CN110724223B - Process method for preparing thickening agent by using ethoxylated bisphenol A diacrylate wastewater - Google Patents
Process method for preparing thickening agent by using ethoxylated bisphenol A diacrylate wastewater Download PDFInfo
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- CN110724223B CN110724223B CN201910852455.9A CN201910852455A CN110724223B CN 110724223 B CN110724223 B CN 110724223B CN 201910852455 A CN201910852455 A CN 201910852455A CN 110724223 B CN110724223 B CN 110724223B
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- ethoxylated bisphenol
- wastewater
- diacrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention discloses a process method for preparing a thickening agent by using ethoxylated bisphenol A diacrylate wastewater, which takes the wastewater for synthesizing the ethoxylated bisphenol A diacrylate as a raw material, and carries out free radical polymerization on the mixed solution of the wastewater, styrene, diallyl terephthalate and acrylamide to prepare the thickening agent.
Description
Technical Field
The invention relates to the field of chemical waste liquid treatment, in particular to a process method for preparing a thickening agent by using ethoxylated bisphenol A diacrylate wastewater.
Background
The high shearing force can reduce the consistency of the color paste in the printing process, and a thickening agent is needed to improve the viscosity of the system, so that the system has good rheological property, and the dye and the fiber can be better combined together. The properties of the thickener determine the properties of the printing paste and directly influence the performances of the printed product, such as color vividness, pattern definition, hand feeling and the like. Therefore, during printing, screening of the thickener which is stable, safe, applicable and high in cost performance is important.
In the process of preparing ethoxylated bisphenol A diacrylate by using acrylic acid and ethoxylated bisphenol A, waste liquid containing acrylic acid and its ester is generated, and the waste liquid is extremely difficult to treat. The existing methods for treating acrylic acid and ester wastewater mainly comprise an incineration method, a wet catalytic oxidation method, a biological method and the like. The treatment method commonly adopted at home and abroad adopts an incineration method, as the waste water can not be directly combusted, heavy oil needs to be added for combustion supporting, the treatment cost per ton is high, if the waste water is not treated in time, the waste liquid can be automatically exploded to generate a large amount of solid waste, the treatment cost is higher, and the secondary pollution caused by the release of dioxin into the atmosphere can be caused; although the catalytic oxidation method can effectively decompose pollutants, the key point is that the catalyst has strong specificity and higher limitation on water inlet conditions, only a few acrylic acid manufacturers adopt the method at present, and in addition, the catalytic wet oxidation method for treating the wastewater needs high-temperature and high-pressure conditions and has potential safety hazards. The anaerobic method, the aerobic method, the ion exchange fiber method and the like of the method also process theoretical research stages, and a great number of technical problems can not be overcome effectively and cannot be popularized. Therefore, the reasonable utilization of the waste liquid is beneficial to realizing the resource saving and the reduction of the waste water treatment cost. It is observed that acrylic acid and its ester are important organic synthetic raw materials besides being used as synthetic ester monomer, and can participate in the synthesis of thickening agent.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a process method for preparing a thickening agent by using ethoxylated bisphenol A diacrylate wastewater.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: a process method for preparing a thickening agent by using ethoxylated bisphenol A diacrylate wastewater comprises the following steps:
feeding waste water containing acrylic acid into a reactor, adding styrene, diallyl terephthalate and acrylamide to obtain a mixed solution, and carrying out free radical copolymerization;
replacing a gas phase part in the reactor with nitrogen, and heating the mixed solution to 75-85 ℃;
adding a sodium persulfate aqueous solution into the reactor for multiple times at regular time, and controlling the mixed solution to be maintained at 75-85 ℃;
and after the mixed solution is subjected to radical co-coalescence, cooling the mixed solution, and adding a sodium hydroxide aqueous solution and water to obtain the thickening agent.
Preferably, the process for producing the wastewater comprises the following steps:
vacuumizing monomer acrylic acid, filling the monomer acrylic acid into a dripping groove, and pumping ethoxylated bisphenol A into a reaction kettle from a tank area;
BHT and p-hydroxyanisole are added into the reaction kettle;
heating the reaction kettle to 110-140 ℃;
continuously dripping acrylic monomers into the dripping tank, adding a catalyst p-toluenesulfonic acid, and carrying out normal pressure esterification reaction;
and after the reaction is finished, cooling the reaction kettle, adding a sodium carbonate aqueous solution with the concentration of 5%, stirring for 30 minutes, standing for layering, and separating the wastewater containing the unreacted acrylic acid monomer to obtain the wastewater.
