CN113214762B - High-molecular adhesive and application thereof - Google Patents

High-molecular adhesive and application thereof Download PDF

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CN113214762B
CN113214762B CN202110545549.9A CN202110545549A CN113214762B CN 113214762 B CN113214762 B CN 113214762B CN 202110545549 A CN202110545549 A CN 202110545549A CN 113214762 B CN113214762 B CN 113214762B
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adhesive
groups
strength
methyl methacrylate
organic glass
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CN113214762A (en
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张凌
康静
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Jilin University
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Jilin University
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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate

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  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to a high-molecular adhesive and application thereof. The high molecular adhesive provided by the invention is a poly (methacrylic acid-methyl methacrylate) copolymer, and the molar ratio of methacrylic acid groups to methyl methacrylate groups in the poly (methacrylic acid-methyl methacrylate) copolymer is 50-99: 1-50. The invention regulates and controls the cohesion and the adhesion force in the adhesive by limiting the content of hydrophilic groups (carboxyl groups) and hydrophobic groups (methyl groups and/or methyl groups) in the high molecular adhesive, thereby achieving the balance between the cohesion and the adhesion force and leading the adhesive to achieve the optimal adhesion strength. The high-strength adhesive prepared by the invention has the adhesive strength of 0.45-7.06 MPa. The invention takes waste organic glass as a raw material, obtains the high-molecular adhesive through hydrolysis, greatly reduces the production cost of the adhesive, and realizes the recycling of wastes.

Description

High-molecular adhesive and application thereof
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a high-molecular adhesive and application thereof.
Background
The adhesive is a widely used material, and plays an important role in the fields of wood processing, construction, decoration, medical treatment, automobiles, electronics, and the like. Most of the currently used adhesives are organic solvent-based adhesives, and although these commercial adhesives have the advantages of strong adhesion and strong adaptability to the types of substrates to be bonded, the use of organic solvents can generate Volatile Organic Compounds (VOC) during the use of the adhesives, which are harmful to human health.
Compared with organic solvent adhesives, the water-based adhesive is nontoxic, safe and environment-friendly. The development and application of the water-based adhesive can effectively solve the problem that the organic solvent-based adhesive generates VOC in the using process. The existing water system adhesives comprise natural high polymer water system adhesives and synthetic water system adhesives, wherein the natural high polymer water system adhesives comprise dextrin, leather glue, bone glue, protein glue, resin glue or natural rubber cement, but the natural high polymer water system adhesives have generally low adhesive strength, can only be applied to the surface of a weak substrate and cannot meet the requirement of large-scale application in life. The adhesive strength of the synthetic water-based adhesive is improved compared with that of the natural polymer water-based adhesive, but the conventional synthetic water-based adhesive is usually only in kPa level.
Disclosure of Invention
In view of the above, the present invention provides a polymer adhesive and an application thereof. The polymer adhesive provided by the invention has higher adhesive strength.
In order to solve the above technical problems, the present invention provides a polymer binder, wherein the polymer binder is a poly (methacrylic acid-methyl methacrylate) copolymer;
the poly (methacrylic acid-methyl methacrylate) copolymer has a molar ratio of methacrylic acid groups to methyl methacrylate groups of 50-99: 1-50.
Preferably, the molar ratio of the methacrylic group to the methyl methacrylate group is 66-99: 1 to 34.
Preferably, the polymer binder is obtained by incomplete hydrolysis of waste organic glass under an alkaline condition.
The invention also provides the application of the polymer adhesive in the technical scheme in a high-strength adhesive.
Preferably, the application is that the high-strength adhesive is directly used after the high-molecular adhesive and water are mixed.
Preferably, the high strength adhesive is used in bonding substrates comprising metal, wood or polymeric materials.
Preferably, the metal comprises iron, stainless steel, copper or aluminum.
Preferably, the polymeric material comprises polymethylmethacrylate, polyethylene terephthalate, polypropylene or polyvinyl chloride.
