CN110669165B - Cationic polyacrylate fluorine-free waterproof agent and preparation method thereof - Google Patents
Cationic polyacrylate fluorine-free waterproof agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cationic polyacrylate fluorine-free waterproof agent which comprises, by mass, 5-40% of butyl acrylate, 5-35% of methyl methacrylate, 0.5-5% of long-chain fatty alcohol acrylate, 0.5-4% of a reactive cationic emulsifier and 45-75% of deionized water, wherein the sum of the mass percentages of the components is 100%. The preparation method comprises the following steps: step 1, preparing a reactive cationic emulsifier; step 2, preparing a pre-emulsion; and 3, preparing the cationic polyacrylate soap-free emulsion. The invention discloses a cationic polyacrylate fluorine-free waterproof agent which does not contain PFOS and PFOA, and has good waterproof property.
Description
Technical Field
The invention belongs to the technical field of waterproof agents and preparation, and particularly relates to a cationic polyacrylate fluorine-free waterproof agent and a preparation method of the waterproof agent.
Background
The polyacrylate waterproof agent is a novel waterproof agent which is developed rapidly in recent years. The polyacrylate emulsion contained in the polyacrylate waterproof agent is a product obtained by emulsion polymerization of acrylates or methacrylates and other vinyl ester monomers, has excellent water resistance, weather resistance, acid-base resistance, corrosion resistance and other properties, is gradually the leading factor of the waterproof coating market, and is the development direction of the modern waterproof industry, but the polyacrylate polymer can only be waterproof and has low waterproof grade, so that organic fluorine and other monomers are added in the synthesis process to improve the water resistance, weather resistance, corrosion resistance and the like, but the use process shows that the fluorine-containing polymer can generate PFOA and PFOS byproducts in the production process, has the characteristics of difficult degradation, in-vivo accumulation, carcinogenicity and the like, and has potential hazards to human bodies and the environment; in addition, the cationic polyacrylate emulsion is electropositive, can be combined with various fabrics with negative charges through an electrostatic effect by ionic bonds, has the advantages of small environmental pollution, safety, no toxicity, excellent mechanical stability, excellent film forming property, convenience in processing and the like, so that the research on the cationic polyacrylate emulsion is very important, most of the current researches on the fluorine-free waterproof agent of the cationic polyacrylate adopt the traditional emulsion polymerization method, and the preparation method can cause the existence of the emulsifier to influence the compactness, the water resistance, the scrubbing resistance, the adhesive force and the like of the film formed by the emulsion.
Disclosure of Invention
The invention aims to provide a cationic polyacrylate fluorine-free waterproof agent which does not contain any PFOS and PFOA and has better waterproof property.
The invention also aims to provide the preparation method of the cationic polyacrylate fluorine-free waterproof agent, which can prepare the synthetic reactive cationic emulsifier and fully improve the waterproof performance of the fluorine-free waterproof agent.
The invention adopts the technical scheme that the cationic polyacrylate fluorine-free waterproof agent comprises, by mass, 5-40% of butyl acrylate, 5-35% of methyl methacrylate, 0.5-5% of long-chain fatty alcohol acrylate, 0.5-4% of reactive cationic emulsifier and 45-75% of deionized water, wherein the sum of the mass percentages of the components is 100%.
The invention adopts another technical scheme that a preparation method of a cationic polyacrylate fluorine-free waterproof agent is implemented according to the following steps:
step 1, preparing reactive cationic emulsifier
Step 1.1, adding a certain amount of acrylate monomer containing reactive amino, bromoalkane and a polar solvent into a flask provided with a condenser tube respectively to obtain a mixture, and standing the mixture at 40-60 ℃ for reaction for 24 hours;
step 1.2, evaporating the mixture after the reaction in the step 1 to obtain a solvent, and recrystallizing to obtain a reactive cationic emulsifier;
step 2, preparing a pre-emulsion
Step 2.1, mixing a certain amount of butyl acrylate, methyl methacrylate, long-chain fatty alcohol acrylate, the reactive cationic emulsifier prepared in the step 1 and a proper amount of deionized water to obtain a mixture, and emulsifying the mixture by a cell crusher to obtain a pre-emulsion;
step 3, preparing the cationic polyacrylate soap-free emulsion
Step 3.1, weighing a quantitative initiator aqueous solution with the mass ratio of 18-46% to the pre-emulsion prepared in the step 2.1, pouring 20-50% of the pre-emulsion prepared in the step 2 into a reactor with a stirrer and a condenser pipe, adding 1/5-1/3 weighed initiator aqueous solution into the reactor, and standing and reacting at 55-75 ℃ for 20-40 min;
and 3.2, after the standing reaction in the step 3.1 is finished, heating to 60-80 ℃, respectively and simultaneously dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution into the reactor, after the dropwise adding lasts for 60-180 min, completely dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution at the same time, after the dropwise adding is finished, carrying out heat preservation reaction for 90-180 min, and after the heat preservation reaction is finished, cooling to room temperature to obtain the cationic polyacrylate soap-free emulsion.
