CN109485767B - Method for synthesizing polyacrylate - Google Patents
Method for synthesizing polyacrylate Download PDFInfo
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- CN109485767B CN109485767B CN201811356716.XA CN201811356716A CN109485767B CN 109485767 B CN109485767 B CN 109485767B CN 201811356716 A CN201811356716 A CN 201811356716A CN 109485767 B CN109485767 B CN 109485767B
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- aqueous solution
- acrylic acid
- reducing agent
- polyacrylate
- oxidant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
Abstract
The invention discloses a method for synthesizing polyacrylate serving as a water treatment agent, which comprises the steps of simultaneously dripping a monomer and an initiator aqueous solution with certain concentration into a kettle to perform polymerization reaction under the stirring condition by taking a water phase as a reaction medium and taking persulfate and sodium metabisulfite oxidation-reduction systems as initiators at the temperature of 60-65 ℃, and then performing heat preservation, distillation, hydrogen peroxide decoloration and sodium hydroxide neutralization to obtain the polyacrylate. The method has the advantages of low initiator consumption, high initiation efficiency, high product purity, phosphorus-free and low-sulfur synthesized product and stable quality. The method has the advantages of simple synthesis process, easily controlled process, simple operation and easy realization of large-scale industrialization. The product can be used as water quality stabilizer, ceramic additive, pigment dispersant, drilling mud fluid loss agent, cement water reducer and other fields in industrial heat exchange equipment.
Description
Technical Field
The invention belongs to the field of polymerization reaction, and particularly relates to a method for synthesizing a water treatment agent polyacrylate.
Technical Field
The polyacrylate is one of acrylic acid fine chemical products developed at home and abroad in recent years, and the product is widely applied to the fields of water quality stabilizers, ceramic additives, pigment dispersants, drilling mud fluid loss additives, cement water reducers and the like in industrial heat exchange equipment.
The synthesis method can select solution method, suspension method and emulsion method to synthesize solution, colloid, slab rubber or powder polymer according to the consideration of the specific relative molecular mass, application function and economic angle. In the actual production, in order to realize easy control of molecular weight and stable product quality, sodium hypophosphite is mostly adopted as a reducing agent of an oxidation-reduction initiation system in the synthesis process of low-molecular-weight polyacrylates, and even in order to meet the requirements of certain application fields on the molecular weight of products, the content of phosphorus in the products can reach a certain limit value. With the discharge of phosphorus-containing wastewater, the eutrophication of water body is increasingly serious, and various countries have developed policies of limiting and prohibiting phosphorus, so that the development of a phosphorus-free polymerization process also becomes a main research direction. In recent years, researchers at home and abroad do a lot of work on the synthesis and application of polyacrylate aiming at the problem, and the U.S. BASF patent US4301266 adopts isopropanol as a chain transfer agent to synthesize polyacrylic acid under the high-temperature (higher than 120 ℃) and high-pressure conditions; preparing sodium polyacrylate with the relative molecular mass of 500-5000 by using propanol as a chain transfer agent; the kudzu red light is prepared into sodium polyacrylate with the relative molecular mass of 2000-3000 by using isopropanol as a chain transfer agent. As a substance used as a chain transfer agent, in addition to a usual substance such as isopropyl alcohol or propyl alcohol, a mercapto compound having a higher boiling point may be selected to adjust the relative molecular mass of the polymer. Generally, the relative molecular mass of a polymer is reduced along with the increase of the concentration of a chain transfer agent, the dosage of the chain transfer agent is 2-4 times of that of a polymerization monomer, the reaction condition is harsh, the chain transfer agent needs to be distilled and recovered in a later process, the energy consumption is large, and a large amount of alcohol-containing wastewater is generated; and because the separation is incomplete, the appearance of the product is always cloudy, and the performance of the product is seriously influenced. Chinese patent CN104151460A discloses a sodium polyacrylate for detergent and a preparation method thereof, wherein a non-traditional solvent adding method is adopted, sodium formate which accounts for 20-30% of the mass of acrylic acid monomers is added to replace the traditional isopropanol to serve as a characteristic molecular weight regulator, persulfate-bisulfite and the like are used as initiators, the temperature is increased to 70-90 ℃ to carry out polymerization reaction, and the amount of the initiators is 80-100% of the mass of the added monomer acrylic acid. The synthesis process has the advantages of high conversion rate, high product purity, distributed molecular weight and the like, but firstly, the molecular weight regulator sodium formate has large use amount and can not be externally steamed for realizing cyclic utilization like isopropanol, thereby increasing the manufacturing cost of the product; secondly, the activity of sodium bisulfite is higher, the utilization rate of active groups generated after decomposition is low, the dosage of the initiator is too large, and a large amount of sulfate ions can be generated after oxidation reduction, so that the product can be separated out in winter or under low-temperature collision, and the product quality is unstable.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for synthesizing polyacrylate serving as a water treatment agent, which is realized by the following steps:
the method for synthesizing the polyacrylate is characterized by comprising the following steps:
respectively preparing a reducing agent, an oxidizing agent and an acrylic acid monomer into aqueous solutions, and then subpackaging the aqueous solutions in different dropwise adding devices for later use;
adding deionized water into a reaction kettle, stirring and heating;
heating to 60-65 ℃, and dripping an oxidant, a reducing agent and an acrylic monomer into the reaction kettle;
preserving the temperature for 0.5 to 1 hour, distilling, decoloring and neutralizing to obtain the polyacrylate.
