CN116622314B - Preparation process of low-temperature-resistant pressure-sensitive adhesive - Google Patents

Preparation process of low-temperature-resistant pressure-sensitive adhesive Download PDF

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CN116622314B
CN116622314B CN202310364026.3A CN202310364026A CN116622314B CN 116622314 B CN116622314 B CN 116622314B CN 202310364026 A CN202310364026 A CN 202310364026A CN 116622314 B CN116622314 B CN 116622314B
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sensitive adhesive
isophorone diisocyanate
temperature
acrylic acid
heating
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CN116622314A (en
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王艳飞
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Shenzhen Guoxing Xiang Adhesive Materials Co ltd
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Shenzhen Guoxing Xiang Adhesive Materials Co ltd
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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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract

The invention discloses a preparation process of a low-temperature-resistant pressure-sensitive adhesive, and relates to the technical field of pressure-sensitive adhesives. The low temperature resistant pressure sensitive adhesive comprises modified acrylic acid and waterborne polyurethane, wherein the modified acrylic acid is prepared by firstly preparing a silicon-containing prepolymer by taking gamma-mercaptopropyl triethoxysilane, isophorone diisocyanate and hydroxyethyl methacrylate as raw materials, and then copolymerizing the silicon-containing prepolymer with acrylic acid to improve the crosslinking density of the acrylic acid and enhance the low temperature resistance of the pressure sensitive adhesive, and the waterborne polyurethane is prepared by preparing polyurethane by reacting isophorone diisocyanate, polyoxypropylene glycol and dimethylolpropionic acid and then crosslinking the polyurethane with hyperbranched alkyd resin; the hyperbranched alkyd resin is prepared by esterification reaction of hydroxyl-terminated hyperbranched polyester and ricinoleic acid, so that the viscosity of the pressure-sensitive adhesive is improved; after the modified acrylic acid and the aqueous polyurethane are mixed, the crosslinking degree of the inside of the pressure-sensitive adhesive is enhanced, so that the three-way network structure of the inside of the pressure-sensitive adhesive is further enhanced, and the low temperature resistance of the pressure-sensitive adhesive is further enhanced.

Description

Preparation process of low-temperature-resistant pressure-sensitive adhesive
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to a preparation process of a low-temperature-resistant pressure-sensitive adhesive.
Background
Pressure-sensitive adhesives are an important branch in the field of adhesives, and are also traditionally pressure-sensitive adhesives because of dry and permanent adhesion, and are characterized by easy adhesion, easy uncovering, and no damage by peeling. The pressure-sensitive adhesive has the advantages of convenient use and wide application, so the development is very rapid, and with the increasing perfection of environmental protection requirements and social regulations, the pressure-sensitive adhesive is changed from solvent to water
The pressure-sensitive adhesive is mainly used for preparing pressure-sensitive adhesive tapes; the single solvent type acrylate pressure-sensitive adhesive is mainly prepared by synthesizing soft monomers, the glass transition temperature of the monomers is low, the structure determines the poor temperature resistance, and the application of the single solvent type acrylate pressure-sensitive adhesive in more fields is limited to a great extent; therefore, the invention researches and prepares the double-component pressure-sensitive adhesive which has low temperature resistance and high viscosity.
Disclosure of Invention
The invention aims to provide a preparation process of a low-temperature-resistant pressure-sensitive adhesive, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the low-temperature-resistant pressure-sensitive adhesive prepared by the preparation process of the low-temperature-resistant pressure-sensitive adhesive comprises modified acrylic acid, waterborne polyurethane, an emulsifying agent, an initiator, a crosslinking agent and deionized water.
Preferably, the modified acrylic acid is prepared by firstly preparing a silicon-containing prepolymer by taking gamma-mercaptopropyl triethoxysilane, isophorone diisocyanate and hydroxyethyl methacrylate as raw materials and then copolymerizing the silicon-containing prepolymer with acrylic acid.
Preferably, the aqueous polyurethane is prepared by reacting isophorone diisocyanate, polyoxypropylene glycol and dimethylolpropionic acid to prepare polyurethane and then crosslinking with hyperbranched alkyd resin; the hyperbranched alkyd resin is prepared by esterification reaction of hydroxyl-terminated hyperbranched polyester and ricinoleic acid.
Preferably, the emulsifier is sodium laurate; the initiator is ammonium persulfate; the cross-linking agent is maleic anhydride.