The present invention is also characterized in that,
the acrylate monomer containing reactive amino group in step 1.1 is any one of N, N-dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate and diethylaminoethyl methacrylate.
The bromoalkane in the step 1.1 is any one of bromo-n-decane, bromo-dodecane, bromo-tetradecane, bromo-hexadecane and bromo-octadecane.
The molar ratio of the acrylate monomer containing the reactive amino group to the bromoalkane in the step 1.1 is 1:1 to 3.
The polar solvent in the step 1.1 is any one of acetone, dioxane, acetonitrile and methanol, and the mass ratio of the polar solvent to the mixture of the acrylate monomer containing the reactive amino and the alkyl bromide is 3-7: 1.
The long-chain acrylic fatty alcohol ester in the step 2.1 is one or a mixture of more of lauryl acrylate, cetyl acrylate and stearyl acrylate in any proportion.
The mass ratio of the butyl acrylate, the methyl methacrylate and the long-chain aliphatic acrylate ester prepared in the step (2.1), the reactive emulsifier prepared in the step (1) and the deionized water is (45-130): (75-120): (6-11): 1-7): 135-175.
In the step 3.1, the solute of the initiator aqueous solution is azo-diisobutymidine hydrochloride, the solvent is water, and the mass ratio of the azo-diisobutymidine hydrochloride to the water is 1: 8-12.
The invention has the beneficial effects that:
(1) according to the invention, an acrylate monomer containing reactive amino is used as a hydrophilic monomer, bromoalkane is used as a hydrophobic monomer, and a reactive cationic emulsifier prepared by free radical polymerization is used for cationic polyacrylate soap-free emulsion polymerization, so that the prepared cationic polyacrylate soap-free emulsion has good stability, small particle size distribution of emulsion particles, positive charges on the surface of the emulsion particles and tight combination with fabrics through electrostatic action, the use of substances such as a color fixing agent is avoided, the acting force between the emulsion and the fabrics is enhanced, and the emulsion has good water repellency;
(2) the cationic polyacrylate fluorine-free waterproof agent has the advantages of safety and environmental protection, and has stronger waterproof performance due to the fluorine-free waterproof agent synthesized by the fluorine-free long-chain alkyl polymerizable monomer.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a cationic polyacrylate fluorine-free waterproof agent which comprises, by mass, 5-40% of butyl acrylate, 5-35% of methyl methacrylate, 0.5-5% of long-chain fatty acrylate, 0.5-4% of a reactive cationic emulsifier and 45-75% of deionized water, wherein the sum of the mass percentages of the components is 100%.
The invention discloses a preparation method of a cationic polyacrylate fluorine-free waterproof agent, which is characterized by comprising the following steps of:
step 1, preparing reactive cationic emulsifier
Step 1.1, adding a certain amount of acrylate monomer containing reactive amino, bromoalkane and a polar solvent into a flask provided with a condenser tube respectively to obtain a mixture, and standing the mixture at 40-60 ℃ for reaction for 24 hours;
step 1.2, evaporating the mixture after the reaction in the step 1 to remove the solvent, and then recrystallizing, wherein the recrystallization adopts anhydrous ether to wash away unreacted monomers and solvent, so as to obtain the reactive cationic emulsifier;
step 2, preparing a pre-emulsion
Step 2.1, mixing a certain amount of butyl acrylate, methyl methacrylate, long-chain fatty alcohol acrylate, the reactive cationic emulsifier prepared in the step 1 and a proper amount of deionized water to obtain a mixture, and emulsifying the mixture by a cell crusher to obtain a pre-emulsion;
step 3, preparing the cationic polyacrylate soap-free emulsion
Step 3.1, weighing a quantitative initiator aqueous solution with the mass ratio of 18-46% to the pre-emulsion prepared in the step 2.1, pouring 20-50% of the pre-emulsion prepared in the step 2 into a reactor with a stirrer and a condenser pipe, adding 1/5-1/3 weighed initiator aqueous solution into the reactor, and standing and reacting at 55-75 ℃ for 20-40 min;
and 3.2, after the standing reaction in the step 3.1 is finished, heating to 60-80 ℃, respectively and simultaneously dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution into the reactor, after the dropwise adding lasts for 60-180 min, completely dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution at the same time, after the dropwise adding is finished, carrying out heat preservation reaction for 90-180 min, and after the heat preservation reaction is finished, cooling to room temperature to obtain the cationic polyacrylate soap-free emulsion.
