CN109929078B - High-performance metal protection emulsion and preparation method thereof - Google Patents
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Abstract
The invention relates to the technical field of metal protection, and provides a preparation method of a high-performance metal protection emulsion, which comprises the following steps: mixing and uniformly dispersing deionized water, a first emulsifier and a monomer to obtain a pre-emulsion, wherein the monomer comprises: tertiary carbonic acid glycidyl ester, urea heterocyclic monomer containing double bonds, styrene, isooctyl acrylate and methacrylic acid; uniformly mixing and dispersing water and a second emulsifier to obtain a first mixed solution; mixing part of the pre-emulsion, the first initiator and the first mixed solution to perform an initiation reaction to obtain a second mixed solution; dropwise adding the remaining pre-emulsion and the second initiator into the second mixed solution to obtain a third mixed solution; adding the second mixed solution into the third mixed solution, and then eliminating the initiator to obtain a fourth mixed solution; and adjusting the pH value of the fourth mixed solution to be alkalescent, and filtering to obtain the high-performance metal protection emulsion provided by the application. The obtained high-performance metal protection emulsion has good water resistance, alkali resistance and the like, and has good protection performance on metals.
Description
Technical Field
The invention relates to the technical field of metal protection, in particular to a high-performance metal protection emulsion and a preparation method thereof.
Background
At present, most of the existing metal protection emulsions are metal protection acrylic emulsions, and the technical scheme of the existing metal protection emulsions is to improve the resistance of the metal emulsions by means of unsaturated phosphate ester monomers, vinyl versatate (VeoVa 10), reactive emulsifiers, phosphate ester emulsifiers, ketone-hydrazine crosslinking systems, unsaturated silicon-containing monomers and the like.
The metal protection emulsion mainly has the following problems that firstly, in order to realize better salt mist resistance, an expensive unsaturated phosphate ester monomer is adopted, so that the cost is higher; secondly, the resistance of most metal emulsions is not ideal, such as water resistance, alkali resistance and the like.
In view of this, the present application is specifically made.
Disclosure of Invention
The invention provides a high-performance metal protection emulsion and a preparation method thereof, and aims to provide an emulsion for improving the problem that the existing metal protection emulsion has poor protection performance on metal.
The invention also provides a high-performance metal protection emulsion which has the advantages of good water resistance and alkali resistance.
The invention is realized by the following steps:
a method for preparing a high performance metal protection emulsion comprising:
mixing deionized water, a first emulsifier and a monomer, and uniformly dispersing to obtain a pre-emulsion, wherein the monomer comprises the following components in percentage by weight: 0.1-10% of tertiary carbonic acid glycidyl ester, 0.1-5% of urea heterocyclic monomer containing double bonds, 40-60% of styrene, 30-55% of isooctyl acrylate and 1-5% of methacrylic acid, wherein the total mass ratio of a first emulsifier to the monomers is 0.1-1: 100, the total mass ratio of deionized water to the monomers is 1: 2-3, the first emulsifier is allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate with 5-15 EO units, the tertiary carbonic acid glycidyl ester has the following structure, wherein R1 and R2 are alkyl, and the carbon atom contained in R1 + the carbon atom contained in R2 are equal to 7;
uniformly mixing and dispersing water and a second emulsifier at a temperature of 80-85 ℃ to obtain a first mixed solution, wherein the total mass ratio of the second emulsifier to the monomers is 0.1-2: 100, and the second emulsifier is allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate with EO unit number of 5-15;
mixing a part of pre-emulsion accounting for 5-10% of the total mass of the pre-emulsion, a first initiator accounting for 0.1-1% of the total mass of the monomers and the first mixed solution for initiating reaction to obtain a second mixed solution;
dropwise adding the rest pre-emulsion and a second initiator accounting for 0.1-1% of the total mass of the monomers into the second mixed solution to obtain a third mixed solution;
adding a post-elimination initiator into the third mixed solution to obtain a fourth mixed solution, wherein the post-elimination initiator comprises at least one of tert-butyl hydroperoxide and ammonium persulfate accounting for 0.1-1% of the total mass of the monomers and isoascorbic acid accounting for 0.05-0.5% of the total mass of the monomers;
and adjusting the pH value of the fourth mixed solution to 7-10, and filtering to obtain the high-performance metal protection emulsion.
A high-performance metal protection emulsion is prepared by the method.
The invention has the beneficial effects that: according to the high-performance metal protection emulsion obtained through the design, as a proper amount of tertiary carbonic acid glycidyl ester, a monomer containing a double-structure urea heterocycle, styrene and isooctyl acrylate are introduced into the preparation raw materials, the monomers are mutually cooperated and are matched with allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate with the EO unit number of 5-15, and meanwhile, the preparation process is combined with a reasonable preparation method, the prepared high-performance metal protection emulsion has excellent water resistance, acid resistance, alkali resistance, weather resistance, high glossiness and good salt fog resistance.
The high-performance metal protection emulsion obtained by the design is good in metal protection performance due to the adoption of the method.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following provides a detailed description of a high-performance metal protection emulsion and a preparation method thereof.