Preferably, the wastewater comprises 30% of acrylic acid, 2% -4% of ethoxylated bisphenol A diacrylate, 0.5-1% of ethoxylated bisphenol A and p-toluenesulfonic acid, antioxidant BHT and polymerization inhibitor p-hydroxyanisole.
Preferably, the weight parts of the wastewater, the styrene, the diallyl terephthalate and the acrylamide are 10-30 parts, 15-35 parts and 25-50 parts, respectively.
Preferably, said step of "adding an aqueous solution of sodium persulfate to said reactor at a plurality of times with timing" comprises: 5-10 parts of aqueous sodium persulfate solution is added into the reactor in a timing manner for a plurality of times.
Preferably, the weight part of the sodium hydroxide aqueous solution is 10 to 20 parts.
Preferably, p-hydroxyanisole as a polymerization inhibitor is added into the reactor.
Due to the application of the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the method has the advantages that the synthesized ethoxylated bisphenol A diacrylate wastewater is used as a raw material, monomer acrylic acid in the wastewater is recycled, the thickener is obtained through preparation, the process flow is complete, the preparation method is simple, the raw material is low in price and easy to operate, the final reaction liquid is directly used as a product output to change waste into valuable, the problems of resource waste and new pollution during wastewater treatment are solved, on the other hand, deep resource utilization and near zero emission of the wastewater are realized, new industrial output is created, and the prepared thickener has reliable performance compared with the existing thickeners in the market, even has part of parameters slightly better than similar products, so that the thickener extracted from the wastewater also has good market competitiveness.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples:
an embodiment of the invention provides a process method for preparing a thickening agent by using ethoxylated bisphenol A diacrylate wastewater, which comprises the following steps:
feeding acrylic acid-containing wastewater into a reactor, adding styrene, diallyl terephthalate and acrylamide to obtain a mixed solution, and carrying out free radical copolymerization;
replacing a gas phase part in the reactor with nitrogen, and heating the mixed solution to 75-85 ℃;
adding a sodium persulfate aqueous solution into the reactor for multiple times at regular time, and controlling the mixed solution to be maintained at 75-85 ℃;
and after the mixed solution is subjected to radical co-coalescence, cooling the mixed solution, adding a sodium hydroxide aqueous solution and water, and adjusting the pH value and the concentration of a reaction solution to obtain the thickening agent. The main technical and performance indexes of the obtained product are as follows:
through the reaction, the molecular weight of the thickener is 300-500 ten thousand.
Further, the wastewater is wastewater produced in a process for producing ethoxylated bisphenol a diacrylate.
Further, the process for producing the wastewater comprises the following steps:
vacuumizing monomer acrylic acid, filling the monomer acrylic acid into a dripping groove, and pumping ethoxylated bisphenol A into a reaction kettle from a tank area;
BHT and p-hydroxyanisole are added into the reaction kettle;
heating the reaction kettle to 110-140 ℃;
continuously dripping acrylic monomers into the dripping tank, adding a catalyst p-toluenesulfonic acid, and carrying out normal pressure esterification reaction;
and after the reaction is finished, cooling the reaction kettle, adding a sodium carbonate aqueous solution with the concentration of 5%, stirring for 30 minutes, standing for layering, and separating the wastewater containing the unreacted acrylic monomers and other organic matters to obtain the wastewater.
Wherein BHT is used as an antioxidant, and a trace amount of antioxidant food-grade BHT is present, so that the color of the final fixer product is colorless to light yellow.
In addition, the ester layer after standing and layering is repeatedly cleaned for 3 times, dewatered, filtered, barreled and sealed for storage, so that an ethoxylated bisphenol A diacrylate product is obtained, and the waste water is used as a byproduct for producing the ethoxylated bisphenol A diacrylate.
