CN116376483A - Adhesive, and preparation method and application thereof - Google Patents

Adhesive, and preparation method and application thereof Download PDF

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Publication number
CN116376483A
CN116376483A CN202310070708.3A CN202310070708A CN116376483A CN 116376483 A CN116376483 A CN 116376483A CN 202310070708 A CN202310070708 A CN 202310070708A CN 116376483 A CN116376483 A CN 116376483A
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China
Prior art keywords
adhesive
alpha
methylstyrene
vinyl
copolymer
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CN202310070708.3A
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Chinese (zh)
Inventor
杨万泰
周玲
赵长稳
马育红
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Priority to CN202310070708.3A priority Critical patent/CN116376483A/en
Publication of CN116376483A publication Critical patent/CN116376483A/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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/32—Multi-ply with materials applied between the sheets

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses an adhesive, a preparation method and application thereof, and belongs to the technical field of adhesives, wherein the adhesive comprises a macromolecular initiator, one or more vinyl monomers and a solvent; the macroinitiator has at least one structural unit of an amide group and a carboxyl group and/or an ammonium salt thereof and an alpha-methylstyrene structural unit, and the adhesive is prepared by means of free radical polymerization. The invention also provides an article of manufacture utilizing the adhesive formed component. The polymer containing alpha-methyl styrene unit and amide group and carboxyl and/or its structural unit serves as initiator, emulsifier and stabilizer in emulsion polymerization process.

Description

Adhesive, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to an adhesive, a preparation method and application thereof.
Background
At present, adhesives and coatings produced by using formaldehyde as a main raw material are widely applied to the production of manufactured boards, paper, fabrics and other products, the preparation is simple and the cost is low, but various products produced by the adhesives or the coatings can continuously release formaldehyde in the use process, and the physical health of residents is seriously threatened. In the case of using no formaldehyde, the binder and the paint can be prepared by emulsion polymerization using monomers such as acrylic esters, styrenes, vinyl acetate, etc. However, components such as an emulsifier, a stabilizer and the like are required to be added in the emulsion polymerization process, which can pollute the surface of latex particles and affect the performance of related products. While this problem can be currently solved by using reactive emulsifiers, such as CN112063246B, allyloxy nonylphenol propanol polyoxyethylene ether sulfate, allyl ether sulfonate, etc., as reactive emulsifiers for emulsion polymerization, the price of such materials is high.
The alpha-methyl styrene is mainly derived from byproducts generated in the industrial preparation of acetone and phenol by the oxidation of dicumyl peroxide, and the price is relatively low. The polymer chain of the alpha-methylstyrene homopolymer can be broken at a certain temperature or above and generate free radicals, and can be used as a macromolecular initiator for free radical polymerization; however, the homopolymer is not water-soluble, lacks an emulsifying or stabilizing effect on the monomer, and is difficult to apply to aqueous polymerization systems (emulsion polymerization, suspension polymerization).
Therefore, if an alpha-methylstyrene copolymer having both an emulsifying effect and an initiating effect can be developed and used for polymerization to prepare a coating and an adhesive, it is of great importance to the coating and adhesive industries.
Disclosure of Invention
The invention aims to provide an adhesive, a preparation method and application thereof, and the adhesive has the advantages of safety, environmental protection, low cost, simple application and excellent performance.
Another object of the present invention is to provide an artificial board formed of a wood veneer and the adhesive and a method of manufacturing the artificial board.
It is a further object of the present invention to provide a method of making facing paper using the binder and paper.
In order to achieve the above object, the present invention provides the following solutions:
an adhesive comprising a macroinitiator, one or more vinyl monomers, and a solvent;
the macromolecular initiator has a hydrophilic unit and an alpha-methylstyrene structural unit; the hydrophilic unit is a structural unit comprising at least one amide group and a carboxyl group and/or an ammonium salt thereof.
The invention develops the alpha-methyl styrene copolymer into a novel macromolecular initiator by utilizing the characteristic that the chain breaking reaction of the polymer chain can occur and free radicals can be generated at a certain temperature. The introduction of the alpha-methylstyrene unit can generate free radicals, the structural unit of the amide group and the carboxyl and/or ammonium salt thereof is a hydrophilic unit, and the alpha-methylstyrene structural unit is a hydrophobic unit, so that the copolymer is endowed with amphipathy, and the oily monomer can be emulsified. Finally, the copolymer can be used as a stabilizer in emulsion polymerization due to the charge action of carboxyl and amide groups. Therefore, the polymer containing alpha-methyl styrene units and amide groups and carboxyl groups and/or structural units of ammonium salts thereof serve as an initiator, an emulsifier and a stabilizer in the emulsion polymerization process, and compared with the traditional emulsion polymerization, the composition of the polymerization system is simple, the surface of an emulsion polymerization product is clean, no residues of the emulsifier or the stabilizer exist, and the performance of the product can be improved.