Preferably, the preparation method of the low-temperature-resistant pressure-sensitive adhesive comprises the following specific steps:
(1) Heating an isopropanol oil bath to 50-55 ℃, adding acrylic acid, a silicon-containing prepolymer and azobisisobutyronitrile, wherein the mass ratio of the isopropanol to the acrylic acid to the silicon-containing prepolymer to the azobisisobutyronitrile is 20:3:1:0.02-40:5:1.8:0.4, stirring uniformly, continuously heating to 70-75 ℃, carrying out heat preservation reaction for 3-5 h, cooling to room temperature, regulating the pH to 7-8 by using triethylamine, and emulsifying by using deionized water for 30-50 min after rotary evaporation to obtain modified acrylic acid;
(2) Mixing isophorone diisocyanate, polypropylene glycol oxide, dimethylolpropionic acid and dibutyltin dilaurate, heating to 93-98 ℃, reacting for 2-3 hours, adding hyperbranched alkyd resin with the mass of 0.16-0.18 times of the isophorone diisocyanate, adjusting the temperature to 82-85 ℃, continuing to react for 2-4 hours, adjusting the temperature to 60-70 ℃, adjusting the pH to 7-8 by triethylamine, adding deionized water with the mass of 1-2 times of the isophorone diisocyanate, stirring and emulsifying for 10-20 minutes at 2000-4000 rpm, and finally adding ethylenediamine with the mass of 0.02-0.03 times of the isophorone diisocyanate, and continuing to react for 20-30 minutes to obtain waterborne polyurethane;
(3) Mixing modified acrylic acid, aqueous polyurethane, an emulsifying agent, an initiator, a crosslinking agent and deionized water, then placing the mixture in a stirring kettle for mixing and stirring, heating to 70-80 ℃, stirring and mixing for 30-50 min, and standing for 1-2 h to prepare the low temperature resistant pressure sensitive adhesive.
Preferably, in the step (1): the preparation method of the silicon-containing prepolymer comprises the following steps: under the nitrogen atmosphere, dropwise adding dibutyl tin dilaurate with the mass of 0.001-0.002 times that of the isophorone diisocyanate and methoxyphenol with the mass of 0.01-0.02 times that of the isophorone diisocyanate into the isophorone diisocyanate, uniformly stirring, heating to 70-75 ℃, dropwise adding hydroxyethyl methacrylate with the mass of 0.45-0.55 times that of the isophorone diisocyanate at the rate of 1-2 ml/min, continuously reacting for 3-5 h, cooling to room temperature, dropwise adding gamma-mercaptopropyl triethoxysilane with the mass of 0.92-0.95 times that of the isophorone diisocyanate at the rate of 3-5 ml/min, heating to 70-75 ℃, continuously reacting for 3-5 h, and cooling to room temperature to obtain the silicon-containing prepolymer.
Preferably, in the step (2): the preparation method of the hyperbranched alkyd resin comprises the following steps: and under the nitrogen atmosphere, mixing hyperbranched polyester, ricinoleic acid, p-toluenesulfonic acid and dimethylbenzene according to the mass ratio of 3:0.4:0.2:20-3:0.5:0.3:30, heating to 200-210 ℃, reacting for 4-6 h, and then placing in a vacuum drying oven to dry for 24h at 50-60 ℃ to prepare the hyperbranched alkyd resin.
Preferably, the preparation method of the hyperbranched polyester comprises the following steps: pentaerythritol, 2-dimethylolpropionic acid and p-toluenesulfonic acid are mixed according to the mass ratio of 1.2:16:0.08-1.4:16:0.084, heated to a molten state, transferred to a nitrogen atmosphere, heated to 130-150 ℃ for reaction for 2-3 h, then subjected to negative pressure to 0.05-0.055 MPa, continuously reacted for 2-3 h, cooled to room temperature, dissolved by acetone, precipitated by diethyl ether, and finally dried, thus obtaining the hyperbranched polyester.
Preferably, in the step (2): the mass ratio of the isophorone diisocyanate to the polypropylene oxide glycol to the dimethylolpropionic acid to the dibutyltin dilaurate is 4:1:3:0.002-4:1.2:3:0.03.
Preferably, in the step (3): the mass ratio of the modified acrylic acid to the aqueous polyurethane to the emulsifier to the initiator to the crosslinking agent to the deionized water is as follows: 25:20:0.5:1:1:5 to 35:30:1.5:3:3:15.