The acrylate monomer containing reactive amino group in step 1.1 is any one of N, N-dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate and diethylaminoethyl methacrylate.
The bromoalkane in the step 1.1 is any one of bromo-n-decane, bromo-dodecane, bromo-tetradecane, bromo-hexadecane and bromo-octadecane.
The molar ratio of the acrylate monomer containing the reactive amino group to the bromoalkane in the step 1.1 is 1:1 to 3.
The polar solvent in the step 1.1 is any one of acetone, dioxane, acetonitrile and methanol, and the mass ratio of the polar solvent to the mixture of the acrylate monomer containing the reactive amino and the alkyl bromide is 3-7: 1.
The long-chain acrylic fatty alcohol ester in the step 2.1 is one or a mixture of more of lauryl acrylate, cetyl acrylate and stearyl acrylate in any proportion.
The mass ratio of the butyl acrylate, the methyl methacrylate and the long-chain aliphatic acrylate ester prepared in the step (2.1), the reactive emulsifier prepared in the step (1) and the deionized water is (45-130): (75-120): (6-11): 1-7): 135-175.
In the step 3.1, the solute of the initiator aqueous solution is azo-diisobutymidine hydrochloride, the solvent is water, and the mass ratio of the azo-diisobutymidine hydrochloride to the water is 1: 8-12.
Example 1
A preparation method of a cationic polyacrylate fluorine-free waterproof agent is specifically implemented according to the following steps:
step 1, preparing reactive cationic emulsifier
Step 1.1, adding a certain amount of N, N-dimethylaminoethyl methacrylate, bromo-N-decane and acetone into a flask with a condensing tube respectively to obtain a mixture, wherein the molar ratio of the N, N-dimethylaminoethyl methacrylate to the bromo-N-decane is 1:1, the mass ratio of acetone to a mixture of N, N-dimethylaminoethyl methacrylate and bromo-N-decane is 3:1, and the mixture is kept stand at 40 ℃ for reaction for 24 hours;
step 1.2, evaporating the mixture after the reaction in the step 1 to remove the solvent, and then recrystallizing, wherein the recrystallization adopts anhydrous ether to wash away unreacted monomers and solvent, so as to obtain the reactive cationic emulsifier;
step 2, preparing a pre-emulsion
Step 2.1, mixing a certain amount of butyl acrylate, methyl methacrylate, lauryl acrylate, the reactive cationic emulsifier prepared in the step 1 and a proper amount of deionized water to obtain a mixture, wherein the mass ratio of the butyl acrylate, the methyl methacrylate, the lauryl acrylate, the reactive cationic emulsifier prepared in the step 1 to the deionized water is 45:97.5:9:7:135, and emulsifying the mixture by a cell crusher to obtain a pre-emulsion;
step 3, preparing the cationic polyacrylate soap-free emulsion
Step 3.1, weighing a quantitative initiator aqueous solution with the mass ratio of 18% to the pre-emulsion prepared in the step 2.1, wherein the initiator aqueous solution is prepared from azodiisobutyramidine hydrochloride and water in a mass ratio of 1:8, pouring 20% of the pre-emulsion prepared in the step 2 into a reactor with a stirrer and a condenser pipe, adding 1/5 amount of the initiator aqueous solution into the reactor, and standing and reacting for 20min at 55 ℃;
and 3.2, after the standing reaction in the step 3.1 is finished, heating to 65 ℃, respectively and simultaneously dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution into the reactor, after the dropwise adding lasts for 60min, completely dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution at the same time, after the dropwise adding is finished, carrying out heat preservation reaction for 90min, and after the heat preservation reaction is finished, cooling to room temperature to obtain the cationic polyacrylate soap-free emulsion.