A method for preparing a high performance metal protection emulsion comprising:
s1, mixing and uniformly dispersing the deionized water, the first emulsifier and the monomers to obtain a pre-emulsion, wherein the monomers comprise the following components in percentage by weight: 0.1-10% of tertiary carbonic acid glycidyl ester, 0.1-5% of urea heterocyclic monomer containing double bonds, 40-60% of styrene, 30-55% of isooctyl acrylate and 1-5% of methacrylic acid, wherein the total mass ratio of a first emulsifier to the monomer is 0.1-1: 100, the total mass ratio of deionized water to the monomer is 1: 2-3, the first emulsifier is allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate with 5-15 EO units, and the tertiary carbonic acid glycidyl ester has the following structure, wherein R1 and R2 are alkyl groups, and the carbon atom contained in R1 + the carbon atom contained in R2 are equal to 7.
Specifically, the materials are prepared according to the weight percentage and the weight ratio, deionized water, a first emulsifier and the monomers in parts by weight are added into a monomer emulsifying tank, the monomer emulsifying tank is started, the stirring speed is adjusted to be 300-1000 r/min, and the pre-emulsion is obtained after dispersion for 10-30 min.
The first emulsifier is allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate with EO unit number of 5-15, and the EO unit number refers to the polyoxyethylene ether unit number. Surfactants are very useful in polymerization, but they impart to the emulsion various disadvantages such as reduced water resistance, tendency to foam during use, etc., due to their migration. The allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate serving as an emulsifier can participate in emulsion free radical polymerization due to double bonds, is grafted to a polymer structure, cannot migrate to the surface of a coating film in a film forming process, and is volatilized by NH3 after the coating film is dried, so that adverse effects on water resistance of the coating film are avoided. Therefore, the emulsifier can impart good polymerization stability and low foam generation rate to the emulsion and also impart good water resistance to the coating film, as compared with conventional emulsifiers such as sodium lauryl sulfate (K12), sodium lauryl polyoxyethylene ether sulfate (AES) and the like.
The glycidyl versatates R1 and R2 are alkyl radicals, the carbon atom contained in R1 + the carbon atom contained in R2 being equal to 7. The tertiary carbonic acid glycidyl ester is used as one of the raw materials of the emulsion, and in the process of film forming, an active epoxy group can react with carboxylic acid, hydroxyl and amino under an alkaline environment. Since the tertiary carbonic acid is a highly branched carboxylic acid containing ten carbon atoms and has a large hydrophobic side chain, ester groups can be protected from hydrolysis, and a coating film has excellent water resistance, acid resistance, alkali resistance and weather resistance. The vinyl versatate with similar structure, which contains unsaturated carbon-carbon double bonds, can be introduced into a polymer structure through free radical polymerization, but has lower polymerization activity due to the steric effect of a side group, and is not suitable to be added too much, while the glycidyl versatate introduced into the polymer structure through an epoxy group does not have the problem, and compared with the vinyl versatate with lower reaction activity, the dosage of the vinyl versatate can be flexibly adjusted according to the active groups of the resin, so that the performance is maximized.
The double bond-containing urea heterocyclic monomer is at least one of bi-building urea heterocyclic compounds. Preferably, the double bond-containing urea heterocyclic monomer in the present application includes at least one of ethylene urea ethoxy methacrylate and ethyl ethylene urea methacrylamide. The unsaturated urea heterocyclic monomer can be introduced into a polymer structure through free radical polymerization, has strong polarity and reactivity due to the special urea heterocyclic molecular structure, has higher rigidity, can generate hydrogen bonds and intermolecular force with a metal surface active group, and provides excellent adhesion and high gloss.
S2, uniformly mixing and dispersing water and a second emulsifier at a temperature of 80-85 ℃ to obtain a first mixed solution, wherein the total mass ratio of the second emulsifier to the monomers is 0.1-2: 100, and the second emulsifier is allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate with EO unit number of 5-15.
Specifically, water and the second emulsifier are added into the reaction kettle according to the proportion to obtain a first mixed solution, the amount of the water can be added according to the consistency requirement of the prepared emulsion, and the water addition amount is generally selected according to the solid content of the prepared emulsion being 30-50%. After the mixture is added into a reaction kettle, the mixture is dispersed for 5-20 min at the rotating speed of 30-80 r/min, so that water and a second emulsifier are completely mixed and uniformly dispersed.
S3, mixing a part of pre-emulsion accounting for 5-10% of the total mass of the pre-emulsion, a first initiator accounting for 0.1-1% of the total mass of the monomers and the first mixed solution to perform an initiation reaction to obtain a second mixed solution.
In each embodiment of the present invention, the first initiator and the second initiator mentioned later are preferably ammonium persulfate, and of course, in other embodiments of the present invention, the first initiator and the second initiator may also be selected from initiators such as sodium persulfate and potassium persulfate containing metal ions, which can also have an initiating effect, but ammonium persulfate may volatilize ammonia gas generated after the emulsion is formed into a film compared with the initiator containing metal ions, and does not affect the water resistance of the coating film, so that the water resistance of the coating film is better.
The first initiator and the second initiator are required to be diluted by a certain times and then are dripped in the solution when in use, and in the application, the dilution times of the first initiator and the second initiator are 50 times.
