个(如2-4个)碳-碳不饱和双键的单体中的碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的碳-碳双键。
所述重复单元(iii)的量可以为0.1-70重量％，例如0.1-30重量％、0.2-20重量％、0.2-10重量％或0.5-5重量％，基于共聚物A的重复单元的总量。
由于共聚物A具有至少一种得自具有至少两个碳-碳不饱和双键的单体的重复单元(iii)，共聚物A一般是交联的。
根据本发明，共聚物A可任选含有补充重复单元。所述补充重复单元例如可以选自得自如下单体的重复单元:
单烯属不饱和C 3-C 8单羧酸、单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯、单烯属不饱和C 3-C 8单羧酸的酰胺、具有C 1-C 8烷基的乙烯基烷基醚、苯乙烯、非α-单烯烃的C 4-C 22单烯烃、被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯、C 1-C 20羧酸的乙烯基酯、乙烯基吡咯烷酮、(甲基)丙烯腈、包含羟基的烯属不饱和单体、N-乙烯基甲酰胺、乙烯基咪唑、烯丙苯、茚、甲茚和含呋喃环的化合物，
或者
所述补充重复单元得自源自汽油、C 4馏分、C 5馏分、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。
关于这些重复单元(i)的单体、以及重复单元(ii)的单体、重复单元(iii)的单体以及补充重复单元的单体以及反应物料的细节在下文中如对共聚物B详细描述。
根据本发明的一个优选实施方案，所述共聚物A衍生自共聚物B，该共聚物B具有：
(i’)至少一种带有酸酐基团的重复单元，
(ii)至少一种得自直链或支化的C 2-C 18α-烯烃的重复单元，和
(iii)至少一种得自具有至少两个碳-碳不饱和双键的单体的重复单元。
在一个优选实施方案中，所述共聚物A得自所述共聚物B与氨的反应。
根据本发明的一个优选实施方案，其中所述共聚物B的带有酸酐基团的重复单元(i’)得自至少一种具有碳-碳不饱和双键和酸酐基团的单体。根据本发明，所述具有碳-碳不饱和双键和酸酐基团的单体可以选自具有4-8个碳原子的单烯属不饱和二羧酸酐，优选马来酸酐、衣康酸酐、柠康酸酐、亚甲基丙二酸酐及其混合物，更优选马来酸酐。
在共聚物B中，重复单元(i’)的量可以为10-80重量％，例如20-80重量％、22-79重量％、22-78重量％、25-75重量％、30-70重量％或35-65重量％，基于共聚物B的重复单元的总量。
共聚物B中的重复单元(ii)如上对共聚物(A)所述。在所述共聚物B中，重复单元(ii)的量可以为10-75重量％、15-74重量％、17-73重量％、20-70重量％、25-65重量％或30-60重量％，基于共聚物B的重复单元的总量。
根据本发明，所述至少一种重复单元(iii)得自具有至少两个碳-碳不饱和双键的单体。根据本发明的一个实施方案，所述具有至少两个(如2-4个)碳-碳不饱和双键的单体中的碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的碳-碳双键。
所述具有至少两个碳-碳不饱和双键的单体例如可以选自具有至少2个羟基的醇的(甲基)丙烯酸酯、具有至少2个羟基的醇的乙烯基醚、具有至少2个羟基的醇的烯丙基醚、氧化乙烯和/氧化丙烯低聚物的二(甲基)丙烯酸酯、(甲基)丙烯酸酯乙烯酯、(甲基)丙烯酸酯烯丙酯、亚甲基二(甲基)丙烯酰胺、具有至少两个乙烯基的芳族化合物和C 4-C 22二烯。
所述具有至少两个羟基的醇例如可以具有2-6个，优选2-4个羟基。这些醇可以选自具有2-6个碳原子的二元醇如乙二醇、丙二醇、丁二醇、戊二醇和己二醇，甘油、三羟甲基丙烷和季戊四醇等。
因此，具有至少2个羟基的醇的(甲基)丙烯酸酯，可以为含有2-6个碳原子的二元醇的二(甲基)丙烯酸酯，其可选自乙二醇二丙烯酸酯，乙二醇二甲基丙烯酸酯，1,2-丙二醇二丙烯酸酯，1,2-丙二醇二甲基丙烯酸酯，丁二醇二(甲基)丙烯酸酯，如丁烷-1,4-二醇二丙烯酸酯，丁烷-1,4-二醇二甲基丙烯酸酯，己二醇二丙烯酸酯，己二醇二甲基丙烯酸酯，新戊二醇二丙烯酸酯，新戊二醇二甲基丙烯酸酯，3-甲基戊二醇二丙烯酸酯和3-甲基戊二醇二甲基丙烯酸酯。
氧化乙烯和/或氧化丙烯低聚物的二(甲基)丙烯酸酯的实例为二甘醇二丙烯酸酯、二甘醇二甲基丙烯酸酯、三甘醇二丙烯酸酯、三甘醇二甲基丙烯酸酯、四甘醇二丙烯酸酯和四甘醇二甲基丙烯酸酯。