Example 2
A preparation method of a cationic polyacrylate fluorine-free waterproof agent is specifically implemented according to the following steps:
step 1, preparing reactive cationic emulsifier
Step 1.1, adding a certain amount of tert-butylaminoethyl methacrylate, bromododecane and dioxane into a flask provided with a condenser respectively to obtain a mixture, wherein the molar ratio of tert-butylaminoethyl methacrylate to bromododecane is 1: 2, the mass ratio of dioxane to a mixture of tert-butylaminoethyl methacrylate and bromododecane is 4:1, and the mixture is kept stand at 45 ℃ for 24 hours;
step 1.2, evaporating the mixture after the reaction in the step 1 to remove the solvent, and then recrystallizing, wherein the recrystallization adopts anhydrous ether to wash away unreacted monomers and solvent, so as to obtain the reactive cationic emulsifier;
step 2, preparing a pre-emulsion
Step 2.1, mixing a certain amount of butyl acrylate, methyl methacrylate and hexadecyl acrylate, the reactive cationic emulsifier prepared in the step 1 and a proper amount of deionized water to obtain a mixture, wherein the mass ratio of the butyl acrylate, the methyl methacrylate and the hexadecyl acrylate to the reactive cationic emulsifier prepared in the step 1 to the deionized water is 60:75:6:4:140, and emulsifying the mixture by a cell crusher to obtain a pre-emulsion;
step 3, preparing the cationic polyacrylate soap-free emulsion
Step 3.1, weighing a quantitative initiator aqueous solution with the mass ratio of 25% to the pre-emulsion prepared in the step 2.1, wherein the initiator aqueous solution is prepared from azodiisobutyramidine hydrochloride and water with the mass ratio of 1:9, pouring 30% of the pre-emulsion prepared in the step 2 into a reactor with a stirrer and a condenser pipe, adding 4/15 amount of the initiator aqueous solution into the reactor, and standing and reacting for 25min at 60 ℃;
and 3.2, after the standing reaction in the step 3.1 is finished, heating to 70 ℃, respectively and simultaneously dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution into the reactor, after the dropwise adding lasts for 120min, completely dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution at the same time, after the dropwise adding is finished, carrying out heat preservation reaction for 180min, and after the heat preservation reaction is finished, cooling to room temperature to obtain the cationic polyacrylate soap-free emulsion.
Example 3
A preparation method of a cationic polyacrylate fluorine-free waterproof agent is specifically implemented according to the following steps:
step 1, preparing reactive cationic emulsifier
Step 1.1, adding a certain amount of diethylaminoethyl methacrylate, bromotetradecane and acetonitrile into a flask with a condensing tube respectively to obtain a mixture, wherein the molar ratio of the diethylaminoethyl methacrylate to the bromotetradecane is 1: 3, keeping the mass ratio of the acetonitrile to the mixture of the diethylaminoethyl methacrylate and the bromotetradecane to be 5:1, and standing the mixture at 50 ℃ for reaction for 24 hours;
step 1.2, evaporating the mixture after the reaction in the step 1 to remove the solvent, and then recrystallizing, wherein the recrystallization adopts anhydrous ether to wash away unreacted monomers and solvent, so as to obtain the reactive cationic emulsifier;
step 2, preparing a pre-emulsion
Step 2.1, mixing a certain amount of butyl acrylate, methyl methacrylate and stearyl acrylate, the reactive cationic emulsifier prepared in the step 1 and a proper amount of deionized water to obtain a mixture, wherein the mass ratio of the butyl acrylate, the methyl methacrylate and the stearyl acrylate to the reactive cationic emulsifier prepared in the step 1 to the deionized water is 87.5:110:11:1:150, and emulsifying the mixture by a cell crusher to obtain a pre-emulsion;
step 3, preparing the cationic polyacrylate soap-free emulsion
Step 3.1, weighing a quantitative initiator aqueous solution with the mass ratio of 32% to the pre-emulsion prepared in the step 2.1, wherein the initiator aqueous solution is prepared from azodiisobutyramidine hydrochloride and water in a mass ratio of 1:10, pouring 35% of the pre-emulsion prepared in the step 2 into a reactor with a stirrer and a condenser pipe, adding 1/3 amount of the initiator aqueous solution into the reactor, and standing and reacting for 30min at 65 ℃;
and 3.2, after the standing reaction in the step 3.1 is finished, heating to 75 ℃, respectively and simultaneously dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution into the reactor, after the dropwise adding lasts for 180min, completely dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution at the same time, after the dropwise adding is finished, carrying out heat preservation reaction for 135min, and after the heat preservation reaction is finished, cooling to room temperature to obtain the cationic polyacrylate soap-free emulsion.