The invention provides a high-molecular adhesive, which is a poly (methacrylic acid-methyl methacrylate) copolymer, wherein the molar ratio of methacrylic acid groups to methyl methacrylate groups in the poly (methacrylic acid-methyl methacrylate) copolymer is 50-99: 1-50. The invention regulates and controls the cohesion and the adhesion force in the adhesive by limiting the content of hydrophilic groups (carboxyl groups) and hydrophobic groups (methyl groups and/or methyl groups) in the high molecular adhesive, thereby achieving the balance between the cohesion and the adhesion force and leading the adhesive to achieve the optimal adhesion strength. According to the embodiments of the present invention, the adhesion strength of the high molecular adhesive provided by the present invention as a high strength adhesive is 0.45 to 7.06 MPa.
The invention takes waste organic glass as a raw material, obtains the high-molecular adhesive through hydrolysis, greatly reduces the production cost of the adhesive, and realizes the recycling of wastes.
Drawings
FIG. 1 is a schematic diagram of the principle of the action of hydrophobic domains in a polymeric binder, wherein (a) is a schematic diagram of the formation of hydrophobic domains between hydrophobic groups (methyl and methyl ester groups) in the polymeric binder, and (b) is a schematic diagram of the opening of the hydrophobic domains under stress to dissipate partial stress;
FIG. 2 is a schematic diagram of the forces that exist between a polymer adhesive and various substrates when used as a high strength adhesive, where Wood is Wood and M is metal;
FIG. 3 is a nuclear magnetic spectrum of waste organic glass;
FIG. 4 is a nuclear magnetic spectrum of the polymeric binder P66 prepared in example 1;
FIG. 5 is a nuclear magnetic spectrum of the polymeric binder P99 prepared in example 2, wherein B is a partial enlarged view of the portion c-a in A;
FIG. 6 is a nuclear magnetic spectrum of the polymeric binder P37 prepared in comparative example 1;
FIG. 7 is an Atomic Force Microscope (AFM) profile of the high molecular weight adhesives obtained in examples 1 and 2 and comparative example 1 as a high strength adhesive;
FIG. 8 is a bar graph of the adhesion strength of the high strength adhesive prepared in example 1;
FIG. 9 is a bar graph of the adhesion strength of the high strength adhesive prepared in example 2;
FIG. 10 is a bar graph of the adhesion strength of the high strength adhesive prepared in comparative example 1;
fig. 11 is a bar graph showing the adhesive strength of the adhesive prepared in comparative example 2.
Detailed Description
The invention provides a high molecular adhesive, which is a poly (methacrylic acid-methyl methacrylate) copolymer;
the molar ratio of the methacrylic group to the methyl methacrylate group in the poly (methacrylic acid-methyl methacrylate) copolymer is 50-99: 1-50, and preferably 66-99: 1-34.
In the present invention, the method for preparing the polymer binder preferably comprises: and (3) incompletely hydrolyzing the waste organic glass raw material under an alkaline condition to obtain the high-molecular adhesive. The method can fully utilize the waste organic glass, and reduces the resource waste.
In the invention, when the molar ratio of the methacrylic group to the methyl methacrylate group in the high polymer adhesive is 50-93: 7-50, the preparation method of the polymer binder preferably comprises the following steps:
dissolving waste organic glass in 1, 4-dioxane to obtain a waste organic glass solution;
and mixing the waste organic glass solution with a saturated strong base methanol solution, and carrying out incomplete hydrolysis reaction to obtain the high polymer adhesive.
The waste organic glass is dissolved in 1, 4-dioxane to obtain a waste organic glass solution. In the invention, the mass concentration of the waste organic glass solution is preferably 8-12%, and more preferably 10%. In the invention, the dissolving temperature is preferably 85-95 ℃, and more preferably 88-90 ℃. The invention has no special requirements on the dissolution, as long as the dissolution can be completed.
In the present invention, the dissolving further preferably includes: and cooling the dissolved solution and filtering. In the invention, the temperature of the cooled solution is preferably room temperature, and more preferably 20-30 ℃. The cooling mode is not particularly limited, and the temperature can be reached. In the present invention, the filtration is preferably a reduced pressure filtration, and the pressure of the reduced pressure filtration is preferably-0.08 to-0.1 MPa, more preferably-0.085 to-0.90 MPa. The invention can remove impurities insoluble in 1, 4-dioxane by adopting reduced pressure filtration.
