CN116751545B - Waterproof adhesive and preparation method thereof - Google Patents

Waterproof adhesive and preparation method thereof Download PDF

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Publication number
CN116751545B
CN116751545B CN202311054256.6A CN202311054256A CN116751545B CN 116751545 B CN116751545 B CN 116751545B CN 202311054256 A CN202311054256 A CN 202311054256A CN 116751545 B CN116751545 B CN 116751545B
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parts
emulsion
hyperbranched polyethyleneimine
nitrate
oxidized
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CN116751545A (en
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程玉国
刘广志
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CHANGSHU IRRADIATION TECHNOLOGY APPLICATION FACTORY
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CHANGSHU IRRADIATION TECHNOLOGY APPLICATION FACTORY
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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/04—Starch derivatives
    • C09J103/10—Oxidised starch
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic

Abstract

The invention discloses a waterproof adhesive and a preparation method thereof, wherein the waterproof adhesive comprises the following components: 100 parts of hyperbranched polyethyleneimine modified acrylate emulsion, 10-30 parts of oxidized polysaccharide, 2.5-10 parts of metal nitrate, 5-15 parts of tricalcium silicate and 0-20 parts of tricalcium aluminate; the adhesive has multiple gel systems which are mutually inserted and compounded, and the obtained adhesive layer has rigidity and flexibility, and has excellent bonding strength, weather resistance, heat resistance, water resistance and flexibility. The gel system is formed by compounding polysaccharide and acrylic ester polymer cross-linked substances with calcium silicate and calcium aluminate gel, the calcium silicate and the calcium aluminate gel become hard crystal structures after drying, and the crystal structures are dispersed among flexible polymers, so that the adhesive layer has higher strength and flexibility.

Description

Waterproof adhesive and preparation method thereof
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a waterproof adhesive and a preparation method thereof.
Background
The adhesive has various types, wherein the polyacrylate adhesive has the characteristics of simple formula, wide bonding range, good weather resistance, low cost and the like, and has been widely used for bonding plastic films, fabrics, metal foils and paper. Compared with solvent polyacrylate adhesives, the aqueous polyacrylate adhesives have the characteristics of environmental protection, high solid content, low cost and the like, and are widely paid attention to by people. At present, the aqueous polyacrylate adhesive still has the defect that the performances such as adhesiveness, adhesive film strength, water resistance and the like are inferior to those of the solvent type polyacrylate adhesive. Therefore, polyurethane resin, epoxy resin or metal chelate and other modifiers are often used to improve the film forming property, flexibility, cohesion, adhesive strength, heat resistance, water resistance and other properties of the polyacrylate adhesive.
Disclosure of Invention
Aiming at how to improve the water resistance and the bonding strength of the water-based polyacrylate adhesive, the invention provides a waterproof adhesive and a preparation method thereof.
The invention aims to provide a waterproof adhesive which comprises the following components in parts by weight: 100 parts of hyperbranched polyethyleneimine modified acrylic emulsion, 10-30 parts of oxidized polysaccharide, 2.5-10 parts of metal nitrate, 5-15 parts of tricalcium silicate and 0-20 parts of tricalcium aluminate.
Hyperbranched polyethyleneimine modified acrylic ester emulsion
The preparation method of the hyperbranched polyethyleneimine modified acrylic ester emulsion comprises the following steps: (1) Activating acrylic acid by using N, N-dicarbonyl imidazole (CDI), and performing amidation reaction with hyperbranched polyethyleneimine to obtain acrylic acid modified hyperbranched polyethyleneimine; (2) And (3) performing emulsion polymerization on the functional monomer, the acrylic acid modified hyperbranched polyethyleneimine and the emulsifier under the action of an initiator to obtain the hyperbranched polyethyleneimine modified acrylate emulsion.
The process for preparing the acrylate emulsion in the step (2) is conventional in the art, and the acrylate emulsion may be prepared by emulsion polymerization processes well known in the art, such as process operation, process conditions, feeding sequence, feeding mode, and step feeding ratio of initiator, emulsifier, etc., which are determined by those skilled in the art according to the conventional technology and reaction requirements, and will not be described herein.
