CN114479716B - Environment-friendly modified polymer hot-melt pressure-sensitive adhesive and processing technology thereof - Google Patents
Environment-friendly modified polymer hot-melt pressure-sensitive adhesive and processing technology thereof Download PDFInfo
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- CN114479716B CN114479716B CN202111652276.4A CN202111652276A CN114479716B CN 114479716 B CN114479716 B CN 114479716B CN 202111652276 A CN202111652276 A CN 202111652276A CN 114479716 B CN114479716 B CN 114479716B
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
- C08G83/004—After treatment of dendrimers
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- 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
- C09J11/08—Macromolecular additives
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Abstract
The invention discloses an environment-friendly modified polymer hot-melt pressure-sensitive adhesive and a processing technology thereof, and relates to the technical field of hot-melt adhesives. When the environment-friendly modified polymer hot-melt pressure-sensitive adhesive is prepared, pyrrole and 3, 5-dihydroxybenzaldehyde are reacted and chelated with zinc particles to prepare zinc metalloporphyrin, the zinc metalloporphyrin is used as a center to react with 5-end hydroxyl n-octyl-1, 3-benzene diester to prepare dendritic macromolecules, the dendritic macromolecules are hydrolyzed and catalyze peroxide to diethyl benzene, then end-capping is carried out to prepare modified pressure-sensitive particles, hot-melt resin, modified pressure-sensitive particles, a dispersing agent, an antioxidant and talcum powder are mixed and stirred in a melting material kettle to prepare melting material, and the melting material is cooled and granulated to prepare the environment-friendly modified polymer hot-melt pressure-sensitive adhesive. The environment-friendly modified polymer hot-melt pressure-sensitive adhesive prepared by the invention has excellent pressure-sensitive adhesive performance.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, in particular to an environment-friendly modified polymer hot melt pressure-sensitive adhesive and a processing technology thereof.
Background
The hot-melt pressure-sensitive adhesive (Hot Melt Pressure Sensitive Adhesive), abbreviated as HMPSA, is an adhesive with thermoplastic polymer as a base material, has the dual characteristics of pressure sensitivity and hot melting, is coated in a molten state, can be quickly bonded by applying light finger pressure after cooling and solidifying, can be easily stripped, and does not pollute the surface of an adherend. Compared with other types of pressure-sensitive adhesives, the hot-melt pressure-sensitive adhesive has the advantages of no organic solvent, environmental protection, high coating speed, high automation degree, high productivity, long storage time, low product cost and the like. The hot-melt pressure-sensitive adhesive has been widely used in the fields of book binding, packaging, labels, shoemaking, medical and sanitary applications, diapers, double-sided tapes, surface protective films, wood processing and the like, and particularly in some developed countries in Europe and America, the annual growth rate of the hot-melt pressure-sensitive adhesive for adhesive tapes is the fastest, and the yield thereof has exceeded that of emulsion pressure-sensitive adhesives and solvent pressure-sensitive adhesives, which are the most important types of pressure-sensitive adhesives. The hot-melt pressure-sensitive adhesive includes acrylic hot-melt pressure-sensitive adhesives, thermoplastic elastomer type hot-melt pressure-sensitive adhesives, amorphous polyolefin hot-melt pressure-sensitive adhesives, and other types. Thermoplastic elastomer type hot melt pressure-sensitive adhesives are dominant, the most important components of which are thermoplastic elastomers and tackifying resins. With the continuous improvement of hot-melt pressure-sensitive adhesive coating equipment, adhesive preparation mode, operation environment and safety, the continuous improvement of raw material performance, the hot-melt pressure-sensitive adhesive has very wide application prospect in the future.
With the development of society and the innovation of science and technology, various properties of hot melt adhesives are improved, and requirements of people on the properties of the hot melt adhesives are higher and higher, so that the hot melt pressure-sensitive adhesive with various effects needs to be developed.
Disclosure of Invention
The invention aims to provide an environment-friendly modified polymer hot-melt pressure-sensitive adhesive and a processing technology thereof, which are used for solving the problems in the prior art.
An environment-friendly modified polymer hot-melt pressure-sensitive adhesive and a processing technology thereof are characterized by mainly comprising the following components in parts by weight: 80-100 parts of hot melt resin, 10-15 parts of modified pressure sensitive particles, 1-2 parts of dispersing agent, 1-2 parts of antioxidant and 1-2 parts of talcum powder.
The modified pressure-sensitive particles are prepared by carrying out end-capping treatment on the p-diethylbenzene modified pressure-sensitive particles subjected to peroxidation treatment after the hydrolysis of dendritic macromolecules.
As optimization, the dendritic macromolecule is prepared by reacting zinc metalloporphyrin serving as a center with 5-hydroxyl-terminated n-octyl-1, 3 benzene diester.
As optimization, the processing technology of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following preparation steps:
(1) Preparing dendritic macromolecules;
(2) Preparing modified pressure-sensitive particles;
(3) Mixing;
(4) Granulating.