Example 4
A preparation method of a cationic polyacrylate fluorine-free waterproof agent is specifically implemented according to the following steps:
step 1, preparing reactive cationic emulsifier
Step 1.1, adding a certain amount of N, N-dimethylaminoethyl methacrylate, bromohexadecane and methanol into a flask with a condensing tube respectively to obtain a mixture, wherein the molar ratio of the N, N-dimethylaminoethyl methacrylate to the bromohexadecane is 1: 2, the mass ratio of the methanol to the mixture of N, N-dimethylaminoethyl methacrylate and bromohexadecane is 6:1, and the mixture is kept stand and reacts for 24 hours at the temperature of 55 ℃;
step 1.2, evaporating the mixture after the reaction in the step 1 to remove the solvent, and then recrystallizing, wherein the recrystallization adopts anhydrous ether to wash away unreacted monomers and solvent, so as to obtain the reactive cationic emulsifier;
step 2, preparing a pre-emulsion
Step 2.1, mixing a certain amount of a mixture of butyl acrylate, methyl methacrylate, lauryl acrylate and cetyl acrylate, the reactive cationic emulsifier prepared in the step 1 and a proper amount of deionized water to obtain a mixture, wherein the mass ratio of the mixture of butyl acrylate, methyl methacrylate, lauryl acrylate and cetyl acrylate, the reactive cationic emulsifier prepared in the step 1 and the deionized water is 110:120:8.5:6:155, and emulsifying the mixture by a cell crusher to obtain a pre-emulsion;
step 3, preparing the cationic polyacrylate soap-free emulsion
Step 3.1, weighing a quantitative initiator aqueous solution with the mass ratio of 39% to the pre-emulsion prepared in the step 2.1, wherein the initiator aqueous solution is prepared from azodiisobutyramidine hydrochloride and water with the mass ratio of 1:11, pouring 40% of the pre-emulsion prepared in the step 2 into a reactor with a stirrer and a condenser pipe, adding 1/5 amount of the initiator aqueous solution into the reactor, and standing and reacting for 35min at 70 ℃;
and 3.2, after the standing reaction in the step 3.1 is finished, heating to 60 ℃, respectively and simultaneously dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution into the reactor, after the dropwise adding lasts for 100min, completely dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution at the same time, after the dropwise adding is finished, carrying out heat preservation reaction for 145min, and after the heat preservation reaction is finished, cooling to room temperature to obtain the cationic polyacrylate soap-free emulsion.