Further, the wastewater contains 30% of acrylic acid, 2% -4% of ethoxylated bisphenol A diacrylate, 0.5-1% of ethoxylated bisphenol A and p-toluenesulfonic acid, antioxidant BHT and polymerization inhibitor p-hydroxyanisole.
Further, the weight parts of the wastewater, the styrene, the diallyl terephthalate and the acrylamide are respectively 10-30 parts, 15-35 parts and 25-50 parts.
In addition, the weight portion of the sodium persulfate is 5-10 portions.
Further, the weight part of the sodium hydroxide aqueous solution is 10-20 parts.
Furthermore, polymerization inhibitor p-hydroxyanisole is added into the reactor, the amount of the polymerization inhibitor p-hydroxyanisole can be small, the ethoxylated bisphenol A existing in the reaction liquid has a chain transfer effect, the polymerization inhibitor enables the reaction temperature to be stable at about 80 ℃, and the anti-strain is milder.
The thickening agent obtained by the process is subjected to performance tests in four aspects of viscosity, salt resistance, water retention, rubbing color fastness and the like, and comparative samples are two types of commercially available thickening agents of PTF and DM-5221G.
1. Viscosity of the oil
A sample is prepared into white slurry with the mass concentration of 1% by using water and is uniformly stirred, and the viscosity of the white slurry is measured according to the operating procedure of a viscometer.
| Thickening agent | Viscosity/(mpa.s) |
| PTF | 35400 |
| DM-5221G | 29000 |
| Thickener sample prepared by the invention | 50000 |
According to the table, the viscosity of the thickener prepared by the invention is not inferior to that of the similar product in the market, and is even better relatively.
2. Salt resistance (viscosity retention after addition of salt):
1mL of a 1.0% anhydrous sodium sulfate solution was pipetted into 100g of the prepared white slurry, stirred uniformly with an electric stirrer, and the viscosity after the addition of the salt was measured according to the protocol of the viscometer.
The viscosity retention after salting of the thickener is expressed as X, and the value is expressed in% and is calculated according to the following formula:
in the formula:
eta-viscosity value of the white pulp after adding salt, with unit of millipascal seconds (mpa · s);
η0viscosity values of unsalted white pulp in millipascal seconds (mpa · s).
As can be seen from the above table, the thickener prepared by the invention has salt resistance and is equivalent to the thickener on the market at a smaller mixing amount.
3. Water holding capacity:
preparing a thickener sample into 1.0% white pulp by using deionized water, inserting medium-speed quantitative filter paper cut into a width of 1cm into the prepared white pulp to a depth of 1cm, starting timing, and keeping the filter paper strips vertical to the liquid level of the white pulp. The height (cm) of the water rising on the filter paper at 30min was measured, and the lower the rising height, the better the water-holding property.
| Thickening agent | Water holding capacity/cm |
| PTF | 1.0 |
| DM-5221G | 1.1 |
| Thickener sample prepared by the invention | 1.2 |
As can be seen from the table above, the water holding capacity of the thickener prepared by the invention is equivalent to that of similar products in the market, and the pattern edge bleeding of the printed fabric can be effectively reduced.
4. Color fastness to rubbing: according to GB/T3920-1997 textile color fastness to rubbing color fastness.
As can be seen from the table, compared with the similar products in the market, the thickener prepared by the invention has consistent influence on the rubbing fastness and can keep a certain fastness on the color and luster of the printed and dyed textiles.
Compared with similar products in the market, the thickening agent prepared by the invention has performance parameters not inferior to those of the similar products in all aspects, and partial parameters are even better than those of the similar products, so that the thickening agent prepared by the invention has reliable effect.
Compared with the prior art, the embodiment has the following beneficial effects:
the method has the advantages that the synthesized ethoxylated bisphenol A diacrylate wastewater is used as a raw material, monomer acrylic acid in the wastewater is recycled, the thickener is obtained through preparation, the process flow is complete, the preparation method is simple, the raw material is low in price and easy to operate, the final reaction liquid is directly used as a product output to change waste into valuable, the problems of resource waste and new pollution during wastewater treatment are solved, on the other hand, deep resource utilization and near zero emission of the wastewater are realized, new industrial output is created, and the prepared thickener has reliable performance compared with the existing thickeners in the market, even has part of parameters slightly better than similar products, so that the thickener extracted from the wastewater also has good market competitiveness.
