CN115612430A - Easily-stripped packaging hot melt adhesive and preparation method thereof - Google Patents
Easily-stripped packaging hot melt adhesive and preparation method thereof Download PDFInfo
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- CN115612430A CN115612430A CN202211628969.4A CN202211628969A CN115612430A CN 115612430 A CN115612430 A CN 115612430A CN 202211628969 A CN202211628969 A CN 202211628969A CN 115612430 A CN115612430 A CN 115612430A
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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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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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
- 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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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention belongs to the technical field of packaging glue, and discloses an easy-to-peel packaging hot melt adhesive and a preparation method thereof, wherein the hot melt adhesive comprises 80-100 parts by weight of SIS thermoplastic elastomer, 25-45 parts by weight of plasticizer, 10-15 parts by weight of nano calcium carbonate, 15-25 parts by weight of composite wax, 25-35 parts by weight of modified rosin glyceride and 10-20 parts by weight of modifier; sequentially adding the raw materials into a stirrer filled with the SIS thermoplastic elastomer, stirring at a constant speed, and adding the modified rosin glyceride; and introducing nitrogen, heating, uniformly stirring for 4 hours, then cooling to room temperature, defoaming in vacuum, cooling and extruding to prepare the easily-stripped packaging hot melt adhesive. According to the invention, the SIS thermoplastic elastomer is used as a matrix, the modified rosin glyceride is added, on one hand, the modified rosin glyceride can be used as a tackifier, on the other hand, long-chain alkyl is introduced through modification of the SIS thermoplastic elastomer, the low temperature resistance of the prepared hot melt adhesive is improved, and the pentaerythritol stearate in the composite wax can reduce the peeling strength of the hot melt adhesive.
Description
Technical Field
The invention belongs to the technical field of packaging glue, and particularly relates to an easily-stripped packaging hot melt adhesive and a preparation method thereof.
Background
At present, when the articles needing refrigeration are packaged, for example, the refrigerated food packaging is taken as an example, and the label paper is easy to tear after the packaging bag or the packaging box is subjected to heat sealing, so that the label paper cannot be completely and cleanly peeled. In order to achieve the technical effect of completely separating the ring logo from the surface of the box body or the bag body, the surface of the paper is coated with water-soluble glue solution, and the water-soluble glue solution is selected from one or more of starch, modified starch, polyacrylamide, plant gum or sodium alginate. However, in practical use, the outer surface of the refrigerated food is condensed to form water drops after being taken out, and the water drops contact with the glue solution to swell, so that the adhesion is not facilitated.
The improved technical scheme adopts the easily stripped hot melt adhesive to replace the water-soluble glue solution, but the existing SIS hot melt adhesive has poor weather resistance, the temperature reduction has obvious influence on the viscosity, and the refrigerated goods need to be stored in a low-temperature environment for a long time, so the formula improvement of the low-temperature resistant easily stripped hot melt adhesive of the existing SIS hot melt adhesive is needed, and the rubber phase of the SIS thermoplastic elastomer contains unsaturated double bonds and is easily subjected to O in the air 2 、O 3 And oxidative aging occurs under the influence of ultraviolet rays.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention aims to provide an easy-to-peel packaging hot melt adhesive and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
an easy-to-peel packaging hot melt adhesive comprises the following raw materials in parts by weight: 80-100 parts of SIS thermoplastic elastomer, 25-45 parts of plasticizer, 10-15 parts of nano calcium carbonate, 15-25 parts of composite wax, 25-35 parts of modified rosin glyceride and 10-20 parts of modifier;
the easy-peeling packaging hot melt adhesive is prepared by the following steps:
sequentially adding a plasticizer, nano calcium carbonate, composite wax and a modifier into a stirrer filled with an SIS thermoplastic elastomer, stirring at a constant speed, adding modified rosin glyceride in three times at equal amount at room temperature, separating every time for 10min, and stirring for 5min after all the modified rosin glyceride are added;
and secondly, introducing nitrogen, heating to 165-180 ℃, stirring at a constant speed for 4h, then cooling to room temperature, continuing stirring for 30min, defoaming in vacuum, cooling and extruding to obtain the easily-stripped packaging hot melt adhesive.
Further, the plasticizer is formed by mixing one or more of naphthenic oil, white mineral oil and dibutyl phthalate according to any proportion.
