CN111777708A - Polymer debonder and preparation method thereof - Google Patents

Polymer debonder and preparation method thereof Download PDF

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CN111777708A
CN111777708A CN202010662838.2A CN202010662838A CN111777708A CN 111777708 A CN111777708 A CN 111777708A CN 202010662838 A CN202010662838 A CN 202010662838A CN 111777708 A CN111777708 A CN 111777708A
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polymer
debonder
water
sodium
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王斌
黄月文
欧阳天生
刘新鸿
冯晓文
赵树录
年福伟
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Zhaoqing Outao New Material Co ltd
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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
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63444—Nitrogen-containing polymers, e.g. polyacrylamides, polyacrylonitriles, polyvinylpyrrolidone [PVP], polyethylenimine [PEI]
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    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
    • 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
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Abstract

The invention belongs to the field of fine chemical engineering, and discloses a polymer debonder and a preparation method thereof, wherein the structural formula of the polymer debonder is shown as a formula (I), and the preparation method comprises the following steps: (1) amino acid salt substituted styrene monomer or its solution and (methyl) acrylate,Maleic anhydride or/and maleate, a P-containing reducing agent and water are mixed and stirred uniformly to obtain a mixed solution H1; (2) and dropwise adding the initiator solution into the mixed solution H1 under stirring, and adding a chain terminator solution after the free radical polymerization reaction under the heating condition to obtain the polymer dispergator. The polymer dispergator and the compound dispergator thereof have the advantages of strong water quality adaptability, good dispergation effect and the like, and have wide application prospects in the aspects of ceramic reuse water utilization, energy conservation and environmental protection.

Description

Polymer debonder and preparation method thereof
Technical Field
The invention relates to the field of ceramic fine chemical industry, in particular to a polymer dispergator for ceramic reuse water and a preparation method thereof.
Background
With the rapid development of Chinese economy, the ceramic production technology is continuously improved, and the ceramic industry generates a large amount of sewage and other negative effects. The sewage generated in the ceramic production process contains various inorganic salts and organic salts, and the direct discharge can cause environmental pollution and waste water resources. With the increasing year by year of energy-saving and environment-friendly requirements, ceramic enterprises need to develop sustainably and are indispensable for treating the three wastes.
At present, ceramic enterprises use sewage treatment chemicals to clarify and recover sewage, and add the sewage into a ball mill for ball milling. However, after the sewage treatment, the surface of the reuse water is clarified, but the water is soluble with high-valence ions (such as Al)3+、Ca2+、Mg2+、Fe2+、Fe3 +) The presence of (a) has a great influence on the disperging of the slurry. If the dispergator is incorrectly designed, manufactured and selected, the slurry will have high moisture, high viscosity, low ball milling efficiency, not only increasing the energy consumption of ball milling and spray drying, but also having a very adverse impact on workability and product quality.
Disclosure of Invention
The invention aims to provide a polymer debonding agent which is convenient to add and use, and is used for fully utilizing ceramic reuse water, reducing production energy consumption and waste discharge, promoting comprehensive utilization of water resources, improving production efficiency and ensuring quality and stability of ceramic products. The structural formula of the polymer debonder is shown as the formula (I):
Figure BDA0002579258890000021
the invention also aims to provide a preparation method of the dispergator.
The purpose of the invention is realized by the following technical scheme:
a preparation method of the polymer dispergator comprises the following steps:
(1) mixing and stirring an amino acid salt substituted styrene monomer or a solution thereof with (methyl) acrylate, maleic anhydride or/and maleate, a P-containing reducing agent solution and water uniformly to obtain a mixed solution H1;
(2) dropwise adding the initiator solution into the mixed solution H1 under stirring, and adding a chain terminator solution after the free radical polymerization reaction under the heating condition to obtain a polymer dispergator;
the amino acid salt substituted styrene monomer has a structure shown in the following formula (II) and/or (III):
Figure BDA0002579258890000022
the preparation method of the amino acid salt substituted styrene monomer solution comprises the following steps:
dissolving iminodiacetate or iminodisuccinate in water, adding a mixed solution of p-chloromethyl styrene and a water-soluble organic solvent under stirring, adding a strong alkali aqueous solution, continuously stirring for reacting for 2-4 hours, heating to 40-50 ℃, reacting for 2-4 hours, and cooling to obtain the amino acid salt substituted styrene type monomer solution;
the mol ratio of the iminodiacetate or iminodisuccinate to the p-chloromethyl styrene to the strong base is 1:1: 1;
the strong base is one or more than two of sodium hydroxide, potassium hydroxide, sodium alkoxide and potassium alkoxide.