Further, in the adhesive, the macroinitiator is obtained by reacting a copolymer a of α -methylstyrene with a monomer having a carbon-carbon unsaturated double bond and an acid anhydride group with ammonia.
Further, in the adhesive, the monomer having a carbon-carbon unsaturated double bond and an acid anhydride group is selected from monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 8 carbon atoms, preferably maleic anhydride, itaconic anhydride, citraconic anhydride, methylenemalonic anhydride, and mixtures thereof, more preferably maleic anhydride.
Further, polymerization of α -methylstyrene with maleic anhydride is carried out in a molar ratio of 1 to 1.
Further, in the adhesive, the vinyl monomer is selected from at least one of the following monomers: monoethylenically unsaturated C 3 -C 8 Monocarboxylic acids, monoethylenically unsaturated C 3 -C 8 C of monocarboxylic acids 1 -C 10 Alkyl esters, monoethylenically unsaturated C 3 -C 8 Amides of monocarboxylic acids having C 1 -C 8 Vinyl alkyl ether of alkyl, C 1 -C 20 Vinyl esters of carboxylic acids, methoxypolyethylene glycol (meth) acrylates, glycidyl (meth) acrylate, ethylenically unsaturated monomers containing hydroxyl groups, styrene, vinyl pyrrolidone, vinyl acrylonitrile, N-vinylformamide or vinyl siloxane monomers substituted with one or more substituents selected from alkyl, alkoxy and halogen.
Further, in the adhesive, the solvent is selected from one or more of water, alcohols, ketones, dioxane, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide.
Further, in the adhesive, the vinyl monomer is used in an amount of 10 to 120% by mass of the solvent;
the macroinitiator is used in an amount of 5 to 60% by mass, preferably 30 to 50% by mass, of the vinyl monomer.
A method of preparing the adhesive comprising the steps of:
a) Providing a reaction mixture comprising a macroinitiator, one or more vinyl monomers, and a solvent;
b) Purging the reaction mixture with an inert gas to exclude oxygen and then polymerizing the reaction mixture by free radical polymerization to obtain the adhesive.
Further, in the method for preparing the adhesive, the reaction temperature of the radical polymerization is 70 to 100 ℃, preferably 80 to 90 ℃, and the reaction time is 0.5 to 8 hours, preferably 2 to 4 hours.
The adhesive form is used for preparing artificial boards, paper, cloth or paint.
Further, the binder is used in an amount of 1 to 200% in terms of solid content with respect to the total mass of the artificial board, facing paper, cloth or paint.
An artificial board is formed from lignocellulosic material and the above binder.
A facing paper formed from paper and the adhesive described above.
The invention discloses the following technical effects:
(1) The adhesive of the invention is in emulsion state, and has simple synthesis steps and low production cost.
(2) The adhesive can be used for cold press bonding of wood at room temperature, hot press bonding of wood at high temperature and wide application.
(3) The copolymer containing alpha-methyl styrene unit, amido, carboxyl and/or carboxylate group, which is developed by the invention, can be used as an initiator and also can be used as an emulsifying agent and a stabilizing agent in the emulsion polymerization process.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The room temperature of the present invention means 25.+ -. 2 ℃.
Unless otherwise indicated, percentages in the examples are by weight and parts in the examples are parts by mass.
The chemical source used is: alpha-methylstyrene (99+% purity, alfa elsa (Tianjin) chemical company limited); dibenzoyl peroxide (97% purity, alfa elsha (Tianjin) chemical company limited); azobisisobutyronitrile (purity 98%, shanghai Ala Biochemical technologies Co., ltd.); ammonia (concentration 20-25%, beijing enokic science and technology Co., ltd.); ammonia gas (purity 99.999%, beijing brand gas limited); methyl methacrylate (99% purity, alfa eastern chemical company limited); vinyl acetate (99% pure, alfa eastern chemical company); other chemical reagents were analytically pure and purchased from beijing welfare fine chemical company.
Adhesive and preparation method thereof
One aspect of the present invention relates to an adhesive comprising a macroinitiator, one or more vinyl monomers and a solvent, prepared by means of free radical polymerization.
The macroinitiator is a macroinitiator having at least one structural unit of an amide group and a carboxyl group and/or an ammonium salt thereof and an alpha-methylstyrene structural unit.
According to a preferred embodiment of the invention, a portion (e.g. 1-10% by weight) of the carboxyl groups of the macroinitiator may take the form of its ammonium salt.
The molecular weight of the macroinitiator may be any molecular weight suitable for free radical polymerization of vinyl monomers. For example, the molecular weight of the macroinitiator may be no more than 2000, such as no more than 3000 or no more than 5000.
According to a preferred embodiment of the invention, the molar content of alpha-methylstyrene building blocks in the macroinitiator may be from 30 to 70%, for example from 40%,50%,60%, based on the total molar amount of repeating units of the macroinitiator.
