CN113621103A - Amine-free elastic acrylate emulsion, waterproof coating and preparation method - Google Patents
Amine-free elastic acrylate emulsion, waterproof coating and preparation method Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
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- C09D133/04—Homopolymers or copolymers of esters
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Abstract
The invention relates to an acrylic ester emulsion, a waterproof coating and a preparation method thereof, wherein the raw material formula of the acrylic ester emulsion comprises an acidic functional monomer, a soft monomer, a crosslinking monomer, a hard monomer, a post-crosslinking agent and the like, wherein the emulsifier at least contains a reactive emulsifier, and the reactive emulsifier contains a carbon-carbon double bond and a hydroxyl group; the crosslinking monomer contains carbon-carbon double bonds; the postcrosslinker is a siloxane having an epoxy group. By using the reactive emulsifier containing double bonds, the crosslinking monomer and the acidic functional monomer in a matching way, the double bonds of the reactive emulsifier can be connected to the polymer through reaction, so that the mechanical stability is improved, and the hydroxyl can react with the carboxyl to form crosslinking, so that the crosslinking degree is improved, and the water resistance is improved; the cross-linking monomer containing double bonds makes molecular chains cross-linked, so that the polymer is more compact, and the waterproof performance is further improved. Meanwhile, the post-crosslinking agent is added, so that after the emulsion is solidified into a film, the binding force among polymer particles is higher, and the water resistance and the mechanical strength are further improved.
Description
Technical Field
The invention belongs to the technical field of waterproof building materials, and particularly relates to an amine-free elastic acrylate emulsion, a waterproof coating and a preparation method thereof.
Background
Water-proof coating materials for buildings, such as water-proof asphalt and water-proof cement mortar, are used as the water-based emulsion. In order to ensure the performance of the emulsion and reduce the production cost, the traditional waterproof emulsion contains the following components:
formaldehyde or formaldehyde-releasing substances, formaldehyde being a well-known carcinogen;
alkylphenol Polyoxyethylene Ether (APEO) emulsifier, APEO has certain influence on ecological safety, such as toxicity, slow degradability, environmental hormone and harmful byproducts generated in the production process;
amides, especially acrylamide, which is a highly toxic substance and also releases ammonia when reacting with strong bases such as cement;
ammonia or amines which release ammonia, which has an irritating odor.
At present, there are also patents related to environment-friendly emulsions, such as the amine-free waterproof emulsion disclosed in chinese patent CN105949381A, the preparation method thereof and the waterproof coating containing the amine-free waterproof emulsion, comprising the following components: 40-50 parts of deionized water, 0.6-12.0 parts of emulsifier, 0.02-20 parts of phosphate monomer, 0.05-20 parts of hydrophilic monomer, 0.05-60 parts of hydrophobic monomer, 0.05-20 parts of polymerization stabilizer, 0.02-5 parts of vinyl siloxane, 0.02-5 parts of initiator, 0.02-5 parts of chain transfer agent, 0.02-5 parts of pH buffering agent, 0.02-5 parts of defoaming agent, 0.02-5 parts of preservative and 0.02-5 parts of alkali liquor.
According to the preparation method, 3 crosslinking monomers, phosphate monomer crosslinking, hydrophilic monomer self-crosslinking and vinyl siloxane crosslinking penetrate through the preparation of the waterproof emulsion, and the three crosslinking are mutually cooperated to finally form a compact protective film. However, the phosphate ester monomer used in the waterproof coating has the function of improving the adhesive force between the coating and a base material and does not have the function of improving the water resistance; vinyl siloxane is added when an emulsifying monomer is prepared, and oligomers are easily formed among vinyl siloxane and vinyl siloxane during reaction, so that the crosslinking density of the emulsion after film formation is influenced, and the problem of insufficient waterproofness exists.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an acrylate emulsion with environmental protection and excellent waterproofness and elasticity and a preparation method thereof.
In order to achieve the purpose, the technical scheme is as follows:
the acrylate emulsion comprises the following raw materials in percentage by mass:
wherein the emulsifier at least contains a reactive emulsifier, and the reactive emulsifier contains carbon-carbon double bonds and hydroxyl;
the crosslinking monomer contains carbon-carbon double bonds;
the post-crosslinker is a siloxane having an epoxy group.