Compared with the prior art, the invention has the following beneficial effects:
the low-temperature-resistant pressure-sensitive adhesive prepared by the invention comprises modified acrylic acid and waterborne polyurethane;
the modified acrylic acid is prepared by firstly preparing a silicon-containing prepolymer by taking gamma-mercaptopropyl triethoxysilane, isophorone diisocyanate and hydroxyethyl methacrylate as raw materials, and then copolymerizing the silicon-containing prepolymer with acrylic acid; the molecular chain of the acrylic acid lacks branched chains and is difficult to form a three-dimensional network structure, so that the defects of low temperature resistance, ductility and the like of the polymer are caused, the silicon-based prepolymer is connected to the acrylic acid to serve as the branched chains, the crosslinking density of the acrylic acid is improved, and the low temperature resistance of the pressure-sensitive adhesive is enhanced;
the aqueous polyurethane is prepared by reacting isophorone diisocyanate, polyoxypropylene glycol and dimethylolpropionic acid to prepare polyurethane and then crosslinking the polyurethane with hyperbranched alkyd resin; the hyperbranched alkyd resin is prepared by esterification reaction of hydroxyl-terminated hyperbranched polyester and ricinoleic acid; crosslinking hyperbranched alkyd resin with hydroxyl ends and long chains with polyurethane to enable molecular chains of the waterborne polyurethane to form a space network structure, so that the crosslinking effect of the molecular chains is enhanced, and the viscosity of the pressure-sensitive adhesive is improved; after the modified acrylic acid and the aqueous polyurethane are mixed, the crosslinking degree of the inside of the pressure-sensitive adhesive is enhanced, so that the three-way network structure of the inside of the pressure-sensitive adhesive is further enhanced, and the low temperature resistance of the pressure-sensitive adhesive is further enhanced.
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 method for testing each index of the low temperature-resistant pressure-sensitive adhesive prepared in the examples and comparative examples as follows:
low temperature resistance: coating the low-temperature-resistant pressure-sensitive adhesive prepared in the examples and the comparative examples on a transparent PET film with the thickness of 50 micrometers, drying for 5 minutes in an oven at 120 ℃, performing viscosity test by using an NDJ-1 type rotary viscometer, transferring to a minus 40 ℃ and standing for 24 hours, and performing viscosity test by using the NDJ-1 type rotary viscometer;
viscosity: the low temperature resistant pressure sensitive adhesives prepared in examples and comparative examples were subjected to viscosity testing using an NDJ-1 type rotary viscometer.
Example 1
(1) Dropwise adding dibutyl tin dilaurate with the mass of 0.001 times of that of the isophorone diisocyanate and methoxyphenol with the mass of 0.01 times of that of the isophorone diisocyanate into the isophorone diisocyanate in a nitrogen atmosphere, uniformly stirring, heating to 70 ℃, dropwise adding hydroxyethyl methacrylate with the mass of 0.45 times of that of the isophorone diisocyanate at the rate of 1ml/min, continuously reacting for 3 hours, cooling to room temperature, dropwise adding gamma-mercaptopropyl triethoxysilane with the mass of 0.92 times of that of the isophorone diisocyanate at the rate of 3ml/min, heating to 70 ℃, continuously reacting for 3 hours, and cooling to room temperature to obtain a silicon-containing prepolymer; heating an isopropanol oil bath to 50 ℃, adding acrylic acid, a silicon-containing prepolymer and azobisisobutyronitrile, wherein the mass ratio of the isopropanol to the acrylic acid to the silicon-containing prepolymer to the azobisisobutyronitrile is 20:3:1:0.02, stirring uniformly, continuously heating to 70 ℃, carrying out heat preservation reaction for 3 hours, cooling to room temperature, regulating the pH to 7 by triethylamine, and emulsifying for 30 minutes by deionized water after rotary evaporation to obtain modified acrylic acid;
(2) Mixing pentaerythritol, 2-dimethylolpropionic acid and p-toluenesulfonic acid according to the mass ratio of 1.2:16:0.08, heating to a molten state, transferring to a nitrogen atmosphere, heating to 130 ℃ for reaction for 2 hours, then carrying out negative pressure to 0.05MPa, continuing to react for 2 hours, cooling to room temperature, dissolving with acetone, precipitating with diethyl ether, and finally drying to obtain hyperbranched polyester; under the nitrogen atmosphere, mixing hyperbranched polyester, ricinoleic acid, p-toluenesulfonic acid and dimethylbenzene according to the mass ratio of 3:0.4:0.2:20, heating to 200 ℃, reacting for 4-6 hours, and then placing in a vacuum drying oven to dry for 24 hours at 50 ℃ to prepare hyperbranched alkyd resin;
(3) Mixing isophorone diisocyanate, polypropylene glycol oxide, dimethylolpropionic acid and dibutyltin dilaurate according to the mass ratio of 4:1:3:0.002, heating to 93 ℃, reacting for 2 hours, adding hyperbranched alkyd resin with the mass of 0.16 times of the isophorone diisocyanate, adjusting the temperature to 82 ℃, continuing to react for 2 hours, adjusting the temperature to 60 ℃, adjusting the pH to 7 by triethylamine, adding deionized water with the mass of 1 time of the isophorone diisocyanate, stirring and emulsifying for 10 minutes at 2000rpm, and finally adding ethylenediamine with the mass of 0.02 time of the isophorone diisocyanate, and continuing to react for 20 minutes to prepare the water-based polyurethane;
(4) Mixing modified acrylic acid, waterborne polyurethane, emulsifier sodium dodecyl, initiator ammonium persulfate, cross-linking agent maleic anhydride and deionized water according to the mass ratio of 25:20:0.5:1:1:5, then placing the mixture in a stirring kettle for mixing and stirring, heating to 70 ℃, stirring and mixing for 30min, and standing for 1h to prepare the low-temperature-resistant pressure-sensitive adhesive.
