CN108276935B - Negative ion environment-friendly adhesive based on acrylic resin and preparation method thereof - Google Patents
Negative ion environment-friendly adhesive based on acrylic resin and preparation method thereof Download PDFInfo
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- CN108276935B CN108276935B CN201810049857.0A CN201810049857A CN108276935B CN 108276935 B CN108276935 B CN 108276935B CN 201810049857 A CN201810049857 A CN 201810049857A CN 108276935 B CN108276935 B CN 108276935B
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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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an acrylic resin-based negative ion environment-friendly adhesive and a preparation method thereof. The anion environment-friendly glue is prepared by the following components in parts by weight through pre-polymerizing the components until the viscosity reaches 1000-30000mpa.s, and then quickly cooling to stop polymerization; 30-300 parts of acrylic acid monomer or methacrylic acid monomer; 0-300 parts of other free radical polymerization monomers not containing carboxylic acid groups; 1-60 parts of negative oxygen ion powder; 0.1-5 parts of free radical polymerization initiator; 0.1-5 parts of copper tropolone salt; 0.1-10 parts of a dispersing agent. Coating the negative oxygen ion powder through carboxyl on an acrylic resin monomer to form a micelle with a core-shell structure; heating to pre-polymerize the micelle to form environment-friendly glue with proper viscosity; the negative oxygen ion powder positioned in the micelle core endows the environment-friendly glue with the negative oxygen ion release function, and can inhibit the release of formaldehyde. The copper tropolone salt is a high-efficiency broad-spectrum antibacterial agent, can inhibit the growth of most harmful microorganisms in the living environment, and has the functions of mildew prevention and virus resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an acrylic resin-based negative ion environment-friendly adhesive and a preparation method thereof.
Background
At present, a large amount of adhesives are used in building construction, plate processing, furniture preparation and home decoration processes, and the adhesives have the problem of formaldehyde release to a greater or lesser extent. Formaldehyde, as a gas harmful to human, is known as indoor "life-saving killer", seriously harms the health of newly decorated families, especially children, pregnant women and old people. In addition, the release process of formaldehyde in furniture and home decoration is long and can last for years and even decades. Furniture and home furnishings can mildew along with environmental changes in the long-term use process and become vectors for virus and germ infection, and the service life and the human health of the furniture and the home furnishings can be influenced if the furniture and the home furnishings cannot be subjected to antibacterial treatment and disinfection in time.
Disclosure of Invention
The invention provides an anionic environment-friendly adhesive based on acrylic resin and a preparation method thereof, aiming at solving the problems of long-time formaldehyde release, mildew resistance and self-disinfection of interior decoration or interior furniture. The anion environment-friendly glue can inhibit the release of formaldehyde, reduce the pollution to the indoor environment caused by decoration or purchase of new furniture, prolong the service life of the furniture and the home furnishings, and inhibit the cross infection and the spread of viruses and germs.
In order to achieve the purpose, the invention adopts the following technical scheme:
the negative ion environment-friendly glue is prepared by the following components in parts by weight through pre-polymerizing the components until the viscosity reaches 1000-30000mpa.s, and then quickly cooling to stop polymerization;
30-300 parts of acrylic acid monomer or methacrylic acid monomer; preferably 30 to 100 parts, more preferably 30 to 50 parts;
0-300 parts of other free radical polymerization monomers not containing carboxylic acid groups; to adjust the amount of carboxyl groups in the polymer;
1-60 parts of negative oxygen ion powder; preferably 3-10 parts;
0.1-5 parts of free radical polymerization initiator;
0.1-5 parts of copper tropolone salt;
0.1-10 parts of dispersing agent.
Preferably, the component further comprises 0.1 to 10 parts by weight of a defoaming agent.
Preferably, the negative oxygen ion powder comprises tourmaline powder and albumen powder.
Preferably, the particle size of the negative oxygen ion powder is larger than 2000 meshes.
Preferably, the radical polymerization initiator is azobisisoheptonitrile, which may also be an analogous compound to azobisisoheptonitrile, as would be readily understood by one skilled in the art.