Preferably, the raw material formula of the acrylate emulsion comprises the following components in percentage by mass:
in some preferred and specific embodiments, the crosslinking monomer is selected from allyl methacrylate. The crosslinking monomer contains two carbon-carbon double bonds, so that crosslinking is generated between molecular chains, the polymer is further more compact, the waterproof performance is improved, meanwhile, the polymer has elasticity, and the cracking problem is reduced.
In some preferred and specific embodiments, the reactive emulsifier accounts for 3-10% of the total mass of the emulsifier.
In some preferred and specific embodiments, the reactive emulsifier is selected from sodium allyloxy hydroxypropyl sulfonate, double bond containing sodium alkyl phenol polyether sulfosuccinate monoester, sodium allyl alkyl sulfosuccinate diester, allyl polyether sulfate, and alkyl propenyl phenoxy polyether sulfate. The double bonds of the reactive emulsifier can react on a polymer chain, so that the mechanical stability is improved; the hydroxyl can react with carboxyl of the acidic functional monomer and silanol generated by hydrolysis of the cycloalkyl siloxane to form crosslinking, so that the crosslinking degree is improved, and the water resistance is improved.
In some preferred and specific embodiments, the emulsifier is a mixture of an anionic emulsifier and a reactive emulsifier, preferably the anionic emulsifier is selected from the group consisting of alkyl polyoxyethylene ether phosphates, fatty alcohol ether sulfates, alkyl sulfates, sodium alkyl benzene sulfonates. Such as branched fatty alcohol polyoxyethylene ether phosphate Rhodafac RS-610 and sodium Disponil FES 32.
The emulsifier avoids the use of APEO type emulsifiers.
In some preferred and specific embodiments, the post-crosslinker is selected from the group consisting of 3- (2, 3-glycidoxy) propyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane. Such as from SILQUEST A-1871, CoatOSil 2287, SILQUEST A-186Silane, SILQUEST A-187 Silane.
Wherein the structural formula of the 3- (2, 3-epoxypropoxy) propyltriethoxysilane is as follows:
the structural formula of the 3-glycidyl ether oxypropyl methyldiethoxysilane is as follows:
the structural formula of the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane is as follows:
the structural formula of the 3- (2, 3-epoxypropoxy) propyl trimethoxy silane is as follows:
the addition of the post-crosslinking agent enables the binding force between polymer particles to be higher after the emulsion is formed into a film, and the water resistance and the mechanical strength are improved.
According to some embodiments of the invention, the acidic functional monomer is selected from acrylic acid, methacrylic acid. Preferably, the acidic functional monomer accounts for 2.5-5% of the total amount of all monomers in the acrylate emulsion. Such monomers contain carboxyl groups and are relatively hydrophilic, and it is generally believed that excessive acidic functional monomers reduce the water-repellent properties of the emulsion. Some implementation aspects of the invention find that the addition of a certain amount of the acidic functional monomer can increase the acid-base reaction between the polymer in the emulsion and the cement, so that the polymer and the cement form stronger bonding force, the performance indexes such as tensile strength of the polymer cement coating can be obviously improved, and the water resistance is hardly influenced.
According to some embodiments of the invention, the soft monomer is selected from butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate.
According to some embodiments of the invention, the hard monomer is selected from styrene, methyl methacrylate, vinyl acetate.
According to some embodiments of the invention, the initiator is selected from the group consisting of sodium persulfate, potassium persulfate, and t-butyl hydroperoxide.
According to some embodiments of the invention, the reducing agent is selected from the group consisting of sodium bisulfite, sodium metabisulfite, isoascorbic acid, Bruggolite-FF 6. The reducing agent has strong oxidation resistance and is not easy to be oxidized, and particularly, the emulsion is not easy to be oxidized and reddened after being stored for a long time.
In some preferred and specific embodiments, the raw material formulation of the acrylate emulsion further comprises an auxiliary agent selected from the group consisting of an antifoaming agent, a wetting agent, a bactericide, a polymerization inhibitor, a catalyst, a chelating agent, a buffering agent, and a pH adjusting agent.
Further, in the raw material formula of the acrylate emulsion, the defoaming agent accounts for 0-1%. The defoamer selection includes but is not limited to polyether modified silicone, mineral oil, fatty acid, polyether defoamer, such as polyether siloxane copolymer defoamer Tego 825.
Further, in the raw material formula of the acrylate emulsion, the wetting agent accounts for 0-5%. The wetting agent is selected from linear dow secondary alcohol polyoxyethylene ether TERGITOL 15-S-40. Preferably, the wetting agent accounts for 1-5%.