As optimization, the processing technology of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following preparation steps:
(1) Under the protection of argon, zinc metalloporphyrin, 5-hydroxyl-terminated butyl-1, 3-benzene diester and tetrahydrofuran are mixed according to the mass ratio of 1:5:25 to 1:6:30, adding triphenylphosphine with the mass of 0.01-0.03 times of zinc metalloporphyrin and diisopropyl azodicarboxylate with the mass of 0.01-0.03 times of zinc metalloporphyrin at 0-5 ℃, stirring and reacting for 8-12 h at 10-30 ℃ and 1500-2000 r/min, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying for 6-8 h at-10 to-1 ℃ and 1-10 Pa pressure to obtain dendritic macromolecules;
(2) Hydrolyzing the dendritic macromolecule, and mixing the hydrolyzed dendritic macromolecule, p-diethylbenzene and dipropylene glycol dimethyl ether according to a mass ratio of 1:1: 8-1: 1:10, uniformly mixing, introducing oxygen at the rate of 0.3-0.5 mL/s, performing ultrasonic reaction for 3-5 hours at the temperature of 130-150 ℃ and the frequency of 30-40 kHz, stopping introducing oxygen, cooling to the temperature of 10-30 ℃, filtering, washing with absolute ethyl alcohol for 3-5 times, and drying for 4-6 hours at the temperature of 60-70 ℃ to prepare the pressure-sensitive particles; and then mixing the pressure-sensitive particles with dimethylol dimethoxy silane and tetrahydrofuran according to a mass ratio of 1:1: 15-1: 2:20, adding triphenylphosphine with the mass of 0.01-0.03 times of that of the dimethylol dimethoxy silane and diisopropyl azodicarboxylate with the mass of 0.01-0.03 times of that of the dimethylol dimethoxy silane at the temperature of 0-5 ℃, stirring at the temperature of 10-30 ℃ for reacting for 8-12 hours at the speed of 1500-2000 r/min, filtering, placing into a silane solution with the mass of 15-20 times of that of the dimethylol dimethoxy silane, stirring at the temperature of 40-50 ℃ for reacting for 60-80 minutes at the speed of 800-1000 r/min, filtering, washing for 3-5 times by absolute ethyl alcohol, and drying at the pressure of 5-10 Pa for 6-8 hours at the temperature of 60-70 ℃ to prepare the modified pressure-sensitive particles;
(3) Heating the hot melt resin to 170-180 ℃ and stirring for 10min at 300-500 r/min, then adding modified pressure sensitive particles with the mass of 0.1-0.2 times of the hot melt resin, dispersing agents with the mass of 0.01-0.03 times of the hot melt resin, antioxidants with the mass of 0.01-0.03 times of the hot melt resin and talcum powder with the mass of 0.01-0.03 times of the hot melt resin, and continuously stirring for 50-60 min to prepare the molten material;
(4) And (3) placing the molten material into a flat plate mold, cooling to 10-30 ℃ under the pressure of 5-10 MPa in a nitrogen atmosphere, forming, and granulating in a granulator to obtain the environment-friendly modified polymer hot-melt pressure-sensitive adhesive.
As optimization, the processing technology of the zinc metalloporphyrin in the step (1) is as follows: pyrrole, 3, 5-dihydroxybenzaldehyde, triethyl acetate and methylene dichloride are mixed according to the mass ratio of 1:2:2:5 to 1:2:3:7, uniformly mixing, adding boron trifluoride with the mass of 0.05-0.1 times of that of pyrrole, reacting for 60-80 min at 40-50 ℃ in nitrogen atmosphere, adding tetrachloro-p-benzoquinone with the mass of 5-10 times of that of pyrrole, refluxing for 3-5 h at 60-80 ℃, keeping the refluxing temperature for concentrating for 8-10 min, cooling to-20-10 ℃ for crystallization and filtration, washing for 3-5 times by absolute ethyl alcohol, placing zinc chloride solution with the mass fraction of 20-30% of that of pyrrole at 10-15, stirring and reacting for 10-15 min at 50-60 ℃ at 1000-1500 r/min, filtering and washing for 3-5 times by pure water, and drying for 4-6 h at-10-5 ℃ and 5-10 Pa.
As an optimization, the hydrolysis treatment method in the step (2) comprises the following steps: placing the mixture into a sodium hydroxide solution with mass fraction of 3-5% and mass fraction of 10-15 times of the dendritic macromolecule, stirring and reacting for 40-50 min at 80-90 ℃ at 1000-1500 r/min, filtering, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying for 6-8 h at-10 to-1 ℃ under 1-10 Pa.
As optimization, the silane solution in the step (2) is prepared from dimethylol dimethoxy silane, absolute ethyl alcohol and pure water according to the mass ratio of 1:4: 4-1: 8:8, uniformly mixing and preparing the product.
As an optimization, the hot melt resin in the step (3) is EVA resin.
Compared with the prior art, the invention has the following beneficial effects:
the environment-friendly modified polymer hot-melt pressure-sensitive adhesive prepared by the invention consists of hot-melt resin, modified pressure-sensitive particles, a dispersing agent, an antioxidant and talcum powder.