Using a monomer of polyacrylic acid or polymethacrylic acid resin as a base material, and coating the negative oxygen ion powder through carboxyl on the monomer to form a micelle with a core-shell structure; the micelle is polymerized in advance under the heating condition to form environment-friendly glue with proper viscosity; the negative oxygen ion powder positioned in the micelle core endows the environment-friendly glue with the negative oxygen ion release function, and can inhibit the release of formaldehyde. The copper tropolone salt is a high-efficiency broad-spectrum antibacterial agent, can inhibit the growth of most harmful microorganisms in the living environment, and has the functions of mildew prevention and virus resistance.
The acrylic acid and methacrylic acid monomers both contain carboxyl, and can be better combined with the negative oxygen ion powder, so that the negative oxygen ion powder is more uniformly dispersed and has better stability; compared with the polymer, the monomer has lower viscosity and higher mixing uniformity with other substances;
the invention also provides a preparation method of the negative ion environment-friendly adhesive, which comprises the following steps:
s1, adding a free radical polymerization initiator, negative oxygen ion powder, copper tropolone salt and a dispersing agent into an acrylic acid or methacrylic acid monomer, and stirring to form micelles;
s2, pre-polymerizing the micelle, and monitoring the viscosity of the prepolymer in real time;
and S3, rapidly cooling the prepolymer after the viscosity of the prepolymer reaches 1000-30000mpa.s to stop polymerization, and heating the prepolymer to room temperature to obtain the negative ion environment-friendly adhesive.
The preparation process of the invention does not use any organic solvent, thus reducing the cost and the emission of formaldehyde.
Preferably, 0.1 to 10 parts by weight of a defoaming agent is added depending on the state of the polymer after the temperature of the prepolymer is raised to room temperature.
Preferably, the preliminary polymerization is carried out by heating to 60 to 80 ℃.
The invention also provides a using method of the anion environment-friendly adhesive, wherein a free radical polymerization initiator is added before the anion environment-friendly adhesive is used, and the anion environment-friendly adhesive is fully stirred; the curing method of thermal curing or light curing is adopted in use.
Preferably, the amount of the radical polymerization initiator supplemented before use is between 0.1 and 3 percent of the total mass of the negative ion environment-friendly adhesive.
The present invention has the following advantageous effects
1) The acrylic acid and methacrylic acid monomers both contain carboxyl, and can be better combined with the negative oxygen ion powder, so that the negative oxygen ion powder is more uniformly dispersed and has better stability; compared with the polymer, the monomer has lower viscosity and higher mixing uniformity with other substances.
2) The negative oxygen ions are added into the corresponding glue as a negative oxygen ion source and can continuously provide negative oxygen ions (H)3O2-) The negative oxygen ions can make the formaldehyde lose volatility through charge interaction, and reduce the content of free formaldehyde in the air.
3) The copper tropolone salt is a high-efficiency broad-spectrum antibacterial agent, can inhibit the growth of most harmful microorganisms in the living environment, and has the functions of mildew prevention and virus resistance.
4) The preparation process does not use any organic solvent, so that the cost can be reduced, and the emission of formaldehyde is reduced.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustration, and are not to be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations to the invention in light of the above teachings. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
Example 1
30 parts of acrylic acid monomer, 0.1 part of copper tropolone salt, 0.1 part of azodiisoheptanonitrile, 0.1 part of dispersant and 3 parts of negative oxygen ion powder are put into a single-neck flask and stirred at the rotating speed of 600r/min until micelle is formed between the acrylic acid monomer and the negative oxygen ion powder. After micelle formation, the temperature is heated to 65 ℃, the viscosity is monitored in real time, after 45 minutes, the viscosity reaches 1600mpa.s, and the flask is transferred to liquid nitrogen for rapid cooling to stop the reaction. After warming to room temperature, 1 part of a defoaming agent was added, and the viscosity was 4300 mpa.s.
0.1 part of azobisisoheptonitrile is added before use. The environment-friendly glue is coated on the surface of wood (the thickness is 1.0mm), and is heated to 100 ℃ for curing for 1 hour, and the negative oxygen ion release amount on the surface of the board can reach 1500-2500 per cubic centimeter.
