CN114736320B - Low molecular weight sodium polyacrylate aqueous solution and preparation method and application thereof - Google Patents
Low molecular weight sodium polyacrylate aqueous solution and preparation method and application thereof Download PDFInfo
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- CN114736320B CN114736320B CN202210330934.6A CN202210330934A CN114736320B CN 114736320 B CN114736320 B CN 114736320B CN 202210330934 A CN202210330934 A CN 202210330934A CN 114736320 B CN114736320 B CN 114736320B
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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
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the field of polymers, in particular to a low molecular weight sodium polyacrylate aqueous solution, a preparation method and application thereof, which are prepared by mixing isopropanol, a solvent and water, dropwise adding an initiator and an acrylic monomer, and preserving heat; adding sodium hydroxide, standing to obtain sodium polyacrylate water solution. The method provided by the invention has simple steps, a solvent which is easily soluble with isopropanol, slightly soluble with water or indissoluble and does not react with acrylic acid monomers is added during the reaction, sodium hydroxide is dropwise added to change polyacrylic acid into sodium salt in an ionic form to be dissolved in water by utilizing the salting-out effect, so that the solubility of isopropanol in water is reduced, the isopropanol is extracted into a solvent layer, the process of separating isopropanol from water is accelerated, the isopropanol is removed by a standing and liquid separation method, distillation is not needed, the time consumption is shorter, the energy consumption is less, the recycled solvent can be recycled, and finally the prepared sodium polyacrylate aqueous solution has low salt content and does not introduce a chain transfer agent with large smell or toxicity.
Description
Technical Field
The invention relates to the field of polymers, in particular to a low molecular weight sodium polyacrylate aqueous solution, a preparation method and application thereof.
Background
Acrylic polymers are an important class of water-soluble high molecular compounds, and polyacrylic acid and salts thereof have very wide application. The application of the sodium polyacrylate has close relation with the molecular weight of the sodium polyacrylate, and the sodium polyacrylate with high molecular weight is mainly used as water absorbent, flocculant and the like; sodium polyacrylate with medium molecular weight is mainly used as a thickening agent, a water-retaining agent, a viscosity stabilizer and the like; the low molecular weight sodium polyacrylate is a water-soluble polymer electrolyte, is widely used as a boiler scale preventing and inhibiting agent, a pigment dispersing agent, a chemical fiber sizing agent, a metal material quenching agent, a detergent auxiliary agent, a granular pesticide carrier and the like, and also has wide application in the aspects of printing industry, plastic industry, medicine, pharmacy, electroplating, metal recovery of metal ion waste liquid and the like.
Low molecular weight sodium polyacrylate generally refers to sodium polyacrylate below 5000 molecular weight, and chain transfer agent is added to control the molecular weight during preparation. Sodium polyacrylate, which has a molecular weight of around 1000, is typically reduced in molecular weight by the addition of mercapto compounds, salts or solvents as chain transfer agents. When a mercapto compound is used as a chain transfer agent, the control effect of molecular weight is good, but the odor is large and part of toxicity is large; when salts such as sodium bisulphite are used as chain transfer agents, the usage amount is large, so that the salt content of the product is large, the actual content of effective matters is low, and the performance is influenced; at present, a solvent is generally used as a chain transfer agent, but when the solvent is used as the chain transfer agent, the solvent is used in a large amount, desolventizing is required, a distillation or washing mode is generally adopted, the time and energy consumption are long, and the salt content in the prepared sodium polyacrylate aqueous solution is high.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the solvent is used as a chain transfer agent, the desolventizing time is long, the energy consumption is high, the salt content in the prepared sodium polyacrylate aqueous solution is high and the like in the prior art, so that the low molecular weight sodium polyacrylate aqueous solution, the preparation method and the application thereof are provided.
A method for preparing a low molecular weight sodium polyacrylate aqueous solution, which comprises the following steps:
mixing isopropanol, a solvent and water, dropwise adding an initiator and an acrylic acid monomer, and preserving heat; adding sodium hydroxide, and standing to obtain sodium polyacrylate water solution;
wherein the solvent is soluble with isopropanol, slightly soluble or insoluble with water, and does not react with the acrylic acid monomer.
Preferably, the initiator accounts for 0.2 to 0.7 percent based on the total mass of the initiator, the acrylic acid monomer and the water; the acrylic acid monomer accounts for 31-41% and the balance is water;
the isopropanol is 5-8 times of the acrylic acid monomer by mass, and the solvent is 1-2 times of the acrylic acid monomer by mass.
Preferably, the solvent comprises: at least one of n-butanol, butyl acetate and isopropyl ether.