After the waste organic glass solution is obtained, the waste organic glass solution and a saturated strong base methanol solution are mixed for incomplete hydrolysis reaction, and the high polymer adhesive is obtained. In the present invention, the strong base in the saturated strong base methanol solution preferably comprises a soluble hydroxide, more preferably comprises sodium hydroxide or potassium hydroxide, and most preferably is potassium hydroxide. In the invention, the mass ratio of the waste organic glass to the strong base in the saturated strong base methanol solution is preferably 1: 1-1.5, and more preferably 1: 1.2.
The present invention does not specifically limit the mixing, as long as the mixing is uniform. In the invention, the temperature of the incomplete hydrolysis reaction is preferably 80-120 ℃, and more preferably 90-100 ℃; the time is preferably 24 to 72 hours, and more preferably 48 to 60 hours.
In the present invention, the incomplete hydrolysis reaction preferably further comprises:
standing the reaction solution obtained by incomplete hydrolysis reaction to remove supernatant, and obtaining hydrolysis reaction precipitate;
dissolving the precipitate of the hydrolysis reaction in water to obtain an aqueous solution;
dropwise adding the aqueous solution into ethanol to obtain a precipitate;
and dissolving the precipitate in water again, and then sequentially dialyzing and drying to obtain the high-molecular adhesive.
The invention makes the reaction liquid obtained by incomplete hydrolysis stand to remove the supernatant, and obtains the precipitate of hydrolysis reaction. The time for the standing is not particularly limited as long as the product after the hydrolysis reaction can be layered. The invention can remove impurities which are dissolved in the 1, 4-dioxane and do not react with alkali by standing and removing the supernatant.
After a hydrolysis reaction precipitate is obtained, the hydrolysis reaction precipitate is dissolved in water to obtain an aqueous solution. In the present invention, the mass ratio of the hydrolysis reaction precipitate to water is preferably 1: 20-30, more preferably 1: 23 to 25. The dissolving mode is not particularly limited, and the conventional technical means in the field can be adopted.
After obtaining the aqueous solution, the invention adds the aqueous solution into ethanol dropwise to obtain the precipitate. In the present invention, the volume ratio of the aqueous solution to ethanol is preferably 1: 10-30, more preferably 1: 15 to 20. In the invention, the dripping speed is preferably 10-50 drops/min, and more preferably 20-30 drops/min. In the present invention, the dropping is preferably accompanied by stirring, and the rotation speed of the stirring is preferably 500 to 1000r/min, more preferably 600 to 850 r/min.
In the present invention, it is also preferable to include, after the dropwise addition of the aqueous solution to ethanol: and (3) performing solid-liquid separation on the product after the dropwise addition is completed, and drying the solid obtained by the solid-liquid separation to obtain the precipitate. In the present invention, the solid-liquid separation method is not particularly limited as long as the solid can be separated. In the invention, the temperature is preferably 50-90 ℃, and more preferably 70-85 ℃; the time is preferably 8 to 24 hours, and more preferably 12 to 15 hours.
After the precipitate is obtained, the precipitate is re-dissolved in water and then dialyzed and dried in sequence to obtain the high molecular adhesive. In the present invention, the mass ratio of the precipitate to water is preferably 1: 50-200, more preferably 1: 80-120 parts. In the present invention, the cut-off molecular weight of the dialysis bag for dialysis is preferably 8000 to 14000 g/mol-1(ii) a The dialysis time is preferably 2 to 4 days, and more preferably 2.5 to 3 days. In the invention, the drying temperature is preferably 60-85 ℃, and more preferably 70-80 ℃; the time is preferably 8 to 24 hours, and more preferably 12 to 15 hours. In the invention, the drying is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 400-1000 r/min, and more preferably 500-800 r/min.
In the present invention, when the molar ratio of the methacrylic group to the methyl methacrylate group in the polymer binder is 93-99: 1-7, the preparation method of the polymer binder preferably includes:
dissolving waste organic glass in 1, 4-dioxane to obtain a waste organic glass solution;
mixing the waste organic glass solution, deionized water and a saturated strong base methanol solution, and performing first incomplete hydrolysis to obtain a first hydrolysis product;
and mixing the first hydrolysate with a strong alkali solution, and then carrying out second incomplete hydrolysis to obtain the polymer adhesive.
The waste organic glass is dissolved in 1, 4-dioxane to obtain a waste organic glass solution. In the invention, the mass concentration of the waste organic glass solution is preferably 8-12%, and more preferably 10%. In the invention, the dissolving temperature is preferably 85-95 ℃, and more preferably 88-90 ℃. The invention has no special requirements on the dissolution, as long as the dissolution can be completed.