Example 2
50 parts of methacrylic acid monomer, 0.2 part of copper tropolone salt, 0.1 part of azodiisoheptanonitrile, 2 parts of dispersant and 10 parts of negative oxygen ion powder are put into a single-neck flask and stirred at the rotating speed of 600r/min until micelle is formed. After micelle formation, the temperature is heated to 65 ℃, the concentration of the micelle is monitored in real time, the viscosity reaches 1500mpa.s after 30 minutes, the flask is transferred to liquid nitrogen for rapid cooling, and the reaction is stopped. After warming to room temperature, 1 part of a defoaming agent was added, the viscosity of which was 4800 mpa.s. 0.5 part of azobisisoheptonitrile is added before use. The environment-friendly glue is coated on the surface (thickness is 1.0mm) of wood, the wood is heated to 100 ℃ and cured for 1 hour, and the release amount of negative oxygen ions on the surface of the cured board can reach 1800-3500 per cubic centimeter.
Example 3
30 parts of acrylic monomer, 20 parts of N-methylmaleimide, 1 part of copper tropolone salt, 0.1 part of azodiisoheptanonitrile, 10 parts of dispersant and 10 parts of negative oxygen ion powder are put into a single-neck flask and stirred at the rotating speed of 600r/min until micelle is formed between the acrylic monomer and the negative oxygen ion powder. After micelle formation, the temperature is heated to 65 ℃, the concentration of the micelle is monitored in real time, after 35 minutes, the viscosity reaches 1500mpa.s, the flask is transferred into liquid nitrogen for rapid cooling, and the reaction is stopped. After warming to room temperature, 1 part of an antifoaming agent was added, and the viscosity was 5300 mpa.s. 1 part of azodiisoheptanonitrile is added before use. The environment-friendly glue is coated on the surface (thickness is 1.0mm) of wood, the surface of the wood is cured by ultraviolet lamp irradiation for 30 seconds, and the release amount of negative oxygen ions on the surface of the cured board can reach 1000-2300 per cubic centimeter.
Example 4
200 parts of acrylic monomer, 4 parts of tropolone copper salt, 0.15 part of azodiisoheptanonitrile, 8 parts of dispersant and 55 parts of negative oxygen ion powder are put into a single-neck flask and stirred at the rotating speed of 600r/min until micelle is formed between the acrylic monomer and the negative oxygen ion powder. After micelle formation, the temperature is heated to 75 ℃, the concentration of the micelle is monitored in real time, after 35 minutes, the viscosity reaches 25000mpa.s, the flask is transferred to liquid nitrogen for rapid cooling, and the reaction is stopped. After warming to room temperature, 0.2 part of an antifoaming agent was added, and the viscosity was 53000 mpa.s. 8 parts of azobisisoheptonitrile is added before use. The environment-friendly glue is coated on the surface (thickness is 10.0mm) of wood, the surface of the wood is cured by ultraviolet lamp irradiation for 30 seconds, and the release amount of negative oxygen ions on the surface of the cured board can reach 1000-3000 per cubic centimeter.
Example 5
200 parts of acrylic monomer, 250 parts of N-methylmaleimide, 5 parts of tropolone copper salt, 5 parts of azodiisoheptanonitrile, 10 parts of dispersant and 60 parts of negative oxygen ion powder are put into a single-neck flask and stirred at the rotating speed of 600r/min until micelle is formed between the acrylic monomer and the negative oxygen ion powder. After micelle formation, heating to 65 ℃, monitoring the concentration in real time, after 35 minutes, the viscosity reaches 6500mpa.s, transferring the flask into liquid nitrogen for rapid cooling, and stopping the reaction. After warming to room temperature, 8 parts of a defoaming agent was added, the viscosity of which was 8000 mpa.s. 12 parts of azobisisoheptonitrile is added before use. The environment-friendly glue is coated on the surface (the thickness is 2.0mm) of wood, the surface of the wood is cured by ultraviolet lamp irradiation for 30 seconds, and the release amount of negative oxygen ions on the surface of the cured board can reach 800-1700 per cubic centimeter.