Specifically, a part of ammonium persulfate solution which accounts for 5-10% of the mass of the pre-emulsion and is diluted by 50 times is taken out of the pre-emulsion and added into a reaction kettle, the adding amount of the ammonium persulfate accounts for 0.1-1% of the total mass of the monomers, the temperature of the reaction kettle is controlled to be 80-85 ℃ after the ammonium persulfate solution is added, blue light can appear within 1-10 minutes, temperature rise can be observed, the temperature of the system is automatically raised to 86-90 ℃, and the initiation is considered to be finished when the temperature begins to fall back. And obtaining a second mixed solution after the initiation reaction is finished.
And S4, dropwise adding the residual pre-emulsion and a second initiator accounting for 0.1-1% of the total mass of the monomers into the second mixed solution to obtain a third mixed solution.
Specifically, the rest pre-emulsion and a 50-time diluted ammonium persulfate solution are added dropwise to the second mixed solution in the reaction kettle, the ammonium persulfate in the ammonium persulfate solution accounts for 0.1-1% of the total mass of the monomers, the temperature of the system in the dropwise adding process is controlled to be 85-92 ℃, dropwise adding is completed in 60-150 min, and heat preservation is performed for 20-60 min after dropwise adding is completed to obtain a third mixed solution.
And S5, adding a post-elimination initiator into the third mixed solution to obtain a fourth mixed solution, wherein the post-elimination initiator comprises at least one of tert-butyl hydroperoxide and ammonium persulfate accounting for 0.1-1% of the total mass of the monomers, and erythorbic acid accounting for 0.05-0.5% of the total mass of the monomers.
Then, the initiator is removed, and the initiator is required to be diluted by a certain time and then is dropwise added, wherein the dilution time in each embodiment of the application is 10 times.
The post-elimination initiator is a redox initiator and comprises an oxidant and a reducing agent, wherein the oxidant is at least one of tert-butyl hydroperoxide and ammonium persulfate, and the total amount of the oxidant accounts for 0.1-1% of the total mass of the monomer. The reducing agent is isoascorbic acid, and the using amount of the reducing agent accounts for 0.05-0.5% of the total mass of the monomers.
Specifically, adding the diluted post-elimination initiator into the third mixed solution in the reaction kettle, adding the diluted post-elimination initiator twice, eliminating the initiator after the first dropwise adding after the temperature of the reaction kettle is reduced to 70-80 ℃, wherein the dropwise adding time is 20-60 min, and then continuously reducing the temperature to 60-65 ℃ for the second dropwise adding, wherein the dropwise adding time is 20-60 min.
For a post-elimination system, compared with oxidants containing metal ions such as potassium persulfate and the like, tert-butyl hydroperoxide or ammonium persulfate is beneficial to improving the water resistance of a paint film; compared with reducing agents containing metal ions such as sodium formaldehyde sulfoxylate, sodium bisulfite and the like, the isoascorbic acid is also favorable for improving the water resistance of a paint film.
S6, adjusting the pH value of the fourth mixed solution to be alkalescent, and filtering to obtain the high-performance metal protection emulsion.
When the temperature in the reaction kettle is reduced to 40 ℃ or below 40 ℃, a pH regulator is dripped into the reaction kettle to regulate the pH to be alkalescent, ammonia water is selected as the pH regulator in the application, and compared with pH regulators such as sodium hydroxide, potassium hydroxide and the like, the ammonia water is neutralized and then NH is used in the film forming process3The water resistance of the paint film can not be affected after the paint is volatilized. Preferably, the concentration of the ammonia water is 10-30%. And filtering after pH adjustment to obtain the high-performance metal protection emulsion provided by the invention. After the pH adjustment is finished, a part of samples are taken out to be diluted ten times, and then the pH is measured within the range of 7-9, so that the weak alkaline requirement can be met.
The following will specifically describe the preparation method of a high-performance metal protection emulsion provided by the present invention with reference to specific examples.
Example 1
The invention provides a high-performance metal protection emulsion and a preparation method thereof.
The preparation method of the high-performance metal protection emulsion comprises the following steps:
0.1kg of glycidyl versatate was prepared, wherein R1 is an alkyl group having 1 carbon atom, R2 is an alkyl group having 6 carbon atoms, 5kg of ethyleneurea ethoxy methacrylate, 40kg of styrene, 50kg of isooctyl acrylate, 4.9kg of methacrylic acid, 0.1kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a first emulsifier, wherein the number of EO units is 15, 50kg of deionized water, 2kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a second emulsifier, wherein the number of EO units is 15, 0.1kg of ammonium persulfate as a first initiator, 0.1kg of ammonium persulfate as a second initiator, 0.15kg of post-elimination initiator, 0.1kg of t-butyl hydroperoxide as an oxidizing agent in the post-elimination initiator, and 0.05kg of erythorbic acid as a reducing agent in the post-elimination initiator. The first initiator and the second initiator are diluted by 50 times for standby, and the later-eliminated initiator is diluted by 10 times for standby.
Adding the deionized water, the first emulsifier and all the monomers (100kg) into the monomer emulsifying tank, starting the monomer emulsifying tank, adjusting the stirring speed to 300r/min, and dispersing for 30min to obtain 150.1kg of pre-emulsion.
Adding about 172kg of water and the second emulsifier with the amount into the reaction kettle, and dispersing for 20min at the rotating speed of 30r/min to ensure that the water and the second emulsifier are completely and uniformly mixed and dispersed to obtain a first mixed solution.
