CN114671984A - Oil-resistant acrylic acid adhesive and preparation method thereof - Google Patents
Oil-resistant acrylic acid adhesive and preparation method thereof Download PDFInfo
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- CN114671984A CN114671984A CN202210377305.9A CN202210377305A CN114671984A CN 114671984 A CN114671984 A CN 114671984A CN 202210377305 A CN202210377305 A CN 202210377305A CN 114671984 A CN114671984 A CN 114671984A
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- 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
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Abstract
The invention discloses an oil-resistant acrylic adhesive and a preparation method thereof, wherein the scheme is that an adhesive with a three-layer core-shell structure is synthesized by taking acrylic ester monomers, dibutyl itaconate copolymer, fluorine-containing vinyl silane and other monomers as main raw materials through emulsion polymerization; when the scheme is prepared, firstly, the core layer monomer, the middle layer monomer and the shell layer monomer are pre-emulsified respectively, and in the step, the component selection and the content of the core layer monomer, the middle layer monomer and the shell layer monomer are limited, so that the oil resistance and the water resistance of the adhesive are improved, and the high temperature resistance of the adhesive is improved. The invention discloses an oil-resistant acrylic adhesive and a preparation method thereof, and the prepared acrylic adhesive with a core layer-intermediate layer-shell layer composite structure has excellent high temperature resistance, excellent water resistance and oil resistance, good chemical corrosion resistance and high practicability.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an oil-resistant acrylic acid adhesive and a preparation method thereof.
Background
The acrylic adhesive is an adhesive with unique performance and wide application range. According to the form and application characteristics of the adhesive, the adhesive can be divided into a solvent type, an emulsion type, a reaction type, a pressure-sensitive type, an instant drying type, an anaerobic type, a photosensitive type, a hot-melt type and the like. From the classification, the application range of the diacidic adhesive is very wide, so that all metal and nonmetal materials can be bonded by the diacidic adhesive, and the diacidic adhesive can be widely applied to life and factory processing.
The oil-resistant acrylic adhesive and the preparation method thereof are used for solving the problem that the existing acrylic adhesive is poor in oil resistance and water resistance and greatly influences the practical application effect of the acrylic adhesive, so that the application discloses the oil-resistant acrylic adhesive and the preparation method thereof for improving the comprehensive performance of the acrylic adhesive.
Disclosure of Invention
The invention aims to provide an oil-resistant acrylic acid adhesive and a preparation method thereof, and aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of oil-resistant acrylic acid adhesive comprises the following steps:
(1) taking an emulsifier, deionized water and a core layer monomer, and pre-emulsifying to obtain a core layer pre-emulsion; the core layer monomer consists of an acrylate monomer and a dibutyl itaconate copolymer;
pre-emulsifying an emulsifier, deionized water and an intermediate layer monomer to obtain an intermediate layer pre-emulsion; the middle layer monomer consists of an acrylate monomer, a dibutyl itaconate copolymer and fluorine-containing vinyl silane;
pre-emulsifying an emulsifier, deionized water and a shell monomer to obtain a shell pre-emulsion; the shell layer monomer consists of an acrylate monomer, methacrylic acid, dibutyl itaconate copolymer and fluorine-containing vinyl silane;
(2) taking an emulsifier and deionized water, and uniformly mixing to obtain a pre-emulsion;
taking the pre-emulsion, dropwise adding the core layer pre-emulsion and 1/4 initiator at 80-85 ℃, reacting for 30-40 min under heat preservation, dropwise adding the middle layer pre-emulsion and 1/4 initiator, reacting for 30-40 min under heat preservation at 80-85 ℃, finally dropwise adding the shell layer pre-emulsion and the rest initiator, continuing reacting for 1-1.2 h under heat preservation, cooling, adding ammonia water, and adjusting the pH value to 7-8 to obtain the adhesive.
According to an optimized scheme, the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the core layer monomer is 9: 2; the mass ratio of the acrylate monomer, the dibutyl itaconate copolymer and the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1: 1; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 1: 2; the methacrylic acid accounts for 8-10 wt% of the monomer amount of the shell layer.