Preferably, the total content of the water-soluble organic solvent and the water in the monomer solution of the step (1) is not higher than 80 wt%, wherein the content of the water-soluble organic solvent is not higher than 30 wt%; the water-soluble organic solvent is one or two of dimethylformamide and dimethylacetamide.
Preferably, the (meth) acrylate is one or more of sodium acrylate, potassium acrylate, sodium methacrylate and sodium potassium methacrylate; the maleate is one or more than two of monopotassium maleate, monosodium maleate, dipotassium maleate and disodium maleate; the P-containing reducing agent is one or more than two of sodium hypophosphite, potassium hypophosphite and ammonium hypophosphite; the initiator is one or more than two of sodium persulfate, potassium persulfate and ammonium persulfate; the chain terminator is one or more than two of potassium phosphite, sodium phosphite and phosphorous acid.
More preferably, the amount of the (meth) acrylate is 40-80 wt% of the total amount of the monomers used in the polymer debonder; the total using amount of the maleate or/and the maleic anhydride is 5-30 wt% of the total amount of the monomers used by the polymer dispergator; the amount of the amino acid salt substituted styrene type monomer is 8-32 wt% of the total amount of the monomers used in the polymer dispergator; the initiator accounts for 0.8-4 wt% of the total amount of all the polymerization monomers; the P-containing reducing agent accounts for 1-12 wt% of the total amount of all the polymerized monomers; the amount of the chain terminator is 0.08-0.5 wt% of the total amount of all the polymerization monomers; the total amount of water and the organic solvent in the mixed solution H1 is 80-50 wt% of the total amount of the mixed solution H1.
More preferably, the concentration of the P-containing reducing agent solution is 5-20 wt%, the concentration of the initiator solution is 1-10 wt%, and the concentration of the chain terminator solution is 2-20 wt%; the dropping speed of the initiator solution is 7-15 drops/min.
Preferably, in the step (2), firstly, 1/2-2/3 of initiator solution is dropwise added into the mixed solution H1 at the temperature of 60-80 ℃ and the stirring speed of 70-300 r/min, the solution temperature is kept at 80-105 ℃ after the dropwise addition, the reaction lasts for 1-2 hours, then, the rest of initiator solution is dropwise added, the reaction lasts for 1-2 hours at 80-105 ℃ after the dropwise addition, a chain terminator solution is added, and the solution is cooled to obtain the polymer debonding agent solution.
Preferably, the polymer dispergator can be further compounded with an inorganic dispergator to obtain the compound dispergator.
More preferably, the inorganic debonder agent is water glass, sodium tripolyphosphate, sodium hexametaphosphate and sodium polyphosphate, the solid content of the inorganic debonder agent is 5-500 wt% of the solid content of the polymer debonder agent, and the solid content of the prepared liquid composite debonder agent is 20-50 wt%.
Experimental results show that the amino acid salt substituted styrene monomer prepared by the invention, and (methyl) acrylate, maleic anhydride or/and maleate monomer are heated in an oxidation-reduction initiation system formed by a P-containing reducing agent and a persulfate chain initiator, the P-containing reducing agent not only plays a role of a reducing agent in free radical redox to initiate into free radicals, but also can have chain transfer and termination effects, and continuously participate in reaction at a higher temperature to enter a polymer main chain to form a-P (O) (OM) -bond, so that an N, P hybrid polycarboxylic acid type polymer with certain viscosity is finally obtained. The amino acid salt substituted styrene monomer and maleic anhydride or/and maleic acid salt monomer have good copolymerization reaction activity, and under the condition of higher total amount of maleic acid salt and maleic anhydride monomer, more polymer electrolytes with polydentate ligand chelation are obtained, and have outstanding dispergation effect on ceramic slurry, and particularly have good dispergation performance under the condition of water quality containing ceramic reuse water. And along with the increase of the total amount of carboxylic acid anions (containing N carboxylic acid anions and butylene dicarboxylic acid anions) and hypophosphorous acid bond anions (-P (O) (O-)) with the multidentate chelating function in the polymer electrolyte, the dispergation performance of the ceramic slurry containing the ceramic reuse water is enhanced.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polymer dispergator contains N, P strong coordination atoms, and a polydentate chelate ring formed by heteroatoms, carboxyl and high-valence metal ions is a five-membered ring or a six-membered ring, so that the structure is stable, and the stability of viscosity and dispergation performance can be maintained for a long time;