Firstly, zinc metalloporphyrin is taken as a core and grows by 5-terminal hydroxybutyl-1, 3-benzenediol to prepare dendritic macromolecules, the branch end formed by the 5-terminal hydroxybutyl-1, 3-benzenediol is benzenediol, the end of the branch is hydrophobic, the phenoxide is protected, the zinc metalloporphyrin can catalyze and oxidize diethylbenzene, hydrogen on alpha position of a plurality of diethylbenzenes is replaced by oxygen to form peroxy bonds to connect adjacent diethylbenzenes, the volume of the peroxy-linked diethylbenzenes is increased, the loss is difficult in branch gaps of the dendritic macromolecules due to steric hindrance, the end is capped by organic silicon to prepare modified pressure sensitive particles, the outer branches are more compact, and the peroxidized-linked diethylbenzenes sealed in the modified pressure sensitive particles are less easy to lose;
when the modified pressure sensitive particle is used, high-temperature pressurization is carried out, the peroxidized and connected diethyl benzene peroxide bonds in the modified pressure sensitive particle are cracked to form two oxygen free radicals, the branch deformation molecular gap is enlarged under the pressure, the oxygen free radicals are released, the oxygen free radicals are high in activity to compete hydrogen on a carbon chain in asphalt to form carbon free radicals, the carbon free radicals are connected with other carbon chains to form carbon free radicals with larger molecular weight so as to initiate crosslinking and cross winding, the combination effect and the mechanical property are improved, and meanwhile, a crosslinking network is inserted into the modified pressure sensitive particle main body to deform branch ends, the branch ends are silicon hydroxyl groups, a silicon-oxygen network is formed between the branch ends, and the bonding effect of the material is further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the method for testing each index of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive prepared in the following examples is as follows:
adhesion: the environment-friendly modified polymer hot-melt pressure-sensitive adhesive obtained in each example is prepared by taking the same mass as that of a comparative example product, hot-melting the same type of drawing head on the same base material at the same temperature under the conditions of applying the same pressure and not applying the pressure to bond the same type of drawing head on the base material for a drawing test, and recording the tensile strength of the drawing head when the drawing head is separated from the base material under each condition.
Example 1
The environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following components in parts by weight: 100 parts of hot melt resin, 10 parts of modified pressure sensitive particles, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
The processing technology of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following preparation steps:
(1) Pyrrole, 3, 5-dihydroxybenzaldehyde, triethyl acetate and methylene dichloride are mixed according to the mass ratio of 1:2:2:5, uniformly mixing, adding boron trifluoride with the mass of 0.05 times of that of pyrrole, reacting for 80min at 40 ℃ in nitrogen atmosphere, adding tetrachloro-p-benzoquinone with the mass of 5 times of that of pyrrole, refluxing for 5h at 60 ℃, keeping the refluxing temperature for 10min, cooling to-20 ℃ for crystallization and filtration, washing 3 times by using absolute ethyl alcohol, placing in zinc chloride solution with the mass fraction of 30% of that of pyrrole at 10, stirring and reacting for 15min at 50 ℃ at 1000r/min, filtering and washing 3 times by using pure water, and drying for 6h at-5 ℃ under 5Pa to obtain zinc metalloporphyrin; under the protection of argon, zinc metalloporphyrin, 5-hydroxyl-terminated butyl-1, 3-benzene diester and tetrahydrofuran are mixed according to the mass ratio of 1:5:25, adding triphenylphosphine with the mass of 0.01 times of zinc metalloporphyrin and diisopropyl azodicarboxylate with the mass of 0.01 times of zinc metalloporphyrin at the temperature of 0 ℃, stirring at the temperature of 10 ℃ and 1500r/min for reaction for 12h, washing with pure water and absolute ethyl alcohol for 3 times respectively, and drying at the temperature of-10 ℃ and the pressure of 1Pa for 8h to obtain dendritic macromolecules;
(2) Putting the dendritic macromolecules into a sodium hydroxide solution with the mass fraction of 5% and the mass of 10 times of the dendritic macromolecules, stirring at 80 ℃ for reaction for 50min at 1000r/min, filtering, washing 3 times by pure water and absolute ethyl alcohol respectively, drying at-10 ℃ under the pressure of 1Pa for 6h, and mixing the hydrolyzed dendritic macromolecules, p-diethylbenzene and dipropylene glycol dimethyl ether according to the mass ratio of 1:1:8, uniformly mixing, introducing oxygen at the rate of 0.3mL/s, performing ultrasonic reaction at 130 ℃ and 30kHz for 5 hours, stopping introducing oxygen, cooling to 10 ℃, filtering, washing with absolute ethyl alcohol for 3 times, and drying at 60 ℃ for 6 hours to obtain pressure-sensitive particles; and then mixing the pressure-sensitive particles with dimethylol dimethoxy silane and tetrahydrofuran according to a mass ratio of 1:1:15, adding triphenylphosphine with the mass of 0.01 times of that of the dimethylol dimethoxy silane and diisopropyl azodicarboxylate with the mass of 0.01 times of that of the dimethylol dimethoxy silane at the temperature of 0 ℃, stirring at the temperature of 10 ℃ for reaction for 12 hours at the speed of 1500r/min, filtering, and placing the mixture in the mixture of dimethylol dimethoxy silane with the mass of 15 times of that of the dimethylol dimethoxy silane, and absolute ethyl alcohol and pure water according to the mass ratio of 1:4:4, uniformly mixing the silane solution prepared, stirring at 40 ℃ for reaction at 800r/min for 80min, filtering, washing with absolute ethyl alcohol for 3 times, and drying at 60 ℃ under 5Pa for 8h to obtain modified pressure-sensitive particles;
(3) Placing hot melt resin into a melting kettle, heating to 170 ℃, stirring at 300r/min for 10min, adding modified pressure-sensitive particles with the mass of 0.1 times of that of the hot melt resin, dispersing agent with the mass of 0.01 times of that of the hot melt resin, antioxidant with the mass of 0.01 times of that of the hot melt resin and talcum powder with the mass of 0.01 times of that of the hot melt resin, and continuously stirring for 50min to obtain a melting stock;
(4) And (3) placing the molten material into a flat plate mold, cooling to 30 ℃ in a nitrogen atmosphere for molding, and granulating in a granulator to obtain the environment-friendly modified polymer hot-melt pressure-sensitive adhesive.