In an optimized scheme, in the step (1), the preparation step of the dibutyl itaconate copolymer is as follows:
s1: taking hydroxyethyl carbazole, p-toluenesulfonic acid and hydroquinone, mixing and stirring for 10-20 min, heating to 85-95 ℃, adding methacrylic acid, heating to 110-120 ℃, reacting for 10-11 h, washing after reaction, separating, and distilling under reduced pressure to obtain ethyl carbazole methacrylate;
s2: mixing and stirring ethyl carbazole methacrylate, dibutyl itaconate, N-vinyl carbazole and toluene uniformly, adding azobisisobutyronitrile, reacting for 20-24 hours in a nitrogen environment at the reaction temperature of 65-70 ℃, precipitating methanol after reaction, filtering and collecting a product, and drying in vacuum to obtain the dibutyl itaconate copolymer.
In an optimized scheme, in step S2, the mass ratio of the ethyl carbazole methacrylate to the dibutyl itaconate to the N-vinyl carbazole is 2: 3: 1; the amount of the azodiisobutyronitrile is 2-2.5 wt% of that of the dibutyl itaconate copolymer.
In a more optimized scheme, in the step (1), the preparation steps of the fluorine-containing vinyl silane are as follows: taking magnesium powder, methyltriethoxysilane, iodine and tetrahydrofuran, uniformly mixing, heating to 65-70 ℃ in a nitrogen environment, dropwise adding 4- (trifluorovinyl ether) bromobenzene, stirring for reacting for 20-24 h, cooling, removing tetrahydrofuran, and collecting a product to obtain the fluorine-containing vinyl silane.
In a more optimized scheme, the molar ratio of the methyltriethoxysilane to the 4- (trifluorovinyl ether) bromobenzene is 4: 3.
according to an optimized scheme, in the step (1), the mass ratio of the core layer monomer to the intermediate layer monomer to the shell layer monomer is 4: 3: 3; the acrylate monomer comprises methyl methacrylate, butyl acrylate and caprolactone acrylate, wherein the weight ratio of the methyl methacrylate to the butyl acrylate to the caprolactone acrylate is 5: 2: 2.
according to an optimized scheme, in the step (2), the amount of the emulsifier is 2-3 wt% of the total amount of shell monomers; the initiator accounts for 2-3 wt% of the total amount of the shell layer monomer, the core layer monomer and the middle layer monomer.
According to an optimized scheme, the emulsifier comprises sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene, and the mass ratio of the sodium dodecyl benzene sulfonate to the alkylphenol polyoxyethylene is 1: 2.
according to an optimized scheme, the adhesive is prepared by the preparation method of the oil-resistant acrylic adhesive.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses an oil-resistant acrylic adhesive and a preparation method thereof, wherein the scheme is that an adhesive with a three-layer core-shell structure is synthesized by taking acrylic ester monomers, dibutyl itaconate copolymer, fluorine-containing vinyl silane and other monomers as main raw materials through emulsion polymerization; when the scheme is prepared, firstly, the core layer monomer, the middle layer monomer and the shell layer monomer are pre-emulsified respectively, and in the step, the component selection and the content of the core layer monomer, the middle layer monomer and the shell layer monomer are limited, so that the oil resistance and the water resistance of the adhesive are improved, and the high temperature resistance of the adhesive is improved.
In this step, the present scheme defines the following conditions:
(1) dibutyl itaconate copolymer is introduced into the core layer monomer, the middle layer monomer and the shell layer monomer; the technical effect realized by the limiting condition is as follows: according to the preparation method, ethyl carbazole methacrylate, dibutyl itaconate and N-vinyl carbazole are used as raw materials, azobisisobutyronitrile is used as an initiator, and a copolymer is obtained through polymerization, on one hand, the oil resistance of the adhesive can be effectively improved due to the introduction of the middle diester group of dibutyl itaconate, and the cross-linking density of the acrylate adhesive is prevented from being influenced due to the introduction of dibutyl itaconate; on the other hand, substances such as N-vinyl carbazole, ethyl carbazole methacrylate and the like introduce a benzene ring structure, so that the high-temperature resistance of the acrylate adhesive can be effectively improved.
(2) Fluorine-containing vinyl silane is introduced into the intermediate layer monomer and the shell layer monomer; the technical effect realized by the limiting condition is as follows: according to the invention, components such as magnesium powder, methyl triethoxysilane, iodine and 4- (trifluorovinyl ether group) bromobenzene are used for synthesizing fluorine-containing vinyl silane monomer ([ 4-trifluorovinyl aryl ether group ] methyl diethoxysilane) through Grignard reaction, on one hand, fluorine element can be introduced into the monomer to improve the water resistance of the acrylate adhesive, the surface hydrophobicity and oleophobicity of the monomer are more excellent, and the oil resistance of the adhesive is improved; on the other hand, the introduction of the monomer can further improve the heat resistance of the acrylate, and the actual application effect is more excellent.