(2) the polymer debonder has obvious water reducing effect, good ceramic slurry fluidity, easy operation and forming, energy conservation and consumption reduction;
(3) the polymer dispergator has strong water quality adaptability, can fully utilize ceramic reuse water, and reduces discharge.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
EXAMPLE 1 preparation of amino acid salt substituted styrene type monomer
(1) Preparation of amino acid salt substituted styrene type monomer DTII solution of formula (II):
dissolving 1 mol of iminodiacetic acid disodium salt (177 g) in 420.4 g of tap water, adding a mixed solution containing 1 mol of p-chloromethyl styrene (152.6 g) and 150 g of dimethylformamide DMF under stirring, slowly adding 100 g of alkaline water containing 1 mol of NaOH, continuously stirring for reaction for 2 hours, heating to 50 ℃ for reaction for 2 hours, and cooling to obtain 1000 g of an amino acid salt substituted styrene type monomer DTII solution (shown as a reaction formula 1) containing 29.3 wt% of amino acid salt represented by a formula (II), wherein the DMF content is 15.0 wt%, the sodium chloride content is 5.85 wt%, and carboxylic acid anions (COO)-) The content of the monomer in the monomer is 30.03 wt% for standby;
Figure BDA0002579258890000051
reaction formula 1: formula (II) amino acid salt substituted styrene type monomer preparation reaction
(2) Preparation of amino acid salt substituted styrene type monomer DTIII solution of formula (III):
dissolving 1 mol of imino disuccinic acid tetrasodium salt (337.1 g) in 610.3 g of tap water, adding a mixed solution containing 1 mol of p-chloromethyl styrene (152.6 g) and 200 g of dimethylacetamide DMA under stirring, slowly adding 200 g of alkaline water containing 1 mol of KOH, continuously stirring for reaction for 2 hours, heating to 40 ℃ for reaction for 4 hours, and cooling to obtain 1500 g of amino acid salt substituted styrene type shown in formula (III) containing 30.2 wt% of amino acid saltA monomer DTIII solution (see reaction formula 2) in which the DMA content was 13.3 wt%, the potassium chloride content was 4.97 wt%, and carboxylic acid anions (COO)-) The content in the monomer was 38.83% by weight for use.
Figure BDA0002579258890000061
Reaction formula 2: preparation reaction of amino acid salt substituted styrene monomer of formula (III)
Example 2 preparation of Polymer debonder
Example 2-1:
(1) 30 g of the DTII solution (containing 8.8 g of DTII and 1.76 g of sodium chloride) prepared in the example 1 is mixed and stirred with 79.2 g of sodium acrylate, 12 g of disodium maleate, 118.8 g of tap water and 10 g of 15 wt% sodium hypophosphite solution to obtain 250 g of mixed solution H1;
(2) dropwise adding 20 g of 5 wt% potassium persulfate solution into the mixed solution H1 at the speed of 10 drops/min at the stirring speed of 150r/min at the temperature of 80 ℃, gradually raising the temperature, keeping the temperature of the solution at 80-105 ℃ for reacting for 1 hour after the dropwise adding is finished, then dropwise adding the rest 10 g of 5 wt% potassium persulfate solution at the speed of 15 drops/min, reacting at 80-105 ℃ for 2 hours after the dropwise adding is finished, adding 2 g of 10 wt% sodium phosphite solution, and cooling to obtain 282 g of polymer debonder PJ1 solution, wherein the solid content is 37.22 wt% (comprising sodium chloride, a reducing agent, an initiator, a chain transfer agent and the like).
Example 2-2:
(1) 30 g of the DTII solution (containing 8.8 g of DTII and 1.76 g of sodium chloride) prepared in the example 1 is mixed and stirred with 79.2 g of sodium acrylate, 12 g of disodium maleate, 78.8 g of tap water and 50 g of 20 wt% sodium hypophosphite solution to obtain 250 g of mixed solution H1; (ii) a
(2) Dropwise adding 15 g of 5 wt% potassium persulfate solution into the mixed solution H1 at a speed of 10 drops/min under the stirring speed of 150r/min at 60 ℃, gradually increasing the temperature, keeping the solution temperature at 80-105 ℃ for reacting for 2 hours after the dropwise adding is finished, then dropwise adding the rest 15 g of 5 wt% potassium persulfate solution at a speed of 15 drops/min, reacting at 80-105 ℃ for 1.5 hours after the dropwise adding is finished, adding 2 g of 10 wt% sodium phosphite solution, and cooling to obtain 282 g of polymer debonder PJ2 solution, wherein the solid content is 40.23 wt% (including sodium chloride, a reducing agent, an initiator, a chain transfer agent and the like).