Furthermore, the composite wax is formed by mixing polyethylene wax and pentaerythritol stearate according to the weight ratio of (4-5) to 1.
Further, the modified rosin glyceride is prepared by the following steps:
grinding the rosin glyceride into powder, adding the powder into a three-neck flask, adding stearic acid, stirring at a constant speed, heating to 250 ℃, and preserving heat for 5 hours to obtain the modified rosin glyceride.
The modified rosin glyceride is prepared by grafting long-chain alkyl on the molecular chain of the rosin glyceride, and is used as a raw material to prepare the hot melt adhesive, so that the low temperature resistance of the hot melt adhesive can be improved.
Further, the modifier is prepared by the following steps:
step S1, adding perfluorooctanoic acid and methanol into a four-neck flask in a nitrogen atmosphere, heating to 40-42 ℃, slowly adding ethanolamine dropwise, heating to 160 ℃ after dropwise addition, keeping the temperature, stirring at a constant speed for 3 hours, adding deionized water after reaction to separate out a precipitate, filtering, drying, and recrystallizing chloroform to obtain a compound a, wherein the weight ratio of the perfluorooctanoic acid to the methanol to the ethanolamine is controlled to be (21.0-21.4) g to (15.5-16.0) g to 4.8g;
in the step S1, perfluorooctanoic acid reacts with ethanolamine to prepare a compound a, and the reaction process is as follows:
step S2, adding the compound a into diethyl ether, stirring at a constant speed for 10min, adding triethylamine and hydroquinone, stirring at room temperature while adding a diethyl ether mixed solution of methacryloyl chloride, heating for reflux reaction for 4h after completely adding, cooling to room temperature after the reaction is finished, washing with deionized water, washing with a sodium bicarbonate aqueous solution with the mass fraction of 5% until the washing solution is neutral, washing with deionized water for 3 times, separating an ether layer from a water phase, drying, distilling, removing diethyl ether, and recrystallizing with carbon tetrachloride to obtain a compound b, wherein the dosage ratio of the compound a, the diethyl ether, the triethylamine, the polymerization inhibitor and the methacryloyl chloride is controlled to be (13.5-13.8) g, 50mL, 6.5g, 0.205g and 3.2g;
in the step S2, diethyl ether is used as a solvent, hydroquinone is used as a polymerization inhibitor, the compound a reacts with methacryloyl chloride to generate a compound b, and the reaction process is as follows:
and S3, adding 2,6-di-tert-butylphenol and a catalyst into a three-neck flask filled with a solvent under the nitrogen atmosphere, heating to 75 ℃, removing water by a vacuum pump, adding a compound b, carrying out heat preservation reaction for 4 hours to obtain a crude product, cooling to room temperature, adding glacial acetic acid to neutralize the catalyst, continuously adding 15 volume percent of methanol aqueous solution, standing for 4 hours at room temperature to form a precipitate, carrying out pressure reduction and suction filtration, separating out the precipitate to obtain a modifier, controlling the molar ratio of 2,6-di-tert-butylphenol to the compound b to be 1: 1.2, controlling the using amount of the catalyst to be 5-8% of the weight of 2,6-di-tert-butylphenol, and controlling the using amount of the methanol aqueous solution to be 5-10 times of the weight of 2,6-di-tert-butylphenol.
In the step S3, a modifier is generated by the reaction of 2,6-di-tert-butylphenol and a compound b through a Michelal addition reaction, and the reaction process is as follows:
the modifier not only contains a hindered phenol structure, but also has a large amount of F element, and when the modifier is used as a modifier and is blended with a matrix, the modifier can endow the hot melt adhesive with excellent yellowing resistance and oxidation resistance.
The solvent is an aryl substituted alpha, beta-unsaturated carbonyl compound and mainly plays a role of an accelerant.
Further, the ether mixture of methacryloyl chloride in step S2 is obtained by mixing methacryloyl chloride and ether in a dosage ratio of 3.2 g: 10 mL.