According to a preferred embodiment of the invention, the macroinitiator is derived from a copolymer a comprising monomers having carbon-carbon unsaturated double bonds and anhydride groups and alpha-methylstyrene, the copolymer having at least one repeating unit bearing an anhydride group. In a preferred embodiment, the macroinitiator is derived from the reaction of the alpha-methylstyrene-anhydride copolymer with ammonia.
According to a preferred embodiment of the present invention, the anhydride groups on the α -methylstyrene-anhydride copolymer are introduced into the α -methylstyrene-anhydride copolymer by polymerization of at least one monomer having a carbon-carbon unsaturated double bond and an anhydride group. The monomer having a carbon-carbon unsaturated double bond and an acid anhydride group may 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.
The polymerization of monomers having carbon-carbon unsaturated double bonds and anhydride groups with other monomers containing carbon-carbon unsaturated double bonds to prepare the alpha-methylstyrene-anhydride copolymer may be performed using an oil-soluble free radical initiator. The oil-soluble radical initiator includes, for example, azo-type initiator or peroxide initiator. The azo initiator comprises: azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), dimethyl azobisisobutyrate, and the like; the peroxide initiator comprises: dibenzoyl peroxide (BPO), dicumyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like. The initiator is used in an amount of 0.05 to 10% by weight, preferably 1 to 6% by weight, based on the weight of the monomers.
The polymerization reaction may be carried out in the presence of a solvent. The solvent may include one or more mixtures of carboxylic acid esters, ketones, aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, cycloalkanes, and the like.
Examples of aromatic hydrocarbons may be mentioned toluene, xylene or ethylbenzene.
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, and specific examples may mention ester 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, isoamyl phenylacetate, and the like.
The ketone may be selected from acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone.
The alkane may be selected from n-pentane, n-hexane, cyclohexane, n-heptane, n-octane and isooctane.
The polymerization reaction may be carried out in the presence of an inert gas such as nitrogen. The polymerization temperature is generally 55 to 120 ℃, preferably 60 to 100 ℃; the polymerization time is usually 1 to 12 hours, preferably 2 to 8 hours. After the polymerization reaction, the resulting α -methylstyrene-anhydride copolymer may be isolated and dried.
In a preferred embodiment, the polymerization is carried out by precipitation polymerization. The precipitation polymerization may be performed by selecting a solvent capable of dissolving the monomer but incapable of dissolving the resulting α -methylstyrene-anhydride copolymer. The alpha-methylstyrene-anhydride copolymer can be obtained directly in powder form by precipitation polymerization.
According to the invention, the alpha-methylstyrene-anhydride copolymer can be reacted with ammonia to give a macroinitiator. The reaction generally involves reacting the alpha-methylstyrene-anhydride copolymer with ammonia gas at a temperature of less than 100 ℃, preferably 15-70 ℃, for example at room temperature with stirring. The reaction time is usually 1 to 16 hours, preferably 6 to 12 hours.
The conversion of the anhydride groups of the alpha-methylstyrene-anhydride copolymer is generally more than 90%, preferably more than 95%, more preferably more than 98%, such as 100%.
In the reaction of the alpha-methylstyrene-anhydride copolymer with ammonia, the carboxyl groups may also form ammonium salts with ammonia.
The molecular weight of the alpha-methylstyrene-anhydride copolymer generally corresponds to the macroinitiator. As mentioned above, the macroinitiator may have any molecular weight suitable for free radical polymerization of vinyl monomers. According to one embodiment of the invention, for example, the molecular weight of the macroinitiator may be no more than 2000, such as no more than 3000 or no more than 5000.
In the specific use of a macroinitiator for vinyl monomer polymerization, the macroinitiator in solid form may be dissolved in a solvent, optionally mixed with at least one vinyl monomer to obtain a reaction mixture, purged with an inert gas to remove oxygen, and then polymerized by free radical polymerization to obtain the adhesive.
The vinyl monomer is selected from at least one of the following: monoethylenically unsaturated C 3 -C 8 Monocarboxylic acids, monoethylenically unsaturated C 3 -C 8 C of monocarboxylic acids 1 -C 10 Alkyl esters, monoethylenically unsaturated C 3 -C 8 Amides of monocarboxylic acids having C 1 -C 8 Vinyl alkyl ether of alkyl, C 1 -C 20 Vinyl esters of carboxylic acids, methoxypolyethylene glycol (meth) acrylates, glycidyl (meth) acrylate, ethylenically unsaturated monomers containing hydroxyl groups, styrene substituted with one or more substituents selected from alkyl, alkoxy and halogen, vinylpyrrolidone, (meth) acrylonitrile, N-vinylformamide, vinylsiloxane monomers.