Example 2
(1) Dropwise adding dibutyl tin dilaurate with the mass of 0.0015 times of that of the isophorone diisocyanate and methoxyphenol with the mass of 0.015 times of that of the isophorone diisocyanate into the isophorone diisocyanate in a nitrogen atmosphere, uniformly stirring, heating to 73 ℃, dropwise adding hydroxyethyl methacrylate with the mass of 0.5 times of that of the isophorone diisocyanate at the rate of 1ml/min, continuously reacting for 4 hours, cooling to room temperature, dropwise adding gamma-mercaptopropyl triethoxysilane with the mass of 0.94 times of that of the isophorone diisocyanate at the rate of 4ml/min, heating to 73 ℃, continuously reacting for 4 hours, and cooling to room temperature to obtain a silicon-containing prepolymer; heating an isopropanol oil bath to 53 ℃, adding acrylic acid, a silicon-containing prepolymer and azobisisobutyronitrile, wherein the mass ratio of the isopropanol to the acrylic acid to the silicon-containing prepolymer to the azobisisobutyronitrile is 30:4:1.5:0.03, stirring uniformly, continuously heating to 73 ℃, keeping the temperature for 4 hours, cooling to room temperature, regulating the pH to 7.5 by triethylamine, and emulsifying by deionized water for 40min after rotary evaporation to obtain modified acrylic acid;
(2) Mixing pentaerythritol, 2-dimethylolpropionic acid and p-toluenesulfonic acid according to the mass ratio of 1.3:16:0.082, heating to a molten state, transferring to a nitrogen atmosphere, heating to 140 ℃ for reaction for 2.5 hours, then carrying out negative pressure to 0.053MPa, continuing to react for 2.5 hours, cooling to room temperature, dissolving with acetone, precipitating with diethyl ether, and finally drying to obtain hyperbranched polyester; under the nitrogen atmosphere, mixing hyperbranched polyester, ricinoleic acid, p-toluenesulfonic acid and dimethylbenzene according to the mass ratio of 3:0.45:0.25:25, heating to 205 ℃, reacting for 5 hours, and then placing in a vacuum drying oven to dry for 24 hours at 55 ℃ to prepare hyperbranched alkyd resin;
(3) Mixing isophorone diisocyanate, polypropylene glycol oxide, dimethylolpropionic acid and dibutyltin dilaurate according to the mass ratio of 4:1.1:3:0.0025, heating to 95 ℃, reacting for 2.5 hours, adding hyperbranched alkyd resin with the mass of 0.17 times of the isophorone diisocyanate, adjusting the temperature to 84 ℃, continuing to react for 3 hours, adjusting the temperature to 65 ℃, adjusting the pH to 7.5 by triethylamine, adding deionized water with the mass of 1.5 times of the isophorone diisocyanate, stirring and emulsifying for 15 minutes at 3000rpm, and finally adding ethylenediamine with the mass of 0.025 times of the isophorone diisocyanate, and continuing to react for 25 minutes to obtain the water-based polyurethane;
(4) Mixing modified acrylic acid, waterborne polyurethane, emulsifier sodium dodecyl, initiator ammonium persulfate, cross-linking agent maleic anhydride and deionized water according to the mass ratio of 20:25:1:2:2:10, then placing the mixture in a stirring kettle for mixing and stirring, heating to 75 ℃, stirring and mixing for 40min, and standing for 1.5h to obtain the low-temperature-resistant pressure-sensitive adhesive.
