CN116376483B - Adhesive, and preparation method and application thereof - Google Patents
Adhesive, and preparation method and application thereofInfo
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- CN116376483B CN116376483B CN202310070708.3A CN202310070708A CN116376483B CN 116376483 B CN116376483 B CN 116376483B CN 202310070708 A CN202310070708 A CN 202310070708A CN 116376483 B CN116376483 B CN 116376483B
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- adhesive
- methylstyrene
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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
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- 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
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- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Forests & Forestry (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (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. Polymers containing alpha-methylstyrene units and structural units of amide groups and carboxyl groups and/or ammonium salts thereof act as initiators, emulsifiers, stabilizers for the emulsion polymerization process, compared with the traditional emulsion polymerization, the composition of the polymerization system is simple, the surface of the emulsion polymerization product is clean, no emulsifying agent or stabilizing agent residue exists, and the performance of the product can be improved.
Description
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, using allyloxy nonylphenol 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 alpha-methyl styrene homopolymer can be broken at a certain temperature or above and generate free radical, and can be used as macromolecular initiator for free radical polymerization, but said homopolymer is insoluble in water, lacks emulsifying or stabilizing effect for monomer, and is difficult to apply in aqueous phase polymerization system (emulsion polymerization and 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, wherein the hydrophilic unit is a structural unit containing at least one amide group and carboxyl and/or 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 monomer selected from monoethylenically unsaturated C 3-C8 monocarboxylic acid, C 1-C10 alkyl esters of monoethylenically unsaturated C 3-C8 monocarboxylic acid, amides of monoethylenically unsaturated C 3-C8 monocarboxylic acid, vinyl alkyl ethers having a C 1-C8 alkyl group, vinyl esters of C 1-C20 carboxylic acid, methoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, ethylenically unsaturated monomers containing hydroxyl groups, styrene substituted with one or more substituents selected from alkyl groups, alkoxy groups and halogens, vinyl pyrrolidone, (meth) acrylonitrile, N-vinylformamide or vinyl siloxane monomers.
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.
Room temperature in the present invention refers to 25±2 ℃.
Unless otherwise indicated, percentages in the examples are by weight and parts in the examples are parts by mass.
The chemical sources used were alpha-methylstyrene (purity 99+%, alfa eastern chemical Co., ltd.), dibenzoyl peroxide (purity 97%, alfa eastern chemical Co., ltd.), azobisisobutyronitrile (purity 98%, shanghai Allatin Biochemical technologies Co., ltd.), ammonia (concentration 20-25%, beijing inoKai Co., ltd.), ammonia (purity 99.999%, beijing sea spectrum gas Co., ltd.), methyl methacrylate (purity 99%, alfa eastern chemical Co., ltd.), vinyl acetate (purity 99%, alfa eastern chemical Co., ltd.), and other chemical reagents were all analytically pure, purchased from Beijing beneficial fine chemical Co., ltd.).
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 Azodiisobutyronitrile (AIBN), azodiisoheptonitrile (ABVN), dimethyl azodiisobutyrate and the like, and the peroxide initiator comprises dibenzoyl peroxide (BPO), dicumyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-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℃and preferably 60 to 100℃and the polymerization time is generally 1 to 12 hours and 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 under agitation at a temperature of less than 100 ℃, preferably 15-70 ℃, for example at room temperature. 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 monoethylenically unsaturated C 3-C8 monocarboxylic acid, C 1-C10 alkyl esters of monoethylenically unsaturated C 3-C8 monocarboxylic acid, amides of monoethylenically unsaturated C 3-C8 monocarboxylic acid, vinyl alkyl ethers having a C 1-C8 alkyl group, vinyl esters of C 1-C20 carboxylic acids, methoxypolyethylene glycol (meth) acrylate, 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, vinyl siloxane 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 an oxygen scavenger, an emulsifier, a dye, a pigment, an anti-migration aid, a UV absorber, a biocide, an antifoaming agent, a colorant, an antistatic agent, and an antioxidant.
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, and 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 the binder is preferably 20 to 140% by mass, more preferably 30 to 120% by mass, still more preferably 60 to 100% by mass, and particularly preferably 80 to 100% by mass, relative to the total amount of the product.