Example 2
The environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following components in parts by weight: 90 parts of hot melt resin, 12 parts of modified pressure sensitive particles, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
The processing technology of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following preparation steps:
(1) Pyrrole, 3, 5-dihydroxybenzaldehyde, triethyl acetate and methylene dichloride are mixed according to the mass ratio of 1:2:2:6, uniformly mixing, adding boron trifluoride with the mass of 0.08 times of pyrrole, reacting for 70min at 45 ℃ in a nitrogen atmosphere, adding tetrachloro-p-benzoquinone with the mass of 8 times of pyrrole, refluxing for 4h at 70 ℃, keeping the refluxing temperature for 9min, cooling to-15 ℃ for crystallization and filtration, washing for 4 times by using absolute ethyl alcohol, placing in zinc chloride solution with the mass fraction of 25% of the mass of pyrrole 12, stirring and reacting for 13min at 55 ℃ at 1300r/min, filtering and washing for 4 times by using pure water, and drying for 5h at-8 ℃ under 8Pa to obtain zinc metalloporphyrin; under the protection of argon, zinc metalloporphyrin, 5-hydroxyl-terminated butyl-1, 3-benzene diester and tetrahydrofuran are mixed according to the mass ratio of 1:5:28, uniformly mixing, adding triphenylphosphine with the mass of 0.02 times of that of zinc metalloporphyrin and diisopropyl azodicarboxylate with the mass of 0.02 times of that of zinc metalloporphyrin at 3 ℃, stirring at 20 ℃ for reaction for 10 hours at 1800r/min, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying at-5 ℃ for 7 hours under the pressure of 5Pa to obtain dendritic macromolecules;
(2) Putting the dendritic macromolecules into a sodium hydroxide solution with the mass fraction of 4% and 12 times of the mass of the dendritic macromolecules, stirring and reacting for 45min at 85 ℃ and 1200r/min, filtering, washing with pure water and absolute ethyl alcohol for 4 times respectively, drying for 7h at-5 ℃ and 5Pa, and mixing the hydrolyzed dendritic macromolecules, p-diethylbenzene and dipropylene glycol dimethyl ether according to the mass ratio of 1:1:9, uniformly mixing, introducing oxygen at the rate of 0.4mL/s, performing ultrasonic reaction for 4 hours at the temperature of 140 ℃ and the frequency of 35kHz, stopping introducing oxygen, cooling to the temperature of 20 ℃, filtering, washing with absolute ethyl alcohol for 4 times, and drying for 5 hours at the temperature of 65 ℃ to obtain pressure-sensitive particles; and then mixing the pressure-sensitive particles with dimethylol dimethoxy silane and tetrahydrofuran according to a mass ratio of 1:1:18, adding triphenylphosphine with the mass of 0.02 times of that of the dimethylol dimethoxy silane and diisopropyl azodicarboxylate with the mass of 0.02 times of that of the dimethylol dimethoxy silane at the temperature of 2 ℃, stirring at 20 ℃ for reaction for 10 hours at 1800r/min, filtering, and placing the mixture in the mixture of the dimethylol dimethoxy silane with the mass of 18 times of that of the dimethylol dimethoxy silane, anhydrous ethanol and pure water according to the mass ratio of 1:6:6, uniformly mixing the prepared silane solution, stirring at 45 ℃ for reaction at 900r/min for 70min, filtering, washing with absolute ethyl alcohol for 4 times, and drying at 65 ℃ under 8Pa for 7h to obtain modified pressure-sensitive particles;
(3) Heating the hot melt resin to 175 ℃ and stirring at 400r/min for 10min, adding modified pressure-sensitive particles with the mass of 0.1 times of the hot melt resin, dispersing agent with the mass of 0.02 times of the hot melt resin, antioxidant with the mass of 0.01 times of the hot melt resin and talcum powder with the mass of 0.02 times of the hot melt resin, and continuously stirring for 55min to prepare a molten material;
(4) And (3) placing the molten material into a flat plate mold, cooling to 20 ℃ in a nitrogen atmosphere for molding, and granulating in a granulator to obtain the environment-friendly modified polymer hot-melt pressure-sensitive adhesive.
Example 3
The environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following components in parts by weight: 80 parts of hot melt resin, 15 parts of modified pressure sensitive particles, 2 parts of dispersing agent, 2 parts of antioxidant and 2 parts of talcum powder.