Example 3
(1) Dropwise adding dibutyl tin dilaurate with the mass of 0.002 times that of the isophorone diisocyanate and methoxyphenol with the mass of 0.02 times that of the isophorone diisocyanate into the isophorone diisocyanate in a nitrogen atmosphere, uniformly stirring, heating to 75 ℃, dropwise adding hydroxyethyl methacrylate with the mass of 0.55 times that of the isophorone diisocyanate at the rate of 2ml/min, continuously reacting for 5 hours, cooling to room temperature, dropwise adding gamma-mercaptopropyl triethoxysilane with the mass of 0.95 times that of the isophorone diisocyanate at the rate of 5ml/min, heating to 75 ℃, continuously reacting for 5 hours, and cooling to room temperature to obtain a silicon-containing prepolymer; heating an isopropanol oil bath to 55 ℃, adding acrylic acid, a silicon-containing prepolymer and azobisisobutyronitrile, wherein the mass ratio of the isopropanol to the acrylic acid to the silicon-containing prepolymer to the azobisisobutyronitrile is 40:5:1.8:0.4, stirring uniformly, continuously heating to 75 ℃, keeping the temperature for reaction for 5 hours, cooling to room temperature, regulating the pH to 8 by triethylamine, and emulsifying with deionized water for 50 minutes after rotary evaporation to obtain modified acrylic acid;
(2) Mixing pentaerythritol, 2-dimethylolpropionic acid and p-toluenesulfonic acid according to the mass ratio of 1.4:16:0.084, heating to a molten state, transferring to a nitrogen atmosphere, heating to 150 ℃ for reaction for 3 hours, then carrying out negative pressure to 0.055MPa, continuing to react for 3 hours, cooling to room temperature, dissolving with acetone, precipitating with diethyl ether, and finally drying to obtain hyperbranched polyester; under the nitrogen atmosphere, mixing hyperbranched polyester, ricinoleic acid, p-toluenesulfonic acid and dimethylbenzene according to the mass ratio of 3:0.5:0.3:30, heating to 210 ℃, reacting for 6 hours, and then placing in a vacuum drying oven to dry for 24 hours at 60 ℃ to prepare hyperbranched alkyd resin;
(3) Mixing isophorone diisocyanate, polypropylene glycol oxide, dimethylolpropionic acid and dibutyltin dilaurate according to the mass ratio of 4:1.2:3:0.03, heating to 98 ℃, reacting for 3 hours, adding hyperbranched alkyd resin with the mass of 0.18 times of the isophorone diisocyanate, adjusting the temperature to 85 ℃, continuing to react for 4 hours, adjusting the temperature to 70 ℃, adjusting the pH to 8 by triethylamine, adding deionized water with the mass of 2 times of the isophorone diisocyanate, stirring and emulsifying for 20 minutes at 4000rpm, and finally adding ethylenediamine with the mass of 0.03 times of the isophorone diisocyanate, and continuing to react for 30 minutes to prepare waterborne polyurethane;
(4) Mixing modified acrylic acid, waterborne polyurethane, emulsifier sodium dodecyl, initiator ammonium persulfate, cross-linking agent maleic anhydride and deionized water according to a mass ratio of 35:30:1.5:3:3:15, then placing the mixture in a stirring kettle for mixing and stirring, heating to 80 ℃, stirring and mixing for 50min, and standing for 2h to obtain the low-temperature-resistant pressure-sensitive adhesive.
Comparative example 1
(1) Mixing pentaerythritol, 2-dimethylolpropionic acid and p-toluenesulfonic acid according to the mass ratio of 1.3:16:0.082, heating to a molten state, transferring to a nitrogen atmosphere, heating to 140 ℃ for reaction for 2.5 hours, then carrying out negative pressure to 0.053MPa, continuing to react for 2.5 hours, cooling to room temperature, dissolving with acetone, precipitating with diethyl ether, and finally drying to obtain hyperbranched polyester; under the nitrogen atmosphere, mixing hyperbranched polyester, ricinoleic acid, p-toluenesulfonic acid and dimethylbenzene according to the mass ratio of 3:0.45:0.25:25, heating to 205 ℃, reacting for 5 hours, and then placing in a vacuum drying oven to dry for 24 hours at 55 ℃ to prepare hyperbranched alkyd resin;
(2) Mixing isophorone diisocyanate, polypropylene glycol oxide, dimethylolpropionic acid and dibutyltin dilaurate according to the mass ratio of 4:1.1:3:0.0025, heating to 95 ℃, reacting for 2.5 hours, adding hyperbranched alkyd resin with the mass of 0.17 times of the isophorone diisocyanate, adjusting the temperature to 84 ℃, continuing to react for 3 hours, adjusting the temperature to 65 ℃, adjusting the pH to 7.5 by triethylamine, adding deionized water with the mass of 1.5 times of the isophorone diisocyanate, stirring and emulsifying for 15 minutes at 3000rpm, and finally adding ethylenediamine with the mass of 0.025 times of the isophorone diisocyanate, and continuing to react for 25 minutes to obtain the water-based polyurethane;
(3) Mixing acrylic acid, waterborne polyurethane, emulsifier sodium dodecyl, initiator ammonium persulfate, cross-linking agent maleic anhydride and deionized water according to the mass ratio of 20:25:1:2:2:10, then placing the mixture in a stirring kettle for mixing and stirring, heating to 75 ℃, stirring and mixing for 40min, and standing for 1.5h to obtain the low-temperature-resistant pressure-sensitive adhesive.