In the present invention, the dissolving further preferably includes: and cooling and filtering the solution obtained after dissolution in sequence. In the present invention, the temperature after cooling is preferably 20 to 30 ℃. In the present invention, the filtration is preferably a reduced pressure filtration, and the pressure of the reduced pressure filtration is preferably-0.08 to-0.1 MPa, more preferably-0.085 to-0.90 MPa. The invention can remove impurities insoluble in 1, 4-dioxane by reduced pressure filtration.
After the waste organic glass solution is obtained, the waste organic glass solution, deionized water and a saturated strong base methanol solution are mixed for first incomplete hydrolysis, and a first hydrolysis product is obtained. In the present invention, the strong base in the saturated strong base methanol solution preferably comprises a soluble hydroxide, more preferably comprises sodium hydroxide or potassium hydroxide, and most preferably is potassium hydroxide. In the invention, the mass ratio of the waste organic glass to the strong base in the saturated strong base methanol solution is preferably 1: 1-1.5, and more preferably 1: 1.2. In the invention, the volume ratio of the deionized water to the saturated strong base methanol solution is preferably 2.8-3.2: 100, and more preferably 3: 100.
The present invention does not specifically limit the mixing, as long as the mixing is uniform. In the invention, the temperature of the first incomplete hydrolysis is preferably 80-120 ℃, and more preferably 90-100 ℃; the time is preferably 24 to 72 hours, and more preferably 48 to 60 hours.
In the present invention, the first incomplete hydrolysis preferably further comprises:
standing the reaction solution obtained by the first incomplete hydrolysis to remove a supernatant to obtain a first incomplete hydrolysis precipitate;
dissolving the first incompletely hydrolyzed precipitate in water to obtain an aqueous solution;
dropwise adding the aqueous solution into ethanol to obtain a precipitate;
and dissolving the precipitate in water again, and then sequentially dialyzing and drying to obtain a first hydrolysate.
The reaction solution obtained by the first incomplete hydrolysis is kept still to remove the supernatant, and a first incomplete hydrolysis precipitate is obtained. The time for the standing is not particularly limited as long as the product after the hydrolysis reaction can be layered. The invention can remove impurities which are dissolved in the 1, 4-dioxane and do not react with alkali by standing and removing the supernatant.
After the first incompletely hydrolyzed precipitate is obtained, the first incompletely hydrolyzed precipitate is dissolved in water to obtain an aqueous solution. In the present invention, the mass ratio of the first incompletely hydrolyzed precipitate to water is preferably 1: 20-30, more preferably 1: 23 to 25. The dissolving mode is not particularly limited, and the conventional technical means in the field can be adopted.
After obtaining the aqueous solution, the invention adds the aqueous solution into ethanol dropwise to obtain the precipitate.
In the present invention, the volume ratio of the aqueous solution to ethanol is preferably 1: 10-30, more preferably 1: 15 to 20. In the invention, the dripping speed is preferably 10-50 drops/min, and more preferably 20-30 drops/min. In the present invention, the dropping is preferably accompanied by stirring, and the rotation speed of the stirring is preferably 500 to 1000r/min, more preferably 600 to 850 r/min.
In the present invention, it is also preferable to include, after the dropwise addition of the aqueous solution to ethanol: and (3) performing solid-liquid separation on the product after the dropwise addition is completed, and drying the solid obtained by the solid-liquid separation to obtain the precipitate. In the present invention, the solid-liquid separation method is not particularly limited as long as the solid can be separated. In the invention, the temperature is preferably 50-90 ℃, and more preferably 70-85 ℃; the time is preferably 8 to 24 hours, and more preferably 11 to 15 hours.
After the precipitate is obtained, the precipitate is redissolved in water and then dialyzed and dried in sequence to obtain a first hydrolysate. In the present invention, the mass ratio of the precipitate to water is preferably 1: 50-200, more preferably 1: 80-120 parts. In the present invention, the cut-off molecular weight of the dialysis bag for dialysis is preferably 8000 to 14000 g/mol-1(ii) a The dialysis time is preferably 2 to 4 days, and more preferably 2.5 to 3 days. In the invention, the drying temperature is preferably 60-85 ℃, and more preferably 70-80 ℃; the time is preferably 8 to 24 hours, and more preferably 12 to 15 hours. In the invention, the drying is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 400-1000 r/min, and more preferably 500-800 r/min.