In the free radical polymerization process of vinyl monomers, the solvent is selected from one or more of water, alcohols, ketones, dioxane, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide.
In the radical polymerization, the vinyl monomer is used in an amount of 10 to 120% by mass of the solvent.
In the radical polymerization, the macroinitiator is used in an amount of 5 to 60% by mass, preferably 30 to 50% by mass, of the vinyl monomer.
In the radical polymerization, the reaction system is stirred at a speed of 100 to 400rpm, preferably 200 to 300rpm. In addition, according to one embodiment of the present invention, the radical polymerization may also be performed without stirring.
In the radical polymerization, the reaction temperature is from 70 to 100℃and preferably from 80 to 90 ℃.
In the radical polymerization, the reaction time is from 0.5 to 8 hours, preferably from 2 to 4 hours.
In the adhesive of the present invention, the adhesive of the present invention may contain at least one additive, if necessary, in addition to the macroinitiator. The additive 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.
In addition, in the present invention, there is also provided the use of the adhesive in the preparation of artificial board, facing paper, cloth or paint.
The amount of the binder is not particularly limited and may be appropriately adjusted according to the actual use. The binder is used in an amount of 1 to 200% in terms of solid content relative to the total mass of the artificial board, facing paper, cloth or paint. In some preferred embodiments, the amount of the binder is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, still more preferably 3 to 35% by mass, still more preferably 5 to 30% by mass, particularly preferably 7 to 25% by mass, in terms of the solid content, relative to the total mass of the article (artificial board, facing paper, cloth or paint).
In other preferred embodiments, the amount of binder is preferably 20 to 140% by mass, more preferably 30 to 120% by mass, still more preferably 60 to 100% by mass, particularly preferably 80 to 100% by mass, relative to the total amount of the article.
In some preferred embodiments, the articles of the present invention are manufactured boards formed from lignocellulosic material and the binder of the present invention. The artificial board according to the invention is to be understood in a broad sense, i.e. a board formed from any lignocellulosic material and the adhesive composition according to the invention. The artificial board of the present invention is not limited to those formed of only wood, but may include a board formed of bamboo, straw, and the like as described below. The artificial board of the present invention may be various types of artificial boards. In one embodiment, the manufactured board includes, but is not limited to, chipboard, plywood, fiberboard, density board, straw board, and finger board.
Lignocellulosic material can be in the form of sawdust, particles, wood chips, strands, flakes, fibers, sheets, wood chips, shavings, particles, and the like, as well as combinations of such materials, such as a combination of strands and sawdust.
Lignocellulosic materials can be processed by a variety of conventional techniques. Large timber can be processed into wood chips in a log flaker. The large pieces of timber and scraps can also be cut into crushed aggregates. The large timber can be sliced in an annular flaker. The large timber is typically peeled prior to flaking.
The artificial board of the present invention may be generally obtained by various methods known in the art. In some specific embodiments, the artificial board of the invention may be prepared by a process comprising pressing a mixture of lignocellulosic material and the binder composition of the invention at a temperature of 105-300 ℃ and at a pressure of 0.4-10 MPa, preferably for 2-60 minutes, more preferably for 3-30 minutes, for example 5-30 minutes. In some preferred embodiments, the pressing is performed at a temperature of 120 to 220 ℃ and/or at a pressure of 1 to 6 MPa.
The mixture of lignocellulosic material and the binder of the invention for compression may be prepared by mixing lignocellulosic material with the binder of the invention.
In addition, in other preferred embodiments of the invention, the binder of the invention fills the interstices between the lignocellulosic materials, preferably at room temperature, i.e. cold press bonding. The method comprises pressing a mixture of lignocellulosic material and the binder composition of the invention at a temperature of 20-70 ℃ and at a pressure of 0.4-10 MPa, preferably for 60-600 minutes, more preferably for 180-300 minutes, e.g. 200-300 minutes.
Finally, the invention also relates to a method for preparing paper products, the operating steps comprise paper dipping, pre-curing and hot pressing steps.
In the paper impregnation, the binder is used in an amount of 1 to 100% by weight, preferably 2 to 40% by weight, more preferably 3 to 35% by weight or 4 to 30% by weight, such as 5 to 25% by weight, 6 to 25% by weight, 7 to 25% by weight, 8 to 19% by weight, based on the total weight of the paper, based on the solid content.
In the pre-curing, it is preferred to remove a portion of the moisture in the paper and the binder, for example to reduce the moisture content of the paper and the binder to less than 30 wt.%, preferably less than 25 wt.%, for example less than 22 wt.%, or less than 18 wt.%. The moisture content of the composite is typically above 5 wt% or above 8 wt%. The removal of the moisture may be carried out by heating, for example, the heating temperature may be 50-90 ℃, preferably 60-80 ℃.
