CN118184866A - Preparation method and application method of polycarboxylic acid sodium salt dispersing agent with adjustable dispersing force for rubber - Google Patents
Preparation method and application method of polycarboxylic acid sodium salt dispersing agent with adjustable dispersing force for rubber Download PDFInfo
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002253 acid Substances 0.000 title claims abstract description 26
- 159000000000 sodium salts Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 238000010992 reflux Methods 0.000 claims abstract description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 16
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 239000000376 reactant Substances 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 15
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003945 anionic surfactant Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- 229920000142 Sodium polycarboxylate Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 239000012943 hotmelt Substances 0.000 claims description 7
- 238000004811 liquid chromatography Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229940067741 sodium octyl sulfate Drugs 0.000 claims description 7
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000003411 electrode reaction Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 4
- 125000002252 acyl group Chemical group 0.000 abstract description 3
- 150000001408 amides Chemical class 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000007596 consolidation process Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- NCCHARWOCKOHIH-UHFFFAOYSA-N n-methylbenzamide Chemical compound CNC(=O)C1=CC=CC=C1 NCCHARWOCKOHIH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 3
- 238000007127 saponification reaction Methods 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- 238000004017 vitrification Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- -1 alkylbenzene sulfonate Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KRWWZDVIEFSIOT-UHFFFAOYSA-N ethenyl acetate;furan-2,5-dione Chemical compound CC(=O)OC=C.O=C1OC(=O)C=C1 KRWWZDVIEFSIOT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
- C08F222/08—Maleic anhydride with vinyl aromatic monomers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a polycarboxylic acid sodium salt dispersing agent with adjustable dispersing force for rubber, which comprises the steps of firstly carrying out polymerization saponification reaction on monomers, when the temperature is increased to meet the requirement of reflux temperature, substituting C element in accelerated chain reaction by carboxyl in a reaction system, accelerating double bond breakage, -synchronously accelerating the speed of ONa groups entering the reaction system, carrying out nucleophilic substitution reaction while carrying out ring opening reaction by phenol matched with an amide type adjustable agent, carrying out substitution reaction on hydroxyl in phenol and acyl in dimethylformamide to generate N-methylbenzamide, having obvious catalytic effect, carrying out ring opening reaction in the reaction system, carrying out the ring opening reaction in a very poor electrolysis, realizing the consolidation of dispersing force of acrylic acid-maleic anhydride copolymer, improving the vitrification temperature of the acrylic acid-maleic anhydride copolymer, and adapting to the requirements of different materials and use environments.
Description
Technical Field
The invention relates to the technical field of dispersant preparation, in particular to a preparation method and a use method of a polycarboxylic acid sodium salt dispersant with adjustable dispersing power for rubber.
Background
In the production process of rubber products, a dispersing agent is often required to realize the dispersion and uniform mixing of additives so as to improve the mechanical property and the processing property of the rubber products. Compared with inorganic dispersing agents or organic dispersing agents such as alkylbenzene sulfonate, alkylphenol polyoxyethylene ether, naphthalene sulfonate formaldehyde condensate, lignin sulfonate and the like, the alpha-olefin and maleic anhydride copolymerization reaction and copolymer dispersing agent is a more environment-friendly dispersing agent which can not only increase electrostatic repulsive force on the particle surface, but also enhance steric hindrance effect by increasing the thickness of a high polymer adsorption layer, thereby achieving more excellent dispersing effect, and the like, and the copolymerization system of styrene-maleic anhydride, dicyclopentadiene-maleic anhydride, vinyl acetate-maleic anhydride and the like is widely applied to industries such as coal water slurry, building concrete, fuel and the like at present.
The acrylic acid-maleic anhydride copolymer system has the advantages of long carbon chain, multiple active adsorption points, stable steric hindrance effect and the like, and has more excellent dispersing effect, but on one hand, the glass transition temperature is lower, the impact of high-temperature use is difficult to withstand, and on the other hand, the component impurities of the copolymer produced in the actual production and application process are more, so that the dispersing force is difficult to regulate and control. Therefore, there is a need for a sodium polycarboxylate dispersant capable of achieving adjustable dispersing power to meet the requirements of different rubber products for dispersing effect.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present invention has been made in view of the above-mentioned problems with the conventional acrylic acid-maleic anhydride copolymer dispersant.