A preparation method of an easy-to-peel packaging hot melt adhesive comprises the following steps:
sequentially adding a plasticizer, nano calcium carbonate, composite wax and a modifier into a stirrer filled with an SIS thermoplastic elastomer, stirring at a constant speed, adding modified rosin glyceride in an equivalent manner for three times at room temperature, wherein the interval of each time is 10min, and stirring for 5min after all the modified rosin glyceride are added;
and secondly, introducing nitrogen, heating to 165-180 ℃, uniformly stirring for 4h, then cooling to room temperature, continuously stirring for 30min, defoaming in vacuum, cooling and extruding to obtain the easily-stripped and packaged hot melt adhesive.
The invention has the beneficial effects that:
the invention provides an easily-stripped packaging hot melt adhesive, which is prepared by taking an SIS thermoplastic elastomer as a matrix, adding modified rosin glyceride, on one hand, the modified rosin glyceride can be used as a tackifier, on the other hand, long-chain alkyl is introduced by modifying the matrix, so that the low temperature resistance of the prepared hot melt adhesive is improved, pentaerythritol stearate in composite wax can reduce the peeling strength of the hot melt adhesive, adding a modifier, reacting perfluorooctanoic acid and ethanolamine to prepare a compound a in the preparation process of the modifier, then reacting the compound a with methacryloyl chloride to generate a compound b, and finally reacting 2,6-di-tert-butylphenol with the compound b to generate the modifier, wherein the modifier contains a hindered phenol structure and a large amount of F elements, and when the modifier is used as a modifier and is blended with the matrix, the hot melt adhesive can have excellent yellowing resistance and oxidation resistance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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
The modifier is prepared by the following steps:
step S1, adding perfluorooctanoic acid and methanol into a four-neck flask in a nitrogen atmosphere, heating to 40 ℃, slowly adding ethanolamine dropwise, heating to 160 ℃ after dropwise addition, keeping the temperature, stirring at a constant speed for 3 hours, adding deionized water after reaction to separate out a precipitate, filtering, drying, and recrystallizing chloroform to obtain a compound a, wherein the weight ratio of the perfluorooctanoic acid to the methanol to the ethanolamine is controlled to be 21.0 g: 15.5 g: 4.8g;
step S2, adding the compound a into diethyl ether, stirring at a constant speed for 10min, adding triethylamine and hydroquinone, stirring at room temperature while adding diethyl ether mixed solution of methacryloyl chloride, heating for reflux reaction for 4h after completely adding, cooling to room temperature after the reaction is finished, washing with deionized water, washing with 5% by mass of sodium bicarbonate aqueous solution until the washing solution is neutral, washing with deionized water for 3 times, separating an ether layer from a water phase, drying, distilling, removing diethyl ether, and recrystallizing with carbon tetrachloride to obtain a compound b, wherein the dosage ratio of the compound a, the diethyl ether, the triethylamine, the polymerization inhibitor and the methacryloyl chloride is controlled to be 13.5 g: 50 mL: 6.5 g: 0.205 g: 3.2g;
the ethyl ether mixed solution of the methacryloyl chloride is formed by mixing the methacryloyl chloride and the ethyl ether according to the dosage ratio of 3.2g to 10 mL.
And S3, adding 2,6-di-tert-butylphenol and a catalyst (Ca, chinese medicine) into a three-neck flask filled with a solvent (an aryl substituted alpha, beta-unsaturated carbonyl compound mainly playing a role of an accelerant, namely alatin), heating to 75 ℃, removing water by a vacuum pump, adding a compound b, carrying out heat preservation reaction for 4 hours to obtain a crude product, cooling to room temperature, adding glacial acetic acid to neutralize the catalyst, continuously adding a methanol aqueous solution with a volume fraction of 15%, standing for 4 hours at room temperature to form a precipitate, reducing pressure, carrying out suction filtration, and separating out the precipitate to obtain a modifier, wherein the molar ratio of 2,6-di-tert-butylphenol to the compound b is controlled to be 1: 1.2, the catalyst is 5% of 2,6-di-tert-butylphenol, and the methanol aqueous solution is 5 times of 2,6-di-tert-butylphenol.
