CN114605943A - Recyclable adhesive lost when heated - Google Patents
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- CN114605943A CN114605943A CN202210306445.7A CN202210306445A CN114605943A CN 114605943 A CN114605943 A CN 114605943A CN 202210306445 A CN202210306445 A CN 202210306445A CN 114605943 A CN114605943 A CN 114605943A
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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
- C09J131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
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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
- C09J11/08—Macromolecular additives
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Abstract
The invention discloses a recyclable adhesive lost when heated. The preparation method of the viscose glue losing under heat comprises the following steps: putting ethyl acetate and toluene into a reaction kettle; heating to 65-75 ℃, and adding butyl acrylate, isooctyl acrylate, a monomer and an initiator; continuously heating to 85-95 ℃, and preserving heat for 3.5-4.5 hours; adding benzoyl peroxide, keeping the temperature for 0.5-1 hour, cooling to 40-50 ℃, adding acrylic acid high polymer, and stirring for 1-1.5 hours to obtain the adhesive lost by heat. According to the scheme, the acrylic acid high polymer with the molecular weight of 60000-80000 is prepared and used for preparing the adhesive losing under heat, and due to the high toughness, the acrylic acid high polymer can automatically fall off from the adhesive at the high temperature of more than 100 ℃ after being added into the adhesive losing under heat, so that the acrylic acid high polymer is recycled and has a recyclable value.
Description
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to a recyclable adhesive losing heat.
Background
Pressure sensitive adhesives are a class of pressure sensitive adhesives having liquid adhesion and solid viscoelasticity. It has good wettability and initial viscosity, and can be extensively used in various industries of packaging, decoration and electronics, etc. Most of the existing pressure-sensitive adhesives are disposable, are not environment-friendly after being discarded after being used, need to be subjected to special post-treatment by departments with relevant qualifications after being recycled, and have high cost and low economic benefit. Meanwhile, with the development of the electronic information industry in China in recent years, the adhesive tape is usually used in the processing process of electronic product elements, but the quality of the electronic elements is affected due to incomplete later peeling. Therefore, there are demands for green development advocated for environmental protection and for the field of electronic component processing; the development direction of pressure-sensitive adhesives is moving towards the development of recyclable, peelable adhesives. On one hand, the adhesive meets good initial adhesion and can be firmly attached to the surface of a device; and on the other hand, the stripping removability is met, the surface of the device can not be polluted, and the quality of the device is ensured.
The existing peelable glue products are usually two peelable glues, namely light response peelable glue and temperature response peelable glue, wherein compared with the light response peelable glue, the temperature response peelable glue has the advantages of simpler product control and lower price. However, the existing peelable glue has insufficient toughness and poor cohesion, and residual glue is easy to generate during peeling; meanwhile, most peelable adhesives have no flame retardance, and the application range is limited.
In conclusion, the preparation of the recyclable preheating lost viscose glue has important significance.
Disclosure of Invention
The invention aims to provide a recyclable adhesive lost when heated so as to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of recyclable viscose lost when heated comprises the following steps: putting ethyl acetate and toluene into a reaction kettle; heating to 65-75 ℃, and adding butyl acrylate, isooctyl acrylate, a monomer and an initiator; continuously heating to 85-95 ℃, and preserving heat for 3.5-4.5 hours; adding benzoyl peroxide, keeping the temperature for 0.5-1 hour, cooling to 40-50 ℃, adding acrylic acid high polymer, and stirring for 1-1.5 hours to obtain the adhesive lost by heat.
Preferably, the raw materials of the viscose lost when heated comprise the following components: the coating comprises, by weight, 5-10 parts of butyl acrylate, 30-40 parts of isooctyl acrylate, 5-10 parts of a monomer, 2-4 parts of an acrylic acid high polymer, 40-50 parts of ethyl acetate, 5-10 parts of toluene, 0.1-0.2 part of an initiator and 0.2-0.4 part of benzoyl peroxide.
Preferably, the monomer is one or two of acrylic acid and methyl acrylate; the initiator is one or more of azobisisobutyronitrile and azobisisovaleronitrile.
Preferably, the molecular weight of the acrylic high polymer is 60000-80000.
Preferably, the preparation method of the acrylic polymer comprises the following steps: adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting at 100-120 ℃ for 3-6 hours to obtain the acrylic polymer.