Comparative example 2
(1) Dropwise adding dibutyl tin dilaurate with the mass of 0.0015 times of that of the isophorone diisocyanate and methoxyphenol with the mass of 0.015 times of that of the isophorone diisocyanate into the isophorone diisocyanate in a nitrogen atmosphere, uniformly stirring, heating to 73 ℃, dropwise adding hydroxyethyl methacrylate with the mass of 0.5 times of that of the isophorone diisocyanate at the rate of 1ml/min, continuously reacting for 4 hours, cooling to room temperature, dropwise adding gamma-mercaptopropyl triethoxysilane with the mass of 0.94 times of that of the isophorone diisocyanate at the rate of 4ml/min, heating to 73 ℃, continuously reacting for 4 hours, and cooling to room temperature to obtain a silicon-containing prepolymer; heating an isopropanol oil bath to 53 ℃, adding acrylic acid, a silicon-containing prepolymer and azobisisobutyronitrile, wherein the mass ratio of the isopropanol to the acrylic acid to the silicon-containing prepolymer to the azobisisobutyronitrile is 30:4:1.5:0.03, stirring uniformly, continuously heating to 73 ℃, keeping the temperature for 4 hours, cooling to room temperature, regulating the pH to 7.5 by triethylamine, and emulsifying by deionized water for 40min after rotary evaporation to obtain modified acrylic acid;
(2) Mixing isophorone diisocyanate, polypropylene glycol oxide, dimethylolpropionic acid and dibutyltin dilaurate according to the mass ratio of 4:1.1:3:0.0025, heating to 95 ℃, reacting for 2.5 hours, adjusting the temperature to 65 ℃, adjusting the pH to 7.5 by triethylamine, adding deionized water with the mass of 1.5 times that of the isophorone diisocyanate, stirring and emulsifying for 15 minutes at 3000rpm, and finally adding ethylenediamine with the mass of 0.025 times that of the isophorone diisocyanate for continuous reaction for 25 minutes to prepare the water-based polyurethane;
(3) Mixing modified acrylic acid, waterborne polyurethane, emulsifier sodium dodecyl, initiator ammonium persulfate, cross-linking agent maleic anhydride and deionized water according to the mass ratio of 20:25:1:2:2:10, then placing the mixture in a stirring kettle for mixing and stirring, heating to 75 ℃, stirring and mixing for 40min, and standing for 1.5h to obtain the low-temperature-resistant pressure-sensitive adhesive.
Comparative example 3
(1) Dropwise adding dibutyl tin dilaurate with the mass of 0.0015 times of that of the isophorone diisocyanate and methoxyphenol with the mass of 0.015 times of that of the isophorone diisocyanate into the isophorone diisocyanate in a nitrogen atmosphere, uniformly stirring, heating to 73 ℃, dropwise adding hydroxyethyl methacrylate with the mass of 0.5 times of that of the isophorone diisocyanate at the rate of 1ml/min, continuously reacting for 4 hours, cooling to room temperature, dropwise adding gamma-mercaptopropyl triethoxysilane with the mass of 0.94 times of that of the isophorone diisocyanate at the rate of 4ml/min, heating to 73 ℃, continuously reacting for 4 hours, and cooling to room temperature to obtain a silicon-containing prepolymer; heating an isopropanol oil bath to 53 ℃, adding acrylic acid, a silicon-containing prepolymer and azobisisobutyronitrile, wherein the mass ratio of the isopropanol to the acrylic acid to the silicon-containing prepolymer to the azobisisobutyronitrile is 30:4:1.5:0.03, stirring uniformly, continuously heating to 73 ℃, keeping the temperature for 4 hours, cooling to room temperature, regulating the pH to 7.5 by triethylamine, and emulsifying by deionized water for 40min after rotary evaporation to obtain modified acrylic acid;
(2) Mixing modified acrylic acid, emulsifier sodium dodecyl, initiator ammonium persulfate, cross-linking agent maleic anhydride and deionized water according to a mass ratio of 20:25:1:2:2:10, placing the mixture in a stirring kettle for mixing and stirring, heating to 75 ℃, stirring and mixing for 40min, and standing for 1.5h to obtain the low-temperature-resistant pressure-sensitive adhesive.