Preferably, the initiator comprises: at least one of ammonium persulfate and potassium persulfate.
Preferably, the sodium hydroxide is prepared as an aqueous solution with a concentration of 30 to 40 wt%.
Preferably, the isopropanol, the solvent and the water are heated to 70-90 ℃ under the condition of stirring, so that the isopropanol, the solvent and the water are mixed, and an initiator and an acrylic acid monomer are dropwise added at 70-90 ℃;
optionally, the stirring speed is 300-800 rpm.
Preferably, the dripping time is 0.5-1 h;
and/or, the incubation conditions include: preserving heat for 1-3 h at 70-95 ℃;
and/or adding sodium hydroxide to a ph=6 to 8;
and/or the standing time is 5-20 min.
Preferably, the solid content of the sodium polyacrylate aqueous solution is 33-37 wt%, the salt content in the solid content is not higher than 0.5wt%, the sodium polyacrylate content is not lower than 33wt%, and the weight average molecular weight is 900-1100.
The invention also protects the application of the low molecular weight sodium polyacrylate in the fields of water treatment, spinning, daily chemicals, printing, electroplating or printing and dyeing.
The invention also protects the application of the low molecular weight sodium polyacrylate as a scale inhibitor, a pigment dispersing agent, a chemical fiber sizing agent, a metal material quenching agent, an electroplating leveling agent, an electroplating brightening agent or a detergent auxiliary agent.
The technical scheme of the invention has the following advantages:
1. the method provided by the invention has simple steps, and the solvent which is easily soluble with isopropanol, slightly soluble with water or indissoluble and does not react with acrylic acid monomers is added during the reaction, and sodium hydroxide is dropwise added to change polyacrylic acid into sodium salt in an ionic form to be dissolved in water by utilizing the salting-out effect, so that the solubility of isopropanol in water is reduced, the isopropanol is extracted into a solvent layer, the process of separating isopropanol from water is accelerated, the isopropanol is removed by a standing and liquid separation method, distillation is not needed, the time consumption is shorter, the energy consumption is less, the recovered solvent does not need to be additionally treated or taken out, the solvent can be directly recycled, the finally prepared sodium polyacrylate aqueous solution has low invalid salt content, and no chain transfer agent with large odor or toxicity is introduced, so that the obtained product is more environment-friendly and efficient.
2. The sodium polyacrylate prepared by the method has low molecular weight and narrow distribution, can be widely applied to the fields of water treatment, spinning, daily chemicals, printing or dyeing, and can be used as a leveling agent and a brightening agent in electroplating. In the electroplating process, leveling agents and brightening agents are added for obtaining flat and bright workpieces, wherein the leveling agents commonly used at present are butynediol or pyridine and quinoline compounds, and the brightening agents are toluene or allyl compounds and the like. If the sodium polyacrylate aqueous solution prepared by the method is added into the electroplating solution, the product can be selectively adsorbed on the surface of the electrode to prevent metal ions from being deposited at the protruding peak position, but is deposited at more directional valleys first, so that a flat surface is obtained; meanwhile, metal ions can be chelated and mixed in the coating, so that the crystal growth structure is changed, and the brightness of the coating is enhanced.
3. When the sodium polyacrylate aqueous solution prepared by the method is used as a scale inhibitor, the scale inhibition rate can reach 97%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic representation of blind hole filling capability;
reference numerals:
a is the thickness from the bottom of the blind hole to the copper layer on the board surface; b is the thickness from the bottom of the blind hole to the most concave part of the copper plating layer on the surface of the blind hole.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The following examples do not identify specific experimental procedures or conditions, which may be followed by procedures or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
A method for preparing a low molecular weight sodium polyacrylate aqueous solution, which comprises the following steps:
15kg of n-butanol, 75kg of isopropanol and 24.8kg of water are taken and poured into a reaction kettle; heating while stirring at 300rpm, heating to 70deg.C to mix n-butanol, isopropanol and water uniformly, slowly dropwise adding 15kg of acrylic acid monomer and 0.09kg of ammonium persulfate for 0.5h, and maintaining at 70deg.C for 1h; adding 30% sodium hydroxide aqueous solution into a reaction kettle while stirring to adjust the pH to be 7, wherein the total dosage of the sodium hydroxide aqueous solution is 27.8kg, standing for 5min, separating the product into two phases, wherein the upper layer and the lower layer are clear liquid, and opening a bottom valve to obtain a reaction product sodium polyacrylate aqueous solution.