Further, in the raw material formula of the acrylate emulsion, the bactericide accounts for 0-1.5%. The bactericide is selected from the group consisting of, but not limited to, 5-chloro-2-methyl-isothiazolin-3-one, methylchloroisothiazolinone, 1, 2-benzisothiazolin-3-one (ROCIMA 640N). Preferably, the bactericide accounts for 0.1-1.5%.
Further, in the raw material formula of the acrylate emulsion, the pH regulator accounts for 0-1.5%. The pH regulator is sodium hydroxide and/or potassium hydroxide, and avoids using inorganic ammonia or substances capable of decomposing and releasing inorganic ammonia, such as ammonia water, ammonium salt and the like. Preferably, the pH regulator accounts for 0.1-1.5%.
Further, in the raw material formula of the acrylate emulsion, the chelating agent accounts for 0-0.05%, and the chelating agent comprises, but is not limited to, ethylenediamine tetraacetic acid and oxalic acid. Preferably, the chelating agent accounts for 0.001-0.05%.
Further, in the raw material formula of the acrylate emulsion, the polymerization inhibitor accounts for 0-0.05%. The polymerization inhibitor comprises, but is not limited to, polyphenols, quinones, aromatic amines, radical polymerization inhibitors, such as 2,2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical TH-701. Preferably, the polymerization inhibitor accounts for 0.0001-0.05%.
Further, in the raw material formula of the acrylate emulsion, the catalyst accounts for 0-0.05%. The catalyst is selected from ferrous sulfate heptahydrate. Preferably, the catalyst accounts for 0.0005-0.05%.
Further, in the raw material formula of the acrylate emulsion, the buffer agent accounts for 0-0.1%. The buffer is strong base weak acid salt, including but not limited to sodium carbonate, sodium bicarbonate. Preferably, the buffer agent accounts for 0.01-0.1%.
In some preferred and specific embodiments, the raw material formula of the acrylate emulsion comprises the following components in percentage by mass:
the invention adopts another technical scheme that: the preparation method of the acrylic ester emulsion comprises the following steps:
step S1: stirring and mixing water, an emulsifier, an acidic functional monomer, a soft monomer, a crosslinking monomer and a hard monomer to form a monomer emulsion, and dividing the monomer emulsion into a first monomer emulsion and a second monomer emulsion;
step S2: stirring and mixing water, an emulsifier, an initiator and the first monomer emulsion in a reaction kettle, and heating for reaction to prepare a seed emulsion;
step S3: respectively dropwise adding an aqueous solution of an initiator, an aqueous solution of a reducing agent and the second monomer emulsion into the seed emulsion, controlling the temperature to be 70-100 ℃ to carry out polymerization reaction, adding a post-crosslinking agent after the reaction is finished, stirring and mixing, then adding the initiator and the reducing agent, and controlling the temperature to be 60-85 ℃ to carry out reaction to prepare the acrylate emulsion.
Further, the preparation method further comprises the step of adding one or more of a buffering agent, a polymerization inhibitor, a catalyst and a chelating agent to the stirring and mixing process in the step S2.
Further, the preparation method comprises the step of S3, after the reaction is carried out at the controlled temperature of 60-85 ℃, cooling the system to below 60 ℃, selectively adding a wetting agent, or/and a pH regulator, or/and a bactericide, or/and a defoaming agent, and stirring and mixing to obtain the acrylate emulsion.
Preferably, in step S1, the solid content of the monomer emulsion is 70-90%.
In some preferred and specific embodiments, the preparation method specifically comprises the steps of:
step S1: the emulsifier is divided into a first emulsifier and a second emulsifier, wherein the first emulsifier accounts for 95-99% of the total mass of the emulsifier, the first emulsifier is an anionic emulsifier and a reactive emulsifier, and the second emulsifier is an anionic emulsifier.