Preferably, the preparation method of the acrylic polymer comprises the following steps: adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting for 3-6 hours at the set temperature of 100-120 ℃; and cooling to 30 ℃, adding 2-hydroxyethyl sorbate, methyl sorbate and 2,2' -azobis (2, 4-dimethylvaleronitrile), and reacting for 1-2 hours to obtain the acrylic polymer.
Preferably, in the acrylic polymer, the mass ratio of the methacrylate, the 2-hydroxyethyl methacrylate phosphate and the methacrylamide composite monomer is 1 (0.08-0.1) to 0.20-0.25; the total weight of the 2-hydroxyethyl sorbate and the methyl sorbate is 5-6 wt% of the first-grade acrylate, and the mass ratio of the 2-hydroxyethyl sorbate to the methyl sorbate is 2: 1.
Preferably, the preparation method of the methacrylamide composite monomer comprises the following steps: sequentially adding hydroxyacetamide, triethylamine and dichloromethane into a reaction kettle, slowly adding methacryloyl chloride at room temperature, and stirring for reacting for 20-24 hours; adding methanol for dilution; washing and drying to obtain methacrylamide; ultrasonically dispersing the mixture in water to obtain a methacrylamide aqueous solution, adding a vinylphosphonic acid aqueous solution, and uniformly stirring; adding potassium persulfate, reacting for 2-3 hours at the set temperature of 60-65 ℃, washing and drying to obtain the methacrylamide composite monomer.
Preferably, the mass ratio of the methacrylamide to the vinylphosphonic acid is 1 (0.8-1); the concentration of the methacrylamide aqueous solution is 35-40 wt%; the concentration of the vinylphosphonic acid aqueous solution is 38-40 wt%.
Preferably, the adhesive which can be recovered and loses after being heated is prepared by the preparation method of the adhesive which loses after being heated.
According to the technical scheme, the acrylic acid high polymer with the molecular weight of 60000-80000 is prepared and used for preparing the adhesive losing under heat, and due to the high toughness, the acrylic acid high polymer can automatically fall off from the adhesive at the high temperature of more than 100 ℃ after being added into the adhesive losing under heat, so that the acrylic acid high polymer is recycled and has a recyclable value.
In the scheme, two acrylic acid high polymers are disclosed, wherein the first acrylic acid high polymer is obtained by taking methacrylic acid ester as a main monomer, 2-hydroxyethyl methacrylate phosphate and methacrylamide composite monomer as auxiliary monomers, n-octyl mercaptan as a chain transfer agent and azobisisobutyronitrile as an initiator through polymerization reaction. The second is to continue grafting sorbate in the first acrylic acid copolymerization to reduce the stripping time.
The 2-hydroxyethyl methacrylate phosphate and methacrylamide composite monomer is added to increase the tensile strength and toughness of the acrylic high polymer, so that the cohesive force of the adhesive during stripping is increased, and if the cohesive force of the adhesive is insufficient, residual adhesive is generated after stripping. On the other hand, the addition of the two substances synergistically enhances the flame retardancy of the adhesive which loses its flame resistance when exposed to heat. It should be noted that: the addition of 2-hydroxyethyl methacrylate phosphate can increase the tensile strength of the acrylic polymer, but when the graft amount thereof exceeds 10% of the methacrylate, the tensile strength is decreased; however, when the addition amount is 10 wt%, the viscose can not generate flame retardance when being heated, so that a methacrylamide composite monomer is introduced in the scheme, and phosphate groups are grafted through reaction to generate flame retardance, so that the flame retardance is synergistically increased with 2-hydroxyethyl methacrylate phosphate. Meanwhile, the methacrylamide composite monomer enhances the toughness of the acrylic acid high polymer and improves the impact strength. Meanwhile, the flexibility of the acrylic polymer molecular chain is improved by adding the two monomers, and the amido bond and the hydroxyl contained in the acrylic polymer molecular chain can form hydrogen bond acting force at high temperature, so that the cohesive force of the viscose is increased when the viscose is lost by heat, the interaction adhesion fails due to the acting force among molecules, and the residue after stripping is reduced.
In addition, the scheme utilizes a free radical reaction to continue grafting the polysorbate in the first acrylic acid copolymerization, and the grafting process further reduces the high-temperature stripping time because the thermal degradation of peroxide chain breakage in the polysorbate can reduce the stripping strength value, and simultaneously gas generated at high temperature (above 100 ℃) effectively reduces the stripping time, and substances such as fumaric monoester, acetaldehyde and the like can be generated in the degradation process, so that the cohesive force is increased, and the stripping acting force is reduced.