The functional monomer at least comprises an acid monomer, an ester monomer and an amide monomer.
The acid monomer is at least one selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid;
the ester monomer is at least one selected from methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isooctyl methacrylate.
The amide monomer is at least one selected from acrylamide and methacrylamide.
The emulsifier adopts a composite emulsifier containing at least polyoxyethylene ether type emulsifier, and in some embodiments, nonylphenol polyoxyethylene ether and dodecyl diphenyl ether disodium disulfonate are adopted as the composite emulsifier.
The specific choice of the initiator is not particularly limited and may be selected by one skilled in the art according to the reaction requirements, and in some embodiments, the initiator is selected from at least one of ammonium persulfate, sodium persulfate, and potassium persulfate.
The step (2) specifically comprises the following sub-steps:
dissolving an emulsifier accounting for 60-80wt% of the total weight of the emulsifier in water accounting for 40-60% of the total weight of the water, adding the functional monomer, and stirring in an emulsifying kettle to form a pre-emulsion;
(1.2) adding the rest of the emulsifier dissolved in the rest of water into a reaction kettle, and adding 10-30wt% of the total weight of the pre-emulsion obtained in the step (1.1) into the reaction kettle at a reaction temperature of 80-90 ℃ to initiate polymerization, wherein the total weight of the added initiator is 10-30wt%;
(1.3) dropwise adding 65-85wt% of the total mass of the residual pre-emulsion and the initiator into the reaction kettle, keeping the reaction temperature at 80-90 ℃, and keeping the dropwise adding duration at 3-6h;
(1.4) dropwise adding an aqueous solution (the concentration is 10 wt%) of acrylic acid modified hyperbranched polyethyleneimine into the reaction kettle, adding the rest 5wt% of initiator, dropwise adding for 0.5-1 h, preserving heat for 2-4 h after dropwise adding, and then cooling to below 30 ℃;
in step (1.3), specifically, after the polymerization in step (1.2) occurs for 30min, the remaining pre-emulsion and the remaining initiator are added dropwise to the reaction vessel.
Oxidized polysaccharide
The oxidized polysaccharide is natural macromolecular polysaccharide, and the alcohol hydroxyl groups of the oxidized polysaccharide are oxidized into aldehyde groups under the action of an oxidant.
The oxidation method of polysaccharide is conventional in the art, and the oxidized polysaccharide can be prepared by methods well known in the art, such as periodate oxidation, sodium hypochlorite oxidation, and hydrogen peroxide oxidation, and can be determined by those skilled in the art according to the conventional techniques and reaction requirements, which are not described herein.
Preferably, some embodiments of the invention will employ periodate oxidation to produce oxidized polysaccharide.
The oxidized polysaccharide is at least one selected from oxidized starch, oxidized alginic acid (sodium), oxidized dextran and oxidized cellulose.
Metal nitrate
The rare earth metal nitrate is at least one selected from cobalt nitrate, ruthenium nitrate, cadmium nitrate, zinc nitrate, nickel nitrate and ferric nitrate.
The invention also provides a preparation method of the waterproof adhesive, which comprises the following steps:
adding oxidized polysaccharide solution and metal nitrate into hyperbranched polyethyleneimine modified acrylic ester emulsion, uniformly stirring in high-speed dispersion, keeping the temperature of the liquid below 40 ℃, the rotating speed of 150-250 r/min, and the stirring time of 10-20 min; and (3) placing the mixed solution into a dispersing machine, adding tricalcium silicate and tricalcium aluminate into the mixed solution, wherein the rotating speed is 500-1000 r/min, and the stirring time is 10-20 min, so as to obtain the waterproof adhesive.
The invention also provides application of the waterproof adhesive and an application method thereof. The waterproof adhesive prepared by the invention can be used for repairing cracks, damages and breaks in concrete, ceramics, glass, engineering plastics, marble, granite and gypsum boards, and is especially suitable for places with high weather resistance and water resistance requirements such as outdoors, underwater and the like.
After cleaning the surface of the section or crack, the waterproof adhesive prepared by the invention is applied to the place, and the adhesive layer is obtained after drying.