Stirring and mixing water, a first emulsifier, an acidic functional monomer, a soft monomer, a crosslinking monomer and a hard monomer to form a monomer emulsion, and dividing the monomer emulsion into a first monomer emulsion and a second monomer emulsion, wherein the first monomer emulsion accounts for 1-5% of the total mass of the monomer emulsion;
dividing the initiator into a first initiator, a second initiator, a third initiator and a fourth initiator according to the mass ratio of 3-6: 1-3: 2-5: 1, and preparing an aqueous solution of the second initiator, an aqueous solution of the third initiator and an aqueous solution of the fourth initiator from the second initiator, the third initiator and the fourth initiator respectively;
dividing the reducing agent into a first reducing agent, a second reducing agent and a third reducing agent according to the mass ratio of 5-9: 4-8: 1, and preparing the first reducing agent, the second reducing agent and the third reducing agent into an aqueous solution of the first reducing agent, an aqueous solution of the second reducing agent and an aqueous solution of the third reducing agent respectively;
step S2: adding water into a reaction kettle, heating to 80-100 ℃, then adding a second emulsifier, adding one or more of a buffering agent, a polymerization inhibitor, a catalyst and a chelating agent into the first monomer emulsion, and adding a first initiator to perform a polymerization reaction to prepare a seed emulsion;
step S3: respectively dropwise adding a second monomer emulsion, an aqueous solution of a second initiator and an aqueous solution of a first reducing agent into the seed emulsion to perform polymerization reaction, wherein the dropwise adding time is controlled to be 90-150 min, and the reaction temperature is controlled to be 75-90 ℃;
after the dropwise addition is finished, adding the post-crosslinking agent, and stirring for 10-30 min;
then dropwise adding the aqueous solution of the third initiator and the aqueous solution of the second reducing agent, controlling the dropwise adding time to be 30-60 min, and controlling the temperature to be 75-80 ℃;
after the dropwise addition is finished, dropwise adding the aqueous solution of the fourth initiator and the aqueous solution of the third reducing agent, wherein the dropwise adding time is controlled to be 10-20 min, and the temperature is controlled to be 65-75 ℃;
after the dropwise adding is finished, selectively adding a defoaming agent into the reaction kettle in order to eliminate bubbles generated in the reaction kettle and prevent the generation of foams after the additive solution is subsequently added;
selectively dropwise adding an aqueous solution of a wetting agent and a pH regulator, controlling the dropwise adding time to be 30-50 min, and controlling the temperature to be 50-60 ℃;
then selectively dropwise adding the aqueous solution of the bactericide, controlling the dropwise adding time to be 10-15 min, and controlling the temperature to be 40-55 ℃;
and (3) selectively adding a defoaming agent, and stirring for 20-30 min to obtain the acrylate emulsion.
The acrylic ester emulsion of the invention is free of formaldehyde and formaldehyde-releasing components, free of Alkylphenol Polyvinyl Ether (APEO) substances, free of amide substances, in particular acrylamide, free of ammonia or amine substances capable of releasing ammonia.
In the invention, the preparation method adopts a redox-initiated semi-continuous seed dripping process, and has the advantages of stable initial polymerization reaction, narrow particle size distribution and good production stability.
The third technical scheme adopted by the invention is as follows: a waterproof coating comprises the acrylic ester emulsion.
In some preferred and specific embodiments, the waterproof coating is formed by mixing a first component and a second component, wherein the first component comprises the acrylate emulsion; the second component includes cement, a filler, and hydroxypropyl methylcellulose.
Preferably, the first component comprises 80-100 parts of the acrylate emulsion, 10-30 parts of water and 0-2 parts of a bactericide.
Preferably, the filler is selected from heavy calcium carbonate and quartz powder. Further preferably, the second component comprises 40-60 parts of cement, 30-50 parts of heavy calcium carbonate, 5-15 parts of quartz powder, 0.05-1 part of defoaming agent and 0.05-1 part of hydroxypropyl methyl cellulose.
Preferably, the mass ratio of the first component to the second component is 1: 1-2.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the reactive emulsifier containing double bonds, the crosslinking monomer containing double structures and the acidic functional monomer are used in a matching manner, so that the double bonds of the reactive emulsifier can be connected to the polymer through reaction, the mechanical stability is improved, and the hydroxyl can react with the carboxyl to form crosslinking, so that the crosslinking degree is improved, and the water resistance is improved; the cross-linking monomer containing double bonds makes molecular chains cross-linked, so that the polymer is more compact, and the waterproof performance is further improved. Meanwhile, the acrylate emulsion is added with the post-crosslinking agent, so that after the emulsion is cured to form a film, the bonding force among polymer particles is higher, and the water resistance and the mechanical strength are further improved.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to specific examples so that those skilled in the art can better understand and implement the technical solutions of the present invention, but the present invention is not limited to the scope of the examples.