Example 2
The modifier is prepared by the following steps:
step S1, adding perfluorooctanoic acid and methanol into a four-neck flask in a nitrogen atmosphere, heating to 40 ℃, slowly adding ethanolamine dropwise, heating to 160 ℃ after dropwise addition, keeping the temperature, stirring at a constant speed for 3 hours, adding deionized water after reaction to separate out a precipitate, filtering, drying, and recrystallizing chloroform to obtain a compound a, wherein the weight ratio of the perfluorooctanoic acid to the methanol to the ethanolamine is controlled to be 21.2 g: 15.8 g: 4.8g;
step S2, adding the compound a into diethyl ether, stirring at a constant speed for 10min, adding triethylamine and hydroquinone, stirring at room temperature while adding diethyl ether mixed solution of methacryloyl chloride, heating for reflux reaction for 4h after completely adding, cooling to room temperature after the reaction is finished, washing with deionized water, washing with 5% by mass of sodium bicarbonate aqueous solution until the washing solution is neutral, washing with deionized water for 3 times, separating an ether layer from a water phase, drying, distilling, removing diethyl ether, and recrystallizing with carbon tetrachloride to obtain a compound b, wherein the dosage ratio of the compound a, the diethyl ether, the triethylamine, the polymerization inhibitor and the methacryloyl chloride is controlled to be 13.68 g: 50 mL: 6.5 g: 0.205 g: 3.2g;
the ethyl ether mixed solution of the methacryloyl chloride is formed by mixing the methacryloyl chloride and the ethyl ether according to the dosage ratio of 3.2g to 10 mL.
S3, adding 2,6-di-tert-butylphenol and a catalyst (Ca, chinese medicine) into a three-neck flask filled with a solvent (aryl substituted alpha, beta-unsaturated carbonyl compound mainly playing a role of an accelerant, namely Aladdin), heating to 75 ℃, removing water by a vacuum pump, adding a compound b, carrying out heat preservation reaction for 4 hours to obtain a crude product, cooling to room temperature, adding glacial acetic acid to neutralize the catalyst, continuously adding a methanol water solution with the volume fraction of 15%, standing for 4 hours at room temperature to form a precipitate, reducing pressure, carrying out suction filtration, separating out the precipitate to obtain a modifier, controlling the molar ratio of 2,6-di-tert-butylphenol to the compound b to be 1: 1.2, controlling the dosage of the catalyst to be 6% of the weight of 2,6-di-tert-butylphenol, and controlling the dosage of the methanol water solution to be 8 times of the weight of 2,6-di-tert-butylphenol.
Example 3
The modifier is prepared by the following steps:
step S1, adding perfluorooctanoic acid and methanol into a four-neck flask in a nitrogen atmosphere, heating to 42 ℃, slowly adding ethanolamine dropwise, heating to 160 ℃ after dropwise addition, keeping the temperature, stirring at a constant speed for 3 hours, adding deionized water after reaction to separate out a precipitate, filtering, drying, and recrystallizing chloroform to obtain a compound a, wherein the weight ratio of the perfluorooctanoic acid to the methanol to the ethanolamine is controlled to be 21.4 g: 16.0 g: 4.8g;
step S2, adding the compound a into diethyl ether, stirring at a constant speed for 10min, adding triethylamine and hydroquinone, stirring at room temperature while adding diethyl ether mixed solution of methacryloyl chloride, heating for reflux reaction for 4h after completely adding, cooling to room temperature after the reaction is finished, washing with deionized water, washing with 5% by mass of sodium bicarbonate aqueous solution until the washing solution is neutral, washing with deionized water for 3 times, separating an ether layer from a water phase, drying, distilling, removing diethyl ether, and recrystallizing with carbon tetrachloride to obtain a compound b, wherein the dosage ratio of the compound a, the diethyl ether, the triethylamine, the polymerization inhibitor and the methacryloyl chloride is controlled to be 13.8 g: 50 mL: 6.5 g: 0.205 g: 3.2g;
the ethyl ether mixed solution of the methacryloyl chloride is formed by mixing the methacryloyl chloride and the ethyl ether according to the dosage ratio of 3.2g to 10 mL.
S3, adding 2,6-di-tert-butylphenol and a catalyst (Ca, chinese medicine) into a three-neck flask filled with a solvent (aryl substituted alpha, beta-unsaturated carbonyl compound mainly playing a role of an accelerant, namely Aladdin), heating to 75 ℃, removing water by a vacuum pump, adding a compound b, carrying out heat preservation reaction for 4 hours to obtain a crude product, cooling to room temperature, adding glacial acetic acid to neutralize the catalyst, continuously adding a methanol water solution with the volume fraction of 15%, standing for 4 hours at room temperature to form a precipitate, reducing pressure, carrying out suction filtration, separating out the precipitate to obtain a modifier, controlling the molar ratio of 2,6-di-tert-butylphenol to the compound b to be 1: 1.2, controlling the dosage of the catalyst to be 8% of the weight of 2,6-di-tert-butylphenol, and controlling the dosage of the methanol water solution to be 10 times of the weight of 2,6-di-tert-butylphenol.