The flame retardance is as follows: phosphoric acid groups in the two monomers and amino groups in the polyamide generate polyphosphoric acid in a flame-retardant process, so that the polymer is dehydrated and carbonized to form a carbon layer and oxygen insulation, and the amino groups can generate ammonia gas to dilute oxygen gas.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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 protection scope of the present invention.
Example 1:
a preparation method of recyclable viscose lost when heated comprises the following steps: putting 40 parts of ethyl acetate and 10 parts of toluene into a reaction kettle; heating to 70 ℃, and adding 5 parts of butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of acrylic acid and 0.2 part of azobisisobutyronitrile; continuously heating to 90 ℃, and preserving heat for 4 hours; adding 0.1 part of benzoyl peroxide, keeping the temperature for 1 hour, and cooling to 45 ℃ to obtain the viscose lost by heat.
Example 2:
a preparation method of recyclable viscose lost by heat comprises the following steps: putting 40 parts of ethyl acetate and 10 parts of toluene into a reaction kettle; heating to 70 ℃, and adding 5 parts of butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate and 0.2 part of azobisisobutyronitrile; continuously heating to 90 ℃, and preserving heat for 4 hours; adding 0.1 part of benzoyl peroxide, keeping the temperature for 1 hour, and cooling to 45 ℃ to obtain the viscose lost by heat.
Example 3:
a preparation method of recyclable viscose lost when heated comprises the following steps:
(1) sequentially adding hydroxyacetamide, triethylamine and dichloromethane into a reaction kettle, slowly adding methacryloyl chloride at room temperature, and stirring for reaction for 22 hours; adding methanol for dilution; washing and drying to obtain methacrylamide; ultrasonically dispersing the mixture in water to obtain a methacrylamide aqueous solution, adding a vinylphosphonic acid aqueous solution, and uniformly stirring; adding potassium persulfate, setting the temperature at 60 ℃, reacting for 2.5 hours, washing and drying to obtain the methacrylamide composite monomer.
(2) Adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting for 4 hours at the set temperature of 110 ℃; cooling to 30 ℃, adding 2-hydroxyethyl sorbate, methyl sorbate and 2,2' -azobis (2, 4-dimethyl valeronitrile), and reacting for 1.5 hours to obtain the acrylic polymer.
(3) Putting 40 parts of ethyl acetate and 10 parts of toluene into a reaction kettle; heating to 70 ℃, and adding 5 parts of butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of acrylic acid and 0.2 part of azobisisobutyronitrile; continuously heating to 90 ℃, and preserving heat for 4 hours; adding 0.1 part of benzoyl peroxide, keeping the temperature for 1 hour, cooling to 45 ℃, and adding 2 parts of acrylic acid high polymer to obtain the adhesive losing heat.
In the scheme, in the step 1, the mass ratio of hydroxyacetamide, triethylamine and methylene dichloride methacryloyl chloride is 1:0.9:10: 0.9; the mass ratio of the methacrylamide to the vinylphosphonic acid is 1: 0.9; the concentration of the aqueous methacrylamide solution was 35 wt%; the concentration of the aqueous solution of vinylphosphonic acid was 38 wt.%. In the step 2, the mass ratio of the methacrylate, the 2-hydroxyethyl methacrylate phosphate and the methacrylamide composite monomer is 1:0.1: 0.23; 2-hydroxyethyl sorbate and methyl sorbate in an amount of 6 wt% of the first-grade acrylateAnd methyl sorbate in a mass ratio of 2: 1; the molecular weight of the acrylic high polymer is 7.3 multiplied by 104。
Example 4:
a preparation method of recyclable viscose lost when heated comprises the following steps:
(1) sequentially adding hydroxyacetamide, triethylamine and dichloromethane into a reaction kettle, slowly adding methacryloyl chloride at room temperature, and stirring for reaction for 22 hours; adding methanol for dilution; washing and drying to obtain methacrylamide; ultrasonically dispersing the mixture in water to obtain a methacrylamide aqueous solution, adding a vinylphosphonic acid aqueous solution, and uniformly stirring; adding potassium persulfate, setting the temperature at 60 ℃, reacting for 2.5 hours, washing and drying to obtain the methacrylamide composite monomer.
(2) Adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting for 4 hours at the set temperature of 110 ℃; and cooling to 30 ℃ to obtain the acrylic acid high polymer.