In a preferred embodiment, the hot pressing process is carried out at a temperature of 120-220 ℃ and/or at a pressure of 1-6MPa, preferably for 2-60 minutes, more preferably for 3-10 minutes, for example 5-10 minutes.
Example 1
(1) 17.7g of alpha-methylstyrene, 14.7g of maleic anhydride and 162g of isoamyl acetate and 0.2g of AIBN were added to a 250mL round bottom flask, thoroughly dissolved and deoxygenated by passing nitrogen gas through it for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product for 3 times by using petroleum ether, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/maleic anhydride copolymer;
(2) Taking 20g of the alpha-methylstyrene/maleic anhydride copolymer, and stirring the copolymer at room temperature for 16 hours under an ammonia atmosphere to obtain the alpha-methylstyrene/maleamic acid copolymer;
(3) 50g of deionized water, 8.59g of butyl acrylate, 6.71g of methyl methacrylate and 6.12g of alpha-methylstyrene/maleamic acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 10 minutes for pre-emulsification; then, the mixture was stirred at 200rpm at 90℃for 4 hours under the protection of nitrogen gas to obtain an emulsion.
Example 2
(1) 17.7g of alpha-methylstyrene, 14.7g of itaconic anhydride and 162g of toluene and 0.3g of ABVN were added to a 250mL round bottom flask, dissolved well and deoxygenated by purging with nitrogen for 30 minutes. The round bottom flask was placed in a 50 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product for 3 times by using petroleum ether, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/itaconic anhydride copolymer;
(2) Taking 20g of the alpha-methylstyrene/itaconic anhydride copolymer, 5g of ammonia water and 100g of deionized water, stirring for 12 hours at room temperature, then adding 100g of acetone to precipitate a product, filtering and drying to obtain the alpha-methylstyrene/itaconamic acid copolymer;
(3) 50g of deionized water, 5g of ethanol, 4.58g of cyclohexyl acrylate, 10.73g of methyl methacrylate and 6.12g of alpha-methylstyrene/itaconamic acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 20 minutes for pre-emulsification; then, the mixture was stirred at 300rpm at 90℃for 2 hours under the protection of nitrogen gas to obtain an emulsion.
Example 3
(1) 17.7g of alpha-methylstyrene, 14.7g of succinic anhydride and 60g of cyclohexanone, 100g of n-hexane and 0.3g of AIBN are added to the 250mL round bottom flask, fully dissolved and then deoxygenated by introducing nitrogen for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product for 3 times by using petroleum ether, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/succinic anhydride copolymer;
(2) Taking 20g of the alpha-methylstyrene/succinic anhydride copolymer and 8g of ammonium carbonate, and stirring at 50 ℃ for 12 hours to obtain the alpha-methylstyrene/butanediamic acid copolymer;
(3) 50g of deionized water, 2g of dioxane, 12.15g of vinyl acetate, 3.16g of methyl methacrylate, 4.22g of styrene and 6.12g of alpha-methylstyrene/succinamic acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 20 minutes for pre-emulsification; then, the mixture was stirred at 300rpm at 90℃for 2 hours under the protection of nitrogen gas to obtain an emulsion.
Example 4
(1) 17.7g of alpha-methylstyrene, 14.7g of sebacic anhydride and 80g of butanone, 60g of cyclohexane and 0.3g of BPO are added to a 250mL round-bottomed flask, dissolved thoroughly and deoxygenated by introducing nitrogen for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product for 3 times by using petroleum ether, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/sebacic anhydride copolymer;
(2) Taking 20g of the alpha-methylstyrene/sebacic anhydride copolymer and 10g of ammonium bicarbonate, and stirring at 50 ℃ for 12 hours to obtain the alpha-methylstyrene/decane diamide copolymer;
(3) 50g of deionized water, 7.12g of butyl acrylate, 16.89g of acrylamide and 9.60g of alpha-methylstyrene/sebacamic acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 20 minutes for pre-emulsification; then, the mixture was stirred at 300rpm at 90℃for 4 hours under the protection of nitrogen gas to obtain an emulsion.
Example 5
(1) 17.7g of alpha-methylstyrene, 14.7g of maleic anhydride and 162g of isoamyl acetate and 0.3g of AIBN were added to a 250mL round bottom flask, thoroughly dissolved and deoxygenated by passing nitrogen gas through it for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product for 3 times by using petroleum ether, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/maleic anhydride copolymer;
(2) Taking 20g of the alpha-methylstyrene/maleic anhydride copolymer, and stirring the copolymer at room temperature for 12 hours under an ammonia atmosphere to obtain the alpha-methylstyrene/maleamic acid copolymer;
(3) 50g of deionized water, 20g of ethanol, 13.37g of ethyl acrylate, 10.44g of methyl methacrylate and 9.52g of alpha-methylstyrene/maleamic acid copolymer are added into a 250mL three-neck flask to obtain clear and transparent solution, and then the solution is reacted for 2 hours at 90 ℃ without stirring to obtain emulsion.