The beneficial effects are that:
the waterproof adhesive provided by the invention has multiple gel systems which are mutually inserted and compounded, and the obtained adhesive layer has rigidity and flexibility, and has excellent bonding strength, weather resistance, heat resistance, water resistance and flexibility. The gel system is formed by compounding polysaccharide and acrylic ester polymer cross-linked substances with calcium silicate and calcium aluminate gel, the calcium silicate and the calcium aluminate gel become hard crystal structures after drying, and the crystal structures are dispersed among flexible polymers, so that the adhesive layer has higher strength and flexibility.
Drawings
FIG. 1 is a graph showing the tensile strength retention calculated from the tensile test performed after the bars of test 4 were immersed in water for several times.
FIG. 2 is the infrared spectra of comparative example 1 and comparative example 4.
Fig. 3 is a Scanning Electron Microscope (SEM) image of example 3 and comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
The sources and specifications of part of raw materials are as follows:
table 1: source and specification of partial raw materials
Example 1
Preparing hyperbranched polyethyleneimine modified acrylic ester emulsion.
(1) Preparation of acrylic acid modified hyperbranched polyethyleneimine
Dissolving 37 parts of acrylic acid in chloroform, adding 80 parts of CDI while stirring, and stirring at room temperature for 2 hours after dripping to obtain an activated acrylic acid chloroform solution; 100 parts of HPEI is dissolved in chloroform, the temperature is raised to 70 ℃, condensation reflux is started, the activated chloroform acrylate solution is slowly dripped, reflux reaction is carried out for 24 hours, after cooling, the reaction solution is concentrated, saturated saline water is added for washing, 3 times of repetition are carried out, an organic phase is dried by anhydrous sodium sulfate, filtered and distilled under reduced pressure, and then the acrylic acid modified hyperbranched polyethyleneimine is obtained, and then the acrylic acid modified hyperbranched polyethyleneimine is dissolved in water to prepare 10wt% aqueous solution for standby.
(2) Preparation of hyperbranched polyethyleneimine modified acrylate emulsion
Dissolving 70% of emulsifying agent in 40% of water, adding functional monomers, and stirring in an emulsifying kettle to form pre-emulsion;
adding the rest 30% of emulsifying agent dissolved in 60% of water into a reaction kettle, adding 10% of pre-emulsion and 30% of initiator at the reaction temperature of 90 ℃ to initiate polymerization, dropwise adding the rest 90% of pre-emulsion and the rest 65% of initiator into the reaction kettle after the reaction is carried out for 30min, keeping the reaction temperature at 90 ℃, dropwise adding for 4h, starting dropwise adding an aqueous solution (with the concentration of 10 wt%) of the acrylic acid modified hyperbranched polyethyleneimine and adding the rest initiator after the dropwise adding of the solution is finished, keeping the temperature for 2h after the dropwise adding is finished, and then cooling to 28 ℃ (room temperature) to obtain the hyperbranched polyethyleneimine modified acrylate emulsion.
Table 2: emulsion formula (unit: parts by mass)
The emulsifier is a compound of nonylphenol polyoxyethylene ether and sodium dodecyl diphenyl ether sulfonate, and the compound mass ratio of the nonylphenol polyoxyethylene ether to the sodium dodecyl diphenyl ether sulfonate is 1:2.
Example 2
Preparation of oxidized sodium alginate:
dissolving sodium alginate in ethanol to form a dispersion solution, slowly dropwise adding 0.5mol/L sodium periodate aqueous solution in a dark place, reacting for 4 hours at normal temperature in a dark place after dripping, stopping the reaction by glycol, dialyzing the reaction solution in water for three days by using a 5000Da dialysis bag, changing water once a day, and freeze-drying to obtain oxidized sodium alginate white powder. The use ratio of the sodium alginate to the ethanol is 1g to 40mL; the molar ratio of the structural unit of sodium alginate to the sodium periodate is 5:2.