具有至少两个乙烯基的芳族化合物的实例可以提及二乙烯基苯、二乙烯基甲苯、三乙烯基苯和二乙烯基萘等。
C 4-C 22二烯可以是链二烯或环二烯。所述C 4-C 22二烯可以是共轭或非共轭的。所述C 4-C 22二烯例如为共轭或非共轭的C 4-C 16或C 5-C 16链二烯或环二烯，共轭或非共轭的C 4-C 12或C 5-C 12链二烯或环二烯，共轭或非共轭的C 4-C 8或C 5-C 8链二烯或环二烯；以及具有8-20个碳原子，优选8-16或8-12个碳原子的双环烯，如双环戊二烯系单体，如双环戊二烯、甲基双环 戊二烯(如2-甲基双环戊二烯、5-甲基双环戊二烯)、乙基双环戊二烯(如2-乙基双环戊二烯)和5,5-二甲基双环戊二烯等。
C 4-C 22链二烯或环二烯的具体实例可以提及1,3-丁二烯、1,3-戊二烯、异戊二烯、1,3-己二烯、环戊二烯、甲基环戊二烯、1,3-环己二烯、1,4-戊二烯、1,4-己二烯、1,5-己二烯、1,4-环己二烯、1,5-环辛二烯等。
具有至少两个(如2-4个)碳-碳不饱和双键的单体其他具体实例可以提及三羟甲基丙烷三(甲基)丙烯酸酯、丁二醇二乙烯基醚、三羟甲基丙烷三乙烯基醚、季戊四醇三烯丙基醚、亚甲基二(甲基)丙烯酰胺、邻苯二甲酸二烯丙基酯等。
所述重复单元(iii)的量可以为0.1-70重量％，例如0.1-30重量％、0.2-20重量％、0.2-10重量％或0.5-5重量％，基于共聚物B的重复单元的总量。
根据本发明，共聚物B可任选含有补充重复单元。所述补充重复单元例如可以选自得自如下单体的重复单元:
单烯属不饱和C 3-C 8单羧酸、单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯、单烯属不饱和C 3-C 8单羧酸的酰胺、具有C 1-C 8烷基的乙烯基烷基醚、苯乙烯、非α-单烯烃的C 4-C 22单烯烃、被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯、C 1-C 20羧酸的乙烯基酯、乙烯基吡咯烷酮、(甲基)丙烯腈、包含羟基的烯属不饱和单体、N-乙烯基甲酰胺、乙烯基咪唑、烯丙苯、茚、甲茚和含呋喃环的化合物，
或者
所述补充重复单元得自源自汽油、C 4馏分、C 5馏分、C 8馏分、C 9馏分或煤焦油轻馏分的反应物料的至少一种含碳-碳不饱和双键的单体。
作为单烯属不饱和C 3-C 8单羧酸的实例可以提及如丙烯酸、甲基丙烯酸、巴豆酸和乙烯基乙酸，优选丙烯酸和甲基丙烯酸。
单烯属不饱和C 3-C 8单羧酸的C 1-C 10烷基酯的实例可以提及C 1-C 10烷基的(甲基)丙烯酸烷基酯，尤其是甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸正丁酯、丙烯酸乙酯和丙烯酸2-乙基己酯或其混合物。
作为单烯属不饱和C 3-C 8单羧酸的酰胺的实例尤其可以提及(甲基)丙烯酰胺。
作为具有C 1-C 8烷基的乙烯基烷基醚，优选可以提及具有C 1-C 4烷基的乙烯基烷基醚，如甲基乙烯基醚、乙基乙烯基醚、异丁基乙烯基醚、正丁基乙烯基醚、叔丁基乙烯基醚、正戊基乙烯基醚、异戊基乙烯基醚、正己基乙烯基醚、正辛基乙烯基醚和2-乙基己基乙烯基醚。
非α-单烯烃的C 4-C 22单烯烃可以是链烯和环烯，例如具有4-20或5-20个碳原子，如4-16或5-16个碳原子，或4-8或5-8个碳原子的链烯或环烯，如2-丁烯、2-戊烯、2-甲基-2-丁烯、环戊烯、环己烯、环庚烯等；具有5-20个碳原子，优选5-16或8-12个碳原子的二氢双环烯，特别是二氢双环戊二烯(如2,3-二氢双环戊二烯)、二氢甲基双环戊二烯和二氢二甲基双环戊二烯等。
对于被一个或多个选自C 1-C 12烷基、C 1-C 12烷氧基和卤素的取代基取代的苯乙烯，其中的烷基或烷氧基优选具有1-10个碳原子，如1-4个碳原子；其中的卤素优选为氯和溴。具体实例可以提及乙烯基甲苯(如α-甲基苯乙烯和对甲基苯乙烯)、α-丁基苯乙烯、4-正丁基苯乙烯、4-正癸基苯乙烯、对甲氧基苯乙烯、氯苯乙烯和溴苯乙烯。
C 1-C 20羧酸的乙烯基酯的实例可以提及月桂酸乙烯酯、硬脂酸乙烯酯、丙酸乙烯酯、新癸酸乙烯基酯和乙酸乙烯酯。
包含羟基的烯属不饱和单体例如包括(甲基)丙烯酸C 1-C 10羟烷基酯，例如丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸2-羟丙酯、丙烯酸3-羟丙酯、甲基丙烯酸2-羟丙酯和甲基丙烯酸3-羟丙酯。