The processing technology of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following preparation steps:
(1) Pyrrole, 3, 5-dihydroxybenzaldehyde, triethyl acetate and methylene dichloride are mixed according to the mass ratio of 1:2:3:7, uniformly mixing, adding boron trifluoride with the mass of 0.1 times of that of pyrrole, reacting for 60min at 50 ℃ in a nitrogen atmosphere, adding tetrachloro-p-benzoquinone with the mass of 10 times of that of pyrrole, refluxing for 3h at 80 ℃, keeping the refluxing temperature, concentrating for 10min, cooling to-10 ℃ for crystallization and filtration, washing 3 times by using absolute ethyl alcohol, placing in zinc chloride solution with the mass fraction of 20% of that of pyrrole at 15, stirring and reacting for 10min at 60 ℃ at 1500r/min, filtering and washing 5 times by using pure water, and drying for 4h at-5 ℃ and 10Pa to obtain zinc metalloporphyrin; under the protection of argon, zinc metalloporphyrin, 5-hydroxyl-terminated butyl-1, 3-benzene diester and tetrahydrofuran are mixed according to the mass ratio of 1:6:30, adding triphenylphosphine with the mass of 0.03 times of that of zinc metalloporphyrin and diisopropyl azodicarboxylate with the mass of 0.03 times of that of zinc metalloporphyrin at 5 ℃, stirring at 30 ℃ and 2000r/min for reaction for 8 hours, washing with pure water and absolute ethyl alcohol for 5 times respectively, and drying at-1 ℃ and 10Pa pressure for 6 hours to prepare dendritic macromolecules;
(2) Putting the dendritic macromolecules into a sodium hydroxide solution with the mass fraction of 5% and 15 times of the mass of the dendritic macromolecules, stirring at 90 ℃ for reaction for 40min at 1500r/min, filtering, washing 5 times by pure water and absolute ethyl alcohol respectively, drying at-1 ℃ under the pressure of 10Pa for 6h, and mixing the hydrolyzed dendritic macromolecules, p-diethylbenzene and dipropylene glycol dimethyl ether according to the mass ratio of 1:1:10, uniformly mixing, introducing oxygen at the rate of 0.5mL/s, performing ultrasonic reaction at the temperature of 150 ℃ and 40kHz for 3 hours, stopping introducing oxygen, cooling to the temperature of 30 ℃, filtering, washing with absolute ethyl alcohol for 5 times, and drying at the temperature of 70 ℃ for 4 hours to obtain pressure-sensitive particles; and then mixing the pressure-sensitive particles with dimethylol dimethoxy silane and tetrahydrofuran according to a mass ratio of 1:2:20, adding triphenylphosphine with the mass of 0.03 times of that of the dimethylol dimethoxy silane and diisopropyl azodicarboxylate with the mass of 0.03 times of that of the dimethylol dimethoxy silane at the temperature of 5 ℃, stirring at the temperature of 30 ℃ for reaction for 8 hours at the speed of 2000r/min, filtering, and placing the mixture in the mixture of the dimethylol dimethoxy silane, anhydrous ethanol and pure water with the mass ratio of 20 times of that of the dimethylol dimethoxy silane according to 1:8:8, uniformly mixing the prepared silane solution, stirring at 50 ℃ for reaction for 60min at 1000r/min, filtering, washing with absolute ethyl alcohol for 5 times, and drying at 70 ℃ under 10Pa for 6h to obtain modified pressure-sensitive particles;
(3) Placing hot melt resin into a melting kettle, heating to 180 ℃, stirring at 500r/min for 10min, adding modified pressure-sensitive particles with the mass of 0.2 times of that of the hot melt resin, dispersing agent with the mass of 0.03 times of that of the hot melt resin, antioxidant with the mass of 0.03 times of that of the hot melt resin and talcum powder with the mass of 0.03 times of that of the hot melt resin, and continuously stirring for 50min to obtain a melting stock;
(4) And (3) placing the molten material into a flat plate mold, cooling to 30 ℃ in a nitrogen atmosphere for molding, and granulating in a granulator to obtain the environment-friendly modified polymer hot-melt pressure-sensitive adhesive.
Comparative example 1
The environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following components in parts by weight: 90 parts of hot melt resin, 12 parts of modified pressure sensitive particles, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
The processing technology of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following preparation steps:
(1) Pyrrole, 3, 5-dihydroxybenzaldehyde, triethyl acetate and methylene dichloride are mixed according to the mass ratio of 1:2:2:6, uniformly mixing, adding boron trifluoride with the mass of 0.08 times of pyrrole, reacting for 70min at 45 ℃ in a nitrogen atmosphere, adding tetrachloro-p-benzoquinone with the mass of 8 times of pyrrole, refluxing for 4h at 70 ℃, keeping the refluxing temperature for 9min, cooling to-15 ℃ for crystallization and filtration, washing for 4 times by using absolute ethyl alcohol, placing in zinc chloride solution with the mass fraction of 25% of the mass of pyrrole 12, stirring and reacting for 13min at 55 ℃ at 1300r/min, filtering and washing for 4 times by using pure water, and drying for 5h at-8 ℃ under 8Pa to obtain zinc metalloporphyrin; under the protection of argon, zinc metalloporphyrin, 5-hydroxyl-terminated butyl-1, 3-benzene diester and tetrahydrofuran are mixed according to the mass ratio of 1:5:28, uniformly mixing, adding triphenylphosphine with the mass of 0.02 times of that of zinc metalloporphyrin and diisopropyl azodicarboxylate with the mass of 0.02 times of that of zinc metalloporphyrin at 3 ℃, stirring at 20 ℃ for reaction for 10 hours at 1800r/min, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying at-5 ℃ for 7 hours under the pressure of 5Pa to obtain dendritic macromolecules;