Therefore, the technical problems solved by the invention are as follows: solves the problems that the prior acrylic acid-maleic anhydride copolymer dispersant has lower glass transition temperature on one hand and difficult regulation and control of the dispersing force on the other hand.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the polycarboxylic acid sodium salt dispersing agent with adjustable dispersion force for rubber specifically comprises the following raw materials in mass fraction: 1.12 to 3.64 parts of maleic anhydride, 1.45 to 4.33 parts of alpha-hydroxy acrylic acid, 0.17 to 0.32 part of styrene, 0.3 to 0.5 part of adjustable agent, 10 to 25 parts of organic solvent, 0.1 to 0.13 part of phenol, 1 to 1.5 parts of anionic surfactant, 0.1 to 0.2 part of stabilizer and 10 parts of sodium hydroxide aqueous solution with the solubility of 0.1 mol/l;
the preparation method specifically comprises the following preparation steps:
S1: adding maleic anhydride, alpha-hydroxy acrylic acid, styrene and an organic solvent into a reaction kettle, gradually heating to 100-120 ℃ at a speed of 5 ℃/min, stopping stirring after a reflux phenomenon occurs and a reflux reaction is kept for more than 0.5h and gradually returning to room temperature after reaching a preset requirement, and collecting distillate for later use;
s2: taking out the mixture in the reaction kettle, heating to 50 ℃, adding an adjustable agent and phenol, stirring and dissolving, and performing ring-opening reaction for 2-6 hours;
S3: adding sodium hydroxide aqueous solution, stirring uniformly, adding an anionic surfactant and a stabilizer, and carrying out electrolysis with 2 v;
s4: measuring the viscosity of a reactant after the electrolysis reaction for 1-3 hours, cooling to room temperature after meeting the requirements, and adding the distillate into the reactant;
S5: mixing and extracting to obtain a lower product, filtering, washing a filter cake with deionized water for 2 times, and drying to obtain the dispersing agent.
As a preferable scheme of the preparation method of the dispersing-force-adjustable polycarboxylic acid sodium salt dispersing agent for rubber, the invention comprises the following steps: the adjustable agent is dimethylformamide.
As a preferable scheme of the preparation method of the dispersing-force-adjustable polycarboxylic acid sodium salt dispersing agent for rubber, the invention comprises the following steps: the organic solvent is ethyl acetate.
As a preferable scheme of the preparation method of the dispersing-force-adjustable polycarboxylic acid sodium salt dispersing agent for rubber, the invention comprises the following steps: the anionic surfactant is a mixture of sodium dodecyl sulfate SDS and sodium octyl sulfate AOS in a mass ratio of 1:1.4.
As a preferable scheme of the preparation method of the dispersing-force-adjustable polycarboxylic acid sodium salt dispersing agent for rubber, the invention comprises the following steps: the stabilizer is polyvinyl alcohol with the concentration of 0.5 mol/l.
As a preferable scheme of the preparation method of the dispersing-force-adjustable polycarboxylic acid sodium salt dispersing agent for rubber, the invention comprises the following steps: and after the heat preservation reflux reaction is carried out for more than 0.5h, monitoring the content of the distillate in real time through liquid chromatography, and when the content of Na element of the distillate which is just distilled out is increased to 3 percent and the content of benzene ring element is increased to more than 5 percent, regulating the heat preservation reflux reaction to meet the set requirement.
As a preferable scheme of the preparation method of the dispersing-force-adjustable polycarboxylic acid sodium salt dispersing agent for rubber, the invention comprises the following steps: when the viscosity of the reactant is measured, the viscosity of the mixed solution is 100-200 mm 2/s, which meets the requirements.
As a preferable scheme of the preparation method of the dispersing-force-adjustable polycarboxylic acid sodium salt dispersing agent for rubber, the invention comprises the following steps: in the step S5, the upper layer of the separated matter after mixing and extraction is subjected to silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate of 10:1, and the mixture is obtained by evaporation and spin drying for standby.