Preparation of oxidized starch:
dissolving corn starch in distilled water, heating to 60 ℃ for dissolution, preparing starch solution with the mass concentration of 4.23wt%, adding sodium periodate solution (with the concentration of 0.5 mol/L) into the starch solution, performing light-proof reaction for 16 hours at room temperature, adding ethylene glycol into the mixed solution, stirring for 1 hour to eliminate unreacted sodium periodate, adding sodium chloride into the reaction solution, adding ethanol to separate out precipitate, separating and purifying the precipitate, and drying to obtain oxidized starch. The mass ratio of sodium periodate to starch is preferably 1:2, the molar ratio of ethylene glycol to sodium periodate is 1:1, and the mass ratio of sodium chloride to starch is 3:1.
Example 3
The waterproof adhesive comprises the following components in parts by weight: 2 parts of hyperbranched polyethyleneimine modified acrylic emulsion L, 20 parts of oxidized starch, 5 parts of cobalt nitrate, 10 parts of tricalcium silicate and 20 parts of tricalcium aluminate.
Mixing oxidized starch, cobalt nitrate and hyperbranched polyethyleneimine modified acrylic ester emulsion, stirring for 20min at 150r/min, and keeping the temperature of the liquid below 40 ℃; and (3) transferring the mixed solution into a dispersing machine, adding tricalcium silicate and tricalcium aluminate, stirring for 10min at the rotating speed of 1000r/min, and obtaining the waterproof adhesive.
Example 4
The waterproof adhesive comprises the following components in parts by weight: hyperbranched polyethyleneimine modified acrylic emulsion L2 100 parts, oxidized starch 20 parts, cobalt nitrate 10 parts, tricalcium silicate 10 parts and tricalcium aluminate 20 parts.
The preparation method is the same as in example 3.
Example 5
The waterproof adhesive comprises the following components in parts by weight: hyperbranched polyethyleneimine modified acrylic emulsion L2 100 parts, oxidized starch 20 parts, cobalt nitrate 5 parts, tricalcium silicate 5 parts and tricalcium aluminate 15 parts.
The preparation method is the same as in example 3.
Example 6
The waterproof adhesive comprises the following components in parts by weight: hyperbranched polyethyleneimine modified acrylic emulsion L2 100 parts, oxidized starch 20 parts, cobalt nitrate 5 parts, tricalcium silicate 15 parts and tricalcium aluminate 20 parts.
The preparation method is the same as in example 3.
Example 7
The waterproof adhesive comprises the following components in parts by weight: hyperbranched polyethyleneimine modified acrylic emulsion L2 100 parts, oxidized starch 20 parts, cobalt nitrate 5 parts, tricalcium silicate 15 parts and tricalcium aluminate 5 parts.
The preparation method is the same as in example 3.
Example 8
The waterproof adhesive comprises the following components in parts by weight: 2 parts of hyperbranched polyethyleneimine modified acrylic emulsion L, 10 parts of oxidized starch, 5 parts of cobalt nitrate, 10 parts of tricalcium silicate and 20 parts of tricalcium aluminate.
The preparation method is the same as in example 3.
Example 9
The waterproof adhesive comprises the following components in parts by weight: hyperbranched polyethyleneimine modified acrylic emulsion L2 100 parts, oxidized starch 30 parts, cobalt nitrate 5 parts, tricalcium silicate 10 parts and tricalcium aluminate 20 parts.
The preparation method is the same as in example 3.
Comparative example 1
The adhesive comprises the following components in parts by weight: hyperbranched polyethyleneimine modified acrylic emulsion L2 parts, oxidized starch 20 parts and cobalt nitrate 5 parts.
Mixing oxidized starch, cobalt nitrate and hyperbranched polyethyleneimine modified acrylic ester emulsion, and stirring for 20min at 1000r/min to obtain the adhesive without containing the aqueous component.
Comparative example 2
The adhesive comprises the following components in parts by weight: 2 parts of hyperbranched polyethyleneimine modified acrylic emulsion L, 5 parts of cobalt nitrate, 10 parts of tricalcium silicate and 20 parts of tricalcium aluminate.
The preparation method is the same as in example 3.
Comparative example 3
The adhesive comprises the following components in parts by weight: hyperbranched polyethyleneimine modified acrylic emulsion L2 100 parts, oxidized starch 20 parts, tricalcium silicate 10 parts and tricalcium aluminate 20 parts.
The preparation method is the same as in example 3.