(3) The mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the core layer monomer is 9: 2; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1: 1; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 1: 2;
the addition amounts of dibutyl itaconate and fluorine-containing vinyl silane added in the core layer monomer, the intermediate layer monomer and the shell layer monomer are limited, fluorine-containing vinyl silane is not introduced in the core layer monomer, and the single dibutyl itaconate copolymer can ensure the crosslinking density of the inner core layer; in the intermediate layer, dibutyl itaconate copolymer and fluorine-containing vinyl silane are added, and the ratio is limited to 1: 1, increasing the amount of fluorine-containing vinyl silane in the shell layer to limit the ratio of dibutyl itaconate copolymer to fluorine-containing vinyl silane to 1: 2; the reason for this is that: introduce fluorine-containing vinyl silane in the intermediate layer and can regard as the transition layer, the content of fluorine-containing vinyl silane increases progressively from inside to outside in proper order moreover, can guarantee the hydrophobic property of fluorine element on the one hand, and on the other hand, the intermediate layer can regard as the transition layer for the bonding effect between nuclear layer, the shell layer is more excellent, and the monomer proportion that the gradient set up makes the holistic resistant oil performance of adhesive obtain improving.
The scheme also introduces an acrylate monomer which comprises caprolactone acrylate, the caprolactone acrylate and monomers such as methacrylic acid and butyl acrylate act together to form a comonomer, and the prepared acrylate adhesive has excellent flexibility, hydrolysis resistance, chemical corrosion resistance, good chemical compatibility and the like, and particularly has strong impact toughness, so that the molecular chain of a colloid is tighter, the cohesive force is larger, and the oil resistance is improved.
The invention discloses an oil-resistant acrylic adhesive and a preparation method thereof, and the prepared acrylic adhesive with a nuclear layer-intermediate layer-shell layer composite structure has excellent high temperature resistance, excellent water resistance and oil resistance, good chemical corrosion resistance and high practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, the preparation of the fluorovinylsilane was carried out by the following steps: taking magnesium powder, methyltriethoxysilane, iodine and tetrahydrofuran, uniformly mixing, heating to 65 ℃ in a nitrogen environment, dropwise adding 4- (trifluorovinyl ether group) bromobenzene, stirring for reacting for 24 hours, cooling, removing tetrahydrofuran, and collecting a product to obtain the fluorine-containing vinyl silane.
The molar ratio of the methyl triethoxysilane to the 4- (trifluorovinyl ether) bromobenzene is 4: 3; the amount of the magnesium powder is 12 wt% of that of the methyltriethoxysilane; the iodine is 0.3 wt% of the amount of methyltriethoxysilane.
In the following examples, dibutyl itaconate copolymers were prepared by the following steps:
s1: mixing hydroxyethyl carbazole, p-toluenesulfonic acid and hydroquinone, stirring for 20min, heating to 85 ℃, adding methacrylic acid, heating to 110 ℃, reacting for 11h, washing with 5% sodium hydroxide solution and saturated salt solution in sequence after reaction, separating, and distilling under reduced pressure to obtain ethyl carbazole methacrylate;
the amount of the p-toluenesulfonic acid is 3 wt% of the amount of the hydroxyethyl carbazole; the content of hydroquinone is 0.3 wt% of the content of hydroxyethyl carbazole; the dosage of the hydroxyethyl carbazole and the methacrylic acid is 4 g: 5 mL.
S2: taking ethyl carbazole methacrylate, dibutyl itaconate, N-vinyl carbazole and toluene, wherein the mass ratio of ethyl carbazole methacrylate to dibutyl itaconate to N-vinyl carbazole is 2: 3: 1; uniformly mixing and stirring, and then adding azobisisobutyronitrile, wherein the amount of the azobisisobutyronitrile is 2.5 wt% of the amount of the dibutyl itaconate copolymer; and (3) reacting for 20 hours in a nitrogen environment at the reaction temperature of 70 ℃, precipitating with methanol after the reaction, filtering and collecting the product, dissolving with tetrahydrofuran, filtering and collecting the product after the precipitation with the methanol, repeating the step for 3 times, and drying in vacuum to obtain the dibutyl itaconate copolymer.