(3) Putting 40 parts of ethyl acetate and 10 parts of toluene into a reaction kettle; heating to 70 ℃, and adding 5 parts of butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate and 0.2 part of azobisisobutyronitrile; continuously heating to 90 ℃, and preserving heat for 4 hours; adding 0.1 part of benzoyl peroxide, keeping the temperature for 1 hour, cooling to 45 ℃, and adding 2 parts of acrylic acid high polymer to obtain the adhesive losing heat.
In the scheme, in the step 1, the mass ratio of hydroxyacetamide, triethylamine and methylene dichloride methacryloyl chloride is 1:0.9:10: 0.9; the mass ratio of the methacrylamide to the vinylphosphonic acid is 1: 0.9; the concentration of the aqueous methacrylamide solution was 35 wt%; the concentration of the aqueous solution of vinylphosphonic acid is 38 wt.%. In the step 2, the mass ratio of the methacrylate, the 2-hydroxyethyl methacrylate phosphate and the methacrylamide composite monomer is 1:0.1: 0.23; the molecular weight of the acrylic high polymer is 6.9 multiplied by 104。
Example 5:
a preparation method of recyclable viscose lost when heated comprises the following steps:
(1) sequentially adding hydroxyacetamide, triethylamine and dichloromethane into a reaction kettle, slowly adding methacryloyl chloride at room temperature, and stirring for reaction for 22 hours; adding methanol for dilution; washing and drying to obtain methacrylamide; ultrasonically dispersing the mixture in water to obtain a methacrylamide aqueous solution, adding a vinylphosphonic acid aqueous solution, and uniformly stirring; adding potassium persulfate, setting the temperature at 60 ℃, reacting for 2.5 hours, washing and drying to obtain the methacrylamide composite monomer.
(2) Adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting for 4 hours at the set temperature of 110 ℃; cooling to 30 ℃, adding 2-hydroxyethyl sorbate, methyl sorbate and 2,2' -azobis (2, 4-dimethyl valeronitrile), and reacting for 1.5 hours to obtain the acrylic polymer.
(3) Putting 40 parts of ethyl acetate and 10 parts of toluene into a reaction kettle; heating to 70 ℃, and adding 5 parts of butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate and 0.2 part of azobisisobutyronitrile; continuously heating to 90 ℃, and preserving heat for 4 hours; adding 0.1 part of benzoyl peroxide, keeping the temperature for 1 hour, cooling to 45 ℃, and adding 2 parts of acrylic acid high polymer to obtain the adhesive losing heat.
In the scheme, in the step 1, the mass ratio of hydroxyacetamide, triethylamine and methylene dichloride methacryloyl chloride is 1:0.9:10: 0.9; the mass ratio of the methacrylamide to the vinylphosphonic acid is 1: 0.9; the concentration of the aqueous methacrylamide solution was 35 wt%; the concentration of the aqueous solution of vinylphosphonic acid is 38 wt.%. In the step 2, the mass ratio of the methacrylate, the 2-hydroxyethyl methacrylate phosphate and the methacrylamide composite monomer is 1:0.1: 0.23; the total weight of the 2-hydroxyethyl sorbate and the methyl sorbate is 6 wt% of the first-grade acrylate, and the mass ratio of the 2-hydroxyethyl sorbate to the methyl sorbate is 2: 1; the molecular weight of the acrylic high polymer is 7.3 multiplied by 104。
Example 6:
a preparation method of recyclable viscose lost when heated is characterized by comprising the following steps: the method comprises the following steps:
(1) sequentially adding hydroxyacetamide, triethylamine and dichloromethane into a reaction kettle, slowly adding methacryloyl chloride at room temperature, and stirring for reacting for 20 hours; adding methanol for dilution; washing and drying to obtain methacrylamide; ultrasonically dispersing the mixture in water to obtain a methacrylamide aqueous solution, adding a vinylphosphonic acid aqueous solution, and uniformly stirring; adding potassium persulfate, setting the temperature at 60 ℃, reacting for 3 hours, washing and drying to obtain the methacrylamide composite monomer.
(2) Adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting for 6 hours at the set temperature of 100 ℃; cooling to 30 ℃, adding 2-hydroxyethyl sorbate, methyl sorbate and 2,2' -azobis (2, 4-dimethyl valeronitrile), and reacting for 1 hour to obtain the acrylic polymer.