Comparative example 4
The adhesive comprises the following components in parts by weight: hyperbranched polyethyleneimine modified acrylic emulsion L2 parts and oxidized starch 30 parts.
Mixing oxidized starch with hyperbranched polyethyleneimine modified acrylic ester emulsion, and stirring for 10min at 1000r/min to obtain the adhesive.
Test 1: determination of drying time
And (3) measuring the surface dry time: the iron sheet was coated with an adhesive, and after waiting for a period of time, the surface of the coated film was gently touched with a finger in a range of more than 10mm from the edge of the adhesive layer, and if some tackiness was felt and the coated film was not adhered to the finger, the coated film was dry, and the time was recorded.
Real-dry time measurement: the adhesive layer made on the iron sheet was cut and brushed with a single-sided safety blade, and if no sticking phenomenon occurred, it was dried, and the time was recorded.
Test 2: tensile Property test
Preparing an adhesive layer stretching spline by adopting a die, and testing the stretching performance of the spline, wherein the stretching speed is 200mm/min, and the specification of the sample is as follows: the spline is dumbbell-shaped with a thickness of 1.5±0.5 mm. The preparation method comprises the following steps:
the freshly prepared adhesive is poured into a mould with a release agent according to the feeding ratio and air bubbles are prevented, the sample is coated with the next layer after the last step of drying, the process is repeated for two to three times, the adhesive is prepared within 72 hours, and the adhesive is tested after being placed for 3 days under standard conditions after being released.
The adhesives prepared in comparative examples 1 and 4 were tested by demolding after curing for 3d in a blow box at 60 ℃.
Test 3: bond strength test
(1) Concrete damaged article
And (3) a prefabricated 8-shaped cement mortar test block (the ratio is cement: standard sand: water=1:2:0.4, cement is 42.5-grade OPC, the die is removed after 24 hours, the cement is cured for 7 d), the cement is broken from the middle, a freshly prepared adhesive is smeared on the section of the mortar by using a putty knife, the bonding section size is 25 mm multiplied by 25 mm, and after curing for 3d in a standard environment, the butt joint bonding strength of the mortar is tested by adopting an electronic tension machine.
The adhesives prepared in comparative examples 1 and 4 were tested after curing for 3 days in a blow box at 60 ℃.
(2) Ceramic tile damaged article
Tensile bond strength was measured according to JC/T547-94.
The adhesives prepared in comparative examples 1 and 4 were tested after curing for 3 days in a blow box at 60 ℃.
(3) Engineering plastic damaged article
Preparing an ABS test piece by adopting a thermoplastic molding method, wherein the test piece is T-shaped, the specification of a horizontal plane is 5cm multiplied by 2cm multiplied by 5mm, the specification of a vertical plane is 3cm multiplied by 2cm multiplied by 5mm, the existing adhesive is smeared on the outside of the horizontal plane, then the other test piece is symmetrically bonded, and stands for 3 days after being compressed, an electronic universal material testing machine is used for testing the tensile strength of the cured connecting piece, the average thickness of an adhesive layer is about 200 mu m, and the stretching speed is 5mm/min.
The adhesives prepared in comparative examples 1 and 4 were tested after curing for 3 days in a blow box at 60 ℃.
Test 4: water resistance test
The sample strip prepared according to the method of test 2 is soaked in water for a plurality of times, taken out, the test paper is used for sucking the water on the surface, and the tensile test of test 4 is carried out to evaluate the water resistance of the adhesive according to the tensile strength.
The results of tests 1-3 are shown in Table 3, and the results of test 4 are shown in FIG. 1.
Table 3: test results
To further understand the crosslinked structure of the waterproof adhesive after curing, the adhesives prepared in comparative examples 1 and 4 were subjected to FT-IR test, and the results are shown in fig. 2; SEM analysis was performed on example 3 and comparative example 3, and the results are shown in fig. 3. The infrared spectrogram result shows that after cobalt nitrate is added, the cobalt nitrate is added at 1590-1750 cm -1 The peak pattern and the peak intensity of the characteristic band (corresponding to c= O, C =n) were changed, indicating the presence of a coordination result.