After the first hydrolysate is obtained, the first hydrolysate and the strong alkali solution are mixed and subjected to second incomplete hydrolysis to obtain the high molecular adhesive. In the present invention, the strong base in the strong base solution preferably comprises a soluble hydroxide, more preferably comprises sodium hydroxide or potassium hydroxide, and most preferably is sodium hydroxide. In the invention, the molar concentration of the strong alkali solution is preferably 0.8-1.2 mol/L, and more preferably 1 mol/L; the volume ratio of the sodium hydroxide solution to the 1, 4-dioxane is preferably 0.8-1.2: 1, and more preferably 1:1. The mixing is not particularly limited in the present invention as long as it can be mixed uniformly. In the invention, the second incomplete hydrolysis is preferably carried out under the condition of reflux, and the temperature of the reflux is preferably 110-130 ℃, more preferably 120-125 ℃; the time is preferably 22 to 26 hours, and more preferably 23 to 24 hours.
In the present invention, the second incomplete hydrolysis preferably further comprises the following steps:
and cooling the reaction liquid obtained by the second incomplete hydrolysis to room temperature, and then sequentially dialyzing and drying to obtain the polymer adhesive.
In the present invention, the cut-off molecular weight of the dialysis bag for dialysis is preferably 8000 to 14000 g/mol-1(ii) a The dialysis time is preferably 2 to 4 days, and more preferably 2.5 to 3 days. In the invention, the drying temperature is preferably 60-85 ℃, and more preferably 70-80 ℃; time of flightThe time is preferably 8 to 24 hours, and more preferably 12 to 15 hours. In the invention, the drying is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 400-1000 r/min, and more preferably 500-800 r/min.
The preparation method of the high-molecular adhesive provided by the invention is simple and convenient, and the incomplete hydrolysis product obtained by hydrolyzing the waste organic glass under an alkaline condition can be directly used as the high-strength adhesive without complex treatment. In the invention, the high molecular adhesive has low production cost, the raw material for preparing the high molecular adhesive is waste organic glass, the high molecular adhesive is a polymer material produced industrially, and the high molecular adhesive is commonly used as a billboard, a key ring, process decoration and the like in life due to the advantages of plasticity, high transparency, high strength and the like, and the recovery price is about 4 yuan/kg; the solvent is 1, 4-dioxane; the raw materials used in the hydrolysis process are common raw materials in chemical experiments, and a precise instrument is not needed in the hydrolysis step.
The invention also provides the application of the polymer adhesive in the technical scheme in a high-strength adhesive. In the present invention, the application is preferably to mix the polymer binder and water and directly use the mixture as a high-strength binder. In the present invention, when the polymer binder is used for bonding, it preferably includes the steps of:
mixing the high-molecular adhesive with water to obtain a high-strength adhesive;
coating the high-strength adhesive on any surface of the substrate to be bonded to obtain the substrate coated with the high-strength adhesive;
and overlapping the other bonding substrate with the substrate coated with the high-strength adhesive and then curing.
The invention mixes the high molecular adhesive with water to obtain the adhesive. In the present invention, the mass ratio of the polymer binder to water is preferably 1:0.5 to 2, more preferably 1 to 0.8: 1.2. the mixing is not particularly limited in the present invention as long as it can be mixed uniformly.
The high-strength adhesive is coated on any surface of the substrate to be bonded to obtain the substrate coated with the high-strength adhesive. In the present inventionIn the present invention, the substrate to be bonded preferably comprises metal, Wood (Wood) or a polymeric material; the metal preferably comprises iron, Stainless Steel (SS), copper or aluminum; the polymer material preferably comprises Polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), polypropylene (PP) or polyvinyl chloride (PVC). In the invention, the coating amount of the coating is preferably 0.5-3 mu L/cm2More preferably 1.0 to 1.8. mu.L/cm2. When the bonding substrate is a metal or polymer material, the surface coated with the high strength adhesive is preferably polished. The mesh number of the sand paper for polishing is preferably 360 meshes, and the polishing time is preferably 28-32 s, and more preferably 30 s.