In order to solve the technical problems, the invention also provides the following technical scheme: the application method of the dispersing agent of the polycarboxylic acid sodium salt with adjustable dispersing force for rubber comprises the steps of adding 10-15 parts of hot-melt high-temperature granules, 1-1.4 parts of film forming agent and 20% of organic adhesive into a reaction kettle, carrying out hot melting at 200 ℃, cooling to room temperature, adding 20-30 parts of dispersing agent and polar solvent, and preparing a dispersing net bag with the aim of determining the aim of dispersing.
In order to solve the technical problems, the invention also provides the following technical scheme: the application method of the dispersing force-adjustable polycarboxylic acid sodium salt dispersing agent for rubber comprises the steps of adding 10-15 parts of hot-melt high-temperature granules, 1-1.4 parts of film forming agent and 20 parts of organic adhesive into a reaction kettle, carrying out hot melting at 200 ℃, cooling to room temperature, adding 20-30 parts of dispersing agent and polar solvent, and preparing a dispersing net bag for determining the purpose of dispersion;
Meanwhile, adding water and a dispersion net bag into a reaction system, configuring corresponding electrode amplitude according to the reaction system and dispersion requirement of the current reactant, measuring the content of the mixture by LC (liquid crystal) in a time interval, and stopping electrode reaction catalysis when the percentage content is unchanged;
the corresponding electrode amplitude is configured according to the reaction system and the dispersion requirement of the current reactant, and is specifically as follows:
Wherein V is the configured electrode amplitude, alpha is the temperature of the reaction system, beta is the viscosity of the reaction system, gamma is the total concentration of the reaction system, and delta is the reaction change value which needs to be achieved compared with the original reaction system after the dispersing agent is added.
The invention has the beneficial effects that: the invention provides a preparation method and a use method of a polycarboxylic acid sodium salt dispersing agent with adjustable dispersion force for rubber, which comprises the steps of firstly carrying out polymerization saponification reaction through basic monomers, accelerating the reaction process by reflux reaction in the process, replacing C element in accelerated chain reaction by carboxyl in a reaction system after the temperature is increased to reach the reflux temperature requirement, accelerating the breakage of double bonds, synchronously accelerating the speed of ONa groups entering the reaction system, simultaneously carrying out nucleophilic substitution reaction while carrying out ring opening reaction by phenol in combination with an amide type adjustable agent, carrying out substitution reaction on hydroxyl in phenol and acyl in dimethylformamide to produce N-methylbenzamide with obvious catalytic effect, accelerating the ring opening reaction in the reaction system, and realizing the consolidation of the dispersion force of an acrylic acid-maleic anhydride copolymer by extra extremely poor electrolysis.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
fig. 1 is a schematic diagram of a conventional net bag according to the present invention.
Detailed Description
So that the manner in which the above recited objects, features and advantages of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments, some of which are illustrated in the appended drawings. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The acrylic acid-maleic anhydride copolymer system has the advantages of long carbon chain, multiple active adsorption points, stable steric hindrance effect and the like, and has more excellent dispersing effect, but on one hand, the glass transition temperature is lower, the impact of high-temperature use is difficult to withstand, and on the other hand, the component impurities of the copolymer produced in the actual production and application process are more, so that the dispersing force is difficult to regulate and control. Therefore, there is a need for a sodium polycarboxylate dispersant capable of achieving adjustable dispersing power to meet the requirements of different rubber products for dispersing effect.
Accordingly, the present invention provides the following examples, and provides a method for preparing a sodium polycarboxylate dispersant with adjustable dispersing power for rubber and a method for using the same.