(3) Putting 40 parts of ethyl acetate and 5 parts of toluene into a reaction kettle; heating to 65 ℃, and adding 5-10 parts of butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of monomer methyl acrylate and 0.1 part of azobisisobutyronitrile; continuously heating to 85 ℃, and preserving heat for 3.5 hours; adding 0.2 part of benzoyl peroxide, keeping the temperature for 0.5 hour, cooling to 40 ℃, adding 2 parts of acrylic acid high polymer, and stirring for 1 hour to obtain the adhesive lost by heat.
In the scheme, in the step 1, the mass ratio of hydroxyacetamide, triethylamine and methylene dichloride methacryloyl chloride is 1:0.9:10: 0.9; the mass ratio of the methacrylamide to the vinyl phosphonic acid is 1: 0.8; the concentration of the aqueous methacrylamide solution was 35 wt%; the concentration of the aqueous solution of vinylphosphonic acid is 38 wt.%. In the step 2, the mass ratio of the methacrylate, the 2-hydroxyethyl methacrylate phosphate and the methacrylamide composite monomer is 1:0.08: 0.20; the total weight of the 2-hydroxyethyl sorbate and the methyl sorbate is 5 wt% of the first-grade acrylate, and the mass ratio of the 2-hydroxyethyl sorbate to the methyl sorbate is 2: 1; the molecular weight of the acrylic high polymer is 6.7 multiplied by 104。
Example 7:
a preparation method of recyclable viscose lost when heated is characterized by comprising the following steps: the method comprises the following steps:
(1) sequentially adding hydroxyacetamide, triethylamine and dichloromethane into a reaction kettle, slowly adding methacryloyl chloride at room temperature, and stirring for reacting for 24 hours; adding methanol for dilution; washing and drying to obtain methacrylamide; ultrasonically dispersing the mixture in water to obtain a methacrylamide aqueous solution, adding a vinylphosphonic acid aqueous solution, and uniformly stirring; adding potassium persulfate, setting the temperature to 65 ℃, reacting for 2 hours, washing and drying to obtain the methacrylamide composite monomer.
(2) Adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting for 3 hours at the set temperature of 120 ℃; cooling to 30 ℃, adding 2-hydroxyethyl sorbate, methyl sorbate and 2,2' -azobis (2, 4-dimethyl valeronitrile), and reacting for 2 hours to obtain the acrylic polymer.
(3) Putting 50 parts of ethyl acetate and 10 parts of toluene into a reaction kettle; heating to 75 ℃, and adding 10 parts of butyl acrylate, 40 parts of isooctyl acrylate, 10 parts of methyl acrylate and 0.2 part of azobisisobutyronitrile; continuously heating to 95 ℃, and preserving heat for 4.5 hours; adding 0.4 part of benzoyl peroxide, keeping the temperature for 1 hour, cooling to 50 ℃, adding 3 parts of acrylic acid high polymer, and stirring for 1-1.5 hours to obtain the adhesive lost by heat.
In the scheme, in the step 1, the mass ratio of hydroxyacetamide, triethylamine and methylene dichloride methacryloyl chloride is 1:0.9:10: 0.9; the mass ratio of the methacrylamide to the vinylphosphonic acid is 1: 1; the concentration of the methacrylamide aqueous solution is 40 wt%; the concentration of the vinylphosphonic acid aqueous solution is 40 wt.%. In the step 2, the mass ratio of the methacrylate, the 2-hydroxyethyl methacrylate phosphate and the methacrylamide composite monomer is 1:0.1: 0.25; the total weight of the 2-hydroxyethyl sorbate and the methyl sorbate is 6 wt% of the first-grade acrylate, and the mass ratio of the 2-hydroxyethyl sorbate to the methyl sorbate is 2: 1; the molecular weight of the acrylic high polymer is 7.8 multiplied by 104。
Example 8:
a preparation method of recyclable viscose lost when heated comprises the following steps:
(1) sequentially adding hydroxyacetamide, triethylamine and dichloromethane into a reaction kettle, slowly adding methacryloyl chloride at room temperature, and stirring for reaction for 22 hours; adding methanol for dilution; washing and drying to obtain methacrylamide; ultrasonically dispersing the mixture in water to obtain a methacrylamide aqueous solution, adding a vinylphosphonic acid aqueous solution, and uniformly stirring; adding potassium persulfate, setting the temperature at 60 ℃, reacting for 2.5 hours, washing and drying to obtain the methacrylamide composite monomer.
(2) Adding methacrylate, 2-hydroxyethyl methacrylate phosphate, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting for 4 hours at the set temperature of 110 ℃; cooling to 30 ℃, adding 2-hydroxyethyl sorbate, methyl sorbate and 2,2' -azobis (2, 4-dimethyl valeronitrile), and reacting for 1.5 hours to obtain the acrylic polymer.