含呋喃环的化合物的实例可以提及呋喃环被一个或多个(如2-4个)选自C 1-C 12烷基和C 1-C 12羟烷基的取代基取代的单体，如糠醇，所述呋喃环还可以进一步与苯环稠合，例如甲基苯并呋喃。
在本发明的一个实施方案中，可以不经过分离直接使用包含所述至少一种含碳-碳不饱和双键的单体以及饱和烃、不参与聚合的其他杂质的反应物料，例如汽油、C 4馏分、C 5馏分、C 8馏分、C 9馏分、煤焦油轻馏分，以得到补充重复单元。在使用这些反应物料形成共聚物B时(如经由自由基聚合)，这些反应物料中的含碳-碳不饱和双键的单体之外的成分可以用作制备过程中的溶剂。当使用这些馏分作为反应物料时，可以进一步降低 本发明粘合剂和人造板的成本。
作为C 4馏分可以提及作为石油裂解或催化裂化制乙烯产生的副产物，其通常含异丁烯、1-丁烯-1、2-丁烯和丁烷等组分。
C 4馏分可以具有如下具体组成：
表1
组分 含量
异丁烷 46.5％
正丁烷 7.1％
1-丁烯 11％
2-丁烯 18.8％
异丁烯 16.6％
异戊烷 1％
C 5馏分通常为来自石油裂解的C 5馏分。C 5馏分中含有约45-55％的二烯烃和8-15％的单烯烃。C 5馏分中的其他组分包括18-25％的烷烃、1％左右的炔烃、10-20％的C 4、苯和其他组分。
C 5馏分可以具有如下具体组成：
表2
Figure PCTCN2021070698-appb-000002
C 8和C 9馏分主要来源于蒸汽裂解制乙烯工艺和石脑油铂重整工艺，还有一部分来源于甲苯歧化或烷基转移产物及煤焦油等。
C 8馏分中通常包含22-35％的单烯烃，例如苯乙烯、烯丙苯、乙烯基甲 苯、茚、甲茚。C 8馏分中的其他组分包括45-55％的芳烃以及约20％的其他未知组分。
C 8馏分可以具有如下具体组成：
表3
Figure PCTCN2021070698-appb-000003
C 9馏分中通常含有20-30％的单烯烃(如苯乙烯、烯丙苯、乙烯基甲苯、茚)、8-15％的二烯。C 9馏分中的其他组分包括约5％的烷烃、40-50％的芳烃以及10％左右的其他未知组分。C 9馏分可以具有如下具体组成：
表4
Figure PCTCN2021070698-appb-000004
煤焦油中的轻油组分主要含苯乙烯、α-甲基苯乙烯、烷基苯、乙烯基甲苯、双环戊二烯、苯并呋喃、茚、甲茚和甲基苯并呋喃等，目前主要作为深色-浅色的古马隆树脂原料。煤焦油轻馏分可以具有如下具体组成：
表5
组分 含量
苯乙烯 2％
α-甲基苯乙烯 1％
烷基苯 30％
乙烯基甲苯 4％
双环戊二烯 5％
苯并呋喃 7％
茚 48％
甲茚和甲基苯并呋喃 3％
制备共聚物B的聚合可以使用油溶性自由基引发剂进行。所述油溶性自由基引发剂例如包括偶氮类引发剂或者过氧化物引发剂。所述的偶氮类引发剂包括：偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁酸二甲酯等；所述过氧化物引发剂包括：过氧化二苯甲酰、过氧化二异丙苯、过氧化二(2,4-二氯苯甲酰)、过氧化二叔丁基、过氧化十二酰、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙基酯和过氧化二碳酸二环己酯等。所述引发剂的用量基于单体重量为0.05-10重量％，优选0.5-6重量％。
聚合反应可以在溶剂存在下进行。溶剂可以包括芳烃，烷烃与酮的混合物，羧酸酯，烷烃和芳烃等混合物，芳烃和羧酸酯的混合物，或者烷烃与羧酸酯的混合物，或者烷烃、芳烃和羧酸酯的混合物。
芳烃的实例可以提及甲苯、二甲苯和乙苯等。
羧酸酯可以包括C 1-C 6羧酸的C 1-C 8烷基酯、苯基酯或苄基酯以及具有6-10个碳原子的芳族羧酸的C 1-C 8烷基酯，具体实例可以提及甲酸乙酯、甲酸丙酯、甲酸异丁酯、甲酸戊酯、乙酸乙酯、乙酸丁酯、乙酸异丁酯、乙酸戊酯、乙酸异戊酯、乙酸苄酯、乙酸苯酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸丁酯、丁酸异丁酯、丁酸异戊酯、异丁酸乙酯、异戊酸乙酯、异戊酸异戊酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯、苯甲酸异戊酯、苯乙酸甲酯、苯乙酸乙酯、苯乙酸丙酯、苯乙酸丁酯、苯乙酸异戊酯等酯类溶剂。