Wherein the mass percentage concentration of the reducing agent aqueous solution is 25-35%, the reducing agent is sodium metabisulfite, and the using amount of the reducing agent aqueous solution accounts for 6-15% of the total mass of the added acrylic acid monomers.
The percentage concentration of the oxidant aqueous solution is 10-20%, wherein the oxidant can be any one of sodium persulfate, potassium persulfate or ammonium persulfate, and the usage amount accounts for 0.45-1.15% of the total mass of the added acrylic monomer.
Wherein the mass ratio of the acrylic acid aqueous solution is 8-20: 1.
And (4) simultaneously dripping the acrylic acid monomer, the oxidant and the reducing agent in the step (3), and controlling the dripping speed to ensure that the reducing agent is completely dripped with the acrylic acid monomer at the same time, and the oxidant lags behind the acrylic acid monomer for 5-10 minutes.
Wherein, the decolorizing agent in the step (4) is aqueous hydrogen peroxide solution with any mass percentage concentration, and the dosage of the decolorizing agent accounts for 1-3 per mill of the total feeding amount of the system according to the hydrogen peroxide.
Wherein the viscosity-average molecular weight of the polyacrylate obtained by the method is 3000-5000, and the polyacrylate is applied to the field of water treatment.
The method comprises the steps of taking a water phase as a reaction medium, taking a persulfate and sodium metabisulfite oxidation-reduction system as an initiator, simultaneously dripping acrylic acid monomers and an initiator aqueous solution with certain concentration into a kettle under the stirring condition to carry out polymerization reaction, strictly controlling the dripping speed and the reaction temperature, controlling the molecular weight of polyacrylic acid by adjusting the polymerization environment on the premise of not using a chain transfer agent such as isopropanol, and then carrying out heat preservation, distillation, hydrogen peroxide decoloration and sodium hydroxide neutralization on low-molecular-weight polyacrylate to obtain the polyacrylate.
The invention has the beneficial effects that:
(1) the invention adopts a persulfate-sodium metabisulfite redox system, and the product does not contain phosphorus, is environment-friendly and has low cost;
(2) the monomer and the initiator are simultaneously dripped into the kettle, so that the monomer concentration of a reaction system can be controlled, and the acrylic monomer is prevented from implosing through low-temperature control; the content of inorganic sulfur in the system is reduced, and the quality stability of the product is improved;
(3) the polyacrylate obtained by synthesis has low molecular weight of 3000-5000, can be dissolved in water, and is suitable for being used as a water treatment agent;
(4) the synthesis process is simple, the operation is convenient, and the industrial production is easy to realize.
Detailed Description
To further illustrate the essence of the present invention, the description is made with reference to the specific embodiments, and it should be construed that the present invention includes, but is not limited to, the following embodiments.
Example 1
(1) 130g of sodium metabisulfite is dissolved in 303g of deionized water to prepare an aqueous solution with the concentration of 30 percent by mass, and the aqueous solution is contained in a dropping device;
(2) dissolving 4.5g of oxidant in 25.5g of deionized water, preparing a 15% aqueous solution by mass percent, and putting the aqueous solution into another drop adding device;
(3) mixing 1000g of acrylic acid and 100g of deionized water uniformly, and injecting the mixture into an acrylic acid dripping device;
(4) putting the rest 551.5g of deionized water into a kettle, starting stirring, heating to 60-65 ℃, simultaneously starting the dripping devices in the step (1), the step (2) and the step (3) and controlling the material dripping speed to finish the simultaneous dripping of the acrylic acid monomer and the reducing agent sodium metabisulfite solution, finishing the dripping of the oxidizing agent after 6 minutes, and finishing the dripping within 1.5 hours;
(5) keeping the temperature at 65 +/-2 ℃ for 1 hour, distilling, adding 11g of 25 mass percent aqueous hydrogen peroxide solution for decoloring, and adding 1096g of 32 mass percent sodium hydroxide solution for neutralization to obtain 2584g of colorless transparent polyacrylate aqueous solution with the solid content of 41.2 percent. Detecting SO in the product with viscosity average molecular weight of 4200 and undetected free monomer (calculated by AA of acrylic acid), and detecting with inductively coupled plasma spectrometer (ICP)4 2-Content of 0.203%, SO3 2-The content is 225ppm, no crystal is separated out after repeated low-temperature freeze-thaw tests of samples, and the product quality is stable.