Example 1:
the preparation method of the oil-resistant acrylic acid adhesive comprises the following steps:
(1) pre-emulsifying an emulsifier, deionized water and a core layer monomer to obtain a core layer pre-emulsion; the core layer monomer consists of an acrylate monomer and a dibutyl itaconate copolymer; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the core layer monomer is 9: 2; the emulsifier in the core layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
pre-emulsifying an emulsifier, deionized water and an intermediate layer monomer to obtain an intermediate layer pre-emulsion; the middle layer monomer consists of an acrylate monomer, a dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1: 1; the emulsifier in the middle layer pre-emulsion is 2 wt% of the core layer monomer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
pre-emulsifying an emulsifier, deionized water and a shell monomer to obtain a shell pre-emulsion; the shell layer monomer consists of an acrylate monomer, methacrylic acid, dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 1: 2; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer;
(2) taking an emulsifier and deionized water, and uniformly mixing to obtain a pre-emulsion; the emulsifier accounts for 1 wt% of the deionized amount; the amount of the emulsifier is 2 wt% of the total amount of shell monomers;
taking the pre-emulsion, dropwise adding the core layer pre-emulsion and 1/4 initiator at 80 ℃, carrying out heat preservation reaction for 40min, dropwise adding the intermediate layer pre-emulsion and 1/4 initiator, carrying out heat preservation reaction for 40min at 80 ℃, finally dropwise adding the shell layer pre-emulsion and the rest initiator, continuing carrying out heat preservation reaction for 1h, cooling, adding ammonia water, and adjusting the pH value to 7 to obtain the adhesive. The initiator accounts for 2.5 wt% of the total amount of the shell layer monomer, the core layer monomer and the middle layer monomer. The mass ratio of the core layer monomer to the intermediate layer monomer to the shell layer monomer is 4: 3: 3.
in this embodiment, the emulsifier includes sodium dodecylbenzene sulfonate and alkylphenol ethoxylate, and the mass ratio of the sodium dodecylbenzene sulfonate to the alkylphenol ethoxylate is 1: 2; the acrylate monomer comprises methyl methacrylate, butyl acrylate and caprolactone acrylate, wherein the weight ratio of the methyl methacrylate to the butyl acrylate to the caprolactone acrylate is 5: 2: 2.
example 2:
the preparation method of the oil-resistant acrylic acid adhesive comprises the following steps:
(1) pre-emulsifying an emulsifier, deionized water and a core layer monomer to obtain a core layer pre-emulsion; the core layer monomer consists of an acrylate monomer and a dibutyl itaconate copolymer; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the core layer monomer is 9: 2; the emulsifier in the core layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
pre-emulsifying an emulsifier, deionized water and an intermediate layer monomer to obtain an intermediate layer pre-emulsion; the middle layer monomer consists of an acrylate monomer, a dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1: 1; the emulsifier in the middle layer pre-emulsion is 2 wt% of the core layer monomer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
pre-emulsifying an emulsifier, deionized water and a shell monomer to obtain a shell pre-emulsion; the shell layer monomer consists of an acrylate monomer, methacrylic acid, dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 1: 2; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer;
(2) taking an emulsifier and deionized water, and uniformly mixing to obtain a pre-emulsion; the emulsifier accounts for 1 wt% of the deionized amount; the amount of the emulsifier is 2 wt% of the total amount of shell monomers;
taking the pre-emulsion, dropwise adding the nuclear layer pre-emulsion and 1/4 initiator at 85 ℃, carrying out heat preservation reaction for 30min, dropwise adding the intermediate layer pre-emulsion and 1/4 initiator, carrying out heat preservation reaction for 40min at 85 ℃, finally dropwise adding the shell layer pre-emulsion and the rest initiator, continuing carrying out heat preservation reaction for 1.2h, cooling, adding ammonia water, and adjusting the pH value to 7 to obtain the adhesive. The initiator accounts for 2.5 wt% of the total amount of the shell layer monomer, the core layer monomer and the middle layer monomer. The mass ratio of the core layer monomer to the intermediate layer monomer to the shell layer monomer is 4: 3: 3.
in this embodiment, the emulsifier includes sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene, and the mass ratio of the sodium dodecyl benzene sulfonate to the alkylphenol polyoxyethylene is 1: 2; the acrylate monomer comprises methyl methacrylate, butyl acrylate and caprolactone acrylate, wherein the weight ratio of the methyl methacrylate to the butyl acrylate to the caprolactone acrylate is 5: 2: 2.