烷烃与酮的混合物中的酮可以选自丙酮、丁酮、环己酮、甲基异丁基酮、甲基异丙基酮，所述的烷烃可以选自正戊烷、正己烷、环己烷、正庚烷、正辛烷和异辛烷等。在烷烃与酮的混合物中，酮通常占5-65体积％。
聚合反应可以在惰性气体如氮气存在下进行。聚合反应的温度通常为 55-120℃，优选60-100℃；聚合反应的时间通常为1-12小时，优选2-8小时。在聚合反应之后，可以将所得共聚物B分离和干燥。
在一个优选实施方案中，所述聚合反应通过沉淀聚合进行。所述沉淀聚合可以通过选择能够溶解单体但是不能溶解所得共聚物B的溶剂而进行。通过沉淀聚合，可以直接得到粉末形式的共聚物B。
根据本发明，如果使用汽油、C 4馏分、C 5馏分、C 8馏分、C 9馏分和煤焦油轻馏分作为反应物料的话，反应完成后未反应的烷烃或芳烃混合物只需简单蒸馏即可分离，进而得到各种高附加值的溶剂和工业原料。
根据本发明，所述共聚物B可以通过与氨反应而得到共聚物A(在下文中进一步详细描述)。
粘合剂
本发明的一个方面涉及包含本发明共聚物A的粘合剂。
在本发明的粘合剂中，除了共聚物A之外，需要的话，本发明的粘合剂还可以包含至少一种添加剂。所述添加剂可以是下面的一种或多种：除氧剂、乳化剂、染料、颜料、防迁移助剂、UV吸收剂、生物杀伤剂、消泡剂、着色剂、抗静电剂和抗氧化剂。
根据一个实施方案，本发明的粘合剂不含能够与共聚物A的酰胺基团和/或羧基发生共价交联反应的有机交联剂，如多元醇，多胺，多链烷醇胺或它们的混合物。
根据本发明，所述粘合剂可以呈固体，优选粉末形式；或者呈含水组合物，优选呈水溶液形式。
在本发明的粘合剂中，共聚物A的量基于粘合剂的总量(如果粘合剂呈液态，如含水组合物或水溶液，则基于固含量)可以为30-100重量％，如50-100重量％，60-100重量％，70-100重量％，80-100重量％，或50-98重量％，或60-90重量％。
若所述粘合剂呈含水组合物，优选水溶液的形式，粘合剂的固含量可以为2-40重量％，或5-30重量％，或8-25重量％。
制备粘合剂的方法
本发明的一个方面涉及一种制备本发明的粘合剂的方法，其包括使共聚物B在反应介质(如水)存在或不存在下与氨反应。
共聚物B可以通过与氨反应，即氨解形成共聚物A。所述反应通常包括使共聚物B在低于100℃，优选15-70℃的温度下，例如在室温下在含水介质中与氨在搅拌下反应。反应时间通常为0.1-10小时，优选0.5-6小时。
在反应之后，所得反应混合物通常为含水组合物，优选呈水溶液形式。所得含水组合物，优选水溶液可以直接用作粘合剂。也可将反应混合物与上述至少一种添加剂混合后用作粘合剂。
优选共聚物B与氨反应之前呈粉末的形式。优选所述粉末形式的共聚物B可以通过沉淀聚合制备。粉末形式的共聚物B也可通过将共聚物B(例如块状)研磨成粉末形式而得到。所述粉末形式的共聚物B的平均粒径可以为0.01-10μm，优选0.05-8μm，更优选0.1-5μm。所述粉末形式的共聚物A的平均粒径可以为0.01-10μm，优选0.05-8μm，更优选0.1-5μm。
固体形式的共聚物B与氨反应时间通常为2-300分钟，如5-120分钟。
在具体应用时，可以将固体形式的共聚物A溶于水中，任选与上述至少一种添加剂混合后再施加。
共聚物B的酸酐基团的转化率通常超过90％，优选超过95％，更优选超过98％，如100％。
在共聚物B与氨的反应中，羧基还可以与氨形成铵盐。
包含由本发明的粘合剂形成的组分的制品
本发明的一个方面涉及包含由本发明粘合剂形成的组分的制品。
根据本发明，所述制品可以为人造板、纸张、布或涂料。
在本发明的制品中，其中以固含量计的粘合剂用量基于制品的总重量可为1-45重量％，优选2-40重量％，更优选3-35重量％或4-30重量％，如5-25重量％，6-25重量％，7-25重量％，8-19重量％。
在本发明的制品中，共聚物A用量基于制品的总重量可为1-40重量％，优选2-30重量％，更优选3-25重量％或4-20重量％，如5-20重量％，6-20 重量％或7-18重量％。
在一个实施方案中，所述制品为由木素纤维素材料和本发明粘合剂形成的人造板。本发明的人造板应在宽的意义上理解，即由任何木素纤维素材料和本发明的粘合剂形成的板材。本发明的人造板并不局限于仅仅由木材形成的那些，还可以包括由竹子和秸秆等如下所述材料形成的板材。本发明的人造板可以是各种类型的人造板。在一个实施方案中，所述人造板包括但不限于刨花板、胶合板、纤维板、密度板、秸秆板和指接板。