Taking 7.5kg (accounting for about 5 percent of the total mass of the pre-emulsion), adding a diluted first initiator into a reaction kettle, controlling the temperature of the reaction kettle to be 80 ℃ after adding, generating blue light within 1-10 minutes, observing temperature rise, automatically heating the system to 86 ℃ after the blue light is generated, and then obtaining a second mixed solution after the initiation reaction is finished after the temperature begins to be reduced.
And dropwise adding the rest pre-emulsion and the diluted ammonium persulfate of the second initiator into the second mixed solution in the reaction kettle, controlling the temperature of the system in the dropwise adding process to be 85 ℃, completing dropwise adding within 150min, and preserving the temperature for 60min after completing dropwise adding to obtain a third mixed solution.
And adding the diluted post-elimination initiator into the third mixed solution in the reaction kettle, wherein the post-elimination initiator is added in two times on average, the initiator is eliminated after the first dropwise adding after the temperature of the reaction kettle is reduced to 80 ℃, the dropwise adding time is 20min, and then the second dropwise adding is carried out when the temperature is continuously reduced to 65 ℃, and the dropwise adding time is 60 min.
And when the temperature in the reaction kettle is reduced to 40 ℃, dropwise adding ammonia water with the mass concentration of 30%, and adjusting the pH to 7-10 to obtain the high-performance metal protection emulsion. After the high-performance metal protection emulsion is prepared, a sample is diluted by 10 times, the pH value is 7.9, and the solid content of the prepared high-performance metal protection emulsion is about 30 percent.
Example 2
The invention provides a high-performance metal protection emulsion and a preparation method thereof.
The preparation method of the high-performance metal protection emulsion comprises the following steps:
10kg of glycidyl versatate were prepared, wherein R1 is an alkyl group having 1 carbon atom, R2 is an alkyl group having 6 carbon atoms, 0.1kg of ethyleneurea ethoxy methacrylate, 54.9kg of styrene, 30kg of isooctyl acrylate, 5kg of methacrylic acid, 1kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a first emulsifier, wherein the number of EO units is 15, 33.3kg of deionized water, 0.1kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a second emulsifier, wherein the number of EO units is 15, 1kg of ammonium persulfate as a first initiator, 1kg of ammonium persulfate as a second initiator, 1.5kg of post-elimination initiator, wherein 1kg of t-butyl hydroperoxide as an oxidizing agent in the post-elimination initiator, and 0.5kg of erythorbic acid as a reducing agent in the post-elimination initiator. The first initiator and the second initiator are diluted by 50 times for standby, and the later-eliminated initiator is diluted by 10 times for standby.
Adding the deionized water, the first emulsifier and all the monomers (100kg) into the monomer emulsifying tank, starting the monomer emulsifying tank, adjusting the stirring speed to 1000r/min, and dispersing for 10min to obtain 134.3kg of pre-emulsion.
Adding 257kg of water and the second emulsifier with the amount into the reaction kettle, and dispersing for 5min at the rotating speed of 80r/min to ensure that the water and the second emulsifier are completely and uniformly mixed and dispersed to obtain a first mixed solution.
Taking 13.43kg (accounting for about 10 percent of the total mass of the pre-emulsion), adding the diluted first initiator into a reaction kettle, controlling the temperature of the reaction kettle to be 85 ℃ after the diluted first initiator is added, enabling blue light to appear within 1-10 minutes, observing temperature rise, automatically heating the system to 90 ℃ after the blue light appears, and then obtaining a second mixed solution after the initiation reaction is finished after the temperature begins to decrease.
And dropwise adding the rest pre-emulsion and the diluted second initiator into the second mixed solution in the reaction kettle, controlling the temperature of a dropwise adding process system to be 92 ℃, dropwise adding the pre-emulsion and the diluted second initiator for 60min, and preserving the temperature for 20min after dropwise adding to obtain a third mixed solution.
And adding the diluted post-elimination initiator into the third mixed solution in the reaction kettle, wherein the post-elimination initiator is added in two times on average, the initiator is eliminated after the first dropwise adding after the temperature of the reaction kettle is reduced to 70 ℃, the dropwise adding time is 60min, and then the temperature is continuously reduced to 60 ℃, the second dropwise adding is carried out, and the dropwise adding time is 20 min.
And when the temperature in the reaction kettle is reduced to 35 ℃, dropwise adding ammonia water with the mass concentration of 10%, and adjusting the pH to 7-10 to obtain the high-performance metal protection emulsion. After the high-performance metal protection emulsion is prepared, a sample is diluted by 10 times, the pH value is measured to be 8.2, and the solid content of the prepared high-performance metal protection emulsion is measured to be about 20%.
Example 3
The invention provides a high-performance metal protection emulsion and a preparation method thereof.