Examples:
Example 1
The preparation method of the polycarboxylic acid sodium salt dispersing agent with adjustable dispersion force for rubber specifically comprises the following raw materials in mass fraction: 1.12 parts of maleic anhydride, 1.45 parts of alpha-hydroxyacrylic acid, 0.17 part of styrene, 0.3 part of dimethylformamide, 10 parts of ethyl acetate, 0.1 part of phenol, 1 part of a mixture of sodium dodecyl sulfate SDS and sodium octyl sulfate AOS in a mass ratio of 1:1.4, 0.1 part of polyvinyl alcohol with a concentration of 0.5mol/l, and 10 parts of sodium hydroxide aqueous solution with a solubility of 0.1 mol/l;
the preparation method specifically comprises the following preparation steps:
S1: adding maleic anhydride, alpha-hydroxy acrylic acid, styrene and an organic solvent into a reaction kettle, gradually heating to 100 ℃ at a speed of 5 ℃/min, after a reflux phenomenon occurs, stopping stirring after the reflux reaction is maintained for more than 0.5h and reaching the set requirement, gradually returning to room temperature, and collecting distillate for later use;
S2: taking out the mixture in the reaction kettle, heating to 50 ℃, adding an adjustable agent and phenol, stirring and dissolving, and performing ring-opening reaction for 2 hours;
S3: adding sodium hydroxide aqueous solution, stirring uniformly, adding an anionic surfactant and a stabilizer, and carrying out electrolysis with 2 v;
S4: measuring the viscosity of a reactant after the electrolysis reaction for 1h, cooling to room temperature after meeting the requirements, and adding a distillate into the reactant;
S5: mixing and extracting to obtain a lower product, filtering, washing a filter cake with deionized water for 2 times, and drying to obtain the dispersing agent.
Further, after the heat-preserving reflux reaction for 0.5h, the content of the distillate is monitored in real time through liquid chromatography, and when the Na element content of the distillate just distilled is increased to 3% and the benzene ring element is increased to more than 5%, the heat-preserving reflux reaction is regulated to meet the set requirement.
Further, when the viscosity of the reactant is measured, the viscosity of the mixed solution is 100-200 mm 2/s, which is satisfactory.
In step S5, the upper layer of the separated mixture after the mixed extraction is subjected to silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate of 10:1, and the mixture is obtained by evaporation and spin-drying.
Example 2
The preparation method of the polycarboxylic acid sodium salt dispersing agent with adjustable dispersion force for rubber specifically comprises the following raw materials in mass fraction: 3.64 parts of maleic anhydride, 4.33 parts of alpha-hydroxyacrylic acid, 0.32 part of styrene, 0.5 part of dimethylformamide, 25 parts of ethyl acetate, 0.13 part of phenol, 1.5 parts of a mixture of sodium dodecyl sulfate SDS and sodium octyl sulfate AOS in a mass ratio of 1:1.4, 0.2 part of polyvinyl alcohol with a concentration of 0.5mol/l, and 10 parts of sodium hydroxide aqueous solution with a solubility of 0.1 mol/l;
the preparation method specifically comprises the following preparation steps:
S1: adding maleic anhydride, alpha-hydroxy acrylic acid, styrene and an organic solvent into a reaction kettle, gradually heating to 120 ℃ at a speed of 5 ℃/min, after a reflux phenomenon occurs, stopping stirring after the reflux reaction is maintained for more than 0.5h and reaching the set requirement, gradually returning to room temperature, and collecting distillate for later use;
s2: taking out the mixture in the reaction kettle, heating to 50 ℃, adding an adjustable agent and phenol, stirring and dissolving, and performing ring-opening reaction for 6 hours;
S3: adding sodium hydroxide aqueous solution, stirring uniformly, adding an anionic surfactant and a stabilizer, and carrying out electrolysis with 2 v;
S4: measuring the viscosity of the reactant after the electrolytic reaction for 3 hours, cooling to room temperature after meeting the requirements, and adding distillate into the reactant;
S5: mixing and extracting to obtain a lower product, filtering, washing a filter cake with deionized water for 2 times, and drying to obtain the dispersing agent.
Further, after the heat preservation reflux reaction is carried out for more than 0.5h, the content of distillate is monitored in real time through liquid chromatography, and when the Na element content of the distillate just distilled is increased to 3% and the benzene ring element is increased to more than 5%, the heat preservation reflux reaction is regulated to meet the set requirement.
Further, when the viscosity of the reactant is measured, the viscosity of the mixed solution is 100-200 mm 2/s, which is satisfactory.
In step S5, the upper layer of the separated mixture after the mixed extraction is subjected to silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate of 10:1, and the mixture is obtained by evaporation and spin-drying.