Example 5
A preparation method of a cationic polyacrylate fluorine-free waterproof agent is specifically implemented according to the following steps:
step 1, preparing reactive cationic emulsifier
Step 1.1, adding a certain amount of diethylaminoethyl methacrylate, bromooctadecane and dioxane into a flask with a condensing tube respectively to obtain a mixture, wherein the molar ratio of the diethylaminoethyl methacrylate to the bromooctadecane is 1: 2, the mass ratio of dioxane to the mixture of diethylaminoethyl methacrylate and bromooctadecane is 7:1, and the mixture is kept stand at 60 ℃ for 24 hours;
step 1.2, evaporating the mixture after the reaction in the step 1 to remove the solvent, and then recrystallizing, wherein the recrystallization adopts anhydrous ether to wash away unreacted monomers and solvent, so as to obtain the reactive cationic emulsifier;
step 2, preparing a pre-emulsion
Step 2.1, mixing a certain amount of a mixture of butyl acrylate, methyl methacrylate, cetyl acrylate and stearyl acrylate, the reactive cationic emulsifier prepared in the step 1 and a proper amount of deionized water to obtain a mixture, wherein the mass ratio of the mixture of butyl acrylate, methyl methacrylate, cetyl acrylate and stearyl acrylate, the reactive cationic emulsifier prepared in the step 1 and the deionized water is 130:80:7:5:175, and emulsifying the mixture by a cell crusher to obtain a pre-emulsion;
step 3, preparing the cationic polyacrylate soap-free emulsion
Step 3.1, weighing a quantitative initiator aqueous solution with the mass ratio of 46% to the pre-emulsion prepared in the step 2.1, wherein the initiator aqueous solution is prepared from azodiisobutyramidine hydrochloride and water with the mass ratio of 1:12, pouring 50% of the pre-emulsion prepared in the step 2 into a reactor with a stirrer and a condenser pipe, adding 1/3 amount of the initiator aqueous solution into the reactor, and standing and reacting for 40min at 75 ℃;
and 3.2, after the standing reaction in the step 3.1 is finished, heating to 80 ℃, respectively and simultaneously dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution into the reactor, after the dropwise adding lasts for 150min, completely dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution at the same time, after the dropwise adding is finished, carrying out heat preservation reaction for 160min, and after the heat preservation reaction is finished, cooling to room temperature to obtain the cationic polyacrylate soap-free emulsion.
Verification examples
The applicant carried out a water contact angle test on the water repellency of the fluorine-free water repellent obtained in examples 1 to 5: the 5 fluorine-free waterproofing agents prepared by the method are respectively used for carrying out waterproof finishing on the same fabric, and the same fabric is wetted by water as a reference, and the waterproof finishing process comprises the following steps: the results of the water contact angle test of the same fabric subjected to waterproof finishing by 5 fluorine-free waterproof agents are shown in table 1, wherein the test results are as follows:
table 1 water contact angle test results for finished fabrics
Generally, when the static contact angle of water to an object exceeds 90 °, the substance is hydrophobic, and when it exceeds 150 °, the fabric is superhydrophobic. As can be seen from table 1, the unfinished fabric was instantly wetted after the water drop contacted the fabric, with a contact angle of 0 °; the surfaces of the fabrics treated by the 5 fluorine-free water-proofing agents are converted from hydrophilicity to hydrophobicity, and the contact angles of the fabrics to water are all more than 130 degrees, which shows that the fabrics have good hydrophobicity after being treated by the emulsion.
Claims (5)
1. The cationic polyacrylate fluorine-free waterproof agent is characterized by comprising, by mass, 5-40% of butyl acrylate, 5-35% of methyl methacrylate, 0.5-5% of long-chain fatty acrylate ester, 0.5-4% of a reactive cationic emulsifier and 45-75% of deionized water, wherein the sum of the mass percentages of the components is 100%.
2. The preparation method of the cationic polyacrylate fluorine-free waterproof agent is characterized in that the waterproof agent comprises, by mass, 5-40% of butyl acrylate, 5-35% of methyl methacrylate, 0.5-5% of long-chain fatty alcohol acrylate, 0.5-4% of a reactive cationic emulsifier, 45-75% of deionized water, and the sum of the mass percentages of the above components is 100%;
the preparation method of the waterproof agent is implemented according to the following steps:
step 1, preparing reactive cationic emulsifier