Example 1
The raw material formula of the acrylate emulsion provided in this example is shown in table 1, and the acrylate emulsion is specifically prepared by the following method:
step S1:
according to the formula, water, an anionic emulsifier, a reactive emulsifier, a stable monomer, a crosslinking monomer, a soft monomer and a hard monomer are put into a container with a stirring function, are stirred and mixed uniformly to form a monomer emulsion, and the monomer emulsion is divided into a first monomer emulsion and a second monomer emulsion according to the mass content for later use, wherein the first monomer emulsion accounts for 2.6 percent, and the second monomer emulsion accounts for 97.4 percent;
dividing the initiator into four parts, namely a first initiator, a second initiator, a third initiator and a fourth initiator, and preparing the second initiator, the third initiator and the fourth initiator into aqueous solutions respectively for later use;
dividing the reducing agent into three parts, namely a first reducing agent, a second reducing agent and a third reducing agent, and preparing aqueous solutions for later use respectively;
step S2:
adding water into a reaction kettle with heating, stirring and cooling functions, heating to 95 ℃, then adding an anionic emulsifier, a buffering agent and a chelating agent, stirring and mixing to obtain a substrate, then adding a first monomer emulsion, then adding a first initiator, starting a polymerization reaction in the reaction kettle, and raising the temperature. When the temperature of the materials in the reaction kettle does not rise any more, the preparation of the seed emulsion is finished.
Step S3:
dropwise adding a second monomer emulsion, a second initiator aqueous solution and a first reducing agent aqueous solution into the reaction kettle of the step S2 at a constant speed, controlling the dropwise adding time to be 90-150 min, and maintaining the reaction temperature to be 88 ℃;
after all the materials are dripped, adding a post-crosslinking agent, and stirring for 20 min;
then cooling the materials in the reaction kettle to 80 ℃, then simultaneously dropwise adding an aqueous solution of a third initiator and an aqueous solution of a second reducing agent, controlling the dropwise adding time to be 30-60 min, and controlling the temperature to be 75-80 ℃;
after the dropwise addition is finished, in order to further eliminate residual monomers, simultaneously dropwise adding an aqueous solution of a fourth initiator and an aqueous solution of a third reducing agent, controlling the dropwise adding time to be 10-20 min and controlling the temperature to be 65-75 ℃;
cooling the materials in the reaction kettle to 55 ℃, then dropwise adding an aqueous solution of additives (a wetting agent and a pH regulator) at a constant speed, and controlling the dropwise adding time to be 30-50 min;
and (3) cooling the materials in the reaction kettle to 50 ℃, dropwise adding the aqueous solution of the bactericide, and controlling the dropwise adding time to be 10-15 min to obtain the acrylate emulsion.
Example 2
The raw material formulation of the acrylate emulsion provided in this example is shown in table 1, and the rest is the same as that of example 1.
Example 3
The raw material formulation of the acrylate emulsion provided in this example is shown in table 1, and the rest is the same as that of example 1.
Table 1 shows the raw material formulations (in mass percent) of the acrylate emulsions of examples 1 to 3
Comparative example 1
The acrylic emulsion provided by the comparative example is different from the acrylic emulsion provided by the example 1 in that: a branched C13 alcohol ether (EFS-1340) was used in place of the reactive emulsifier. The rest is basically the same as example 1.
Comparative example 2
The acrylic emulsion provided by the comparative example is different from the acrylic emulsion provided by the example 1 in that: the methacrylic acid content was adjusted to 0.45% and the water content in the monomer emulsion was adjusted to 11.96%. The rest is basically the same as example 1.
Comparative example 3
The acrylic emulsion provided by the comparative example is different from the acrylic emulsion provided by the example 1 in that: in the preparation method, A-1871 is added to the second monomer emulsion in step S3, and then polymerization is performed. The rest is basically the same as example 1.
The acrylate emulsions of examples 1 to 3 and comparative examples 1 to 3 were subjected to performance tests, the results of which are shown in table 2, and the test methods were as follows:
1. mechanical stability: the prepared acrylate emulsion was dispersed for 30min at 4000rpm using a dispersion machine with a dispersion pan, and whether flocculation or delamination occurred in the appearance was observed.
2. Storage stability: and placing the emulsion in a 250mL measuring cylinder, standing for 30 days, and respectively testing the solid contents of the upper layer and the lower layer, wherein the storage stability is obtained by subtracting the difference value of the upper layer from the lower layer.