Example 2
A method for preparing a low molecular weight sodium polyacrylate aqueous solution, which comprises the following steps:
20kg of butyl acetate, 160kg of isopropanol and 29.3kg of water are taken and poured into a reaction kettle; heating under 500rpm, stirring, heating to 80deg.C, mixing n-butanol, isopropanol and water uniformly, slowly dropwise adding 20kg of acrylic acid monomer and 0.35kg of ammonium persulfate for 0.5h, and keeping the temperature at 85deg.C for 2h; adding 30% sodium hydroxide aqueous solution into a reaction kettle while stirring to adjust the pH value to be 8, wherein the total dosage of the sodium hydroxide aqueous solution is 37.1kg, standing for 15min, separating the product into two phases, wherein the upper layer and the lower layer are clear liquid, and opening a bottom valve to obtain a reaction product sodium polyacrylate aqueous solution.
Example 3
A method for preparing a low molecular weight sodium polyacrylate aqueous solution, which comprises the following steps:
34kg of n-butanol, 100kg of isopropanol and 37.5kg of water are poured into a reaction kettle; heating under stirring at 800rpm, heating to 90deg.C to mix n-butanol, isopropanol and water uniformly, slowly dropwise adding 17kg acrylic acid monomer and 0.32kg ammonium persulfate for 1 hr, and maintaining at 95deg.C for 3 hr; adding 40% sodium hydroxide aqueous solution into a reaction kettle while stirring to adjust the pH to be 7, wherein the total dosage of the sodium hydroxide aqueous solution is 23.6kg, standing for 20min, observing that the product is divided into two phases, the upper layer and the lower layer are clear solutions, and opening a bottom valve to obtain a reaction product sodium polyacrylate aqueous solution.
Example 4
A method for preparing a low molecular weight sodium polyacrylate aqueous solution, which comprises the following steps:
20kg of isopropyl ether, 110kg of isopropanol and 29.8kg of water are taken and poured into a reaction kettle; heating under stirring at 800rpm, heating to 90deg.C to mix n-butanol, isopropanol and water uniformly, slowly dropwise adding 16kg acrylic acid monomer and 0.1kg potassium persulfate for 1 hr, and maintaining at 70deg.C for 1 hr; adding 30% sodium hydroxide aqueous solution into a reaction kettle while stirring to adjust the pH to be=6, wherein the total dosage of the sodium hydroxide aqueous solution is 20kg, standing for 20min, observing that the product is divided into two phases, the upper layer and the lower layer are clear liquid, and opening a bottom valve to obtain a reaction product sodium polyacrylate aqueous solution.
Example 5
A method for preparing a low molecular weight sodium polyacrylate aqueous solution, which comprises the following steps: 34kg of isopropyl ether, 130kg of isopropanol and 32.5kg of water are taken and poured into a reaction kettle; heating under 300rpm, stirring, heating to 90deg.C, mixing n-butanol, isopropanol and water uniformly, slowly dropwise adding 17kg of acrylic acid monomer and 0.15kg of potassium persulfate for 0.5h, and maintaining at 95deg.C for 3h; adding 40% sodium hydroxide aqueous solution into a reaction kettle while stirring to adjust the pH value to be 8, wherein the total dosage of the sodium hydroxide aqueous solution is 24kg, standing for 5min, observing that the product is divided into two phases, the upper layer and the lower layer are clear liquid, and opening a bottom valve to obtain a reaction product sodium polyacrylate aqueous solution.
Comparative example 1
A method for preparing a low molecular weight sodium polyacrylate aqueous solution, which comprises the following steps:
firstly, adding 9.00kg of acrylic acid monomer and 20L of water into a material kettle at room temperature, uniformly stirring, adding 37.7L of isopropanol and 8.10kg of potassium persulfate, and fully and uniformly stirring;
secondly, placing the tubular reactor in a constant-temperature water bath at 90 ℃, wherein the temperature of the constant-temperature water bath is controlled to be 90+/-3 ℃; the materials uniformly mixed in the first step are measured by a metering pump, and the output flow of the metering pump is regulated to 62L/h, so that the reaction time of the materials in the pipe is 3h; after cooling the output material to room temperature, 16.7kg of 30% sodium hydroxide solution was added to adjust ph=7;
and thirdly, distilling to remove isopropanol and water after the reaction is finished, washing and drying to obtain sodium polyacrylate. (mw=970, pdi=1.52, solids content 100%).
Experimental example 1:
the weight average molecular weight and distribution coefficient of examples 1 to 5 and comparative example 1 were measured by GPC test, which was performed by using the shimadzu gel permeation chromatography system: polyethylene glycol is used as a standard substance, the mobile phase is 0.1mol/L sodium nitrate, the column temperature is 40 ℃, the flow rate is 0.8mL/min, the sample injection amount is 100 mu L, the sample concentration is 2g/L, and the experimental results are shown in Table 1.