Example 4
An easy-to-peel packaging hot melt adhesive comprises the following raw materials in parts by weight: 80 parts of SIS thermoplastic elastomer, 25 parts of naphthenic oil, 10 parts of nano calcium carbonate, 15 parts of composite wax, 25 parts of modified rosin glyceride and 10 parts of the modifier prepared in example 1;
the easy-peeling packaging hot melt adhesive is prepared by the following steps:
sequentially adding naphthenic oil, nano calcium carbonate, composite wax and a modifier into a stirrer filled with an SIS thermoplastic elastomer, stirring at a constant speed, adding modified rosin glyceride in an equivalent manner for three times at room temperature, wherein the interval of each time is 10min, and stirring for 5min after all the modified rosin glyceride are added;
and secondly, introducing nitrogen, heating to 165 ℃, uniformly stirring for 4h, then cooling to room temperature, continuously stirring for 30min, defoaming in vacuum, cooling and extruding to obtain the easily-stripped and packaged hot melt adhesive.
The composite wax is prepared by mixing polyethylene wax and pentaerythritol stearate according to the weight ratio of 4: 1.
The modified rosin glyceride is prepared by the following steps:
grinding the rosin glyceride into powder, adding the powder into a three-neck flask, adding stearic acid, stirring at a constant speed, heating to 250 ℃, and preserving heat for 5 hours to obtain the modified rosin glyceride.
Example 5
An easy-to-peel packaging hot melt adhesive comprises the following raw materials in parts by weight: 90 parts of SIS thermoplastic elastomer, 35 parts of white mineral oil, 12 parts of nano calcium carbonate, 20 parts of composite wax, 30 parts of modified rosin glyceride and 15 parts of the modifier prepared in example 1;
the easy-peeling packaging hot melt adhesive is prepared by the following steps:
sequentially adding white mineral oil, nano calcium carbonate, composite wax and a modifier into a stirrer filled with an SIS thermoplastic elastomer, stirring at a constant speed, adding modified rosin glyceride in an equal amount for three times at room temperature, wherein the interval of each time is 10min, and stirring for 5min after all the modified rosin glyceride are added;
and secondly, introducing nitrogen, heating to 170 ℃, uniformly stirring for 4h, then cooling to room temperature, continuously stirring for 30min, defoaming in vacuum, cooling and extruding to obtain the easily-stripped and packaged hot melt adhesive.
The composite wax is prepared by mixing polyethylene wax and pentaerythritol stearate according to the weight ratio of 5: 1.
The modified rosin glyceride is prepared by the following steps:
grinding rosin glyceride into powder, adding the powder into a three-neck flask, adding stearic acid, stirring at a constant speed, heating to 250 ℃, and preserving heat for 5 hours to obtain the modified rosin glyceride.
Example 6
An easy-to-peel packaging hot melt adhesive comprises the following raw materials in parts by weight: 100 parts of SIS thermoplastic elastomer, 45 parts of dibutyl phthalate, 15 parts of nano calcium carbonate, 25 parts of composite wax, 35 parts of modified rosin glyceride and 20 parts of the modifier prepared in example 1;
the easy-to-peel packaging hot melt adhesive is prepared by the following steps:
sequentially adding dibutyl phthalate, nano calcium carbonate, composite wax and a modifier into a stirrer filled with an SIS thermoplastic elastomer, stirring at a constant speed, adding modified rosin glyceride in an equal amount for three times at room temperature, wherein the interval of each time is 10min, and stirring for 5min after all the modified rosin glyceride are added;
and secondly, introducing nitrogen, heating to 180 ℃, uniformly stirring for 4h, then cooling to room temperature, continuously stirring for 30min, defoaming in vacuum, cooling and extruding to obtain the easily-stripped and packaged hot melt adhesive.
The composite wax is prepared by mixing polyethylene wax and pentaerythritol stearate according to the weight ratio of 5: 1.