(3) Putting 40 parts of ethyl acetate and 10 parts of toluene into a reaction kettle; heating to 70 ℃, and adding 5 parts of butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate and 0.2 part of azobisisobutyronitrile; continuously heating to 90 ℃, and preserving heat for 4 hours; adding 0.1 part of benzoyl peroxide, keeping the temperature for 1 hour, cooling to 45 ℃, and adding 2 parts of acrylic acid high polymer to obtain the adhesive losing heat.
In the scheme, in the step 1, the mass ratio of hydroxyacetamide, triethylamine and methylene dichloride methacryloyl chloride is 1:0.9:10: 0.9; the mass ratio of the methacrylamide to the vinylphosphonic acid is 1: 0.9; the concentration of the aqueous methacrylamide solution was 35 wt%; the concentration of the aqueous solution of vinylphosphonic acid is 38 wt.%. In the step 2, the mass ratio of the methacrylate to the 2-hydroxyethyl methacrylate phosphate is 1: 0.3; the total weight of the 2-hydroxyethyl sorbate and the methyl sorbate is 6 wt% of the methyl acrylate, and the mass ratio of the 2-hydroxyethyl sorbate to the methyl sorbate is 2: 1; the molecular weight of the acrylic high polymer is 7.1 multiplied by 104。
Example 9:
a preparation method of recyclable viscose lost when heated comprises the following steps:
(1) sequentially adding hydroxyacetamide, triethylamine and dichloromethane into a reaction kettle, slowly adding methacryloyl chloride at room temperature, and stirring for reaction for 22 hours; adding methanol for dilution; washing and drying to obtain methacrylamide; ultrasonically dispersing the mixture in water to obtain a methacrylamide aqueous solution, adding a vinylphosphonic acid aqueous solution, and uniformly stirring; adding potassium persulfate, setting the temperature at 60 ℃, reacting for 2.5 hours, washing and drying to obtain the methacrylamide composite monomer.
(2) Adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting for 4 hours at the set temperature of 110 ℃; cooling to 30 ℃, adding 2-hydroxyethyl sorbate, methyl sorbate and 2,2' -azobis (2, 4-dimethyl valeronitrile), and reacting for 1.5 hours to obtain the acrylic polymer.
(3) Putting 40 parts of ethyl acetate and 10 parts of toluene into a reaction kettle; heating to 70 ℃, and adding 5 parts of butyl acrylate, 30 parts of isooctyl acrylate, 5 parts of methyl acrylate and 0.2 part of azobisisobutyronitrile; continuously heating to 90 ℃, and preserving heat for 4 hours; adding 0.1 part of benzoyl peroxide, keeping the temperature for 1 hour, cooling to 45 ℃, and adding 2 parts of acrylic acid high polymer to obtain the adhesive losing heat.
In the scheme, in the step 1, the mass ratio of hydroxyacetamide, triethylamine and methylene dichloride methacryloyl chloride is 1:0.9:10: 0.9; the mass ratio of the methacrylamide to the vinylphosphonic acid is 1: 0.9; the concentration of the aqueous methacrylamide solution was 35 wt%; the concentration of the aqueous solution of vinylphosphonic acid is 38 wt.%. In the step 2, the mass ratio of the methacrylate and methacrylamide composite monomer is 1: 0.3; the total weight of the 2-hydroxyethyl sorbate and the methyl sorbate is 6 wt% of the first-grade acrylate, and the mass ratio of the 2-hydroxyethyl sorbate to the methyl sorbate is 2: 1; the molecular weight of the acrylic high polymer is 5.5 multiplied by 104。
Experiment: performing performance test on the recyclable adhesive lost when heated prepared in the embodiments 1 to 9; wherein the viscidity can be lost by heating, the prepared viscidity can be hung on a PET film with the coating thickness of 50 μm, and the PET film is put into a 70 ℃ oven to be dried for 30 minutes. After 24 hours of standing, the film was immersed in 100 ℃ hot water to see whether the glue could be separated from the PET film. The data obtained are shown in the following table:
| examples | Hot water soaking time | Situation of separation | LOI |
| Example 1 | 3min | Can not be separated | 17.9％ |
| Example 2 | 3min | Can not be separated | 18.0％ |
| Example 3 | 3min | Partial separation | 22.5％ |
| Example 4 | 3min | All separate | 22.7％ |
| Example 5 | 1min | All separate | 23.1％ |
| Example 6 | 3min | All separate | 23.0％ |
| Example 7 | 3min | All separate | 23.2％ |
| Example 8 | 5min | With residual glue | 23.1％ |
| Example 9 | 5min | With residual glue | 23.5％ |
And (4) conclusion: from the data in the table, it can be seen that the prepared adhesive which loses adhesion when heated has the performance of quick debonding, the fastest time is as low as 2 minutes, and meanwhile, the prepared adhesive has the flame retardant performance.