example 3:
the preparation method of the oil-resistant acrylic acid adhesive comprises the following steps:
(1) pre-emulsifying an emulsifier, deionized water and a core layer monomer to obtain a core layer pre-emulsion; the core layer monomer consists of an acrylate monomer and a dibutyl itaconate copolymer; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the core layer monomer is 9: 2; the emulsifier in the core layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
taking an emulsifier, deionized water and an intermediate layer monomer, and pre-emulsifying to obtain an intermediate layer pre-emulsion; the middle layer monomer consists of an acrylate monomer, a dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1: 1; the emulsifier in the middle layer pre-emulsion is 2 wt% of the core layer monomer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
pre-emulsifying an emulsifier, deionized water and a shell monomer to obtain a shell pre-emulsion; the shell layer monomer consists of an acrylate monomer, methacrylic acid, a dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 1: 2; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer;
(2) taking an emulsifier and deionized water, and uniformly mixing to obtain a pre-emulsion; the emulsifier accounts for 1 wt% of the deionized amount; the amount of the emulsifier is 2 wt% of the total amount of shell monomers;
taking the pre-emulsion, dropwise adding the nuclear layer pre-emulsion and 1/4 initiator at 85 ℃, carrying out heat preservation reaction for 40min, dropwise adding the intermediate layer pre-emulsion and 1/4 initiator, carrying out heat preservation reaction for 40min at 85 ℃, finally dropwise adding the shell layer pre-emulsion and the rest initiator, continuing carrying out heat preservation reaction for 1.2h, cooling, adding ammonia water, and adjusting the pH value to 7 to obtain the adhesive. The initiator accounts for 2.5 wt% of the total amount of the shell layer monomer, the core layer monomer and the middle layer monomer. The mass ratio of the core layer monomer to the intermediate layer monomer to the shell layer monomer is 4: 3: 3.
in this embodiment, the emulsifier includes sodium dodecylbenzene sulfonate and alkylphenol ethoxylate, and the mass ratio of the sodium dodecylbenzene sulfonate to the alkylphenol ethoxylate is 1: 2; the acrylate monomer comprises methyl methacrylate, butyl acrylate and caprolactone acrylate, wherein the weight ratio of the methyl methacrylate to the butyl acrylate to the caprolactone acrylate is 5: 2: 2.
comparative example 1: comparative example 1 in comparison with example 2, in comparative example 1, the ratio of each monomer in the core layer monomer, the intermediate layer monomer and the shell layer monomer is adjusted, and the rest steps are consistent.
The specific variables are:
in the step (1): the middle layer monomer consists of an acrylate monomer, a dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 2: 1; the emulsifier in the middle layer pre-emulsion is 2 wt% of the core layer monomer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
the shell layer monomer consists of an acrylate monomer, methacrylic acid, dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 2: 1; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer.
Comparative example 2: comparative example 2 the comparative example 2 was used as a control, and in comparative example 2, the proportions of the monomers in the core layer monomer, the intermediate layer monomer and the shell layer monomer were adjusted, and the remaining steps were identical.
The specific variables are:
in the step (1): the middle layer monomer consists of an acrylate monomer, a dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer, the dibutyl itaconate copolymer and the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1: 2; the emulsifier in the middle layer pre-emulsion is 2 wt% of the core layer monomer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
the shell layer monomer consists of an acrylate monomer, methacrylic acid, dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 1: 2; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer.
Comparative example 3: comparative example 3 in comparison to example 2, comparative example 3 does not incorporate fluorovinylsilane into the shell monomer and the remaining steps are identical.
The specific variables are:
in the step (1): the shell layer monomer consists of acrylate monomer, methacrylic acid and dibutyl itaconate copolymer; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the shell layer monomer is 9: 1; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer.
Comparative example 4: comparative example 4 comparative example 3 was used as a control, and in comparative example 4, the fluorine-containing vinylsilane was not introduced into the shell layer monomer and the intermediate layer monomer, and the remaining steps were identical.
The specific variables are:
in the step (1): the middle layer monomer consists of an acrylate monomer and a dibutyl itaconate copolymer; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the intermediate layer monomer is 9: 1; the emulsifier in the middle layer pre-emulsion is 2 wt% of the core layer monomer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
the shell layer monomer consists of acrylate monomer, methacrylic acid and dibutyl itaconate copolymer; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the shell layer monomer is 9: 1; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer.
Comparative example 5: comparative example 5 example 2 was used as a control, and in comparative example 5, dibutyl itaconate copolymer was not introduced into the core layer monomer, the shell layer monomer, and the intermediate layer monomer, and the remaining steps were identical.