木素纤维素材料可以得自各种木素纤维素材料，例如木材、竹子、甘蔗渣、秸秆(如麦秆)、亚麻残渣、坚果壳、谷粒壳等，以及它们的混合物。其中木材包括各种软木和/或硬木。
木素纤维素材料可以呈锯末、碎料、木片、条料、薄片、纤维、片材、木屑、刨花、颗粒和类似材料形式以及这些材料的组合的形式如条料和锯末的组合。
木素纤维素材料可以通过各种常规技术进行加工。可以将大木料在圆木刨片机中加工为木片。也可将大块木料和边角料切成碎料。还可将大木料在环形刨片机中刨片。通常在刨片之前将大木料去皮。
木素纤维素材料的尺寸通常并不关键。针对不同类型的人造板可以使用不同的尺寸。例如木素纤维素材料的尺寸可以为1-30目，优选2-15目。对于片材类的木素纤维素材料，片材的厚度可以例如为0.5mm-5cm，优选1mm-3cm。
在本发明的人造板中，所述粘合剂用作基体树脂，优选所述粘合剂填充木素纤维素材料之间的缝隙。
本发明的另一方面涉及一种制备本发明制品的方法，所述方法包括使用本发明的粘合剂。
根据本发明，人造板可以通过如下方法制备，所述方法包括将木素纤维素材料和本发明的粘合剂的混合物在105-300℃的温度下和在0.4-10MPa的压力下压制，优选压制2-60分钟，更优选压制3-30分钟，例如5-30分钟。
用于压制的木素纤维素材料和本发明的粘合剂的混合物可以通过将木 素纤维素材料与本发明的粘合剂混合而制备。当粘合剂为固体时，可以首先将粘合剂溶于水中后再与木素纤维素材料混合。
在压制之前，优选除去木素纤维素材料和粘合剂的混合物中的一部分水分，例如将木素纤维素材料和粘合剂的混合物的水份含量降至低于30重量％，优选低于25重量％，例如低于22重量％，或低于18重量％。所述混合物的水份含量通常高于5重量％或高于8重量％。所述水份的除去可以通过加热进行，例如加热温度可以为50-90℃，优选60-80℃。
在一个优选实施方案中，所述压制在120-220℃的温度下和/或在1-6MPa的压力下进行。
当共聚物A具有呈其铵盐形式的羧基时，羧基的铵盐在压制条件下又分解为羧基。
粘合剂的用途
最后，本发明还涉及本发明的粘合剂在制备人造板、纸张、布或涂料中的用途。
包含本发明共聚物A的粘合剂安全、环保，没有甲醛等有毒有害物质的释放，施加简单且成本低，同时本发明的粘合剂性能优异，特别适用于人造板、纸张、布或涂料的制造，尤其是木素纤维素基人造板的制造，并且用本发明的粘合剂制造的制品具有优异的机械性能和耐水性。
实施例
以下结合本发明中的具体实施例，对本发明中的技术方案进一步描述，但不应将其理解为对本发明保护范围的限制。以下所描述的实施例仅是本发明一部分实施例，并非全部的实施例。基于本发明中所列举的实施例，本领域其他技术人员在没有采用创造性劳动的前提下所提出的其他实施例，均属于本发明保护的范围。除非另有说明，实施例中的百分数为重量百分数，实施例中的份数为质量份。
实施例1：乙烯共聚物体系
按照质量份数，将5.8份乙烯，19.6份马来酸酐，0.3份交联剂二乙烯基苯，300份苯和0.5份偶氮二异丁腈在高压反应釜内混合溶解，升温至70℃反应6小时。将产物离心分离，用苯洗涤，干燥后获得粉末状产物为交联的乙烯-马来酸酐共聚物，其中马来酸酐单元质量分数约为78％。
将10份该乙烯-马来酸酐共聚物，5份37％氨水，85份水在室温下搅拌4小时，获得质量浓度10％的乙烯-马来酰胺酸共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)悬浮液。将该悬浮液与杨木刨花(含水量5％，5-10目)混合均匀，每100份刨花中该共聚物用量8份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量15％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度170℃，压力0.4MPa，热压时间15分钟，获得厚度为3mm刨花板。
实施例2：(正丁烯共聚物体系)
按照质量份数，将11.2份正丁烯，19.6份马来酸酐，0.4份交联剂双甲基丙烯酸乙二醇酯，300份乙酸异戊酯和0.7份偶氮二异丁腈在高压反应釜内混合溶解，升温至70℃反应6小时。将产物离心分离、洗涤、干燥后获得粉末状产物为交联的正丁烯-马来酸酐共聚物，其中马来酸酐单元质量分数约为64％。