Comparing the data of examples 1-2 with those of examples 3-4, it can be seen that the adhesive without acrylic polymer is not degummed and has no flame retardancy after being treated at 100 ℃ for 3 minutes; the performance of quick viscosity loss under heat is shown to come from acrylic acid high polymer, because the acrylic acid high polymer has toughness, and amido bond and hydroxyl contained in the acrylic acid high polymer can form hydrogen bond acting force at high temperature, thereby increasing the cohesive force of the viscosity loss under heat, and causing the interaction adhesion failure due to the intermolecular acting force. Further comparing the data of examples 3-4, it can be found that the selection of acrylic acid or methyl acrylate as the monomer has an influence on the degumming effect; the reason is that the boiling point of methyl acrylate is 80 ℃, which is beneficial to debonding.
Comparing the data of example 5 with the data of example 4, it can be found that: the debonding time was further increased because the acrylic polymer of example 5 was grafted with polysorbate (boiling point 100 deg.C), which thermally degrades and can reduce the peel strength value, effectively reducing the peel time. In comparison with the data of examples 8 to 9, it can be found that: in example 8, the peeling time was increased without adding a methacrylamide complex monomer; the reason is that: the toughness of the acrylic acid high polymer is enhanced, and meanwhile, the amido bond contained in the acrylic acid high polymer has a heat induction effect and can form a hydrogen bond acting force; and the total added 2-hydroxyethyl methacrylate phosphate exceeds 10 wt%, so that the tensile property of the adhesive is reduced, and the cohesive force of the adhesive and the 2-hydroxyethyl methacrylate phosphate is reduced, so that the degumming property is reduced. In the embodiment ratio 9, since 2-hydroxyethyl methacrylate phosphate is not added and the methacrylamide composite monomer is added, the copolymerization performance with the methacrylate is also reduced, the molecular weight is reduced, and the debonding performance is reduced.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of recyclable viscose lost when heated is characterized by comprising the following steps: the method comprises the following steps: putting ethyl acetate and toluene into a reaction kettle; heating to 65-75 ℃, and adding butyl acrylate, isooctyl acrylate, a monomer and an initiator; continuously heating to 85-95 ℃, and preserving heat for 3.5-4.5 hours; adding benzoyl peroxide, keeping the temperature for 0.5-1 hour, cooling to 40-50 ℃, adding acrylic acid high polymer, and stirring for 1-1.5 hours to obtain the adhesive lost by heat.
2. The method for preparing the recyclable viscose glue capable of being lost when exposed to heat according to claim 1, wherein the method comprises the following steps: the raw materials of the viscose which loses viscose when being heated comprise the following components: the coating comprises, by weight, 5-10 parts of butyl acrylate, 30-40 parts of isooctyl acrylate, 5-10 parts of a monomer, 2-4 parts of an acrylic acid high polymer, 40-50 parts of ethyl acetate, 5-10 parts of toluene, 0.1-0.2 part of an initiator and 0.2-0.4 part of benzoyl peroxide.
3. The method for preparing the recyclable viscose glue capable of being lost when exposed to heat according to claim 1, wherein the method comprises the following steps: the monomer is one or two of acrylic acid and methyl acrylate; the initiator is one or more of azobisisobutyronitrile and azobisisovaleronitrile.
4. The method for preparing the recyclable viscose glue capable of being lost when exposed to heat according to claim 1, wherein the method comprises the following steps: the molecular weight of the acrylic acid high polymer is 60000-80000.
5. The method for preparing the recyclable viscose glue capable of being lost when exposed to heat according to claim 1, wherein the method comprises the following steps: the preparation method of the acrylic high polymer comprises the following steps: adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azobisisobutyronitrile into a reaction kettle, and reacting at 100-120 ℃ for 3-6 hours to obtain the acrylic polymer.