As can be seen from the test results, the adhesive layer had a crystalline structure, and also contained imine bonds (shiff bonds) and shiff-Co coordination bonds, indicating that the adhesive layer had a composite crosslinked structure. The polymer segment acts as a continuous phase providing toughness to the adhesive layer and adhesion at the initial contact with the substrate; the crystals serving as a disperse phase can improve the mechanical property, cracking resistance and weather resistance of the adhesive layer. In addition, due to the existence of the shiff-Co coordination bond, the crystallized grains are smaller and arranged more precisely.
Example 10
The waterproof adhesive comprises the following components in parts by weight: 1 part of hyperbranched polyethyleneimine modified acrylic emulsion L, 20 parts of oxidized starch, 5 parts of cobalt nitrate, 10 parts of tricalcium silicate and 20 parts of tricalcium aluminate.
The preparation method is the same as in example 3.
The tensile strength obtained by the test was 3.48MPa, and the elongation at break was 206%.
Example 11
The waterproof adhesive comprises the following components in parts by weight: 3 parts of hyperbranched polyethyleneimine modified acrylic emulsion L, 20 parts of oxidized starch, 5 parts of cobalt nitrate, 10 parts of tricalcium silicate and 20 parts of tricalcium aluminate.
The preparation method is the same as in example 3.
The tensile strength obtained by the test was 4.02MPa, and the elongation at break was 237%.
Example 12
The waterproof adhesive comprises the following components in parts by weight: 2 parts of hyperbranched polyethyleneimine modified acrylic emulsion L, 20 parts of oxidized sodium alginate, 5 parts of cobalt nitrate, 10 parts of tricalcium silicate and 20 parts of tricalcium aluminate.
The preparation method is the same as in example 3.
The tensile strength obtained by the test was 3.51MPa, and the elongation at break was 231%.
Example 13
The waterproof adhesive comprises the following components in parts by weight: 2 parts of hyperbranched polyethyleneimine modified acrylic emulsion L, 20 parts of oxidized starch, 5 parts of ferric nitrate, 10 parts of tricalcium silicate and 20 parts of tricalcium aluminate.
The preparation method is the same as in example 3.
The tensile strength obtained by the test was 3.62MPa, and the elongation at break was 217%.
Example 14
The waterproof adhesive comprises the following components in parts by weight: 2 parts of hyperbranched polyethyleneimine modified acrylic emulsion L, 20 parts of oxidized starch, 5 parts of zinc nitrate, 10 parts of tricalcium silicate and 20 parts of tricalcium aluminate.
The preparation method is the same as in example 3.
The tensile strength obtained by the test was 3.69MPa, and the elongation at break was 239%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (7)

1. The waterproof adhesive is characterized by comprising the following components in parts by weight: 100 parts of hyperbranched polyethyleneimine modified acrylate emulsion, 10-30 parts of oxidized polysaccharide, 2.5-10 parts of metal nitrate, 5-15 parts of tricalcium silicate and 0-20 parts of tricalcium aluminate;
the preparation method of the hyperbranched polyethyleneimine modified acrylic ester emulsion comprises the following steps: (1) Activating acrylic acid by using N, N-dicarbonyl imidazole (CDI), and performing amidation reaction with hyperbranched polyethyleneimine to obtain acrylic acid modified hyperbranched polyethyleneimine; (2) Performing emulsion polymerization on functional monomers, acrylic acid modified hyperbranched polyethyleneimine and an emulsifier under the action of an initiator to prepare hyperbranched polyethyleneimine modified acrylate emulsion; the functional monomer at least comprises an acid monomer, an ester monomer and an amide monomer; the acid monomer is acrylic acid, the ester monomer is one or a combination of ethyl acrylate and butyl acrylate, and the amide monomer is methacrylamide;
the oxidized polysaccharide is natural macromolecular polysaccharide, and alcohol hydroxyl groups of the oxidized polysaccharide are oxidized into aldehyde groups under the action of an oxidant; the polysaccharide is at least one selected from starch, alginic acid or its salt, dextran and cellulose;
the metal nitrate is at least one selected from cobalt nitrate, ruthenium nitrate, cadmium nitrate, zinc nitrate, nickel nitrate and ferric nitrate.