It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
Claims (9)
1. The negative ion environment-friendly adhesive based on acrylic resin is characterized by being prepared by pre-polymerizing components with the following weight parts until the viscosity reaches 1000-30000mpa.s, and then rapidly cooling and stopping polymerization;
30-300 parts of acrylic acid monomer or methacrylic acid monomer;
1-60 parts of negative oxygen ion powder;
0.1-5 parts of free radical polymerization initiator;
0.1-5 parts of copper tropolone salt;
0.1-10 parts of a dispersant;
the preparation method of the negative ion environment-friendly adhesive comprises the following steps:
s1, adding a free radical polymerization initiator, negative oxygen ion powder, copper tropolone salt and a dispersing agent into an acrylic acid or methacrylic acid monomer, and stirring to form micelles;
s2, pre-polymerizing the micelle, and monitoring the viscosity of the prepolymer in real time;
s3, rapidly cooling the prepolymer after the viscosity of the prepolymer reaches 1000-30000mpa.s to stop polymerization, and heating the prepolymer to room temperature to obtain the negative ion environment-friendly adhesive;
wherein the micelle is heated to 60-80 ℃ to be polymerized in advance.
2. The negative ion environment-friendly adhesive according to claim 1, further comprising 0.1 to 10 parts by weight of a defoaming agent.
3. The negative ion environment-friendly adhesive as claimed in claim 1, wherein the negative oxygen ion powder comprises tourmaline powder and albumen powder.
4. The negative ion environment-friendly adhesive as claimed in claim 1, wherein the particle size of the negative oxygen ion powder is larger than 2000 meshes.
5. The negative ion environment-friendly adhesive as claimed in claim 1, wherein the radical polymerization initiator is azobisisoheptonitrile.
6. The preparation method of the negative ion environment-friendly adhesive as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
s1, adding a free radical polymerization initiator, negative oxygen ion powder, copper tropolone salt and a dispersing agent into an acrylic acid or methacrylic acid monomer, and stirring to form micelles;
s2, pre-polymerizing the micelle, and monitoring the viscosity of the prepolymer in real time;
s3, rapidly cooling the prepolymer to stop polymerization after the viscosity of the prepolymer reaches 1000-30000mpa.s, and heating the prepolymer to room temperature to obtain the negative ion environment-friendly adhesive
Wherein the micelle is heated to 60-80 ℃ to be polymerized in advance.
7. The method according to claim 6, wherein 0.1 to 10 parts by weight of the antifoaming agent is added after the temperature of the prepolymer is raised to room temperature.
8. The use method of the anion environment-friendly glue as claimed in any one of claims 1 to 5, characterized in that a free radical polymerization initiator is added before use, and the mixture is fully stirred; the curing method of thermal curing or light curing is adopted in use.
9. The use method of claim 8, wherein the amount of the radical polymerization initiator added before use is between 0.1 and 3 percent of the total mass of the negative ion environment-friendly adhesive.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810049857.0A CN108276935B (en) | 2018-01-18 | 2018-01-18 | Negative ion environment-friendly adhesive based on acrylic resin and preparation method thereof |
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| CN201810049857.0A CN108276935B (en) | 2018-01-18 | 2018-01-18 | Negative ion environment-friendly adhesive based on acrylic resin and preparation method thereof |
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| CN108276935A CN108276935A (en) | 2018-07-13 |
| CN108276935B true CN108276935B (en) | 2020-06-02 |
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| CN111172332B (en) * | 2020-01-13 | 2022-05-20 | 兴业皮革科技股份有限公司 | Negative oxygen ion chrome tanning agent and preparation method and application thereof |
| CN112980358A (en) * | 2021-03-04 | 2021-06-18 | 吉安迅达科技有限公司 | Environment-friendly energy-saving adhesive and preparation method thereof |
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| KR101346442B1 (en) * | 2008-06-25 | 2014-01-15 | 바스프 에스이 | Cosmetic compositions, benzotropolone derivatives, and methods for synthesizing benzotropolone derivatives |
| CN102528866A (en) * | 2012-01-11 | 2012-07-04 | 辽宁科技大学 | Preparation method for novel wood preservative |
| CN107163667A (en) * | 2016-03-07 | 2017-09-15 | 许继胜 | Negative oxygen ion emulsion auxiliary agent |
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