Example 3
The preparation method of the polycarboxylic acid sodium salt dispersing agent with adjustable dispersion force for rubber specifically comprises the following raw materials in mass fraction: 2 parts of maleic anhydride, 2 parts of alpha-hydroxy acrylic acid, 0.27 part of styrene, 0.4 part of dimethylformamide, 20 parts of ethyl acetate, 0.11 part of phenol, 1.3 parts of a mixture of Sodium Dodecyl Sulfate (SDS) and sodium octyl sulfate (AOS) in a mass ratio of 1:1.4, 0.15 part of polyvinyl alcohol with a concentration of 0.5mol/l, and 10 parts of sodium hydroxide aqueous solution with a solubility of 0.1 mol/l;
the preparation method specifically comprises the following preparation steps:
S1: adding maleic anhydride, alpha-hydroxy acrylic acid, styrene and an organic solvent into a reaction kettle, gradually heating to 110 ℃ at a speed of 5 ℃/min, after a reflux phenomenon occurs, stopping stirring after the reflux reaction is maintained for more than 0.5h and reaching the set requirement, gradually returning to room temperature, and collecting distillate for later use;
s2: taking out the mixture in the reaction kettle, heating to 50 ℃, adding an adjustable agent and phenol, stirring and dissolving, and performing ring-opening reaction for 4 hours;
S3: adding sodium hydroxide aqueous solution, stirring uniformly, adding an anionic surfactant and a stabilizer, and carrying out electrolysis with 2 v;
s4: measuring the viscosity of the reactant after the electrolysis reaction for 2 hours, cooling to room temperature after meeting the requirements, and adding distillate into the reactant;
S5: mixing and extracting to obtain a lower product, filtering, washing a filter cake with deionized water for 2 times, and drying to obtain the dispersing agent.
Further, after the heat preservation reflux reaction is carried out for more than 0.5h, the content of distillate is monitored in real time through liquid chromatography, and when the Na element content of the distillate just distilled is increased to 3% and the benzene ring element is increased to more than 5%, the heat preservation reflux reaction is regulated to meet the set requirement.
Further, when the viscosity of the reactant is measured, the viscosity of the mixed solution is 100-200 mm 2/s, which is satisfactory.
In step S5, the upper layer of the separated mixture after the mixed extraction is subjected to silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate of 10:1, and the mixture is obtained by evaporation and spin-drying.
Example 4
The preparation method of the polycarboxylic acid sodium salt dispersing agent with adjustable dispersion force for rubber specifically comprises the following raw materials in mass fraction: 3 parts of maleic anhydride, 3 parts of alpha-hydroxy acrylic acid, 0.22 part of styrene, 0.5 part of dimethylformamide, 23 parts of ethyl acetate, 0.12 part of phenol, 1.4 parts of a mixture of Sodium Dodecyl Sulfate (SDS) and sodium octyl sulfate (AOS) in a mass ratio of 1:1.4, 0.16 part of polyvinyl alcohol with a concentration of 0.5mol/l, and 10 parts of sodium hydroxide aqueous solution with a solubility of 0.1 mol/l;
the preparation method specifically comprises the following preparation steps:
S1: adding maleic anhydride, alpha-hydroxy acrylic acid, styrene and an organic solvent into a reaction kettle, gradually heating to 120 ℃ at a speed of 5 ℃/min, after a reflux phenomenon occurs, stopping stirring after the reflux reaction is maintained for more than 0.5h and reaching the set requirement, gradually returning to room temperature, and collecting distillate for later use;
s2: taking out the mixture in the reaction kettle, heating to 50 ℃, adding an adjustable agent and phenol, stirring and dissolving, and performing ring-opening reaction for 5 hours;
S3: adding sodium hydroxide aqueous solution, stirring uniformly, adding an anionic surfactant and a stabilizer, and carrying out electrolysis with 2 v;
s4: measuring the viscosity of the reactant after the electrolysis reaction for 1-3 hours, cooling to room temperature after meeting the requirements, and adding distillate into the reactant;
S5: mixing and extracting to obtain a lower product, filtering, washing a filter cake with deionized water for 2 times, and drying to obtain the dispersing agent.