2. The water-resistant adhesive according to claim 1, wherein the emulsifier is a mixture of nonylphenol polyoxyethylene ether and disodium dodecyl diphenyl ether disulfonate.
3. The water-resistant adhesive according to claim 1, wherein the initiator is at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate.
4. The waterproofing adhesive according to claim 1 wherein step (2) specifically comprises the sub-steps of: dissolving an emulsifier accounting for 60-80wt% of the total weight of the emulsifier in water accounting for 40-60% of the total weight of the water, adding the functional monomer, and stirring in an emulsifying kettle to form a pre-emulsion; (1.2) adding the rest of the emulsifier dissolved in the rest of water into a reaction kettle, and adding 10-30wt% of the total weight of the pre-emulsion obtained in the step (1.1) into the reaction kettle at a reaction temperature of 80-90 ℃ to initiate polymerization, wherein the total weight of the added initiator is 10-30wt%; (1.3) dropwise adding 65-85wt% of the total mass of the residual pre-emulsion and the initiator into the reaction kettle, keeping the reaction temperature at 80-90 ℃, and keeping the dropwise adding duration at 3-6h; (1.4) dropwise adding an aqueous solution of acrylic acid modified hyperbranched polyethyleneimine into the reaction kettle, adding the rest 5wt% of initiator, keeping the dropwise adding duration for 0.5-1 h, preserving the heat for 2-4 h after the dropwise adding is finished, and then cooling to below 30 ℃.
5. The waterproof adhesive according to claim 1, wherein the oxidized polysaccharide is oxidized starch, and the preparation method comprises the following steps: dissolving starch in distilled water, heating to dissolve, adding sodium periodate solution into the starch solution, reacting in dark at room temperature, stopping the reaction with ethylene glycol, purifying the reaction solution, and drying to obtain oxidized starch.
6. The method for preparing a waterproof adhesive according to claim 1, comprising the steps of: adding oxidized polysaccharide solution and metal nitrate into hyperbranched polyethyleneimine modified acrylic ester emulsion, uniformly stirring in high-speed dispersion, keeping the temperature of the liquid below 40 ℃, the rotating speed of 150-250 r/min, and the stirring time of 10-20 min; and (3) placing the mixed solution into a dispersing machine, adding tricalcium silicate and tricalcium aluminate into the mixed solution, wherein the rotating speed is 500-1000 r/min, and the stirring time is 10-20 min, so as to obtain the waterproof adhesive.
7. The use of a waterproofing adhesive according to claim 1, wherein the adhesive is applied to repair of cracks, damages, discontinuities in concrete, ceramics, glass, engineering plastics, marble, granite, gypsum board; the application method comprises the following steps: and cleaning the surface of the section or the crack, applying the waterproof adhesive obtained in the prior art to the place, and drying to obtain the adhesive layer.
CN202311054256.6A 2023-08-22 2023-08-22 Waterproof adhesive and preparation method thereof Active CN116751545B (en)

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US3444037A (en) * 1965-06-08 1969-05-13 Nat Starch Chem Corp Water resistant polyvinyl acetate adhesive compositions
WO2012002696A2 (en) * 2010-06-30 2012-01-05 대상 주식회사 Method for preparing adhesive material for aqueous paint
CN111808228A (en) * 2020-07-15 2020-10-23 万华化学集团股份有限公司 Hyperbranched polyethyleneimine doped modified acrylic emulsion and preparation method thereof

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GB201408909D0 (en) * 2014-05-20 2014-07-02 Knauf Insulation Ltd Binders
CN109266265B (en) * 2018-09-14 2019-10-25 江南大学 A kind of thermosetting property wood-based plate starch adhesive and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3444037A (en) * 1965-06-08 1969-05-13 Nat Starch Chem Corp Water resistant polyvinyl acetate adhesive compositions
WO2012002696A2 (en) * 2010-06-30 2012-01-05 대상 주식회사 Method for preparing adhesive material for aqueous paint
CN111808228A (en) * 2020-07-15 2020-10-23 万华化学集团股份有限公司 Hyperbranched polyethyleneimine doped modified acrylic emulsion and preparation method thereof

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