The modified rosin glyceride is prepared by the following steps:
grinding the rosin glyceride into powder, adding the powder into a three-neck flask, adding stearic acid, stirring at a constant speed, heating to 250 ℃, and preserving heat for 5 hours to obtain the modified rosin glyceride.
Comparative example 1
Compared with example 4, the preparation method of the comparative example, in which antioxidant 1010 is added to replace the modifier, is as follows:
sequentially adding naphthenic oil, nano calcium carbonate, composite wax and an antioxidant 1010 into a stirrer filled with an SIS thermoplastic elastomer, stirring at a constant speed, adding modified rosin glyceride in an equivalent manner for three times at room temperature, wherein the interval of each time is 10min, and stirring for 5min after all the modified rosin glyceride are added;
and secondly, introducing nitrogen, heating to 165 ℃, uniformly stirring for 4h, then cooling to room temperature, continuously stirring for 30min, defoaming in vacuum, cooling and extruding to obtain the easily-stripped and packaged hot melt adhesive.
Comparative example 2
Compared with example 4, the preparation method of the comparative example without adding the modified rosin glyceride is as follows:
sequentially adding naphthenic oil, nano calcium carbonate, composite wax and a modifier into a stirrer filled with an SIS thermoplastic elastomer, stirring at a constant speed, and stirring for 30min;
and secondly, introducing nitrogen, heating to 165 ℃, uniformly stirring for 4h, then cooling to room temperature, continuously stirring for 30min, defoaming in vacuum, cooling and extruding to obtain the easily-stripped and packaged hot melt adhesive.
Comparative example 3
This comparative example is a commercially available SIS hot melt adhesive from a company.
The hot melt adhesives prepared in examples 4 to 6 and comparative examples 2 to 3 were formed into hot melt adhesive label paper, and the low temperature resistance and yellowing resistance thereof were measured, and the results are shown in the following tables 1 to 2:
table 1: test results of Low temperature resistance
Yellowing resistance: the hot melt adhesives prepared in examples 4 to 6 and comparative examples 1 and 3 were coated to form a film layer having a thickness of 0.5cm, placed in an outdoor visible light for 90 days, and evaluated according to the following criteria: 1= yellow opaque, 2= yellowish translucent, 3= completely transparent without yellowing, the results are shown in table 2 below.
Table 2: yellowing resistance test results
It can be seen from the above table 1-table 2 that the hot melt adhesives prepared in examples 4-6 of the present invention have excellent low temperature resistance and yellowing resistance.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (10)
1. The easy-to-peel packaging hot melt adhesive is characterized by comprising the following raw materials in parts by weight: 80-100 parts of SIS thermoplastic elastomer, 25-45 parts of plasticizer, 10-15 parts of nano calcium carbonate, 15-25 parts of composite wax, 25-35 parts of modified rosin glyceride and 10-20 parts of modifier;
the modifier has the following structure:
2. the easy-to-peel packaging hot melt adhesive according to claim 1, wherein the plasticizer is one or more of naphthenic oil, white mineral oil and dibutyl phthalate.
3. The easy-to-peel hot melt adhesive for packaging as claimed in claim 1, wherein the composite wax is prepared by mixing polyethylene wax and pentaerythritol stearate in a weight ratio of (4-5) to 1.
4. The easy-to-peel packaging hot melt adhesive according to claim 1, wherein the modified rosin glyceride is prepared by the following steps:
grinding the rosin glyceride into powder, adding the powder into a three-neck flask, adding stearic acid, stirring at a constant speed, heating to 250 ℃, and preserving heat for 5 hours to obtain the modified rosin glyceride.