After the substrate coated with the high-strength adhesive is obtained, the invention carries out lap joint on the other substrate to be bonded and the substrate coated with the high-strength adhesive and then carries out curing. In the invention, the material of the substrate coated with the high-strength binder and the material of the other substrate to be bonded are preferably the same material. In the present invention, when the bonding substrate is a metal or polymer material, it is preferable to grind the lapping surface of the bonding substrate to be lapped. The mesh number of the sand paper for polishing is preferably 360 meshes, and the polishing time is preferably 28-32 s, and more preferably 30 s.
In the invention, the lapping area of the lapping joint is preferably 0.8-1.2 cm2More preferably 1cm2. In the invention, after the lapping is finished, the pressure of 8-12 kPa is preferably applied to the lapping surface. In the invention, the curing is preferably carried out at room temperature, and the curing time is preferably 2 to 5 days, and more preferably 3 to 4 days.
In the present invention, the adhesion strength of the polymer adhesive as a high strength adhesive is preferably 0.45 to 7.06 MPa. The invention controls the content of hydrophilic group (carboxyl) and hydrophobic group (methyl group and/or methyl) in the high molecular adhesive by limiting the molar ratio of methacrylic group to methyl methacrylate group in the high molecular adhesive, thereby regulating and controlling the cohesive force and the adhesive force in the adhesive, and further achieving the balance between the cohesive force and the adhesive force and enabling the high-strength adhesive to achieve the optimal adhesive strength. In the invention, the hydrophobic groups in the high molecular adhesive can form hydrophobic structural domains, thereby improving the adhesive strength of the adhesive.
In the present invention, the principle schematic diagram of the hydrophobic domain effect in the polymeric binder is shown in fig. 1; wherein (a) is a schematic diagram of hydrophobic domain formation between hydrophobic groups (methyl and methyl ester groups) in the poly (methacrylic acid-methyl methacrylate) copolymer, and (b) is a schematic diagram of the opening of the hydrophobic domain under the action of stress and the dissipation of partial stress.
In the present invention, a schematic diagram of the acting force between the polymer adhesive and different bonding substrates when the polymer adhesive is used as the adhesive is shown in fig. 2; when the bonding substrate is Wood, Wood in the figure is Wood, and lignin in the Wood and hydroxyl in cellulose form hydrogen bonds with carboxyl or carbonyl on methyl ester in the high molecular adhesive, so that the adhesion between the Wood and the poly (methacrylic acid-methyl methacrylate) copolymer is improved;
when the substrate to be bonded is metal, M in the figure is metal such as Fe, Cu, Al or SS, and the metal material and the carboxyl in the polymer adhesive form a coordination bond, so that the adhesion between the polymer adhesive and the metal material is improved;
when the substrate to be bonded is a polymer material, such as PMMA, PET, PVC or PP, R in the figure is a hydrophobic domain formed by hydrophobic groups in the poly (methacrylic acid-methyl methacrylate) copolymer, and hydrophobic-hydrophobic interaction is formed between the polymer material and the hydrophobic domain in the poly (methacrylic acid-methyl methacrylate) copolymer, so that the adhesion strength is improved.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Waste organic glass is purchased from a waste recycling station in the embodiment of the invention; 1, 4-dioxane was purchased from Xin platinum speciality chemical Co., Tianjin; potassium hydroxide was purchased from shin-shin science and technology development ltd, Tianjin; sodium hydroxide was purchased from the national pharmaceutical group chemical agents limited.
Example 1
Dissolving 10g of waste organic glass in 100mL of 1, 4-dioxane at 90 ℃, cooling the dissolved solution to 25 ℃, and filtering under reduced pressure (-0.09MPa) to obtain a waste organic glass solution;
mixing 100mL of waste organic glass solution with 30mL of saturated potassium hydroxide methanol solution (the mass ratio of the waste organic glass to the potassium hydroxide is 1:1.2), and carrying out hydrolysis reaction on the mixed solution at 90 ℃ for 48 h;
standing the hydrolysis reaction product, and removing a supernatant to obtain a hydrolysis reaction precipitate; dissolving 9.2g of a precipitate of hydrolysis reaction in 200mL of water to obtain an aqueous solution; dropwise adding the aqueous solution into 1.5L ethanol at a dropwise adding rate of 25 drops/min (with stirring at 600 r/min), carrying out solid-liquid separation, and drying the solid obtained by the solid-liquid separation at 75 ℃ for 12h to obtain a precipitate; redissolving 8g of precipitate in 500mL of water, and then retaining the molecular weight of the precipitate at 8000-14000 g & mol-1Dialyzing in a dialysis bag for 3 days, and drying at 80 deg.C and 600r/min for 12h to obtain polymer binder P66.