(2) Putting the dendritic macromolecules into a sodium hydroxide solution with the mass fraction of 4% and 12 times of the mass of the dendritic macromolecules, stirring and reacting for 45min at 85 ℃ and 1200r/min, filtering, washing for 4 times by using pure water and absolute ethyl alcohol respectively, drying for 7h at-5 ℃ and 5Pa, and mixing the hydrolyzed dendritic macromolecules with dimethyloldimethoxy silane and tetrahydrofuran according to the mass ratio of 1:1:18, adding triphenylphosphine with the mass of 0.02 times of that of the dimethylol dimethoxy silane and diisopropyl azodicarboxylate with the mass of 0.02 times of that of the dimethylol dimethoxy silane at the temperature of 2 ℃, stirring at 20 ℃ for reaction for 10 hours at 1800r/min, filtering, and placing the mixture in the mixture of the dimethylol dimethoxy silane with the mass of 18 times of that of the dimethylol dimethoxy silane, anhydrous ethanol and pure water according to the mass ratio of 1:6:6, uniformly mixing the prepared silane solution, stirring at 45 ℃ for reaction at 900r/min for 70min, filtering, washing with absolute ethyl alcohol for 4 times, and drying at 65 ℃ under 8Pa for 7h to obtain modified pressure-sensitive particles;
(3) Heating the hot melt resin to 175 ℃ and stirring at 400r/min for 10min, adding modified pressure-sensitive particles with the mass of 0.1 times of the hot melt resin, dispersing agent with the mass of 0.02 times of the hot melt resin, antioxidant with the mass of 0.01 times of the hot melt resin and talcum powder with the mass of 0.02 times of the hot melt resin, and continuously stirring for 55min to prepare a molten material;
(4) And (3) placing the molten material into a flat plate mold, cooling to 20 ℃ in a nitrogen atmosphere for molding, and granulating in a granulator to obtain the environment-friendly modified polymer hot-melt pressure-sensitive adhesive.
Comparative example 2
The environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following components in parts by weight: 90 parts of hot melt resin, 12 parts of pressure sensitive particles, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
The processing technology of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following preparation steps:
(1) Pyrrole, 3, 5-dihydroxybenzaldehyde, triethyl acetate and methylene dichloride are mixed according to the mass ratio of 1:2:2:6, uniformly mixing, adding boron trifluoride with the mass of 0.08 times of pyrrole, reacting for 70min at 45 ℃ in a nitrogen atmosphere, adding tetrachloro-p-benzoquinone with the mass of 8 times of pyrrole, refluxing for 4h at 70 ℃, keeping the refluxing temperature for 9min, cooling to-15 ℃ for crystallization and filtration, washing for 4 times by using absolute ethyl alcohol, placing in zinc chloride solution with the mass fraction of 25% of the mass of pyrrole 12, stirring and reacting for 13min at 55 ℃ at 1300r/min, filtering and washing for 4 times by using pure water, and drying for 5h at-8 ℃ under 8Pa to obtain zinc metalloporphyrin; under the protection of argon, zinc metalloporphyrin, 5-hydroxyl-terminated butyl-1, 3-benzene diester and tetrahydrofuran are mixed according to the mass ratio of 1:5:28, uniformly mixing, adding triphenylphosphine with the mass of 0.02 times of that of zinc metalloporphyrin and diisopropyl azodicarboxylate with the mass of 0.02 times of that of zinc metalloporphyrin at 3 ℃, stirring at 20 ℃ for reaction for 10 hours at 1800r/min, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying at-5 ℃ for 7 hours under the pressure of 5Pa to obtain dendritic macromolecules;
(2) Putting the dendritic macromolecules into a sodium hydroxide solution with the mass fraction of 4% and 12 times of the mass of the dendritic macromolecules, stirring and reacting for 45min at 85 ℃ and 1200r/min, filtering, washing with pure water and absolute ethyl alcohol for 4 times respectively, drying for 7h at-5 ℃ and 5Pa, and mixing the hydrolyzed dendritic macromolecules, p-diethylbenzene and dipropylene glycol dimethyl ether according to the mass ratio of 1:1:9, uniformly mixing, introducing oxygen at the rate of 0.4mL/s, performing ultrasonic reaction for 4 hours at the temperature of 140 ℃ and the frequency of 35kHz, stopping introducing oxygen, cooling to the temperature of 20 ℃, filtering, washing with absolute ethyl alcohol for 4 times, and drying for 5 hours at the temperature of 65 ℃ to obtain pressure-sensitive particles; and then mixing the pressure-sensitive particles with dimethylol dimethoxy silane and tetrahydrofuran according to a mass ratio of 1:1:18, adding triphenylphosphine with the mass of 0.02 times of that of the dimethylol dimethoxy silane and diisopropyl azodicarboxylate with the mass of 0.02 times of that of the dimethylol dimethoxy silane at the temperature of 2 ℃, stirring at 20 ℃ for reaction for 10 hours at 1800r/min, filtering, and placing the mixture in the mixture of the dimethylol dimethoxy silane with the mass of 18 times of that of the dimethylol dimethoxy silane, anhydrous ethanol and pure water according to the mass ratio of 1:6:6, uniformly mixing the prepared silane solution, stirring at 45 ℃ for reaction at 900r/min for 70min, filtering, washing with absolute ethyl alcohol for 4 times, and drying at 65 ℃ under 8Pa for 7h to obtain modified pressure-sensitive particles;
(3) Heating the hot melt resin to 175 ℃ and stirring at 400r/min for 10min, adding modified pressure-sensitive particles with the mass of 0.1 times of the hot melt resin, dispersing agent with the mass of 0.02 times of the hot melt resin, antioxidant with the mass of 0.01 times of the hot melt resin and talcum powder with the mass of 0.02 times of the hot melt resin, and continuously stirring for 55min to prepare a molten material;
(4) And (3) placing the molten material into a flat plate mold, cooling to 20 ℃ in a nitrogen atmosphere for molding, and granulating in a granulator to obtain the environment-friendly modified polymer hot-melt pressure-sensitive adhesive.