将10份该正丁烯-马来酸酐共聚物，5份37％氨水，85份水在室温下搅拌4小时，获得质量浓度10％的正丁烯-马来酰胺酸共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)悬浮液。将该悬浮液与杨木刨花(含水量5％，5-10目)混合均匀，每100份刨花中该共聚物用量8份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量10％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度160℃，压力0.8MPa，热压时间12分钟，获得厚度为3mm刨花板。
实施例3：(异丁烯共聚物体系)
按照质量份数，将11.2份异丁烯，19.6份马来酸酐，0.4份交联剂双甲基丙烯酸乙二醇酯，300份乙酸异戊酯和0.6份偶氮二异丁腈在高压反 应釜内混合溶解，升温至70℃反应6小时。将产物离心分离、洗涤、干燥后获得粉末状产物为交联的异丁烯-马来酸酐共聚物，其中马来酸酐单元质量分数约为64％。
将10份该异丁烯-马来酸酐共聚物，5份37％氨水，85份水在室温下搅拌4小时，获得质量浓度10％的异丁烯-马来酰胺酸共聚物(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)悬浮液。将该悬浮液与杨木刨花(含水量5％，5-10目)混合均匀，每100份刨花中该共聚物用量8份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量15％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度170℃，压力0.4MPa，热压时间15分钟，获得厚度为3mm刨花板。
图1中由下往上分别为1：交联的异丁烯-马来酸酐共聚物的红外谱图，2：转化为酰胺酸的共聚物的红外谱图，3：热压后的共聚物的红外谱图，其中：
曲线1：1858cm -1，1778cm -1处为酸酐上两个羰基C＝O伸缩振动峰；
曲线2：1661cm -1处为酰胺C＝O伸缩振动峰，1557cm -1处为羧酸盐C＝O振动峰，原来的酸酐基团特征峰基本消失；
曲线3：1778cm -1，1715cm -1处为环状酰亚胺的特征峰。
实施例4：(1-戊烯共聚物体系)
按照质量份数，将14份1-戊烯，19.6份马来酸酐，0.3份交联剂二乙烯基苯，300份乙酸异戊酯和0.7份偶氮二异丁腈混合溶解，体系通氮气20分钟后在70℃反应6小时。将产物离心，洗涤，干燥获得白色粉末形式的交联的1-戊烯-马来酸酐共聚物，共聚物中马来酸酐单体单元的质量百分数为58％。
将20份该1-戊烯-马来酸酐共聚物，10份37％氨水，70份水在室温下搅拌4小时，获得质量浓度20％的1-戊烯-马来酰胺酸共聚物悬浮液(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)。将该悬浮液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量12份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量20％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度180℃，压力1MPa，热压时间15分钟，获得厚度为3mm刨花板。
实施例5：(1-癸烯共聚物体系)
按照质量份数，将28份1-癸烯，19.6份马来酸酐，0.3份交联剂二乙烯基苯，300份乙酸异戊酯和0.7份偶氮二异丁腈混合溶解，体系通氮气20分钟后在70℃反应6小时。将产物离心，洗涤，干燥获得白色粉末形式的交联1-癸烯-马来酸酐共聚物，共聚物中马来酸酐单体单元的质量百分数为41％。
将20份该1-癸烯-马来酸酐共聚物，10份37％氨水，70份水在室温下搅拌4小时，获得质量浓度20％的1-癸烯-马来酰胺酸共聚物悬浮液(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)。将该悬浮液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量12份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量10％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度160℃，压力1MPa，热压时间15分钟，获得厚度为3mm刨花板。
实施例6：(1-十四烯共聚物体系)