Example 2
Dissolving 10g of waste organic glass in 100mL of 1, 4-dioxane at 90 ℃, cooling the dissolved solution to 25 ℃, and filtering under reduced pressure (-0.09MPa) to obtain a waste organic glass solution;
mixing 100mL of waste organic glass solution with 30mL of saturated potassium hydroxide methanol solution (the mass ratio of the waste organic glass to the potassium hydroxide is 1:2), adding 3mL of deionized water into the mixed solution, and performing first incomplete hydrolysis at 90 ℃ for 48 h;
standing the first incomplete hydrolysis product, and removing a supernatant to obtain a first incompletely hydrolyzed precipitate; dissolving 9.5g of the first incompletely hydrolyzed precipitate in 200mL of water to obtain an aqueous solution; dropwise adding the aqueous solution into 3L of ethanol at a dropping rate of 30 drops/min (with stirring at a rotating speed of 850 r/min), carrying out solid-liquid separation, and drying the solid obtained by the solid-liquid separation at 80 ℃ for 11h to obtain a precipitate; dissolving 9g of precipitate in 500g of water, and then keeping the molecular weight cutoff at 8000-14000 g & mol-1Dialysis ofDialyzing in bag for 3 days; drying the water solution obtained by dialysis for 12 hours at the temperature of 85 ℃ and the rotating speed of 650r/min to obtain a first hydrolysate;
mixing 10g of first hydrolysate with 100mL of sodium hydroxide with the molar concentration of 1mol/L, refluxing at 120 ℃ for 24h, cooling the refluxed product to room temperature, and then keeping the molecular weight cutoff at 8000-14000 g & mol-1Dialyzing in the dialysis bag for 3 days; and (3) drying the water solution obtained by dialysis for 12 hours at the temperature of 90 ℃ and the rotating speed of 650r/min to obtain the polymer adhesive, which is recorded as P99.
Comparative example 1
Dissolving 10g of waste organic glass in 100mL of 1, 4-dioxane at 90 ℃, cooling to 25 ℃, and filtering under reduced pressure (-0.09MPa) to obtain a waste organic glass solution;
mixing the organic glass solution with a saturated potassium hydroxide methanol solution (the mass ratio of waste organic glass to potassium hydroxide is 1:0.84), and carrying out hydrolysis reaction on the mixed solution at 90 ℃ for 48 h;
standing the hydrolysis reaction product, and removing a supernatant to obtain a hydrolysis reaction precipitate; putting the precipitate of the hydrolysis reaction into water to obtain hydrogel; the molecular weight cut-off of the hydrogel is 8000-14000 g & mol-1Dialyzing in the dialysis bag for 3 days, and drying at 80 deg.C and 500r/min for 10 hr to obtain polymer binder P37.
Comparative example 2
Dissolving polyacrylic acid (PAA) with a relative molecular mass of 450000 in water to obtain a solution with a mass concentration of 50mg/ml, and adjusting the pH value of the solution to 10 by using sodium hydroxide; and volatilizing the water in the solution to obtain a sodium polymethacrylate solid.
Test example
P66 prepared in example 1 represents the molar ratio of methacrylic groups to methyl methacrylate groups in the polymeric binder is 66: 34; p99 prepared in example 2 represents that the molar ratio of methacrylic groups to methyl methacrylate groups in the polymeric binder is 99: 1; p37 prepared in comparative example 1 represents a molar ratio of methacrylic groups to methyl methacrylate groups in the polymeric binder of 37: 63.
Respectively carrying out nuclear magnetic detection on the waste organic glass, the polymer binders prepared in the examples 1 and 2 and the comparative example 1 to obtain a nuclear magnetic resonance spectrogram, as shown in fig. 3-6. Wherein, fig. 3 is a nuclear magnetic spectrum of waste organic glass; FIG. 4 is a nuclear magnetic spectrum of P66; FIG. 5 is a nuclear magnetic spectrum of P99, wherein B is a partial enlarged view of the part c-a in A; FIG. 6 is a nuclear magnetic spectrum of P37.