The specific variables are:
in the step (1): the core layer monomer consists of acrylate monomers; the emulsifier in the core layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water is 25 wt% of the amount of the core layer monomer.
The intermediate layer monomer consists of an acrylate monomer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1; the emulsifier in the middle layer pre-emulsion is 2 wt% of the core layer monomer; the deionized water is 25 wt% of the amount of the core layer monomer.
The shell layer monomer consists of an acrylate monomer, methacrylic acid and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 2; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer.
Comparative example 6: comparative example 6 comparative example 2 was used as a control, and comparative example 6 did not incorporate an interlayer, and the remaining steps were identical.
The specific variables are:
in the step (1): the core layer monomer consists of an acrylate monomer and a dibutyl itaconate copolymer; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the core layer monomer is 9: 2; the emulsifier in the core layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
the shell layer monomer consists of an acrylate monomer, methacrylic acid, dibutyl itaconate copolymer and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 1: 2; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer;
in the step (2): and (3) dropwise adding the nuclear layer pre-emulsion and 1/3-amount initiator into the pre-emulsion at 85 ℃, carrying out heat preservation reaction for 30min, dropwise adding the shell layer pre-emulsion and the rest initiator, continuing to carry out heat preservation reaction for 1.2h, cooling, and adding ammonia water to adjust the pH value to 7 to obtain the adhesive. The initiator accounts for 2.5 wt% of the total amount of the shell layer monomer and the core layer monomer. The mass ratio of the core layer monomer to the shell layer monomer is 4: 3.
comparative example 7: comparative example 7 example 2 was used as a control, and comparative example 7 was carried out in which dibutyl itaconate copolymer was replaced with dibutyl itaconate, and the remaining steps were identical.
The specific variables are:
in the step (1): the core layer monomer consists of an acrylate monomer and dibutyl itaconate; the mass ratio of the acrylate monomer to the dibutyl itaconate in the core layer monomer is 9: 2; the emulsifier in the core layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the amount of the core layer monomer;
the middle layer monomer consists of an acrylate monomer, dibutyl itaconate and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate to the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1: 1; the emulsifier in the middle layer pre-emulsion is 2 wt% of the core layer monomer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
the shell layer monomer consists of an acrylate monomer, methacrylic acid, dibutyl itaconate and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the dibutyl itaconate to the fluorine-containing vinyl silane in the shell layer monomer is 9: 1: 2; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the core layer monomer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer.
Comparative example 8: comparative example 8 example 2 was used as a control, and comparative example 8 was carried out in which dibutyl itaconate copolymer was replaced with N-vinylcarbazole, and the remaining steps were identical.
The specific variables are:
in the step (1): the core layer monomer consists of an acrylate monomer and N-vinyl carbazole; the mass ratio of the acrylate monomer to the N-vinyl carbazole in the core layer monomer is 9: 2; the emulsifier in the core layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
the intermediate layer monomer consists of an acrylate monomer, N-vinyl carbazole and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer, the N-vinyl carbazole and the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1: 1; the emulsifier in the middle layer pre-emulsion is 2 wt% of the core layer monomer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer;
the shell layer monomer consists of an acrylate monomer, methacrylic acid, N-vinyl carbazole and fluorine-containing vinyl silane; the mass ratio of the acrylate monomer to the N-vinyl carbazole to the fluorine-containing vinyl silane in the shell monomer is 9: 1: 2; the emulsifier in the shell layer pre-emulsion accounts for 2 wt% of the monomer amount of the core layer; the deionized water accounts for 25 wt% of the monomer amount of the nuclear layer; the methacrylic acid accounts for 8 wt% of the monomer amount of the shell layer;
detection experiment:
1. the adhesive prepared in the examples 1-3 and the comparative examples 1-8 is used for detecting 180-degree peel strength according to the GB/T2792-2014 standard, during the test, the adhesive is coated on the surface of a PI film with the width of 25mm and the length of 150mm to prepare a sample, the sample is placed in a 100 ℃ oven to be dried for 10min, the sample is taken out and cooled, the sample is adhered to a tinplate, the rolling is uniform, and the 180-degree peel strength (N/25mm) is tested at the test speed of 300 mm/min.
2. The adhesive prepared in the examples 1-3 and the comparative examples 1-8 is dried at room temperature to form a film, weighed and recorded, then soaked in deionized water for 48 hours, taken out, sucked by filter paper to remove water, weighed again, and the water absorption rate is calculated and recorded.