Example 6
(1) 17.7g of alpha-methylstyrene, 14.7g of maleic anhydride and 162g of isoamyl acetate and 0.3g of BPO were added to a 250mL round bottom flask, dissolved thoroughly, and deoxygenated by purging with nitrogen for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product for 3 times by using petroleum ether, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/maleic anhydride copolymer;
(2) Taking 20g of the alpha-methylstyrene/maleic anhydride copolymer, and stirring the copolymer at room temperature for 12 hours under an ammonia atmosphere to obtain the alpha-methylstyrene/maleamic acid copolymer;
(3) 50g of deionized water, 18.89g of methyl acrylate, 2.92g of acrylonitrile and 9.52g of alpha-methylstyrene/maleamic acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 20 minutes for pre-emulsification; then, the mixture was stirred at 300rpm at 90℃for 2 hours under the protection of nitrogen gas to obtain an emulsion.
Example 7
(1) 17.7g of alpha-methylstyrene, 14.7g of maleic anhydride and 162g of isoamyl acetate, 0.3g of AIBN, are added to a 250mL round bottom flask, dissolved thoroughly, and deoxygenated by purging with nitrogen for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product for 3 times by using petroleum ether, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/maleic anhydride copolymer;
(2) Taking 20g of the alpha-methylstyrene/maleic anhydride copolymer, and stirring the copolymer at room temperature for 12 hours under an ammonia atmosphere to obtain the alpha-methylstyrene/maleamic acid copolymer;
(3) 50g of deionized water, 10.68g of butyl acrylate, 25.03g of vinyl acetate and 14.28g of alpha-methylstyrene/maleamic acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 20 minutes for pre-emulsification; then, the mixture was stirred at 300rpm at 90℃for 4 hours under the protection of nitrogen gas to obtain an emulsion.
Example 8
(1) 17.7g of alpha-methylstyrene, 14.7g of maleic anhydride and 162g of isoamyl acetate, 0.3g of AIBN, are added to a 250mL round bottom flask, dissolved thoroughly, and deoxygenated by purging with nitrogen for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product with petroleum ether for 3 times, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/maleamic acid copolymer;
(2) Taking 20g of the alpha-methylstyrene/maleic anhydride copolymer, and stirring the copolymer at room temperature for 12 hours under an ammonia atmosphere to obtain the alpha-methylstyrene/maleamic acid copolymer;
(3) 50g of deionized water, 20.05g of butyl acrylate, 15.66g of 2-ethoxyethyl acrylate and 14.28g of alpha-methylstyrene/maleamic acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 20 minutes for pre-emulsification; then, the mixture was stirred at 300rpm at 90℃for 2 hours under the protection of nitrogen gas to obtain an emulsion.
Example 9
(1) 17.7g of alpha-methylstyrene, 14.7g of maleic anhydride and 162g of isoamyl acetate, 0.3g of AIBN, are added to a 250mL round bottom flask, dissolved thoroughly, and deoxygenated by purging with nitrogen for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product with petroleum ether for 3 times, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/maleamic acid copolymer;
(2) Taking 20g of the alpha-methylstyrene/maleic anhydride copolymer, and stirring the copolymer at room temperature for 12 hours under an ammonia atmosphere to obtain the alpha-methylstyrene/maleamic acid copolymer;
(3) 50g of deionized water, 28.34g of butyl acrylate, 7.38g of isobornyl acrylate and 14.28g of alpha-methylstyrene/maleamic acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 20 minutes for pre-emulsification; then, the mixture was stirred at 300rpm at 90℃for 2 hours under the protection of nitrogen gas to obtain an emulsion.
Example 10
(1) 17.7g of alpha-methylstyrene, 14.7g of maleic anhydride and 162g of isoamyl acetate, 0.3g of AIBN, are added to a 250mL round bottom flask, dissolved thoroughly, and deoxygenated by purging with nitrogen for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product for 3 times by using petroleum ether, and drying the product in a 50 ℃ oven until the weight is constant to obtain an alpha-methylstyrene/maleic anhydride copolymer;
(2) Taking 20g of the alpha-methylstyrene/maleic anhydride copolymer, 12g of ammonia water, 100g of deionized water, stirring at room temperature for 12 hours, adding 100g of acetone to precipitate a product, filtering and drying to obtain the alpha-methylstyrene/maleate copolymer;
(3) 50g of deionized water, 28.34g of vinyl acetate, 7.38g of methyl styrene and 14.28g of alpha-methyl styrene/maleate copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 20 minutes for pre-emulsification; then, the mixture was stirred at 300rpm at 90℃for 2 hours under the protection of nitrogen gas to obtain an emulsion.
The properties of the resulting emulsion are shown in Table 1.