TABLE 1 detection results of average molecular weight and distribution coefficient
| Weight average molecular weight g/mol | Distribution coefficient | |
| Example 1 | 1095 | 1.30 |
| Example 2 | 981 | 1.43 |
| Example 3 | 1003 | 1.33 |
| Example 4 | 955 | 1.38 |
| Example 5 | 923 | 1.35 |
| Comparative example 1 | 970 | 1.52 |
Experimental example 2:
the solid content percentages of examples 1 to 5 and comparative example 1 were measured by the "sodium polyacrylate solid content measurement method of GB 12005.2-1989" and the percentage of effective content was obtained by calculating the percentage of salt content, and the experimental results are shown in Table 2, since the solid contents of the products in examples and comparative examples are the sum of the sodium polyacrylate content (effective content) and the ineffective salt content, the solid content (%) -ineffective salt content (%) = effective content (%), and since the ineffective salt introduced is only the initiator potassium persulfate or ammonium persulfate, and no ineffective salt was generated during the reaction or neutralization, the ineffective salt content was obtained according to the addition amount of the initiator.
In the examples: salt content = initiator mass/(acrylic monomer mass + water mass + sodium hydroxide aqueous solution mass + initiator mass) x 100%;
in the comparative example: salt content = initiator mass/(acrylic monomer mass + mass of sodium in sodium hydroxide solution + mass of initiator) x 100%.
Table 2 results of the percent solids and percent effective tests
As can be seen from Table 2, the sodium polyacrylate prepared according to the present invention has a lower ineffective salt content than the sodium polyacrylate obtained in comparative example 1.
Experimental example 3:
the scale inhibition of the sodium polyacrylate aqueous solutions prepared in examples 1 to 5 and comparative examples 1 to 2 was examined using a commercially available sodium polyacrylate scale inhibitor (eastern Xintai PAAS 210103) as comparative example 2;
the detection method comprises the following steps: the sodium polyacrylate aqueous solutions prepared in comparative examples and examples 1 to 5 were tested according to the GB/T16632-2019 scale inhibition performance measurement of water treatment agent-calcium carbonate deposition method, and the test results are shown in Table 3.
TABLE 3 scale inhibition test results
As the ion concentration in the blank experiment is less than 0.005mg/mL, the calculation of the scale inhibition performance can be omitted, and as can be seen from the table 3, compared with the scale inhibitors of comparative examples 1-2, the scale inhibition performance of the low molecular sodium polyacrylate aqueous solution prepared in examples 1-5 is more than 97%, and the scale inhibition performance is better.
Experimental example 4:
the plating effect of the plating solutions prepared in examples 1 to 5 and comparative examples 1 and 3 was examined using a commercially available plating assistant (Coke copper gloss agent of Guangdong Bigley technology Co., ltd.) as comparative example 3;
the detection method comprises the following steps: the aqueous sodium polyacrylate solutions prepared in comparative examples and examples 1 to 5 were prepared into plating solutions: 220g/L of copper sulfate pentahydrate and 60g/L of sulfuric acid, adding the sodium polyacrylate aqueous solution or the sodium polyacrylate prepared in the example or the comparative example, wherein the content of the sodium polyacrylate in the electroplating solution is 850ppm by mass of the sodium polyacrylate, and electroplating is carried out for 45 minutes at 1.8 asd.
The specification of the blind hole test board (FR-4 copper-clad plate) is that the aperture of the blind hole is 100-125 um, the thickness of the dielectric layer is 75um, and the total thickness of the copper plating layer in the hole is 4-6 um after copper deposition and flash plating.
The filling rate= (B/a) ×100%, where a is the thickness from the bottom of the blind hole to the copper layer on the surface of the board, and B is the thickness from the bottom of the blind hole to the most concave part of the copper layer on the surface of the hole, see specifically fig. 1. The values of A and B were obtained by observing 200-fold amplified sections with a metallographic microscope. The thickness of the plated layer on the cross section of the blind hole test plate after plating was measured by using a scanning electron microscope, and the specific results are shown in Table 4.