Further, after the heat preservation reflux reaction is carried out for more than 0.5h, the content of distillate is monitored in real time through liquid chromatography, and when the Na element content of the distillate just distilled is increased to 3% and the benzene ring element is increased to more than 5%, the heat preservation reflux reaction is regulated to meet the set requirement.
Further, when the viscosity of the reactant is measured, the viscosity of the mixed solution is 100-200 mm 2/s, which is satisfactory.
In step S5, the upper layer of the separated mixture after the mixed extraction is subjected to silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate of 10:1, and the mixture is obtained by evaporation and spin-drying.
Example 5
The preparation method of the polycarboxylic acid sodium salt dispersing agent with adjustable dispersion force for rubber specifically comprises the following raw materials in mass fraction: 3.25 parts of maleic anhydride, 4 parts of alpha-hydroxy acrylic acid, 0.28 part of styrene, 0.3 part of dimethylformamide, 15 parts of ethyl acetate, 0.1 part of phenol, 1.1 parts of a mixture of Sodium Dodecyl Sulfate (SDS) and sodium octyl sulfate (AOS) in a mass ratio of 1:1.4, 0.17 part of polyvinyl alcohol with a concentration of 0.5mol/l, and 10 parts of sodium hydroxide aqueous solution with a solubility of 0.1 mol/l;
the preparation method specifically comprises the following preparation steps:
S1: adding maleic anhydride, alpha-hydroxy acrylic acid, styrene and an organic solvent into a reaction kettle, gradually heating to 120 ℃ at a speed of 5 ℃/min, after a reflux phenomenon occurs, stopping stirring after the reflux reaction is maintained for more than 0.5h and reaching the set requirement, gradually returning to room temperature, and collecting distillate for later use;
S2: taking out the mixture in the reaction kettle, heating to 50 ℃, adding an adjustable agent and phenol, stirring and dissolving, and performing ring-opening reaction for 3 hours;
S3: adding sodium hydroxide aqueous solution, stirring uniformly, adding an anionic surfactant and a stabilizer, and carrying out electrolysis with 2 v;
S4: measuring the viscosity of a reactant after the electrolysis reaction for 1h, cooling to room temperature after meeting the requirements, and adding a distillate into the reactant;
S5: mixing and extracting to obtain a lower product, filtering, washing a filter cake with deionized water for 2 times, and drying to obtain the dispersing agent.
Further, after the heat preservation reflux reaction is carried out for more than 0.5h, the content of distillate is monitored in real time through liquid chromatography, and when the Na element content of the distillate just distilled is increased to 3% and the benzene ring element is increased to more than 5%, the heat preservation reflux reaction is regulated to meet the set requirement.
Further, when the viscosity of the reactant is measured, the viscosity of the mixed solution is 100-200 mm 2/s, which is satisfactory.
In step S5, the upper layer of the separated mixture after the mixed extraction is subjected to silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate of 10:1, and the mixture is obtained by evaporation and spin-drying.
In addition, the invention also improves the using method of the polycarboxylic acid sodium salt dispersing agent with adjustable dispersing force for rubber, 10-15 parts of hot-melt high-temperature granules, 1-1.4 parts of film forming agent and 20 parts of organic adhesive are added into a reaction kettle, the mixture is cooled to room temperature after hot melting at 200 ℃, and 20-30 parts of dispersing agent and polar solvent are added into the mixture to prepare a dispersing net bag with the aim of determining the aim for use.
It should be noted that the hot-melt high-temperature granule, the film forming agent, the organic binder and the polar solvent related in the invention are all conventional chemical substances, and the achieved object is that the forming net bag can refer to the preparation process of the plastic forming mold, and the description is not needed here.
Specifically, referring to fig. 1, the present invention provides a conventional usage style of a net bag.