3. Gel content: quantitatively weighing a certain amount of emulsion, passing through a 100-mesh screen, washing the residual emulsion on the screen, drying in an oven at 150 ℃ for 7 minutes, and weighing the mass difference before and after filtering by the screen to obtain the gel content in the emulsion.
4. The ammonia content was tested according to JC 1066-2008.
5. The total content of alkylphenol ethoxylates is tested according to GB/T31414-2015.
Table 2 shows the results of the performance test of the acrylate emulsions of examples 1 to 3 and comparative examples 1 to 3
In the embodiments 1 to 3, ammonia water, ammonium salt and alkylphenol ethoxylates are not added, and the total content of ammonia and alkylphenol ethoxylates is 0, so that the characteristics of low odor and high environmental protection are achieved.
In comparative example 1, a conventional non-ionic emulsifier was used, and its mechanical stability was poor. In comparative example 2, the methacrylic acid content was small, the number of charges on the polymer surface was reduced, the electrostatic repulsive force was weakened, gel was easily formed during polymerization, and delamination was easily caused by sedimentation during storage. Comparative example 3 epoxysiloxane was added to the second monomer emulsion, which was susceptible to gel formation during polymerization, i.e., cross-linking between molecular chains.
Application examples
The acrylic ester emulsions of examples 1 to 3 and comparative examples 1 to 3 were used to prepare a polymer cement waterproof coating, and the preparation method of the waterproof coating was as follows:
liquid material: 90 parts of acrylate emulsion, 20 parts of water and 1 part of bactericide KORDEK MLX
Powder lot: 50 parts of 42.5 Portland cement, 40 parts of 400-mesh coarse whiting, 10 parts of 100-mesh 200-mesh quartz powder, 0.2 part of defoaming agent SD-806 and 0.2 part of 100 Pa.s hydroxypropyl methyl cellulose.
And (3) stirring the liquid material and the powder material according to the mass ratio of 1:1.2 at the rotating speed of 300rpm for 10-15 minutes to obtain the polymer cement waterproof coating.
The tensile strength, elongation at break, adhesive strength, water absorption and other indexes are tested according to the standards GB/T23445-.
Table 3 shows the results of performance tests of the waterproof coatings prepared using the acrylate emulsions of examples 1 to 3 and comparative examples 1 to 3
As can be seen from Table 3, the performance indexes of the coating obtained by applying examples 1-3 can meet the requirements of the I-type polymer cement waterproof coating in GB/T23445-2009.
In the case of comparative example 1, flocculation occurred during the preparation of polymer cement coating due to poor mechanical stability, and the next test could not be performed. By applying the comparative example 2, the content of the methacrylic acid is less, so the acid-base reaction between the emulsion and the cement is less, the binding force between the polymer and the cement powder is weaker, and the indexes such as tensile strength, elongation at break and the like are reduced compared with the examples. In application comparative example 3, since the epoxysiloxane takes part in the reaction in the polymerization stage and mostly forms cross-linking between molecular chains, the degree of cross-linking between polymer particles is not substantially increased during the film forming process of the coating, and although the initial performance index is almost the same as that of application example 1, tensile strength, elongation at break and adhesive strength are remarkably reduced after the water immersion treatment, and the water absorption rate is also remarkably increased after 7 days.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (12)
1. The acrylic ester emulsion is characterized in that the raw material formula of the acrylic ester emulsion comprises the following components in percentage by mass:
1-5% of an acidic functional monomer;
15-30% of a soft monomer;
0.1-1.5% of a crosslinking monomer;
15-30% of hard monomer;
0.5-1.5% of post-crosslinking agent;
1-5% of an emulsifier;
0.1-2% of an initiator;
0.01-1% of a reducing agent;
the balance of water,
wherein the emulsifier at least contains a reactive emulsifier, and the reactive emulsifier contains carbon-carbon double bonds and hydroxyl;
the crosslinking monomer contains carbon-carbon double bonds;
the post-crosslinker is a siloxane having an epoxy group.
2. The acrylate emulsion according to claim 1, characterized in that: the crosslinking monomer is selected from allyl methacrylate.
3. The acrylate emulsion according to claim 1, characterized in that: the reactive emulsifier accounts for 3-10% of the total mass of the emulsifier; and/or the reactive emulsifier is selected from sodium allyloxy hydroxypropyl sulfonate, alkylphenol polyether sulfosuccinic acid monoester sodium containing double bonds, allyl alkyl sulfosuccinic acid diester sodium, allyl polyether sulfate and alkyl propenyl phenoxy polyether sulfate.