按照质量份数，将39.2份1-十四烯，19.6份马来酸酐，0.4份交联剂双甲基丙烯酸乙二醇酯，300份乙酸异戊酯和0.7份偶氮二异丁腈混合溶解，体系通氮气20分钟后在70℃反应6小时。将产物离心，洗涤，干燥获得白色粉末形式的交联的1-十四烯-马来酸酐共聚物，共聚物中马来酸酐单体单元的质量百分数为33％。
将20份该1-十四烯-马来酸酐共聚物，10份37％氨水，70份水在室温下搅拌4小时，获得质量浓度20％的1-十四烯-马来酰胺酸共聚物悬浮液(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)。将该悬浮液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量12份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量20％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度170℃， 压力0.5MPa，热压时间15分钟，获得厚度为3mm刨花板。
实施例7：(1-十八烯共聚物体系)
按照质量份数，将50.4份1-十八烯，19.6份马来酸酐，0.3份交联剂二乙烯基苯，300份乙酸异戊酯和0.7份偶氮二异丁腈混合溶解，体系通氮气20分钟后在70℃反应6小时。将产物离心，洗涤，干燥获得白色粉末形式的交联的1-十八烯-马来酸酐共聚物，共聚物中马来酸酐单体单元的质量百分数为28％。
将20份该1-十八烯-马来酸酐共聚物，10份37％氨水，70份水在室温下搅拌4小时，获得质量浓度20％的1-十八烯-马来酰胺酸共聚物悬浮液(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)。将该悬浮液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量12份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量15％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度160℃，压力1MPa，热压时间15分钟，获得厚度为3mm刨花板。
实施例8：(混合α-烯烃共聚物体系)
按照质量份数，将4.7份1-戊烯，9.3份1-癸烯和14.9份1-十六烯，0.3份交联剂二乙烯基苯，19.6份马来酸酐，300份乙酸异戊酯和0.7份偶氮二异丁腈混合溶解，体系通氮气20分钟后在70℃反应6小时。将产物离心，洗涤，干燥获得白色粉末形式的混合烯烃-马来酸酐共聚物，共聚物中马来酸酐单体单元的质量百分数为43％。
将20份该混合烯烃-马来酸酐共聚物，10份37％氨水，70份水在室温下搅拌4小时，获得质量浓度20％的混合烯烃-马来酰胺酸共聚物悬浮液(共聚物中已氨解的马来酸酐单体单元的摩尔百分数为99％)。将该悬浮液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量12份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量20％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度180℃，压力1MPa，热压时间15分钟，获得厚度为3mm刨花板。
对比例1
按照质量份数，将10份异丁烯，17.5份马来酸酐，100份乙酸异戊酯和0.3份BPO混合溶解，体系通氮气20分钟后在70℃反应8小时。将产物离心，用石油醚洗涤三次，干燥获得白色粉末形式的异丁烯-马来酸酐共聚物，共聚物中马来酸酐单体单元的质量百分数为63％。
将10份异丁烯-马来酸酐共聚物与10份37％氨水，80份水在室温下搅拌4小时，获得质量浓度10％的粘稠液。将该粘稠液与杨木刨花(含水量5％，5-10目)混合，每100份刨花中该共聚物用量20份，混合均匀，获得预混料。将预混料在70℃下烘除水份至含水量10％。
将上述预混料置于25cm×25cm×2.5cm的压模中，热压温度170℃，压力0.4MPa，热压时间12分钟，获得厚度为3mm刨花板。
性能测试
根据GB/T 4897-2015对实施例1-8和对比例1得到的刨花板进行内结合强度、24h吸水厚度膨胀率以及防潮性能(沸水煮后内结合强度)进行测试，结果列于下表6中。
表6：实施例1-8和对比例1中的刨花板的性能数据