Example 2
(1) Dissolving 106g of sodium metabisulfite in 318g of deionized water to prepare an aqueous solution with the concentration of 25 percent by mass, and putting the aqueous solution into a dripping device;
(2) dissolving 11.5g of oxidant in 52.4g of deionized water, preparing an aqueous solution with the concentration of 18 percent by mass, and putting the aqueous solution into another drop adding device;
(3) mixing 1000g of acrylic acid and 150g of deionized water uniformly, and injecting the mixture into an acrylic acid dripping device;
(4) putting the balance of 429.6g of deionized water into a kettle, starting stirring, heating to 60-65 ℃, simultaneously starting the dripping devices in the step (1), the step (2) and the step (3) and controlling the material dripping speed to finish the simultaneous dripping of the acrylic acid monomer and the reducing agent sodium metabisulfite solution, finishing the dripping of the oxidizing agent after 10 minutes, and finishing the dripping of all the oxidizing agents after 1 hour and 45 minutes;
(5) keeping the temperature at 65 +/-2 ℃ for 1 hour, distilling, adding 8g of 25 mass percent aqueous hydrogen peroxide solution for decoloring, and adding 1096g of 32 mass percent sodium hydroxide solution for neutralization to obtain 2616g of light yellow transparent polyacrylic acid aqueous salt solution with the solid content of 40.6 percent. Detecting viscosity average molecular weight of product as 3800, not detecting free monomer (based on acrylic acid AA), and performing inductively coupled plasma spectroscopySO in Instrument (ICP) detecting system4 2-Content of 0.54%, SO3 2-The content is 310ppm, no crystal is separated out after repeated low-temperature freeze-thaw tests, and the product quality is stable.
Example 3
(1) Dissolving 109g of sodium metabisulfite in 389g of deionized water to prepare an aqueous solution with the mass percentage concentration of 28 percent, and filling the aqueous solution into a dripping device;
(2) dissolving 8g of oxidant in 45.3g of deionized water, preparing a 15% aqueous solution by mass percent, and putting the aqueous solution into another drop adding device;
(3) mixing 1000g of acrylic acid and 120g of deionized water uniformly, and injecting the mixture into an acrylic acid dripping device;
(4) adding the balance of 445.7g of deionized water into a kettle, starting stirring, heating to 60-65 ℃, simultaneously starting the dripping devices in the step (1), the step (2) and the step (3) and controlling the dripping speed of the materials to ensure that the acrylic acid monomer and the reducing agent sodium metabisulfite solution are dripped simultaneously, and after the oxidant is dripped for 8 minutes, finishing the dripping within 2 hours;
(5) keeping the temperature at 65 +/-2 ℃ for 1 hour, distilling, adding 10g of 25 mass percent aqueous hydrogen peroxide solution for decoloring, and adding 1096g of 32 mass percent sodium hydroxide solution for neutralization to obtain 2701g of colorless transparent polyacrylate aqueous solution with the solid content of 40.3 percent. Detecting SO in the product with viscosity average molecular weight of 4500 and undetected free monomer (calculated by acrylic acid AA) by inductively coupled plasma spectrometer (ICP)4 2-Content of 0.41%, SO3 2-The content is 293ppm, no crystal is separated out after repeated low-temperature freeze thawing test of the sample, and the product quality is stable.
Example 4
(1) Dissolving 80g of sodium metabisulfite in 320g of deionized water to prepare an aqueous solution with the mass percentage concentration of 20 percent, and putting the aqueous solution into a dripping device;
(2) dissolving 6.5g of oxidant in 58.5g of deionized water, preparing a 10 mass percent aqueous solution, and putting the aqueous solution into another drop adding device;
(3) mixing 1000g of acrylic acid and 100g of deionized water uniformly, and injecting the mixture into an acrylic acid dripping device;
(4) adding the balance of 511.5g of deionized water into a kettle, starting stirring, heating to 60-65 ℃, simultaneously starting the dripping devices in the step (1), the step (2) and the step (3) and controlling the material dripping speed to finish the simultaneous dripping of the acrylic acid monomer and the reducing agent sodium metabisulfite solution, finishing the dripping of the oxidizing agent after 5 minutes, and finishing the dripping of all the oxidizing agents after 1.5 hours;
(5) keeping the temperature at 65 +/-2 ℃ for 1 hour, distilling, adding 8g of 25 mass percent aqueous hydrogen peroxide solution for decoloring, and adding 1096g of 32 mass percent sodium hydroxide solution for neutralization to obtain 2606g of light yellow transparent polyacrylic acid saline solution with the solid content of 41.6 percent. The viscosity average molecular weight of the product is 4800, the content of free monomer (calculated by acrylic acid AA) is 0.07 percent, and SO in the system is detected by an inductively coupled plasma spectrometer (ICP)4 2-Content of 0.29% and SO3 2- The content is 350ppm, no crystal is separated out after repeated low-temperature freeze thawing test of the sample, and the product quality is stable.