Comparative example 4
(1) Mixing isophorone diisocyanate, polypropylene glycol oxide, dimethylolpropionic acid and dibutyltin dilaurate according to the mass ratio of 4:1.1:3:0.0025, heating to 95 ℃, reacting for 2.5 hours, adjusting the temperature to 65 ℃, adjusting the pH to 7.5 by triethylamine, adding deionized water with the mass of 1.5 times that of the isophorone diisocyanate, stirring and emulsifying for 15 minutes at 3000rpm, and finally adding ethylenediamine with the mass of 0.025 times that of the isophorone diisocyanate for continuous reaction for 25 minutes to prepare polyurethane;
(2) Mixing acrylic acid, polyurethane, emulsifier sodium dodecyl, initiator ammonium persulfate, cross-linking agent maleic anhydride and deionized water according to a mass ratio of 20:25:1:2:2:10, placing the mixture in a stirring kettle for mixing and stirring, heating to 75 ℃, stirring and mixing for 40min, and standing for 1.5h to obtain the low-temperature-resistant pressure-sensitive adhesive.
Effect example
The following table 1 gives the results of performance analysis of low temperature resistant pressure sensitive adhesives employing examples 1 to 3 of the present invention and comparative examples 1 to 4:
TABLE 1
As is evident from comparison of the experimental data of examples in Table 1 with that of comparative examples, the low temperature resistant pressure sensitive adhesives prepared in examples 1, 2 and 3 have better low temperature resistance and adhesion.
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 (8)

1. The preparation process of the low-temperature-resistant pressure-sensitive adhesive is characterized in that the low-temperature-resistant pressure-sensitive adhesive prepared by the preparation process of the low-temperature-resistant pressure-sensitive adhesive comprises modified acrylic acid, waterborne polyurethane, an emulsifying agent, an initiator, a crosslinking agent and deionized water;
the preparation method of the modified acrylic acid comprises the following steps: heating an isopropanol oil bath to 50-55 ℃, adding acrylic acid, a silicon-containing prepolymer and azobisisobutyronitrile, wherein the mass ratio of the isopropanol to the acrylic acid to the silicon-containing prepolymer to the azobisisobutyronitrile is 20:3:1:0.02-40:5:1.8:0.4, stirring uniformly, continuously heating to 70-75 ℃, carrying out heat preservation reaction for 3-5 h, cooling to room temperature, regulating the pH to 7-8 by using triethylamine, and emulsifying by using deionized water for 30-50 min after rotary evaporation;
the preparation method of the silicon-containing prepolymer comprises the following steps: dropwise adding dibutyl tin dilaurate with the mass of 0.001-0.002 times that of the isophorone diisocyanate and methoxyphenol with the mass of 0.01-0.02 times that of the isophorone diisocyanate into the isophorone diisocyanate in a nitrogen atmosphere, uniformly stirring, heating to 70-75 ℃, dropwise adding hydroxyethyl methacrylate with the mass of 0.45-0.55 times that of the isophorone diisocyanate at the rate of 1-2 ml/min, continuously reacting for 3-5 h, cooling to room temperature, dropwise adding gamma-mercaptopropyl triethoxysilane with the mass of 0.92-0.95 times that of the isophorone diisocyanate at the rate of 3-5 ml/min, heating to 70-75 ℃, continuously reacting for 3-5 h, and cooling to room temperature to obtain the silicon-containing prepolymer.
2. The preparation process of the low-temperature-resistant pressure-sensitive adhesive according to claim 1, wherein the aqueous polyurethane is prepared by reacting isophorone diisocyanate, polyoxypropylene glycol and dimethylolpropionic acid to prepare polyurethane and then crosslinking with hyperbranched alkyd resin; the hyperbranched alkyd resin is prepared by esterification reaction of hydroxyl-terminated hyperbranched polyester and ricinoleic acid.
3. The process for preparing the low-temperature-resistant pressure-sensitive adhesive according to claim 1, wherein the emulsifier is sodium laurate; the initiator is ammonium persulfate; the cross-linking agent is maleic anhydride.