Step 1.1, adding a certain amount of acrylate monomer containing reactive amino, bromoalkane and a polar solvent into a flask provided with a condenser tube respectively to obtain a mixture, and standing the mixture at 40-60 ℃ for reaction for 24 hours; the molar ratio of the acrylate monomer containing reactive amino groups to the bromoalkane is 1: 1-3; the polar solvent is any one of acetone, dioxane, acetonitrile and methanol, and the mass ratio of the polar solvent to the mixture of the acrylate monomer containing reactive amino and bromoalkane is 3-7: 1;
step 1.2, evaporating the mixture after the reaction in the step 1 to obtain a solvent, and recrystallizing to obtain a reactive cationic emulsifier;
step 2, preparing a pre-emulsion
Step 2.1, mixing a certain amount of butyl acrylate, methyl methacrylate, long-chain fatty alcohol acrylate, the reactive cationic emulsifier prepared in the step 1 and a proper amount of deionized water to obtain a mixture, and emulsifying the mixture by a cell crusher to obtain a pre-emulsion;
the mass ratio of the butyl acrylate, the methyl methacrylate and the long-chain aliphatic acrylate ester, the reactive emulsifier prepared in the step 1 and the deionized water is (45-130): 75-120): 6-11): 1-7): 135-175;
step 3, preparing the cationic polyacrylate soap-free emulsion
Step 3.1, weighing a quantitative initiator aqueous solution with the mass ratio of 18-46% to the pre-emulsion prepared in the step 2.1, pouring 20-50% of the pre-emulsion prepared in the step 2 into a reactor with a stirrer and a condenser pipe, adding 1/5-1/3 weighed initiator aqueous solution into the reactor, and standing and reacting at 55-75 ℃ for 20-40 min; the solute of the initiator aqueous solution is azodiisobutyl amidine hydrochloride, the solvent is water, and the mass ratio of the azodiisobutyl amidine hydrochloride to the water is 1: 8-12;
and 3.2, after the standing reaction in the step 3.1 is finished, heating to 60-80 ℃, respectively and simultaneously dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution into the reactor, after the dropwise adding lasts for 60-180 min, completely dropwise adding the rest of the pre-emulsion and the rest of the initiator aqueous solution at the same time, after the dropwise adding is finished, carrying out heat preservation reaction for 90-180 min, and after the heat preservation reaction is finished, cooling to room temperature to obtain the cationic polyacrylate soap-free emulsion.
3. The method of claim 2, wherein the reactive amino group-containing acrylate monomer in step 1.1 is any one of N, N-dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, and diethylaminoethyl methacrylate.
4. The method of claim 2, wherein the alkyl bromide in step 1.1 is any one of n-decane bromide, dodecane bromide, tetradecane bromide, hexadecane bromide and octadecane bromide.
5. A method for preparing a cationic polyacrylate fluorine-free waterproof agent according to claim 2, wherein the long-chain fatty alcohol acrylate in the step 2.1 is one or a mixture of more of lauryl acrylate, cetyl acrylate and stearyl acrylate in any proportion.
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| CN112745450B (en) * | 2020-12-29 | 2022-05-13 | 九洲生物技术（苏州）有限公司 | Preparation method of cationic fluorine-free oil-proof emulsion |
| CN112898477A (en) * | 2021-02-08 | 2021-06-04 | 浙江工业职业技术学院 | Preparation method and application of nano-silica modified soap-free fluorine-free cationic polyacrylate waterproof agent |
| CN112961271A (en) * | 2021-02-08 | 2021-06-15 | 浙江工业职业技术学院 | Preparation method and application of nano-silica modified fluoride-free cationic polyacrylate waterproof agent |
| CN115595795B (en) * | 2021-07-07 | 2024-07-26 | 佳化化学(上海)有限公司 | Non-fluorine polymer composition emulsion and preparation method and application thereof |
| CN114656586B (en) * | 2022-04-08 | 2023-03-28 | 浙江理工大学 | Composite fluoride-free polyacrylate waterproof emulsion and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165264A (en) * | 2006-10-16 | 2008-04-23 | 恒源祥（集团）有限公司 | Nano type textile fabric multifunctional finishing agent and finishing method thereof |
| CN102605650A (en) * | 2012-03-23 | 2012-07-25 | 陕西科技大学 | Polyacrylate adhesive for pigment dyeing and soap-free emulsion polymerization method thereof |
| CN103265655A (en) * | 2013-03-15 | 2013-08-28 | 北京印刷学院 | Reactive cationic polyacrylate emulsion and preparation method and application thereof |
-
2019
- 2019-09-24 CN CN201910903695.7A patent/CN110669165B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165264A (en) * | 2006-10-16 | 2008-04-23 | 恒源祥（集团）有限公司 | Nano type textile fabric multifunctional finishing agent and finishing method thereof |
| CN102605650A (en) * | 2012-03-23 | 2012-07-25 | 陕西科技大学 | Polyacrylate adhesive for pigment dyeing and soap-free emulsion polymerization method thereof |
| CN103265655A (en) * | 2013-03-15 | 2013-08-28 | 北京印刷学院 | Reactive cationic polyacrylate emulsion and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 稳定高固含量阳离子丙烯酸酯乳液的合成;何笑凡等;《涂料工业》;20120901;第42卷(第9期);第40-41页第1.1-1.3部分 * |
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