Comparative example 1
The procedure of example 1 was followed except that the alpha-methylstyrene was replaced by styrene, as follows:
(1) 15.9g of styrene, 14.7g of maleic anhydride and 162g of isoamyl acetate and 0.2g of AIBN were added to the 250mL round bottom flask, dissolved thoroughly, and deoxygenated by purging with nitrogen for 30 minutes. The round bottom flask was placed in a 70 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product with petroleum ether for 3 times, and drying the product in a 50 ℃ oven until the weight is constant to obtain a styrene/maleic anhydride copolymer;
(2) Taking 20g of the styrene/maleic anhydride copolymer, and stirring the copolymer at room temperature for 16 hours under an ammonia atmosphere to obtain a styrene/maleamic acid copolymer;
(3) 50g of deionized water, 8.59g of butyl acrylate, 6.71g of methyl methacrylate and 6.12g of styrene/maleamic acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 10 minutes for pre-emulsification; then, under the protection of nitrogen, stirring was carried out at 200rpm for 4 hours at 90℃and polymerization did not occur, and an emulsion was not obtained.
Comparative example 2
The only difference from example 2 is that the alpha-methylstyrene is replaced by styrene, the specific method is as follows:
1) 15.9g of styrene, 14.7g of itaconic anhydride and 162g of toluene and 0.3g of ABVN were added to a 250mL round bottom flask, dissolved well, and deoxygenated by passing nitrogen gas for 30 minutes. The round bottom flask was placed in a 50 ℃ oil bath and reacted for 12 hours. After the reaction is finished, separating a product, washing the product with petroleum ether for 3 times, and drying the product in a 50 ℃ oven until the weight is constant to obtain a styrene/itaconic anhydride copolymer;
(2) Taking 20g of the alpha-methyl styrene/itaconic anhydride copolymer, 5g of ammonia water and 100g of deionized water, stirring for 12 hours at room temperature, then adding 100g of acetone to precipitate a product, filtering and drying to obtain a styrene/itaconamic acid copolymer;
(3) 50g of deionized water, 5g of ethanol, 4.58g of cyclohexyl acrylate, 10.73g of methyl methacrylate and 6.12g of styrene/itaconate acid copolymer are added into a 250mL three-neck flask, and the mixture is stirred at 300rpm for 20 minutes for pre-emulsification; then, under the protection of nitrogen, stirring was carried out at 300rpm for 4 hours at 90℃and polymerization did not occur, and an emulsion was not obtained.
The reason why emulsion polymerization cannot be performed after the alpha-methylstyrene is replaced with styrene is as follows:
steric hindrance
The alpha-methyl styrene has a phenyl group and a methyl group on the alpha-C atom, so that the steric hindrance is large. When alpha-methylstyrene is copolymerized with maleic anhydride, a small amount of two closely linked alpha-methylstyrene units will be formed, which constitute about 2.7% of the total structural units. The steric hindrance at this structural unit is extremely large and the stability is poor. Thus, above a certain temperature, the structural unit breaks, free radicals are generated and polymerization is initiated.
And styrene, because it does not have C atom of alpha position, the steric hindrance is small, so the polymer chain of styrene/maleic anhydride copolymer has good stability, will not break under the condition of 70-90 deg.C emulsion polymerization temperature of the invention, will not produce free radical, so can not initiate emulsion polymerization.
Table 1 properties of the emulsions
Figure BDA0004064678880000121
Example 11
The emulsions prepared in examples 7-9 were subjected to bonding of plywood at room temperature and tested for bonding strength. The plate is made of poplar veneer with the size of 15cm multiplied by 0.2cm, and is bonded at room temperature with the coating weight of 20-60g/m 2 Standing for 4 hours, and solidifying. Then cut it into 2.5cm x 10cm bars. The adhesive strength of the samples was tested according to the method of national standard GB/T7124-2008, each sample was tested 6 times, and the specific results are shown in Table 2.
Table 2 bonding strength of room temperature bonded plywood
Coating amount (g/m) 2 ) 20 40 60
Example 7 1.01MPa 1.67MPa 2.01MPa
Example 8 1.60MPa 3.40MPa 3.67MPa
Example 9 0.90MPa 1.52MPa 2.00MPa
Example 12
And (3) hot-press bonding: examples 4 to 7 were applied in an amount of 20 to 60g/m 2 Under the condition of (2) carrying out hot pressing treatment at 180 ℃ and 1MPa for 3 minutes to obtain the plywood. According to the method of GB/T9846-2015, it was cut into 2.5cm by 10cm strips, and the strips were soaked in water at 63℃for 3 hours, after which the samples were immediately tested for glue strength. Each sample was tested 6 times and,the results are shown in Table 3. It can be seen that after hot pressing treatment, a stable waterproof bonding layer is formed between the adhesive and the wood, and the bonding strength can reach 2.80MPa.