From FIG. 3, the methylene group (-CH) in the waste organic glass can be seen2-) has a single peak at a, and the methyl on the carbomethoxy group in the waste organic glass has a single peak at c, the corresponding relative integral areas of which are respectively 3 and 2, and the rest peaks are impurity peaks. As can be seen from fig. 4 to 6, the peak c in fig. 4 to 6 gradually decreases due to the progress of hydrolysis, the corresponding relative integral area also decreases, and the impurity peak disappears after the impurity removal. When the relative integrated area of the peak a is set to 2, the corresponding relative integrated area d of the peak c is calculated, and the degree of hydrolysis x% is (1-d/3) × 100. That is, in this copolymer, there are x% carboxyl groups and (100-x)% methyl esters; the carboxyl content of the three copolymers was calculated to be 66%, 99% and 37%, respectively.
0.5g of the polymer binder prepared in examples 1 and 2 and comparative example 1 was mixed with 0.5mL of water to obtain a high strength binder. After mixing 0.5g of the solid sodium polymethacrylate of comparative example 2 with 0.5mL of water, an adhesive was obtained.
The adhesives obtained in examples 1 and 2 and comparative example 1 were examined by atomic force microscopy to obtain a height map of atomic force microscopy, as shown in fig. 7. From fig. 7, it can be seen that the lower the carboxyl content of the hydrophilic group in the polymer binder, the higher the methyl ester content of the hydrophobic group, and the larger the hydrophobic domain formed. The stronger the intermolecular forces are demonstrated.
Detecting the adhesion strength:
grinding any one surface of an iron sheet, a stainless steel sheet, a copper sheet, an aluminum sheet, PMMA, PET, PP and PVC for 30s by using sand paper with the mesh number of 360;
respectively at 1cm2Surface painting after polishingAdhesive (coating amount is 1 μ L), so as to obtain a substrate coated with the adhesive;
lapping the polished surface of another substrate bonded with the same material with the substrate coated with the adhesive (the lapping area is 1 cm)2) Then applying pressure of 10kPa on the lapping surface, and curing for 2 days at room temperature to obtain an adhesive;
applying stress in the parallel direction to two sides of the bonding substrate of the bonding object, and continuously increasing the stress until the bonding object is disconnected to obtain the maximum stress; the maximum stress is divided by the overlap area to obtain the adhesive strength of the adhesive.
The adhesion strength of any adhesive to different substrates was measured in parallel 5 times and the average values are listed in table 1.
TABLE 1 adhesion Strength of adhesives of examples 1 and 2 and comparative examples 1 and 2 in different adhered substrates
Figure BDA0003073509270000131
The data in table 1 are used to plot a bar graph of the adhesive strength of the adhesives of examples 1 and 2 and comparative examples 1 and 2 in different adhesive substrates, as shown in fig. 8-11, and fig. 8 is a bar graph of the adhesive strength of the adhesive prepared in example 1; FIG. 9 is a bar graph of the adhesion strength of the adhesive prepared in example 2; FIG. 10 is a bar graph of the adhesive strength of the adhesive prepared in comparative example 1; fig. 11 is a bar graph showing the adhesive strength of the adhesive prepared in comparative example 2.
It can be seen from the table 1 and fig. 8-11 that the polymer adhesive provided by the present invention has high adhesion strength to different substrates.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (6)

1. A high molecular binder, wherein the high molecular binder is a poly (methacrylic acid-methyl methacrylate) copolymer;
the poly (methacrylic acid-methyl methacrylate) copolymer has a molar ratio of methacrylic acid groups to methyl methacrylate groups of 50-93: 7-50;
the high molecular adhesive is obtained by incomplete hydrolysis of waste organic glass under an alkaline condition.
2. The use of the polymeric binder of claim 1 in a high strength adhesive.
3. The use of claim 2, wherein the polymer binder is mixed with water and directly used as a high-strength binder.
4. The use according to claim 3, wherein the high strength adhesive is used in bonding substrates comprising metal, wood or polymeric materials.
5. Use according to claim 4, wherein the metal comprises iron, stainless steel, copper or aluminium.
6. Use according to claim 4, wherein the polymeric material comprises polymethylmethacrylate, polyethylene terephthalate, polypropylene or polyvinyl chloride.
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