3. Oil resistance: the adhesive prepared in the examples 1-3 and the comparative examples 1-8 is dried at room temperature to form a film, the film is soaked in engine oil for 48 hours, the film is taken out and wiped to dry the engine oil on the surface, and the weight is weighed and the oil absorption rate is calculated.
4. The initial adhesion (N/25mm) was determined according to GB/T4852-.
5. Taking a GB/T2792-2014 standard preparation sample, standing for 20min at room temperature, then placing in an oven at 170 ℃ for processing for 1h, cooling, slowly peeling, and observing whether the surface of an adherend has an adhesive residue phenomenon.
Item | Water absorption% | Initial adhesion N/25mm | Peel strength N/25mm | Oil absorption rate | 170℃;1h |
Example 1 | 3.15% | 5.24 | 16.7 | 4.28% | No adhesive residue |
Example 2 | 2.97% | 5.37 | 16.9 | 4.13% | No adhesive residue |
Example 3 | 3.01% | 5.28 | 16.3 | 4.19% | No adhesive residue |
Comparative example 1 | 4.53% | / | 15.1 | 6.52% | / |
Comparative example 2 | 4.32% | / | 15.2 | 6.38% | / |
Comparative example 3 | 9.16% | / | 16.4 | 11.21% | / |
Comparative example 4 | 10.71% | / | 17.6 | 12.54% | / |
Comparative example 5 | 8.58% | / | 13.8 | 10.63% | / |
Comparative example 6 | 6.52% | / | 14.2 | 8.27% | / |
Comparative example 7 | 4.87% | / | 14.9 | 6.89% | / |
Comparative example 8 | 5.63% | / | 14.6 | 7.65% | / |
And (4) conclusion: the invention discloses an oil-resistant acrylic adhesive and a preparation method thereof, and the prepared acrylic adhesive with a nuclear layer-intermediate layer-shell layer composite structure has excellent high-temperature resistance, excellent water resistance and oil resistance, insolubility in soaking machine oil for 48 hours, no obvious change in appearance, good chemical corrosion resistance and high practicability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the oil-resistant acrylic acid adhesive is characterized by comprising the following steps: the method comprises the following steps:
(1) taking an emulsifier, deionized water and a core layer monomer, and pre-emulsifying to obtain a core layer pre-emulsion; the core layer monomer consists of an acrylate monomer and a dibutyl itaconate copolymer;
pre-emulsifying an emulsifier, deionized water and an intermediate layer monomer to obtain an intermediate layer pre-emulsion; the middle layer monomer consists of an acrylate monomer, a dibutyl itaconate copolymer and fluorine-containing vinyl silane;
pre-emulsifying an emulsifier, deionized water and a shell monomer to obtain a shell pre-emulsion; the shell layer monomer consists of an acrylate monomer, methacrylic acid, dibutyl itaconate copolymer and fluorine-containing vinyl silane;
(2) taking an emulsifier and deionized water, and uniformly mixing to obtain a pre-emulsion;
taking the pre-emulsion, dropwise adding the core layer pre-emulsion and 1/4 initiator at 80-85 ℃, reacting for 30-40 min under heat preservation, dropwise adding the middle layer pre-emulsion and 1/4 initiator, reacting for 30-40 min under heat preservation at 80-85 ℃, finally dropwise adding the shell layer pre-emulsion and the rest initiator, continuing reacting for 1-1.2 h under heat preservation, cooling, adding ammonia water, and adjusting the pH value to 7-8 to obtain the adhesive.
2. The method for preparing the oil-resistant acrylic adhesive according to claim 1, wherein the method comprises the following steps: the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer in the core layer monomer is 9: 2; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the intermediate layer monomer is 9: 1: 1; the mass ratio of the acrylate monomer to the dibutyl itaconate copolymer to the fluorine-containing vinyl silane in the shell layer monomer is 9: 1: 2; the methacrylic acid accounts for 8-10 wt% of the monomer amount of the shell layer.
3. The method for preparing the oil-resistant acrylic adhesive according to claim 1, wherein the method comprises the following steps: in the step (1), the dibutyl itaconate copolymer is prepared by the following steps:
s1: mixing and stirring hydroxyethyl carbazole, p-toluenesulfonic acid and hydroquinone for 10-20 min, heating to 85-95 ℃, adding methacrylic acid, heating to 110-120 ℃, reacting for 10-11 h, washing after reaction, separating, and distilling under reduced pressure to obtain ethyl carbazole methacrylate;
s2: mixing and stirring ethyl carbazole methacrylate, dibutyl itaconate, N-vinyl carbazole and toluene uniformly, adding azobisisobutyronitrile, reacting for 20-24 hours in a nitrogen environment at the reaction temperature of 65-70 ℃, precipitating methanol after reaction, filtering and collecting a product, and drying in vacuum to obtain the dibutyl itaconate copolymer.