TABLE 3 bonding strength of plywood after hot pressing (63 ℃ C. Water bath soaking for 3 hours)
Coating amount (g/m) 2 ) 20 40 60
Example 4 1.80MPa 2.40MPa 2.80MPa
Example 5 0.90MPa 1.67MPa 2.20MPa
Example 6 1.20MPa 2.10MPa 2.50MPa
Example 7 1.40MPa 2.30MPa 2.67MPa
Example 13
Facing papers were prepared using the emulsions obtained in examples 1-4. First, the base paper of the facing paper (80 g/m) 2 Is prepared by soaking white paper of Chengyuan Chengda decorative materials Co., ltd.) in emulsion, drying in oven at 70deg.C for 10 min, and removing water to obtain pre-cured facing paper with resin content of 100% of paper quality. And then, through hot pressing treatment, the surface facing paper is tightly attached to the surface of the plywood by hot pressing for 3 minutes at 180 ℃ and 1 MPa. Its relevant properties were tested according to GB/T17657-2013 and the results are shown in Table 4. It can be seen that each performance is far higher than the national standard.
Table 4 properties of facing paper
Surface adhesion strength Wear resistance Scratch resistance
Example 1 0.77MPa 26.9mg/100r No obvious scratch
Example 2 0.82MPa 28.3mg/100r No obvious scratch
Implementation of the embodimentsExample 3 1.08MPa 25.3mg/100r No obvious scratch
Example 4 1.00MPa 26.3mg/100r No obvious scratch
Without wishing to be bound by any theory, it is believed that the amide groups and carboxyl groups on the polymer in the binder of the present invention may dehydrate under pressing conditions to form imide groups, while the carboxyl groups may also dehydrate to form anhydride groups, and the resulting anhydride groups may react with hydroxyl groups on the lignocellulosic material to form esters, which may help to improve the mechanical properties and water resistance of the resulting manufactured board.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims (10)

1. An adhesive comprising a macroinitiator, one or more vinyl monomers and a solvent;
the macromolecular initiator has a hydrophilic unit and an alpha-methylstyrene structural unit; the hydrophilic unit is a structural unit comprising at least one amide group and a carboxyl group and/or an ammonium salt thereof.
2. The adhesive of claim 1 wherein the macroinitiator is derived from the reaction of copolymer a with ammonia, the copolymer a being a copolymer of alpha-methylstyrene with monomers having carbon-carbon unsaturated double bonds and anhydride groups.
3. The adhesive according to claim 2, wherein the monomer having a carbon-carbon unsaturated double bond and an acid anhydride group is selected from monoethylenically unsaturated dicarboxylic acid anhydrides having 4 to 8 carbon atoms.
4. The adhesive of claim 1, wherein the vinyl monomer is selected from at least one of the following monomers: monoethylenically unsaturated C 3 -C 8 Monocarboxylic acids, monoethylenically unsaturated C 3 -C 8 C of monocarboxylic acids 1 -C 10 Alkyl esters, monoethylenically unsaturated C 3 -C 8 Amides of monocarboxylic acids having C 1 -C 8 Vinyl alkyl ether of alkyl, C 1 -C 20 Vinyl esters of carboxylic acids, methoxypolyethylene glycol (meth) acrylates, glycidyl (meth) acrylate, ethylenically unsaturated monomers containing hydroxyl groups, styrene, vinyl pyrrolidone, vinyl acrylonitrile, N-vinylformamide or vinyl siloxane monomers substituted with one or more substituents selected from alkyl, alkoxy and halogen;
the solvent is selected from one or more of water, alcohols, ketones, dioxane, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide.
5. The adhesive of claim 1, wherein the vinyl monomer is used in an amount of 10 to 120% by mass of the solvent;
the dosage of the macromolecular initiator is 5-60% of the mass of the vinyl monomer.
6. A method of preparing the adhesive of any one of claims 1-5, comprising the steps of:
a) Providing a reaction mixture comprising a macroinitiator, one or more vinyl monomers, and a solvent;
b) The reaction mixture was purged with an inert gas, and then polymerized by radical polymerization to obtain an adhesive.
7. The method for preparing an adhesive according to claim 6, wherein the reaction temperature of the radical polymerization is 70 to 100℃and the reaction time is 0.5 to 8 hours.
8. Use of the adhesive according to any of claims 1-5 for the preparation of artificial boards, facing papers, cloths or paints, wherein the adhesive is used in an amount of 1-200% by solids content relative to the total mass of the artificial board, facing paper, cloth or paint.
9. An artificial board, characterized in that it is formed of a lignocellulosic material and a binder according to any one of claims 1-5.
10. A facing paper formed from a paper sheet and the adhesive of any one of claims 1-5.
CN202310070708.3A 2023-02-07 2023-02-07 Adhesive, and preparation method and application thereof Pending CN116376483A (en)

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