Comparative example 3
The environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following components in parts by weight: 90 parts of hot melt resin, 12 parts of dendritic macromolecules, 1 part of dispersing agent, 1 part of antioxidant and 1 part of talcum powder.
The processing technology of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive mainly comprises the following preparation steps:
(1) Pyrrole, 3, 5-dihydroxybenzaldehyde, triethyl acetate and methylene dichloride are mixed according to the mass ratio of 1:2:2:6, uniformly mixing, adding boron trifluoride with the mass of 0.08 times of pyrrole, reacting for 70min at 45 ℃ in a nitrogen atmosphere, adding tetrachloro-p-benzoquinone with the mass of 8 times of pyrrole, refluxing for 4h at 70 ℃, keeping the refluxing temperature for 9min, cooling to-15 ℃ for crystallization and filtration, washing for 4 times by using absolute ethyl alcohol, placing in zinc chloride solution with the mass fraction of 25% of the mass of pyrrole 12, stirring and reacting for 13min at 55 ℃ at 1300r/min, filtering and washing for 4 times by using pure water, and drying for 5h at-8 ℃ under 8Pa to obtain zinc metalloporphyrin; under the protection of argon, zinc metalloporphyrin, 5-hydroxyl-terminated butyl-1, 3-benzene diester and tetrahydrofuran are mixed according to the mass ratio of 1:5:28, uniformly mixing, adding triphenylphosphine with the mass of 0.02 times of that of zinc metalloporphyrin and diisopropyl azodicarboxylate with the mass of 0.02 times of that of zinc metalloporphyrin at 3 ℃, stirring at 20 ℃ for reaction for 10 hours at 1800r/min, washing with pure water and absolute ethyl alcohol for 4 times respectively, and drying at-5 ℃ for 7 hours under the pressure of 5Pa to obtain dendritic macromolecules;
(2) Heating the hot melt resin to 175 ℃ and stirring at 400r/min for 10min, adding modified pressure-sensitive particles with the mass of 0.1 times of the hot melt resin, dispersing agent with the mass of 0.02 times of the hot melt resin, antioxidant with the mass of 0.01 times of the hot melt resin and talcum powder with the mass of 0.02 times of the hot melt resin, and continuously stirring for 55min to prepare a molten material;
(3) And (3) placing the molten material into a flat plate mold, cooling to 20 ℃ in a nitrogen atmosphere for molding, and granulating in a granulator to obtain the environment-friendly modified polymer hot-melt pressure-sensitive adhesive.
Effect example
The following table 1 shows the results of performance analysis of adhesion under different conditions using the environmentally-friendly modified polymeric hot-melt pressure-sensitive adhesives of examples 1 to 3 of the present invention and comparative examples 1 to 3.
TABLE 1
From comparison of the experimental data in table 1, it can be found that the addition of the modified pressure sensitive particles can significantly improve the adhesion of the material for pressurized use; as can be seen from comparison of experimental data of examples 1, 2 and 3 and comparative example 1 in Table 1, the examples 1, 2 and 3 have large compression tensile strength compared with comparative example 1, which indicates that zinc metalloporphyrin can catalyze and oxidize diethylbenzene, hydrogen on alpha position of several diethylbenzenes is replaced by oxygen to form peroxy bond to connect adjacent diethylbenzenes, when in use, pressurization is carried out at high temperature, peroxy bond of peroxidized and connected diethylbenzene in modified pressure sensitive particles is homolytic to form two oxygen free radicals, branch deformation molecular gap is enlarged under pressure, oxygen free radicals are released, high activity of oxygen free radicals is used for competing hydrogen on carbon chains in asphalt to form carbon free radicals, and the carbon free radicals are connected with other carbon chains to form carbon free radicals with larger molecular weight to initiate crosslinking and cross winding, so that compression adhesion of the environment-friendly modified polymer hot melt pressure sensitive adhesive is improved; from the comparison of experimental data of examples 1, 2 and 3 and comparative example 2, the comparison of examples 1, 2 and 3 with comparative example 2 shows that the compression tensile strength is large and the non-compression tensile strength is small, and the reaction end capping with dimethylol dimethoxy silicon ensures that the outer branches grow and are more compact, and the peroxidized and connected diethylbenzene in the modified pressure sensitive particles is more difficult to run off, thereby improving the stability of the environment-friendly modified polymer hot melt pressure sensitive adhesive in the non-compression process, and simultaneously the growing branch ends are silicon hydroxyl groups, forming a silicon-oxygen network between the two branches, so as to improve the compression adhesion of the environment-friendly modified polymer hot melt pressure sensitive adhesive.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (5)