Comparative example 1
The traditional dripping temperature of the industrial polyacrylic acid, namely the reflux state of a system at 80-100 ℃, is adopted for dripping, the proportion of other materials and the operation steps are the same as those of the example 1, and the time for 3 hours and 20 minutes are taken after all the dripping is finished. Detecting SO in product with viscosity average molecular weight of 10800 and free monomer content (calculated by acrylic acid AA) of 0.29% by inductively coupled plasma spectral generator (ICP)4 2-Content of 0.29% and SO3 2-The content is 350ppm, no crystal is separated out after repeated low-temperature freeze thawing test of the sample, and the product quality is stable.
Comparative example 2
Accelerating the dropping speed, starting the dropping, simultaneously dropping the acrylic acid monomer, the reducing agent and the oxidant aqueous solution within half an hour, and finishing the dropping, wherein the rest steps are the same as the example 2, the viscosity average molecular weight of the product is detected to be 14200, the free monomer (counted by acrylic acid AA) is 0.12 percent, and SO in a system is detected by an inductively coupled plasma spectrometer (ICP)4 2-Content of 0.57% and SO3 2-The content is 430ppm, no crystal is separated out after repeated low-temperature freeze-thaw tests of samples, and the product quality is stable.
Claims (4)
1. The method for synthesizing the polyacrylate is characterized by comprising the following steps:
1) respectively preparing a reducing agent, an oxidizing agent and an acrylic acid monomer into aqueous solutions, and then subpackaging the aqueous solutions in different dropwise adding devices for later use;
2) adding deionized water into a reaction kettle, stirring and heating;
3) heating to 60-65 ℃, and dripping an oxidant, a reducing agent and an acrylic monomer into the reaction kettle; ensuring that the reducing agent and the acrylic monomer are dripped simultaneously, the oxidant lags behind the acrylic monomer for 5-10 minutes, and the dripping is completed within 1.5-2 hours;
4) preserving the heat for 0.5 to 1 hour, distilling, decoloring and neutralizing to obtain polyacrylate;
the mass percentage concentration of the reducing agent aqueous solution is 25-35%, the reducing agent is sodium metabisulfite, and the using amount of the reducing agent aqueous solution accounts for 6-15% of the total mass of the added acrylic acid monomers;
the percentage concentration of the oxidant aqueous solution is 10-20%, wherein the oxidant can be any one of sodium persulfate, potassium persulfate or ammonium persulfate, and the usage amount of the oxidant aqueous solution accounts for 0.45-1.15% of the total mass of the added acrylic acid monomer.
2. The synthesis method according to claim 1, wherein the mass ratio of the acrylic acid aqueous solution is 8-20: 1.
3. The synthesis method according to claim 1, wherein the decolorizing agent in the step (4) is aqueous hydrogen peroxide solution with any mass percentage concentration, and the dosage of the decolorizing agent is 1-3 per mill of the total dosage of the system according to hydrogen peroxide.
4. The synthesis method according to any one of claims 1 to 3, wherein the polyacrylate obtained by the method has a viscosity average molecular weight in the range of 3000 to 5000, and is applied to the field of water treatment.
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| CN201811356716.XA CN109485767B (en) | 2018-11-15 | 2018-11-15 | Method for synthesizing polyacrylate |
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| CN201811356716.XA CN109485767B (en) | 2018-11-15 | 2018-11-15 | Method for synthesizing polyacrylate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4622425A (en) * | 1979-08-24 | 1986-11-11 | Rhone-Poulenc Industries | Process for the preparation of aqueous solutions of low molecular weight polyacrylic acids or their salts |
| CN104327203A (en) * | 2014-09-22 | 2015-02-04 | 湖州超能生化有限公司 | Sodium polyacrylate preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4622425A (en) * | 1979-08-24 | 1986-11-11 | Rhone-Poulenc Industries | Process for the preparation of aqueous solutions of low molecular weight polyacrylic acids or their salts |
| CN104327203A (en) * | 2014-09-22 | 2015-02-04 | 湖州超能生化有限公司 | Sodium polyacrylate preparation method |
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