The preparation method of the high-performance metal protection emulsion comprises the following steps:
0.5kg of glycidyl versatate was prepared, wherein R1 is an alkyl group having 3 carbon atoms, R2 is an alkyl group having 4 carbon atoms, 2kg of ethyleneurea ethoxy methacrylate, 60kg of styrene, 36.5kg of isooctyl acrylate, 1kg of methacrylic acid, 0.2kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a first emulsifier, wherein the number of EO units is 7, 40kg of deionized water, 2kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a second emulsifier, wherein the number of EO units is 7, 0.2kg of ammonium persulfate as a first initiator, 0.2kg of ammonium persulfate as a second initiator, 0.3kg of post-elimination initiator, 0.2kg of t-butyl hydroperoxide as an oxidizing agent in the post-elimination initiator, and 0.1kg of erythorbic acid as a reducing agent in the post-elimination initiator. The first initiator and the second initiator are diluted by 50 times for standby, and the later-eliminated initiator is diluted by 10 times for standby.
Adding the deionized water, the first emulsifier and all the monomers (100kg) into the monomer emulsifying tank, starting the monomer emulsifying tank, adjusting the stirring speed to 800r/min, and dispersing for 20min to obtain 140.2kg of pre-emulsion.
Adding about 37kg of water and the second emulsifier with the amount into the reaction kettle, and dispersing for 20min at the rotating speed of 50r/min to ensure that the water and the second emulsifier are completely and uniformly mixed and dispersed to obtain a first mixed solution.
Taking 11.22kg (accounting for about 8 percent of the total mass of the pre-emulsion), adding the diluted first initiator into a reaction kettle, controlling the temperature of the reaction kettle to be 82 ℃ after the diluted first initiator is added, generating blue light within 1-10 minutes, observing temperature rise, automatically heating the system to 88 ℃ after the blue light is generated, and then obtaining a second mixed solution after the initiation reaction is finished after the temperature begins to be reduced.
And (3) dropwise adding the rest pre-emulsion and the diluted second initiator into the second mixed solution in the reaction kettle, controlling the temperature of the dropwise adding process system to be 88 ℃, dropwise adding the pre-emulsion for 100min, and preserving the temperature for 30min after dropwise adding to obtain a third mixed solution.
And adding the diluted post-elimination initiator into the third mixed solution in the reaction kettle, uniformly adding the post-elimination initiator twice, dropwise adding the post-elimination initiator for 30min after the temperature of the reaction kettle is reduced to 75 ℃ for the first time, and then dropwise adding the post-elimination initiator for the second time when the temperature is continuously reduced to 62 ℃, wherein the dropwise adding time is 30 min.
And when the temperature in the reaction kettle is reduced to 30 ℃, dropwise adding ammonia water with the mass concentration of 20%, and adjusting the pH to 7-10 to obtain the high-performance metal protection emulsion. After the high-performance metal protection emulsion is prepared, a sample is diluted by 10 times, the pH value is measured to be 8.8, and the solid content of the prepared high-performance metal protection emulsion is measured to be about 50%.
Example 4
The invention provides a high-performance metal protection emulsion and a preparation method thereof.
The preparation method of the high-performance metal protection emulsion comprises the following steps:
2kg of glycidyl versatate were prepared, wherein R1 is an alkyl group having 3 carbon atoms, R2 is an alkyl group having 4 carbon atoms, 1kg of ethyleneurea ethoxy methacrylate, 50kg of styrene, 45kg of isooctyl acrylate, 3kg of methacrylic acid, 0.5kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a first emulsifier, wherein the number of EO units is 10, 40kg of deionized water, 1.5kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a second emulsifier, wherein the number of EO units is 10, 0.5kg of ammonium persulfate as a first initiator, 0.5kg of ammonium persulfate as a second initiator, 0.75kg of post-elimination initiator, 0.5kg of t-butyl hydroperoxide as an oxidizing agent in the post-elimination initiator, and 0.25kg of erythorbic acid as a reducing agent in the post-elimination initiator. The first initiator and the second initiator are diluted by 50 times for standby, and the later-eliminated initiator is diluted by 10 times for standby.
Adding the deionized water, the first emulsifier and all the monomers (100kg) into the monomer emulsifying tank, starting the monomer emulsifying tank, adjusting the stirring speed to 900r/min, and dispersing for 25min to obtain 140.5kg of pre-emulsion.
Adding about 52.5kg of water and the second emulsifier with the amount into the reaction kettle, and dispersing for 15min at the rotating speed of 70r/min to ensure that the water and the second emulsifier are completely and uniformly mixed and dispersed to obtain a first mixed solution.
Taking 8.43kg (accounting for about 6 percent of the total mass of the pre-emulsion), adding the diluted first initiator into a reaction kettle, controlling the temperature of the reaction kettle to be 84 ℃ after the diluted first initiator is added, enabling blue light to appear within 1-10 minutes, observing temperature rise, automatically heating the system to 87 ℃ after the blue light appears, and then obtaining a second mixed solution after the initiation reaction is finished after the temperature begins to decrease.
And (3) dropwise adding the rest pre-emulsion and the diluted second initiator into the second mixed solution in the reaction kettle, controlling the temperature of the dropwise adding process system to be 90 ℃, completing dropwise adding for 120min, and preserving the temperature for 40min after completing dropwise adding to obtain a third mixed solution.
And adding the diluted post-elimination initiator into the third mixed solution in the reaction kettle, wherein the post-elimination initiator is added in two times on average, the initiator is eliminated after the first dropwise adding after the temperature of the reaction kettle is reduced to 78 ℃, the dropwise adding time is 40min, and then the temperature is continuously reduced to 64 ℃, and the second dropwise adding is carried out, wherein the dropwise adding time is 50 min.