4. The preparation process of the low-temperature-resistant pressure-sensitive adhesive according to claim 1, which is characterized by comprising the following specific steps:
(1) Heating an isopropanol oil bath to 50-55 ℃, adding acrylic acid, a silicon-containing prepolymer and azobisisobutyronitrile, wherein the mass ratio of the isopropanol to the acrylic acid to the silicon-containing prepolymer to the azobisisobutyronitrile is 20:3:1:0.02-40:5:1.8:0.4, stirring uniformly, continuously heating to 70-75 ℃, carrying out heat preservation reaction for 3-5 h, cooling to room temperature, regulating the pH to 7-8 by using triethylamine, and emulsifying for 30-50 min by using deionized water after rotary evaporation to obtain modified acrylic acid;
(2) Mixing isophorone diisocyanate, polypropylene glycol oxide, dimethylolpropionic acid and dibutyltin dilaurate, heating to 93-98 ℃, reacting for 2-3 hours, adding hyperbranched alkyd resin with the mass of 0.16-0.18 times of the isophorone diisocyanate, adjusting the temperature to 82-85 ℃, continuing to react for 2-4 hours, adjusting the temperature to 60-70 ℃, adjusting the pH to 7-8 by triethylamine, adding deionized water with the mass of 1-2 times of the isophorone diisocyanate, stirring and emulsifying for 10-20 minutes at 2000-4000 rpm, and finally adding ethylenediamine with the mass of 0.02-0.03 times of the isophorone diisocyanate, and continuing to react for 20-30 minutes to obtain waterborne polyurethane;
(3) And mixing the modified acrylic acid, the aqueous polyurethane, the emulsifier, the initiator, the crosslinking agent and the deionized water, then placing the mixture in a stirring kettle for mixing and stirring, heating to 70-80 ℃, stirring and mixing for 30-50 min, and standing for 1-2 h to obtain the low-temperature-resistant pressure-sensitive adhesive.
5. The process for preparing a low temperature-resistant pressure-sensitive adhesive according to claim 4, wherein in the step (2): the preparation method of the hyperbranched alkyd resin comprises the following steps: and under the nitrogen atmosphere, mixing hyperbranched polyester, ricinoleic acid, p-toluenesulfonic acid and dimethylbenzene according to a mass ratio of 3:0.4:0.2:20-3:0.5:0.3:30, heating to 200-210 ℃, reacting for 4-6 hours, and then placing in a vacuum drying oven to dry for 24 hours at 50-60 ℃ to prepare the hyperbranched alkyd resin.
6. The preparation process of the low-temperature-resistant pressure-sensitive adhesive according to claim 5, wherein the preparation method of the hyperbranched polyester is as follows: mixing pentaerythritol, 2-dimethylolpropionic acid and p-toluenesulfonic acid according to the mass ratio of 1.2:16:0.08-1.4:16:0.084, heating to a molten state, transferring to a nitrogen atmosphere, heating to 130-150 ℃ for reaction for 2-3 h, then, carrying out negative pressure to 0.05-0.055 MPa, continuing to react for 2-3 h, cooling to room temperature, dissolving with acetone, precipitating with diethyl ether, and finally drying to obtain the hyperbranched polyester.
7. The process for preparing a low temperature-resistant pressure-sensitive adhesive according to claim 4, wherein in the step (2): the mass ratio of the isophorone diisocyanate to the polyoxypropylene glycol to the dimethylolpropionic acid to the dibutyltin dilaurate is 4:1:3:0.002-4:1.2:3:0.03.
8. The process for preparing a low temperature-resistant pressure-sensitive adhesive according to claim 4, wherein in the step (3): the mass ratio of the modified acrylic acid to the aqueous polyurethane to the emulsifier to the initiator to the crosslinking agent to the deionized water is as follows: 25:20:0.5:1:5 to 35:30:1.5:3:3:15.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105295781A (en) * 2015-11-27 2016-02-03 上海九元石油化工有限公司 Water-based pressure sensitive adhesive as well as preparation method and application thereof
WO2019052203A1 (en) * 2017-09-15 2019-03-21 江苏景宏新材料科技有限公司 Method for preparing acrylic pressure-sensitive adhesive emulsion with block structure
CN112724324A (en) * 2020-12-22 2021-04-30 安徽明讯新材料科技股份有限公司 High-performance polyurethane-acrylate pressure-sensitive adhesive emulsion and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105295781A (en) * 2015-11-27 2016-02-03 上海九元石油化工有限公司 Water-based pressure sensitive adhesive as well as preparation method and application thereof
WO2019052203A1 (en) * 2017-09-15 2019-03-21 江苏景宏新材料科技有限公司 Method for preparing acrylic pressure-sensitive adhesive emulsion with block structure
CN112724324A (en) * 2020-12-22 2021-04-30 安徽明讯新材料科技股份有限公司 High-performance polyurethane-acrylate pressure-sensitive adhesive emulsion and preparation method thereof

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