Furthermore, the invention also provides a using method of the polycarboxylic acid sodium salt dispersing agent with adjustable dispersing force for rubber, which comprises the steps of adding 10-15 parts of hot-melt high-temperature granules, 1-1.4 parts of film forming agent and 20 parts of organic adhesive into a reaction kettle, carrying out hot melting at 200 ℃, cooling to room temperature, adding 20-30 parts of dispersing agent and polar solvent, and preparing a dispersing net bag with the aim of determining the aim for use;
Meanwhile, adding water and a dispersion net bag into a reaction system, configuring corresponding electrode amplitude according to the reaction system and dispersion requirement of the current reactant, measuring the content of the mixture by LC (liquid crystal) in a time interval, and stopping electrode reaction catalysis when the percentage content is basically unchanged;
the corresponding electrode amplitude is configured according to the reaction system and the dispersion requirement of the current reactant, and is specifically as follows:
Wherein V is the configured electrode amplitude, alpha is the temperature of the reaction system, beta is the viscosity of the reaction system, gamma is the total concentration of the reaction system, and delta is the reaction change value which needs to be achieved compared with the original reaction system after the dispersing agent is added.
Comparative example (tested using conventional comparative tests):
The monomers MAH, AA and St are added into a reaction device provided with a thermometer, an electric stirrer and a condenser according to the mol ratio of 1:1:0, and the polymerization temperature is controlled between 65 and 70 ℃ and the polymerization time is 3 hours. After the polymerization reaction is finished, 15% NaOH solution is added into a polymerized system according to the molar ratio of 1:2, the mixture is saponified for 2 hours at the temperature of 80 ℃, the saponified system is kept stand for 2-3 hours, the lower solution is obtained through oil-water separation, and the lower solution is subjected to suction filtration through 120-mesh diatomite to obtain a pale yellow transparent solution.
In summary, the table is compared with the following table (hereinafter, the table is a data comparison of the dispersant used after the electrode amplitude is correspondingly configured):
The following description is needed:
Pdi (aggregation index): the aggregation index of the initial particles and the aggregation index of the final particles after the experiment. The smaller the PDI value, the more uniform the particle dispersion.
Zeta potential: the charge state of the particles, positive values indicate that the particles are positively charged and negative values indicate that the particles are negatively charged. Higher absolute values generally indicate better dispersion properties.
3. Evaluation of dispersing effect: the dispersion effect is classified into different grades (such as poor, medium, good and excellent) by comprehensively considering various indexes.
The invention provides a preparation method and a use method of a polycarboxylic acid sodium salt dispersing agent with adjustable dispersion force for rubber, which comprises the steps of firstly carrying out polymerization saponification reaction through basic monomers, accelerating the reaction process by reflux reaction in the process, replacing C element in accelerated chain reaction by carboxyl in a reaction system after the temperature is increased to reach the reflux temperature requirement, accelerating the breakage of double bonds, synchronously accelerating the speed of ONa groups entering the reaction system, simultaneously carrying out nucleophilic substitution reaction while carrying out ring opening reaction by phenol in combination with an amide type adjustable agent, carrying out substitution reaction on hydroxyl in phenol and acyl in dimethylformamide to produce N-methylbenzamide with obvious catalytic effect, accelerating the ring opening reaction in the reaction system, and realizing the consolidation of the dispersion force of an acrylic acid-maleic anhydride copolymer by extra extremely poor electrolysis.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. The preparation method of the polycarboxylic acid sodium salt dispersing agent with adjustable dispersing force for rubber is characterized by comprising the following raw materials in percentage by mass: 1.12 to 3.64 parts of maleic anhydride, 1.45 to 4.33 parts of alpha-hydroxy acrylic acid, 0.17 to 0.32 part of styrene, 0.3 to 0.5 part of adjustable agent, 10 to 25 parts of organic solvent, 0.1 to 0.13 part of phenol, 1 to 1.5 parts of anionic surfactant, 0.1 to 0.2 part of stabilizer and 10 parts of sodium hydroxide aqueous solution with the solubility of 0.1 mol/l;
the preparation method specifically comprises the following preparation steps:
S1: adding maleic anhydride, alpha-hydroxy acrylic acid, styrene and an organic solvent into a reaction kettle, gradually heating to 100-120 ℃ at a speed of 5 ℃/min, stopping stirring after a reflux phenomenon occurs and a reflux reaction is kept for more than 0.5h and gradually returning to room temperature after reaching a preset requirement, and collecting distillate for later use;
s2: taking out the mixture in the reaction kettle, heating to 50 ℃, adding an adjustable agent and phenol, stirring and dissolving, and performing ring-opening reaction for 2-6 hours;
S3: adding sodium hydroxide aqueous solution, stirring uniformly, adding an anionic surfactant and a stabilizer, and carrying out electrolysis with 2 v;
s4: measuring the viscosity of a reactant after the electrolysis reaction for 1-3 hours, cooling to room temperature after meeting the requirements, and adding the distillate into the reactant;
S5: mixing and extracting to obtain a lower product, filtering, washing a filter cake with deionized water for 2 times, and drying to obtain the dispersing agent.