5. The easy-to-peel packaging hot melt adhesive as claimed in claim 1, wherein the modifier is prepared by the following steps:
step S1, adding perfluorooctanoic acid and methanol into a four-neck flask in a nitrogen atmosphere, heating to 40-42 ℃, slowly adding ethanolamine dropwise, heating to 160 ℃ after dropwise addition, keeping the temperature, stirring at a constant speed for 3 hours, adding deionized water after reaction to separate out a precipitate, filtering, drying, and recrystallizing chloroform to obtain a compound a;
step S2, adding the compound a into diethyl ether, stirring at a constant speed for 10min, adding triethylamine and hydroquinone, adding diethyl ether mixed solution of methacryloyl chloride at room temperature while stirring, heating and refluxing for 4h after complete addition, cooling to room temperature after reaction, washing with deionized water, washing with 5% by mass of sodium bicarbonate aqueous solution until the washing solution is neutral, then washing with deionized water for 3 times, separating an ether layer from a water phase, drying, distilling, and recrystallizing with carbon tetrachloride to obtain a compound b;
and S3, adding 2,6-di-tert-butylphenol and a catalyst into a three-neck flask filled with a solvent in a nitrogen atmosphere, heating to 75 ℃, connecting with a vacuum pump for dewatering, adding a compound b, carrying out heat preservation reaction for 4 hours to obtain a crude product, cooling to room temperature, adding glacial acetic acid, continuing adding a methanol aqueous solution with the volume fraction of 15%, standing for 4 hours at room temperature to form a precipitate, reducing pressure, carrying out suction filtration, separating out the precipitate, and thus obtaining the modifier.
6. The easy-to-peel packaging hot melt adhesive according to claim 5, wherein the weight ratio of the perfluorooctanoic acid to the methanol to the ethanolamine in step S1 is controlled to be (21.0-21.4) g to (15.5-16.0) g to 4.8g.
7. The easy-to-peel packaging hot melt adhesive according to claim 5, wherein the dosage ratio of the compound a, the diethyl ether, the triethylamine, the polymerization inhibitor and the methacryloyl chloride in the step S2 is controlled to be (13.5-13.8) g, 50mL, 6.5g, 0.205g and 3.2g.
8. The easy-to-peel package hot melt adhesive according to claim 5, wherein the ether mixture of methacryloyl chloride in step S2 is prepared by mixing methacryloyl chloride and ether in a dosage ratio of 3.2g to 10 mL.
9. The easy-to-peel packaging hot melt adhesive as claimed in claim 5, wherein the molar ratio of 2,6-di-tert-butylphenol to the compound b in step S3 is controlled to be 1: 1.2, the amount of the catalyst is 5-8% of the weight of 2,6-di-tert-butylphenol, and the amount of the methanol aqueous solution is 5-10 times of the weight of 2,6-di-tert-butylphenol.
10. The preparation method of the easy-peel packaging hot melt adhesive according to any one of claims 1 to 9, characterized by comprising the following steps:
sequentially adding a plasticizer, nano calcium carbonate, composite wax and a modifier into a stirrer filled with an SIS thermoplastic elastomer, stirring at a constant speed, adding modified rosin glyceride in an equivalent manner for three times at room temperature, wherein the interval of each time is 10min, and stirring for 5min after all the modified rosin glyceride are added;
and secondly, introducing nitrogen, heating to 165-180 ℃, stirring at a constant speed for 4h, then cooling to room temperature, continuing stirring for 30min, defoaming in vacuum, cooling and extruding to obtain the easily-stripped packaging hot melt adhesive.
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CA2184743A1 (en) * | 1995-08-31 | 1997-03-01 | Mitchell J. Blumenthal | Hot melt adhesives based on sulfonated polyesters |
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CN112322233A (en) * | 2020-11-23 | 2021-02-05 | 广东能辉新材料科技有限公司 | Hot-melt pressure-sensitive adhesive containing modified SIS thermoplastic elastomer and preparation method thereof |
CN112521563A (en) * | 2020-11-23 | 2021-03-19 | 广东能辉新材料科技有限公司 | Modified SIS (styrene-isoprene-styrene) thermoplastic elastomer, preparation method thereof and hot-melt pressure-sensitive adhesive containing modified SIS |
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CA2184743A1 (en) * | 1995-08-31 | 1997-03-01 | Mitchell J. Blumenthal | Hot melt adhesives based on sulfonated polyesters |
CN101472986A (en) * | 2006-06-20 | 2009-07-01 | 科聚亚公司 | Liquid phosphite blends as stabilizers |
JP2015074713A (en) * | 2013-10-08 | 2015-04-20 | 積水フーラー株式会社 | Hot melt adhesive |
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CN112322233A (en) * | 2020-11-23 | 2021-02-05 | 广东能辉新材料科技有限公司 | Hot-melt pressure-sensitive adhesive containing modified SIS thermoplastic elastomer and preparation method thereof |
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