The above-mentioned embodiments are merely illustrative of the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the scope of the present invention.
Claims (7)
1. A process method for preparing a thickening agent by using ethoxylated bisphenol A diacrylate wastewater is characterized by comprising the following steps:
feeding wastewater containing acrylic acid and ester thereof into a reactor, adding styrene, diallyl terephthalate and acrylamide to obtain a mixed solution, and carrying out free radical copolymerization;
replacing a gas phase part in the reactor with nitrogen, and heating the mixed solution to 75-85 ℃;
adding a sodium persulfate aqueous solution into the reactor for multiple times at regular time, and controlling the mixed solution to be maintained at 75-85 ℃;
and after the mixed solution is subjected to radical co-coalescence, cooling the mixed solution, and adding a sodium hydroxide aqueous solution and water to obtain the thickening agent.
2. The process for preparing thickening agent by using ethoxylated bisphenol A diacrylate waste water according to claim 1, wherein the process comprises the following steps: the production process of the wastewater comprises the following steps:
vacuumizing monomer acrylic acid, filling the monomer acrylic acid into a dripping groove, and pumping ethoxylated bisphenol A into a reaction kettle from a tank area;
BHT and p-hydroxyanisole are added into the reaction kettle;
heating the reaction kettle to 110-140 ℃;
continuously dripping acrylic monomers into the dripping tank, adding a catalyst p-toluenesulfonic acid, and carrying out normal pressure esterification reaction;
and after the reaction is finished, cooling the reaction kettle, adding a sodium carbonate aqueous solution with the concentration of 5%, stirring for 30 minutes, standing for layering, and separating the wastewater containing the unreacted acrylic acid monomer to obtain the wastewater.
3. The process for preparing thickening agent by using ethoxylated bisphenol A diacrylate waste water according to claim 2, wherein: the wastewater comprises 30% of acrylic acid, 2% -4% of ethoxylated bisphenol A diacrylate, 0.5-1% of ethoxylated bisphenol A and p-toluenesulfonic acid, antioxidant BHT and polymerization inhibitor p-hydroxyanisole.
4. The process for preparing thickening agent by using ethoxylated bisphenol A diacrylate waste water according to claim 3, wherein: the weight parts of the wastewater, the styrene, the diallyl terephthalate and the acrylamide are respectively 10-30 parts, 15-35 parts and 25-50 parts.
5. The process for preparing thickening agent by using ethoxylated bisphenol A diacrylate waste water according to claim 4, wherein the process comprises the following steps: the step of adding the aqueous solution of sodium persulfate into the reactor for a plurality of times at regular time comprises the following steps: 5-10 parts of aqueous sodium persulfate solution is added into the reactor in a timing manner for a plurality of times.
6. The process for preparing thickening agent by using ethoxylated bisphenol A diacrylate waste water according to claim 3, wherein: the weight portion of the sodium hydroxide aqueous solution is 10-20 portions.
7. The process for preparing thickening agent by using ethoxylated bisphenol A diacrylate waste water according to claim 1, wherein the process comprises the following steps: and adding polymerization inhibitor p-hydroxyanisole into the reactor.
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| CN201910852455.9A CN110724223B (en) | 2019-09-09 | 2019-09-09 | Process method for preparing thickening agent by using ethoxylated bisphenol A diacrylate wastewater |
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| CN201910852455.9A CN110724223B (en) | 2019-09-09 | 2019-09-09 | Process method for preparing thickening agent by using ethoxylated bisphenol A diacrylate wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4423199A (en) * | 1982-09-30 | 1983-12-27 | Rohm And Haas Company | Acrylamide containing emulsion copolymers for thickening purposes |
| KR950001398B1 (en) * | 1989-12-02 | 1995-02-18 | 니혼 쇼꾸바이 가가꾸고오교오 가부시끼가이샤 | Waste water treatment in acryl acid plant |
| CN109455856A (en) * | 2018-11-09 | 2019-03-12 | 东华大学 | A method of waste water containing acrylic acid is handled using microwave irradiation technology |
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