TABLE 4 electroplating test results
| Group of | Filling rate% | Coating thickness μm |
| Example 1 | 93.1 | 12.1 |
| Example 2 | 95.2 | 12.4 |
| Example 3 | 94.9 | 12.5 |
| Example 4 | 98.1 | 13.1 |
| Example 5 | 99.5 | 12.7 |
| Comparative example 1 | 88.9 | 10.1 |
| Comparative example 3 | 93.2 | 12.4 |
As can be seen from Table 4, the low molecular weight sodium polyacrylate aqueous solutions prepared in examples 1 to 5 were each 93% or more in porosity, and were each 12 μm or more in copper surface thickness, and were excellent in plating effect, as compared with the commercial product of comparative example 3.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The preparation method of the low molecular weight sodium polyacrylate aqueous solution is characterized by comprising the following steps of:
mixing isopropanol, a solvent and water, dropwise adding an initiator and an acrylic acid monomer, and preserving heat; adding sodium hydroxide, and standing to obtain sodium polyacrylate water solution;
wherein the solvent comprises: at least one of n-butanol, butyl acetate and isopropyl ether.
2. The method for producing a low molecular weight sodium polyacrylate aqueous solution according to claim 1, wherein the initiator is 0.2 to 0.7% based on the total mass of the initiator, acrylic acid monomer and water; the acrylic acid monomer accounts for 31-41% and the balance is water;
the isopropanol is 5-8 times of the acrylic acid monomer by mass, and the solvent is 1-2 times of the acrylic acid monomer by mass.
3. The method for preparing a low molecular weight sodium polyacrylate aqueous solution according to any one of claims 1 to 2, wherein the initiator comprises: at least one of ammonium persulfate and potassium persulfate.
4. The method for preparing a low molecular weight sodium polyacrylate aqueous solution according to claim 1, wherein the sodium hydroxide is formulated into an aqueous solution having a concentration of 30 to 40 wt%.
5. The method for preparing a low molecular weight aqueous sodium polyacrylate solution according to claim 1, wherein the isopropyl alcohol, the solvent and the water are heated to 70 to 90 ℃ with stirring, the isopropyl alcohol, the solvent and the water are mixed, and the initiator and the acrylic acid monomer are added dropwise at 70 to 90 ℃.
6. The method for producing an aqueous solution of low molecular weight sodium polyacrylate according to claim 5, wherein the stirring speed is 300 to 800rpm.
7. The method for producing a low molecular weight sodium polyacrylate aqueous solution according to any one of claims 1 to 2 or 4 to 6, wherein the dropping time is 0.5 to 1 hour;
and/or, the incubation conditions include: preserving heat for 1-3 h at 70-95 ℃;
and/or adding sodium hydroxide to a ph=6 to 8;
and/or the standing time is 5-20 min.
8. The low molecular weight sodium polyacrylate aqueous solution prepared by the preparation method of any one of claims 1 to 7, wherein the solid content of the sodium polyacrylate aqueous solution is 33 to 37wt%, the salt content in the solid content is not higher than 0.5wt%, the sodium polyacrylate content is not lower than 33wt%, and the weight average molecular weight is 900 to 1100.
9. Use of the aqueous low molecular weight sodium polyacrylate solution of claim 8 in the fields of water treatment, textile, daily use chemicals, printing, dyeing or electroplating.
10. Use of the low molecular weight aqueous sodium polyacrylate solution according to claim 9 as scale inhibitor, pigment dispersant, chemical fiber sizing agent, metal material quenching agent, detergent auxiliary agent, plating leveling agent or plating brightening agent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301266A (en) * | 1977-12-22 | 1981-11-17 | Basf Aktiengesellschaft | Manufacture of polymers of acrylic acid or methacrylic acid |
| JPH01190702A (en) * | 1988-01-26 | 1989-07-31 | Nikka Chem Co Ltd | Production of aqueous solution of low-mw polysodium acrylate |
| JP2008037967A (en) * | 2006-08-03 | 2008-02-21 | Toagosei Co Ltd | Manufacturing method of acrylic acid polymer |
| CN102492067A (en) * | 2011-12-01 | 2012-06-13 | 河南省科学院高新技术研究中心 | Preparation method of low-molecular-weight ammonium polyacrylate |
-
2022
- 2022-03-30 CN CN202210330934.6A patent/CN114736320B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301266A (en) * | 1977-12-22 | 1981-11-17 | Basf Aktiengesellschaft | Manufacture of polymers of acrylic acid or methacrylic acid |
| JPH01190702A (en) * | 1988-01-26 | 1989-07-31 | Nikka Chem Co Ltd | Production of aqueous solution of low-mw polysodium acrylate |
| JP2008037967A (en) * | 2006-08-03 | 2008-02-21 | Toagosei Co Ltd | Manufacturing method of acrylic acid polymer |
| CN102492067A (en) * | 2011-12-01 | 2012-06-13 | 河南省科学院高新技术研究中心 | Preparation method of low-molecular-weight ammonium polyacrylate |
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