And when the temperature in the reaction kettle is reduced to 30 ℃, dropwise adding ammonia water with the mass concentration of 15%, and adjusting the pH to 7-10 to obtain the high-performance metal protection emulsion. After the high-performance metal protection emulsion is prepared, a sample is diluted by 10 times, the pH value is measured to be 9, and the solid content of the prepared high-performance metal protection emulsion is measured to be about 40%.
Example 5
The invention provides a high-performance metal protection emulsion and a preparation method thereof.
The preparation method of the high-performance metal protection emulsion comprises the following steps:
5kg of glycidyl versatate were prepared, wherein R1 is an alkyl group having 3 carbon atoms, R2 is an alkyl group having 4 carbon atoms, 4kg of ethyleneurea ethoxy methacrylate, 45kg of styrene, 42kg of isooctyl acrylate, 4kg of methacrylic acid, 0.8kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a first emulsifier, wherein the number of EO units is 12, 40kg of deionized water, 1.6kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a second emulsifier, wherein the number of EO units is 12, 0.8kg of ammonium persulfate as a first initiator, 0.8kg of ammonium persulfate as a second initiator, 1.2kg of post-elimination initiator, 0.8kg of t-butyl hydroperoxide as an oxidizing agent in the post-elimination initiator, and 0.4kg of erythorbic acid as a reducing agent in the post-elimination initiator. The first initiator and the second initiator are diluted by 50 times for standby, and the later-eliminated initiator is diluted by 10 times for standby.
Adding the deionized water, the first emulsifier and all the monomers (100kg) into the monomer emulsifying tank, starting the monomer emulsifying tank, adjusting the stirring speed to 900r/min, and dispersing for 25min to obtain 140.8kg of pre-emulsion.
Adding about 53.7kg of water and the second emulsifier with the amount into the reaction kettle, and dispersing for 15min at the rotating speed of 70r/min to ensure that the water and the second emulsifier are completely and uniformly mixed and dispersed to obtain a first mixed solution.
Taking 12.67kg (accounting for about 9 percent of the total mass of the pre-emulsion) of a part of the pre-emulsion, adding the diluted first initiator, controlling the temperature of the reaction kettle to be 84 ℃, generating blue light within 1-10 minutes, observing temperature rise, automatically heating the system to 87 ℃ after the blue light is generated, and then reducing the temperature to obtain a second mixed solution after the initiation reaction is finished.
And (3) dropwise adding the rest pre-emulsion and the diluted second initiator into the second mixed solution in the reaction kettle, controlling the temperature of the dropwise adding process system to be 90 ℃, completing dropwise adding for 120min, and preserving the temperature for 40min after completing dropwise adding to obtain a third mixed solution.
And adding the diluted post-elimination initiator into the third mixed solution in the reaction kettle, wherein the post-elimination initiator is added in two times on average, the initiator is eliminated after the first dropwise adding after the temperature of the reaction kettle is reduced to 78 ℃, the dropwise adding time is 40min, and then the temperature is continuously reduced to 64 ℃, and the second dropwise adding is carried out, wherein the dropwise adding time is 50 min.
When the temperature in the reaction kettle is reduced to 30 ℃, ammonia water with the mass concentration of 15% is dripped into the reaction kettle, the pH is adjusted to 7-10 to obtain 7.5, and the solid content of the high-performance metal protection emulsion is measured to be about 35%.
Example 6
The invention provides a high-performance metal protection emulsion and a preparation method thereof.
The preparation method of the high-performance metal protection emulsion comprises the following steps:
8kg of glycidyl versatate were prepared, wherein R1 is an alkyl group having 3 carbon atoms, R2 is an alkyl group having 4 carbon atoms, 0.8kg of ethyleneurea ethoxy methacrylate, 55kg of styrene, 34.7kg of isooctyl acrylate, 1.5kg of methacrylic acid, 0.9kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a first emulsifier, wherein the number of EO units was 14, 40kg of deionized water, 1.5kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a second emulsifier, wherein the number of EO units was 12, 0.9kg of ammonium persulfate as a first initiator, 0.9kg of ammonium persulfate as a second initiator, 1.35kg of post-elimination initiator, wherein 0.9kg of t-butyl hydroperoxide as an oxidizing agent in the post-elimination initiator, and 0.045kg of erythorbic acid as a reducing agent in the post-elimination initiator. The first initiator and the second initiator are diluted by 50 times for standby, and the later-eliminated initiator is diluted by 10 times for standby.
Adding the deionized water, the first emulsifier and all the monomers (100kg) into the monomer emulsifying tank, starting the monomer emulsifying tank, adjusting the stirring speed to 900r/min, and dispersing for 25min to obtain 140.9kg of pre-emulsion.
Adding 156.5kg of water and the second emulsifier with the amount into the reaction kettle, and dispersing for 15min at the rotating speed of 70r/min to ensure that the water and the second emulsifier are completely and uniformly mixed and dispersed to obtain a first mixed solution.
And (3) taking 7kg (accounting for about 5 percent of the total mass of the pre-emulsion), adding the diluted first initiator into the reaction kettle, controlling the temperature of the reaction kettle to be 84 ℃ after the diluted first initiator is added, enabling blue light to appear within 1-10 minutes, observing temperature rise, automatically heating the system to 87 ℃ after the blue light appears, and then obtaining a second mixed solution after the initiation reaction is finished after the temperature begins to decrease.