Figure PCTCN2021070698-appb-000005
*表中的每个数据为6次测量的平均值。
实施例1-8中的刨花板的各项性能都优于国标中对于在潮湿状态下使 用的家具型刨花板的性能要求，同时优于对比例1的刨花板的性能。
不希望受到任何理论的束缚，据信本发明粘合剂中的聚合物上的酰胺基团与羧基在压制条件下可以脱水生成酰亚胺基团，而羧基还可以脱水生成酸酐基团，所得酸酐基团可以与木素纤维素材料上的羟基发生反应形成酯，这有助于提高所得人造板的机械性能和耐水性。
以上所述仅仅为本发明的优选实施方式，需要指出的是，对于本技术领域的技术人员来说，在本发明原理的范围内，所作出的若干改进和修饰，这些改进和修饰也应被同样视为本发明的保护范围。

Claims (20)

  1. 一种共聚物A，其具有
    (i)至少一种带有酰胺基团与羧基和/或其铵盐的重复单元，
    (ii)至少一种得自直链或支化的C 2-C 18α-单烯烃的重复单元，和
    (iii)至少一种得自具有至少两个碳-碳不饱和双键的单体的重复单元。
  2. 根据权利要求1的共聚物A，其中在所述共聚物A中，重复单元(i)的量为10-80重量％，优选20-80重量％或22-79重量％，基于共聚物A的重复单元的总量。
  3. 根据权利要求1或2的粘合剂，其中所述直链或支化的C 2-C 18α-单烯烃为直链或支化的C 2-C 12α-单烯烃，优选直链或支化的C 2-C 8α-单烯烃。
  4. 根据权利要求1-3中任一项的共聚物A，其中在所述共聚物A中，重复单元(ii)的量为10-75重量％，优选15-74重量％或20-70重量％，基于共聚物A的重复单元的总量。
  5. 根据权利要求1-4中任一项的共聚物A，其中所述具有至少两个碳-碳不饱和双键的单体中的碳-碳不饱和双键选自(甲基)丙烯酸酯基团、(甲基)丙烯酰胺基团、乙烯基、烯丙基以及链烯或环烯中的碳-碳双键。
  6. 根据权利要求1-5中任一项的共聚物A，其中在所述共聚物A中，重复单元(iii)的量为0.1-70重量％，优选0.1-30重量％，基于共聚物A的重复单元的总量。
  7. 根据权利要求1-6中任一项共聚物A，其中所述共聚物A衍生自共聚物B，该共聚物B具有：
    (i’)至少一种带有酸酐基团的重复单元，
    (ii)至少一种得自直链或支化的C 2-C 18α-单烯烃的重复单元，和
    (iii)至少一种得自具有至少两个碳-碳不饱和双键的单体的重复单元。
  8. 根据权利要求7的共聚物A，其中所述共聚物B的带有酸酐基团的重复单元(i’)得自至少一种具有碳-碳不饱和双键和酸酐基团的单体。
  9. 根据权利要求8的共聚物A，其中所述具有碳-碳不饱和双键和酸酐 基团的单体选自具有4-8个碳原子的单烯属不饱和二羧酸酐，优选马来酸酐、衣康酸酐、柠康酸酐和亚甲基丙二酸酐，更优选马来酸酐。
  10. 根据权利要求1-9中任一项的共聚物A，其中所述共聚物A得自共聚物B与氨的反应。
  11. 一种包含权利要求1-10中任一项的共聚物A的粘合剂。
  12. 根据权利要求11的粘合剂，其中所述粘合剂呈固体，优选粉末形式；或者呈含水组合物，优选呈水溶液形式，优选所述共聚物A的含量为2-40重量％，尤其是5-30重量％，基于含水组合物的总重量。
  13. 根据权利要求11或12的粘合剂，其中所述粘合剂不含能够与共聚物A的酰胺基团和/或羧基发生共价交联反应的有机交联剂。
  14. 一种包含由权利要求11-13中任一项的粘合剂形成的组分的制品。
  15. 根据权利要求14的制品，其中所述制品为人造板、纸张、布或涂料。
  16. 根据权利要求15的制品，其中所述制品为由木素纤维素材料和所述粘合剂形成的人造板。
  17. 根据权利要求16的制品，其中所述粘合剂用作基体树脂，优选所述粘合剂填充木素纤维素材料之间的缝隙。
  18. 根据权利要求14-17中任一项的制品，其中以固含量计的粘合剂用量基于制品的总重量为1-45重量％，优选2-35重量％，更优选3-30重量％。
  19. 根据权利要求14-18中任一项的制品，其中如权利要求1-10中任一项所定义的共聚物A的用量基于制品的总重量为1-40重量％，优选2-30重量％，更优选3-25重量％。
  20. 如权利要求11-13中任一项的粘合剂在制备人造板、纸张、布或涂料中的用途。
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