1. The preparation method of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive is characterized by mainly comprising the following preparation steps of:
(1) Under the protection of argon, zinc metalloporphyrin, 5-hydroxyl-terminated butyl-1, 3-benzene diester and tetrahydrofuran are mixed according to the mass ratio of 1:5:25 to 1:6:30, adding triphenylphosphine with the mass of 0.01-0.03 times of zinc metalloporphyrin and diisopropyl azodicarboxylate with the mass of 0.01-0.03 times of zinc metalloporphyrin at 0-5 ℃, stirring and reacting for 8-12 h at 10-30 ℃ and 1500-2000 r/min, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying for 6-8 h at-10 to-1 ℃ and 1-10 Pa pressure to obtain dendritic macromolecules;
(2) Hydrolyzing the dendritic macromolecule, and mixing the hydrolyzed dendritic macromolecule, p-diethylbenzene and dipropylene glycol dimethyl ether according to a mass ratio of 1:1: 8-1: 1:10, uniformly mixing, introducing oxygen at the rate of 0.3-0.5 mL/s, performing ultrasonic reaction for 3-5 hours at the temperature of 130-150 ℃ and the frequency of 30-40 kHz, stopping introducing oxygen, cooling to the temperature of 10-30 ℃, filtering, washing with absolute ethyl alcohol for 3-5 times, and drying for 4-6 hours at the temperature of 60-70 ℃ to prepare the pressure-sensitive particles; and then mixing the pressure-sensitive particles with dimethylol dimethoxy silane and tetrahydrofuran according to a mass ratio of 1:1: 15-1: 2:20, adding triphenylphosphine with the mass of 0.01-0.03 times of that of the dimethylol dimethoxy silane and diisopropyl azodicarboxylate with the mass of 0.01-0.03 times of that of the dimethylol dimethoxy silane at the temperature of 0-5 ℃, stirring at the temperature of 10-30 ℃ for reacting for 8-12 hours at the speed of 1500-2000 r/min, filtering, placing into a silane solution with the mass of 15-20 times of that of the dimethylol dimethoxy silane, stirring at the temperature of 40-50 ℃ for reacting for 60-80 minutes at the speed of 800-1000 r/min, filtering, washing for 3-5 times by absolute ethyl alcohol, and drying at the pressure of 5-10 Pa for 6-8 hours at the temperature of 60-70 ℃ to prepare the modified pressure-sensitive particles;
(3) Heating the hot melt resin to 170-180 ℃ and stirring for 10min at 300-500 r/min, then adding modified pressure sensitive particles with the mass of 0.1-0.2 times of the hot melt resin, dispersing agents with the mass of 0.01-0.03 times of the hot melt resin, antioxidants with the mass of 0.01-0.03 times of the hot melt resin and talcum powder with the mass of 0.01-0.03 times of the hot melt resin, and continuously stirring for 50-60 min to prepare the molten material;
(4) And (3) placing the molten material into a flat plate mold, cooling to 10-30 ℃ under the pressure of 5-10 MPa in a nitrogen atmosphere, forming, and granulating in a granulator to obtain the environment-friendly modified polymer hot-melt pressure-sensitive adhesive.
2. The method for preparing the environment-friendly modified polymer hot-melt pressure-sensitive adhesive according to claim 1, wherein the method for preparing the zinc metalloporphyrin in the step (1) is as follows: pyrrole, 3, 5-dihydroxybenzaldehyde, triethyl acetate and methylene dichloride are mixed according to the mass ratio of 1:2:2:5 to 1:2:3:7, uniformly mixing, adding boron trifluoride with the mass of 0.05-0.1 times of that of pyrrole, reacting for 60-80 min at 40-50 ℃ in nitrogen atmosphere, adding tetrachloro-p-benzoquinone with the mass of 5-10 times of that of pyrrole, refluxing for 3-5 h at 60-80 ℃, keeping the refluxing temperature for concentrating for 8-10 min, cooling to-20-10 ℃ for crystallization and filtration, washing for 3-5 times by absolute ethyl alcohol, placing zinc chloride solution with the mass fraction of 20-30% of that of pyrrole at 10-15, stirring and reacting for 10-15 min at 50-60 ℃ at 1000-1500 r/min, filtering and washing for 3-5 times by pure water, and drying for 4-6 h at-10-5 ℃ and 5-10 Pa.
3. The method for preparing the environment-friendly modified polymer hot-melt pressure-sensitive adhesive according to claim 1, wherein the method for hydrolysis treatment in the step (2) is as follows: placing the mixture into a sodium hydroxide solution with mass fraction of 3-5% and mass fraction of 10-15 times of the dendritic macromolecule, stirring and reacting for 40-50 min at 80-90 ℃ at 1000-1500 r/min, filtering, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, and drying for 6-8 h at-10 to-1 ℃ under 1-10 Pa.
4. The preparation method of the environment-friendly modified polymer hot-melt pressure-sensitive adhesive according to claim 1, wherein the silane solution in the step (2) is prepared from dimethylol dimethoxy silane, absolute ethyl alcohol and pure water according to a mass ratio of 1:4: 4-1: 8:8, uniformly mixing and preparing the product.
5. The method for preparing the environment-friendly modified polymer hot-melt pressure-sensitive adhesive according to claim 1, wherein the hot-melt resin in the step (3) is EVA resin.
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