4. The acrylate emulsion according to claim 1, characterized in that: the emulsifier is a mixture of the reactive emulsifier and an anionic emulsifier; and/or the anionic emulsifier is selected from alkyl polyoxyethylene ether phosphate, fatty alcohol ether sulfate, alkyl sulfate and sodium alkyl benzene sulfonate.
5. The acrylate emulsion according to claim 1, characterized in that: the post-crosslinking agent is selected from 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidyloxypropylmethyldiethoxysilane.
6. The acrylate emulsion according to claim 1, characterized in that: the acid functional monomer is selected from acrylic acid and methacrylic acid; and/or the soft monomer is selected from butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate; and/or the hard monomer is selected from styrene, methyl methacrylate and vinyl acetate; and/or the initiator is selected from sodium persulfate, potassium persulfate, tert-butyl hydroperoxide; and/or the reducing agent is selected from sodium bisulfite, sodium metabisulfite, isoascorbic acid, Bruggolite-FF 6.
7. The acrylate emulsion according to claim 1, characterized in that: the raw material formula of the acrylate emulsion also comprises an auxiliary agent, wherein the auxiliary agent is selected from a defoaming agent, a wetting agent, a bactericide, a polymerization inhibitor, a catalyst, a chelating agent, a buffering agent and a pH regulator.
8. The acrylate emulsion according to claim 7, characterized in that: in the raw material formula of the acrylate emulsion, the wetting agent accounts for 1-5%; and/or the bactericide accounts for 0.1-1.5%; and/or the pH regulator accounts for 0.1-1.5%.
9. The acrylate emulsion according to claim 1, characterized in that: the raw material formula of the acrylate emulsion comprises the following components in percentage by mass:
1-5% of an acidic functional monomer;
15-30% of a soft monomer;
0.1-1.5% of a crosslinking monomer;
15-30% of hard monomer;
0.5-1.5% of post-crosslinking agent;
1-5% of an emulsifier;
0.1-2% of an initiator;
0.01-1% of a reducing agent;
0.1-1.5% of a bactericide;
1-5% of a wetting agent;
0.1-1.5% of a pH regulator;
40-60% of water.
10. The method for preparing the acrylate emulsion according to any one of claims 1 to 9, wherein the method comprises the following steps:
step S1: stirring and mixing water, an emulsifier, an acidic functional monomer, a soft monomer, a crosslinking monomer and a hard monomer to form a monomer emulsion, and dividing the monomer emulsion into a first monomer emulsion and a second monomer emulsion;
step S2: stirring and mixing water, an emulsifier, an initiator and the first monomer emulsion in a reaction kettle, and heating for reaction to prepare a seed emulsion;
step S3: respectively dropwise adding an aqueous solution of an initiator, an aqueous solution of a reducing agent and the second monomer emulsion into the seed emulsion, controlling the temperature to be 70-100 ℃ to carry out polymerization reaction, adding a post-crosslinking agent after the reaction is finished, stirring and mixing, then adding the initiator and the reducing agent, and controlling the temperature to be 60-85 ℃ to carry out reaction to prepare the acrylate emulsion.
11. The method of manufacturing according to claim 10, wherein: the preparation method further comprises the step of adding one or more of a buffering agent, a polymerization inhibitor, a catalyst and a chelating agent into the stirring and mixing process in the step S2;
and/or in the step S3, after the reaction is carried out at the controlled temperature of 60-85 ℃, the temperature of the system is reduced to below 60 ℃, a wetting agent, or/and a pH regulator, or/and a bactericide, or/and a defoaming agent are selectively added, and the mixture is stirred and mixed to obtain the acrylate emulsion.
12. A waterproof coating is characterized in that: the waterproof coating is prepared by mixing a first component and a second component, wherein the first component comprises the acrylate emulsion disclosed by any one of claims 1-9, and the second component comprises cement, a filler and hydroxypropyl methyl cellulose.
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| PCT/CN2022/108491 WO2023006016A1 (en) | 2021-07-29 | 2022-07-28 | Amine-free elastic acrylate emulsion, waterproof coating, and preparation method |
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| WO2023006016A1 (en) * | 2021-07-29 | 2023-02-02 | 江苏凯伦建材股份有限公司 | Amine-free elastic acrylate emulsion, waterproof coating, and preparation method |
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