6. The method for preparing the recyclable adhesive lost when heat according to claim 5, wherein the method comprises the following steps: the preparation method of the acrylic high polymer comprises the following steps: adding methacrylate, 2-hydroxyethyl methacrylate phosphate, a methacrylamide composite monomer, n-octyl mercaptan and azodiisobutyronitrile into a reaction kettle, and reacting for 3-6 hours at the set temperature of 100-120 ℃; and cooling to 30 ℃, adding 2-hydroxyethyl sorbate, methyl sorbate and 2,2' -azobis (2, 4-dimethylvaleronitrile), and reacting for 1-2 hours to obtain the acrylic polymer.
7. The method for preparing the recyclable viscose glue capable of being lost when exposed to heat according to claim 6, wherein the method comprises the following steps: in the acrylic polymer, the mass ratio of the methacrylate, the 2-hydroxyethyl methacrylate phosphate and the methacrylamide composite monomer is 1 (0.08-0.1) to 0.20-0.25; the total weight of the 2-hydroxyethyl sorbate and the methyl sorbate is 5-6 wt% of the first-grade acrylate.
8. The method for preparing the recyclable viscose glue capable of being lost when exposed to heat according to claim 6, wherein the method comprises the following steps: the preparation method of the methacrylamide composite monomer comprises the following steps: sequentially adding hydroxyacetamide, triethylamine and dichloromethane into a reaction kettle, slowly adding methacryloyl chloride at room temperature, and stirring for reacting for 20-24 hours; adding methanol for dilution; washing and drying to obtain methacrylamide; ultrasonically dispersing the mixture in water to obtain a methacrylamide aqueous solution, adding a vinylphosphonic acid aqueous solution, and uniformly stirring; adding potassium persulfate, reacting for 2-3 hours at the set temperature of 60-65 ℃, washing and drying to obtain the methacrylamide composite monomer.
9. The method for preparing the recyclable adhesive lost when heat according to claim 8, wherein the method comprises the following steps: the mass ratio of the methacrylamide to the vinylphosphonic acid is 1 (0.8-1); the concentration of the methacrylamide aqueous solution is 35-40 wt%; the concentration of the vinylphosphonic acid aqueous solution is 38-40 wt%.
10. The thermally-damaged adhesive prepared by the method for preparing the recyclable thermally-damaged adhesive according to any one of claims 1 to 9.
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| JPS572374A (en) * | 1980-06-04 | 1982-01-07 | Soken Kagaku Kk | Pressure-sensitive adhesive composition |
| JPH11293207A (en) * | 1998-04-03 | 1999-10-26 | Nitto Denko Corp | Thermally eliminable pressure-sensitive adhesive sheet |
| CN105131869A (en) * | 2015-09-10 | 2015-12-09 | 深圳市美信电子有限公司 | Thermal viscosity loss pressure-sensitive adhesive, thermally peelable adhesive tape and preparation methods of thermal viscosity loss pressure-sensitive adhesive and thermally peelable adhesive tape |
| CN109666427A (en) * | 2018-12-28 | 2019-04-23 | 东莞市骏青电子科技有限公司 | A kind of acrylate pressure-sensitive adhesive, preparation method and application method that heat is inharmonious |
| CN109749674A (en) * | 2019-01-25 | 2019-05-14 | 苏州义铠轩电子科技有限公司 | Inharmonious adhesive tape of reusable high-strength hot and preparation method thereof |
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2022
- 2022-03-25 CN CN202210306445.7A patent/CN114605943B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS572374A (en) * | 1980-06-04 | 1982-01-07 | Soken Kagaku Kk | Pressure-sensitive adhesive composition |
| JPH11293207A (en) * | 1998-04-03 | 1999-10-26 | Nitto Denko Corp | Thermally eliminable pressure-sensitive adhesive sheet |
| CN105131869A (en) * | 2015-09-10 | 2015-12-09 | 深圳市美信电子有限公司 | Thermal viscosity loss pressure-sensitive adhesive, thermally peelable adhesive tape and preparation methods of thermal viscosity loss pressure-sensitive adhesive and thermally peelable adhesive tape |
| CN109666427A (en) * | 2018-12-28 | 2019-04-23 | 东莞市骏青电子科技有限公司 | A kind of acrylate pressure-sensitive adhesive, preparation method and application method that heat is inharmonious |
| CN109749674A (en) * | 2019-01-25 | 2019-05-14 | 苏州义铠轩电子科技有限公司 | Inharmonious adhesive tape of reusable high-strength hot and preparation method thereof |
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