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 present invention may be prepared by a method comprising pressing a mixture of a lignocellulosic material and the adhesive composition of the present invention at a temperature of 105 to 300 ℃ and at a pressure of 0.4 to 10mpa, preferably for 2 to 60 minutes, more preferably for 3 to 30 minutes, for example 5 to 30 minutes. In some preferred embodiments, the pressing is performed at a temperature of 120-220 ℃ and/or at a pressure of 1-6 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, for example 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 performed 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 with petroleum ether for 3 times, and drying the product in a 50 ℃ oven to constant weight 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, stirred at 300rpm for 10 minutes for pre-emulsification, and stirred at 200rpm for 4 hours under the protection of nitrogen at 90 ℃ to obtain 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 with petroleum ether for 3 times, and drying the product in a 50 ℃ oven to constant weight 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, the mixture is stirred at 300rpm for 20 minutes for pre-emulsification, and then stirred at 300rpm for 2 hours under the protection of nitrogen at 90 ℃ to obtain 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 with petroleum ether for 3 times, and drying the product in a 50 ℃ oven to constant weight 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, the mixture is stirred at 300rpm for 20 minutes to perform pre-emulsification, and then the mixture is stirred at 300rpm for 2 hours under the protection of nitrogen at 90 ℃ to obtain 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 with petroleum ether for 3 times, and drying the product in a 50 ℃ oven to constant weight 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 for 12 hours at 50 ℃ to obtain the alpha-methylstyrene/decane diamide copolymer;
(3) 50g of deionized water, 7.12g of butyl acrylate, 16.89g of acrylamide, 9.60g of alpha-methylstyrene/sebacamic acid copolymer are added into a 250mL three-neck flask, stirred at 300rpm for 20 minutes for pre-emulsification, and then stirred at 300rpm for 4 hours under the protection of nitrogen at 90 ℃ to obtain 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 with petroleum ether for 3 times, and drying the product in a 50 ℃ oven to constant weight 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 with petroleum ether for 3 times, and drying the product in a 50 ℃ oven to constant weight 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, the mixture is stirred at 300rpm for 20 minutes for pre-emulsification, and then stirred at 300rpm for 2 hours under the protection of nitrogen at 90 ℃ to obtain 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 with petroleum ether for 3 times, and drying the product in a 50 ℃ oven to constant weight 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, the mixture is stirred at 300rpm for 20 minutes to perform pre-emulsification, and then the mixture is stirred at 300rpm for 4 hours at 90 ℃ under the protection of nitrogen to obtain 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 to constant weight 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, the mixture is stirred at 300rpm for 20 minutes for pre-emulsification, and then stirred at 300rpm for 2 hours under the protection of nitrogen at 90 ℃ to obtain 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 to constant weight 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, are stirred at 300rpm for 20 minutes to perform pre-emulsification, and are stirred at 300rpm for 2 hours under the protection of nitrogen at 90 ℃ to obtain 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 with petroleum ether for 3 times, and drying the product in a 50 ℃ oven to constant weight 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, stirred at 300rpm for 20 minutes for pre-emulsification, and stirred at 300rpm for 2 hours under the protection of nitrogen at 90 ℃ to obtain 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 to constant weight 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 a styrene/maleamic acid copolymer were added to a 250mL three-neck flask, and the mixture was stirred at 300rpm for 10 minutes to pre-emulsify the mixture, and then stirred at 200rpm for 4 hours under the protection of nitrogen at 90 ℃ to polymerize without emulsion.
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 to constant weight 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/itaconamic acid copolymer are added into a 250mL three-neck flask, stirred at 300rpm for 20 minutes for pre-emulsification, and stirred at 300rpm for 4 hours under the protection of nitrogen at 90 ℃ for polymerization, so that emulsion is 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, at the emulsion polymerization temperature of 70-90 deg.C of the invention, will not break, will not produce free radical, so can not initiate emulsion polymerization.
Table 1 properties of the emulsions
Example 11
The emulsions prepared in examples 7-9 were subjected to bonding of plywood at room temperature and tested for bonding strength. The used plate is a poplar veneer with the size of 15cm multiplied by 0.2cm, the bonding is carried out at room temperature, the coating amount is 20-60g/m 2, and the plate is stood for 4 hours to solidify the plate. 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 quantity (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, namely carrying out hot-press treatment on the adhesive of the embodiment 4-7 under the condition that the coating weight is 20-60g/m 2, and carrying out hot-press for 3 minutes at 180 ℃ under the condition of 1MPa 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 quantity (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. The raw paper of the facing paper (plain paper of 80g/m 2, hangzhou Tianyuan Chengda decorative material Co., ltd.) is soaked in the emulsion, and then dried in a 70 ℃ oven for 10 minutes, and the moisture is removed, so that the pre-cured facing paper with the resin content of 100% of the paper quality is obtained. And then, through hot pressing treatment, the surface facing paper is tightly attached to the surface of the plywood at 180 ℃ and 1MPa for 3 minutes. 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 |
| Example 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 present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (8)
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