2. The method for preparing a dispersing agent of sodium polycarboxylate with adjustable dispersing force for rubber according to claim 1, wherein the method comprises the following steps: the adjustable agent is dimethylformamide.
3. The method for preparing a dispersing agent of sodium polycarboxylate with adjustable dispersing force for rubber according to claim 2, wherein the method comprises the following steps: the organic solvent is ethyl acetate.
4. The method for preparing a dispersing agent of sodium polycarboxylate with adjustable dispersing force for rubber according to claim 3, wherein the dispersing agent comprises the following steps: the anionic surfactant is a mixture of sodium dodecyl sulfate SDS and sodium octyl sulfate AOS in a mass ratio of 1:1.4.
5. The method for preparing a dispersing agent of sodium polycarboxylate with adjustable dispersing force for rubber according to claim 4, wherein the method comprises the following steps: the stabilizer is polyvinyl alcohol with the concentration of 0.5 mol/l.
6. The method for preparing a dispersing agent of sodium polycarboxylate with adjustable dispersing force for rubber according to claim 5, wherein the method comprises the following steps: and after the heat preservation reflux reaction is carried out for more than 0.5h, monitoring the content of the distillate in real time through liquid chromatography, and when the content of Na element of the distillate which is just distilled out is increased to 3 percent and the content of benzene ring element is increased to more than 5 percent, regulating the heat preservation reflux reaction to meet the set requirement.
7. The method for preparing a dispersing agent of sodium polycarboxylate with adjustable dispersing force for rubber according to claim 6, wherein the dispersing agent comprises the following steps: when the viscosity of the reactant is measured, the viscosity of the mixed solution is 100-200 mm 2/s, which meets the requirements.
8. The method for preparing a dispersing agent of sodium polycarboxylate with adjustable dispersing force for rubber according to claim 7, wherein the dispersing agent comprises the following steps: in the step S5, the upper layer of the separated matter after mixing and extraction is subjected to silica gel column chromatography with the volume ratio of petroleum ether to ethyl acetate of 10:1, and the mixture is obtained by evaporation and spin drying for standby.
9. The application method of the dispersing agent of the polycarboxylic acid sodium salt with adjustable dispersing force for rubber is characterized by comprising the following steps of: adding 10-15 parts of hot-melt high-temperature granules, 1-1.4 parts of film forming agent and 20 parts of organic adhesive into a reaction kettle, carrying out hot melting at 200 ℃, cooling to room temperature, adding 20-30 parts of dispersing agent and polar solvent, and preparing a dispersing net bag with a dispersing purpose being a determined target purpose for use.
10. The application method of the dispersing agent of the polycarboxylic acid sodium salt with adjustable dispersing force for rubber is characterized by comprising the following steps of: adding 10-15 parts of hot-melt high-temperature granules, 1-1.4 parts of film forming agent and 20% of organic adhesive into a reaction kettle, carrying out hot melting at 200 ℃, cooling to room temperature, adding 20-30 parts of dispersing agent and polar solvent, and preparing a dispersing net bag with a dispersing purpose being a determined target purpose for use;
Meanwhile, adding water and a dispersion net bag into a reaction system, configuring corresponding electrode amplitude according to the reaction system and dispersion requirement of the current reactant, measuring the content of the mixture by LC (liquid crystal) in a time interval, and stopping electrode reaction catalysis when the percentage content is unchanged;
the corresponding electrode amplitude is configured according to the reaction system and the dispersion requirement of the current reactant, and is specifically as follows:
Wherein V is the configured electrode amplitude, alpha is the temperature of the reaction system, beta is the viscosity of the reaction system, gamma is the total concentration of the reaction system, and delta is the reaction change value which needs to be achieved compared with the original reaction system after the dispersing agent is added.
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