4. The method for preparing the oil-resistant acrylic adhesive according to claim 3, wherein the method comprises the following steps: in step S2, the mass ratio of ethyl carbazole methacrylate, dibutyl itaconate, and N-vinylcarbazole is 2: 3: 1; the amount of the azodiisobutyronitrile is 2-2.5 wt% of the amount of the dibutyl itaconate copolymer.
5. The method for preparing the oil-resistant acrylic adhesive according to claim 1, wherein the method comprises the following steps: in the step (1), the preparation of the fluorine-containing vinyl silane comprises the following steps: taking magnesium powder, methyltriethoxysilane, iodine and tetrahydrofuran, uniformly mixing, heating to 65-70 ℃ in a nitrogen environment, dropwise adding 4- (trifluorovinyl ether) bromobenzene, stirring for reacting for 20-24 h, cooling, removing tetrahydrofuran, and collecting a product to obtain the fluorine-containing vinyl silane.
6. The method for preparing the oil-resistant acrylic adhesive according to claim 5, wherein the method comprises the following steps: the molar ratio of the methyl triethoxysilane to the 4- (trifluorovinyl ether) bromobenzene is 4: 3.
7. the method for preparing the oil-resistant acrylic adhesive according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of the core layer monomer to the intermediate layer monomer to the shell layer monomer is 4: 3: 3; the acrylate monomer comprises methyl methacrylate, butyl acrylate and caprolactone acrylate, wherein the weight ratio of the methyl methacrylate to the butyl acrylate to the caprolactone acrylate is 5: 2: 2.
8. the method for preparing the oil-resistant acrylic adhesive according to claim 1, wherein the method comprises the following steps: in the step (2), the amount of the emulsifier is 2-3 wt% of the total amount of the shell monomers; the initiator accounts for 2-3 wt% of the total amount of the shell layer monomer, the core layer monomer and the middle layer monomer.
9. The method for preparing the oil-resistant acrylic adhesive according to claim 1, wherein the method comprises the following steps: the emulsifier comprises sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the alkylphenol polyoxyethylene is 1: 2.
10. the adhesive prepared by the preparation method of the oil-resistant acrylic adhesive according to any one of claims 1 to 9.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4625006A (en) * | 1982-07-23 | 1986-11-25 | Dynamit Nobel Aktiengesellschaft | Adhesivizing agent copolymers containing both acrylate or methacrylate groups and alkoxysilyl groups |
US5534579A (en) * | 1991-11-18 | 1996-07-09 | Nippon Shokubai Co., Ltd. | Highly weather-resistant, single package, crosslinkable emulsion |
CN102206299A (en) * | 2010-03-30 | 2011-10-05 | 大金工业株式会社 | Aqueous dispersoid of fluorine-containing seed polymer particles and aqueous coating combination |
CN105367703A (en) * | 2014-08-27 | 2016-03-02 | 齐鲁工业大学 | Three-layer core-shell structure epoxy modified acrylate emulsion |
CN113402674A (en) * | 2021-06-30 | 2021-09-17 | 山西省应用化学研究所(有限公司) | Aqueous medium for wallpaper printing and preparation method thereof |
-
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- 2022-04-11 CN CN202210377305.9A patent/CN114671984B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4625006A (en) * | 1982-07-23 | 1986-11-25 | Dynamit Nobel Aktiengesellschaft | Adhesivizing agent copolymers containing both acrylate or methacrylate groups and alkoxysilyl groups |
US5534579A (en) * | 1991-11-18 | 1996-07-09 | Nippon Shokubai Co., Ltd. | Highly weather-resistant, single package, crosslinkable emulsion |
CN102206299A (en) * | 2010-03-30 | 2011-10-05 | 大金工业株式会社 | Aqueous dispersoid of fluorine-containing seed polymer particles and aqueous coating combination |
CN105367703A (en) * | 2014-08-27 | 2016-03-02 | 齐鲁工业大学 | Three-layer core-shell structure epoxy modified acrylate emulsion |
CN113402674A (en) * | 2021-06-30 | 2021-09-17 | 山西省应用化学研究所(有限公司) | Aqueous medium for wallpaper printing and preparation method thereof |
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