And (3) dropwise adding the rest pre-emulsion and the diluted second initiator into the second mixed solution in the reaction kettle, controlling the temperature of the dropwise adding process system to be 90 ℃, completing dropwise adding for 120min, and preserving the temperature for 40min after completing dropwise adding to obtain a third mixed solution.
And adding the diluted post-elimination initiator into the third mixed solution in the reaction kettle, wherein the post-elimination initiator is added in two times on average, the initiator is eliminated after the first dropwise adding after the temperature of the reaction kettle is reduced to 78 ℃, the dropwise adding time is 40min, and then the temperature is continuously reduced to 64 ℃, and the second dropwise adding is carried out, wherein the dropwise adding time is 50 min.
When the temperature in the reaction kettle is reduced to 30 ℃, ammonia water with the mass concentration of 15% is dripped into the reaction kettle, the pH is adjusted to 7-10 to obtain 7.5, and the solid content of the high-performance metal protection emulsion is measured to be about 25%.
Example 7
The invention provides a high-performance metal protection emulsion and a preparation method thereof.
The preparation method of the high-performance metal protection emulsion comprises the following steps:
0.8kg of glycidyl versatate was prepared, wherein R1 is an alkyl group having 3 carbon atoms, R2 is an alkyl group having 4 carbon atoms, 0.5kg of ethyleneurea ethoxy methacrylate, 46.7kg of styrene, 50kg of isooctyl acrylate, 2kg of methacrylic acid, 0.5kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a first emulsifier, wherein the number of EO units is 6, 40kg of deionized water, 1kg of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate salt as a second emulsifier, wherein the number of EO units is 6, 0.5kg of ammonium persulfate as a first initiator, 0.5kg of ammonium persulfate as a second initiator, 0.75kg of post-elimination initiator, wherein 0.5kg of t-butyl hydroperoxide as an oxidizing agent in the post-elimination initiator, and 0.25kg of erythorbic acid as a reducing agent in the post-elimination initiator. The first initiator and the second initiator are diluted by 50 times for standby, and the later-eliminated initiator is diluted by 10 times for standby.
Adding the deionized water, the first emulsifier and all the monomers (100kg) into the monomer emulsifying tank, starting the monomer emulsifying tank, adjusting the stirring speed to 900r/min, and dispersing for 25min to obtain 140.5kg of pre-emulsion.
Adding about 24.7kg of water and the second emulsifier with the amount into the reaction kettle, and dispersing for 15min at the rotating speed of 70r/min to ensure that the water and the second emulsifier are completely and uniformly mixed and dispersed to obtain a first mixed solution.
Taking 14.05kg (accounting for about 10 percent of the total mass of the pre-emulsion) of a part of the pre-emulsion, adding the diluted first initiator into a reaction kettle, controlling the temperature of the reaction kettle to be 84 ℃ after the diluted first initiator is added, generating blue light within 1-10 minutes, observing temperature rise, automatically heating the system to 87 ℃ after the blue light is generated, and then obtaining a second mixed solution after the initiation reaction is finished after the temperature begins to be reduced.
And (3) dropwise adding the rest pre-emulsion and the diluted second initiator into the second mixed solution in the reaction kettle, controlling the temperature of the dropwise adding process system to be 90 ℃, completing dropwise adding for 120min, and preserving the temperature for 40min after completing dropwise adding to obtain a third mixed solution.
And adding the diluted post-elimination initiator into the third mixed solution in the reaction kettle, wherein the post-elimination initiator is added in two times on average, the initiator is eliminated after the first dropwise adding after the temperature of the reaction kettle is reduced to 78 ℃, the dropwise adding time is 40min, and then the temperature is continuously reduced to 64 ℃, and the second dropwise adding is carried out, wherein the dropwise adding time is 50 min.
When the temperature in the reaction kettle is reduced to 30 ℃, ammonia water with the mass concentration of 18% is dripped into the reaction kettle, the pH is adjusted to 7-10 to obtain 7.5, and the solid content of the high-performance metal protection emulsion is measured to be about 45%.
Examples of the experiments
The properties of the high performance metal protection emulsions prepared according to the examples of the present invention were determined and reported in table 1. The product test refers to chemical standard HG/T4758-.
TABLE 1 Properties of the high Performance Metal protective emulsions provided in the examples
As can be seen from Table 1, the high-performance metal protection emulsion provided by the embodiments of the invention has good glossiness and water resistance exceeding 240H, and is alkali-resistant exceeding 168H when placed in an NaOH solution with a mass concentration of 10%, and is placed in H with a mass concentration of 10%2SO4In the environment of the solution, the acid resistance is over 240 hours, the medium salt fog resistance is over 240 hours, and the weather resistance is over 500 hours. Therefore, the high-performance metal protection emulsion provided by the invention has excellent water resistance, acid resistance, alkali resistance, weather resistance, high glossiness and good salt fog resistance.
In conclusion, according to the preparation method of the high-performance metal protection emulsion provided by the invention, as a proper amount of tertiary carbonic acid glycidyl ester, a monomer containing a double-structure urea heterocycle, styrene and isooctyl acrylate are introduced into the preparation raw materials, the monomers are mutually cooperated and act with allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate with the EO unit number of 5-15, and the preparation process is combined with a reasonable preparation method, the prepared high-performance metal protection emulsion has excellent water resistance, acid resistance, alkali resistance, weather resistance, high glossiness and good salt fog resistance.
The high-performance metal protection emulsion provided by the invention has excellent water resistance, acid resistance, alkali resistance, weather resistance, high glossiness and good salt fog resistance because of being prepared by the method provided by the invention.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall be included in the protection of the present invention.
Claims (12)
1. A preparation method of a high-performance metal protection emulsion is characterized by comprising the following steps:
mixing and uniformly dispersing deionized water, a first emulsifier and a monomer to obtain a pre-emulsion, wherein the monomer comprises the following components in percentage by weight: 0.1-10% of tertiary carbonic acid glycidyl ester, 0.1-5% of double bond-containing urea heterocyclic monomer, 40-60% of styrene, 30-55% of isooctyl acrylate and 1-5% of methacrylic acid, wherein the ratio of the total mass of the first emulsifier to the total mass of the monomers is 0.1-1: 100, the ratio of deionized water to the total mass of the monomers is 1: 2-3, the double bond-containing urea heterocyclic monomer is at least one selected from ethylene urea ethoxy methacrylate and ethyl ethylene urea methacrylamide, the first emulsifier is allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate with 5-15 EO units, and the tertiary carbonic acid glycidyl ester has the following structure, wherein R1 and R2 are alkyl groups, and the carbon atom contained in R1 + the carbon atom contained in R2 is equal to 7;
uniformly mixing and dispersing water and a second emulsifier at a temperature of 80-85 ℃ to obtain a first mixed solution, wherein the total mass ratio of the second emulsifier to the monomers is 0.1-2: 100, and the second emulsifier is allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate with EO unit number of 5-15;
mixing a part of pre-emulsion accounting for 5-10% of the total mass of the pre-emulsion, a first initiator accounting for 0.1-1% of the total mass of the monomers and the first mixed solution to perform an initiation reaction to obtain a second mixed solution;
dropwise adding the rest pre-emulsion and a second initiator accounting for 0.1-1% of the total mass of the monomers into the second mixed solution to obtain a third mixed solution;
adding a post-elimination initiator into the third mixed solution to obtain a fourth mixed solution, wherein the post-elimination initiator comprises at least one of tert-butyl hydroperoxide and ammonium persulfate accounting for 0.1-1% of the total mass of the monomers, and erythorbic acid accounting for 0.05-0.5% of the total mass of the monomers;
and adjusting the pH value of the fourth mixed solution to be alkalescent, and filtering to obtain the high-performance metal protection emulsion.
2. The method for preparing a high-performance metal protection emulsion according to claim 1, wherein the first initiator and the second initiator are ammonium persulfate.
3. The method for preparing the high-performance metal protective emulsion according to claim 1, wherein the step of uniformly mixing and dispersing the water and the second emulsifier is to disperse the mixture for 5 to 20min at a stirring speed of 30 to 80 r/min.
4. The method for preparing the high-performance metal protection emulsion according to claim 1, wherein the temperature is controlled to be 80-85 ℃ when the partial pre-emulsion, the first initiator and the first mixed solution are mixed, the system temperature automatically rises to 86-90 ℃ after blue light appears, and the initiation reaction is considered to be finished when the temperature begins to drop.
5. The method for preparing the high-performance metal protection emulsion according to claim 1, wherein the temperature of the system in the dripping process is controlled to be 85-92 ℃ when the residual pre-emulsion and the second initiator are dripped, the dripping is finished within 60-150 min, and the temperature is kept for 20-60 min after the dripping is finished.
6. The method for preparing a high-performance metal protection emulsion according to claim 1, wherein the step of adding the post-elimination initiator to the third mixed solution is to drop the third mixed solution after the system temperature is reduced to 60-80 ℃.
7. The method for preparing the high-performance metal protection emulsion according to claim 6, wherein the step of adding the post-elimination initiator to the third mixed solution is to add the post-elimination initiator in two times, wherein the first addition is to drop the post-elimination initiator after the temperature is reduced to 70-80 ℃ for 20-60 min, and then to drop the post-elimination initiator for a second time when the temperature is continuously reduced to 60-65 ℃, and the dropping time is 20-60 min.
8. The method for preparing the high-performance metal protection emulsion according to claim 1, wherein the deionized water, the first emulsifier and the monomer are mixed and uniformly dispersed to obtain a pre-emulsion, and the deionized water, the first emulsifier and the monomer are mixed and then dispersed for 10-30 min at a stirring speed of 300-1000 r/min.
9. The method of claim 1, wherein the fourth mixture is further subjected to pH adjustment when the temperature is reduced to 40 ℃ or below 40 ℃.
10. The method of claim 9, wherein the pH adjustment is performed with ammonia.
11. The method for preparing the high-performance metal protection emulsion according to claim 10, wherein the mass concentration of the ammonia water is 10-30%.
12. A high performance metal protection emulsion prepared by the method of preparing a high performance metal protection emulsion according to any one of claims 1 to 11.
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