Examples 2 to 3:
(1) 60 g of the DTII solution (containing 17.6 g of DTII and 3.5 g of sodium chloride) prepared in the example 1 is mixed and stirred with 70.4 g of sodium acrylate, 12 g of disodium maleate, 97.6 g of tap water and 60 g of 10 wt% sodium hypophosphite solution to obtain 300 g of mixed solution H1;
(2) and (2) dropwise adding 10 g of 5 wt% ammonium persulfate solution into the mixed solution H1 at the speed of 10 drops/min at the stirring speed of 65 ℃ and 200r/min, gradually raising the temperature, keeping the solution temperature at 80-105 ℃ for reacting for 1 hour after the dropwise adding is finished, then dropwise adding the rest 10 g of 5 wt% ammonium persulfate solution at the speed of 10 drops/min, reacting at 80-105 ℃ for 2 hours after the dropwise adding is finished, adding 5 g of 10 wt% potassium phosphite solution, and cooling to obtain 325 g of polymer debonder PJ3 solution, wherein the solid content is 34.15 wt% (comprising sodium chloride, a reducing agent, an initiator, a chain transfer agent and the like).
Examples 2 to 4:
(1) 100 g of DTII solution (containing 29.3 g of DTII and 5.85 g of sodium chloride) prepared in example 1 is mixed and stirred with 46.7 g of sodium acrylate, 23 g of maleic acid disodium salt, 1 g of maleic anhydride, 69.3 g of tap water and 60 g of 10 wt% sodium hypophosphite solution to obtain 300 g of mixed solution H1;
(2) dropwise adding 20 g of 2.5 wt% sodium persulfate solution into the mixed solution H1 at the speed of 10 drops/min under the stirring speed of 70 ℃ and 250r/min, gradually raising the temperature, keeping the temperature of the solution at 80-105 ℃ for reaction for 1 hour after the dropwise adding is finished, then dropwise adding the rest 20 g of 2.5 wt% sodium persulfate solution at the speed of 15 drops/min, reacting at 80-105 ℃ for 2 hours after the dropwise adding is finished, adding 1 g of 10 wt% sodium phosphite solution, and cooling to obtain 341 g of polymer debonder PJ4 solution, wherein the solid content is 33.12 wt% (including sodium chloride, reducing agent, initiator, chain transfer agent and the like).
Examples 2 to 5:
(1) 60 g of the DTIII solution (containing 18.1 g of DTIII and 3.0 g of potassium chloride) prepared in the example 1 is mixed and stirred with 69.9 g of sodium acrylate, 12 g of disodium maleate, 98.1 g of tap water and 60 g of 10 wt% ammonium hypophosphite solution to obtain 300 g of mixed solution H1;
(2) 10 g of 10 wt% ammonium persulfate solution is dripped into the mixed solution H1 at the speed of 10 drops/min at the stirring speed of 65 ℃ and 200r/min, the temperature is gradually increased at the moment, the solution temperature is kept at 80-105 ℃ for reaction for 1 hour after the dripping is finished, then the rest 10 g of 10 wt% ammonium persulfate solution is dripped at the speed of 10 drops/min, the reaction is carried out at 80-105 ℃ for 2 hours after the dripping is finished, 5 g of 10 wt% potassium phosphite solution is added, and the solution is cooled to obtain 325 g of polymer debonder PJ5 solution, wherein the solid content is 34.31 wt% (comprising potassium chloride, reducing agent, initiator, chain transfer agent and the like).
Examples 2 to 6:
(1) 90 g of the DTIII solution (containing 27.2 g of DTIII and 4.5 g of potassium chloride) prepared in example 1 is mixed and stirred with 48.8 g of sodium methacrylate, 23 g of dipotassium maleate, 1 g of maleic anhydride, 77.2 g of tap water and 60 g of 10 wt% potassium hypophosphite solution to obtain 300 g of mixed solution H1;
(2) dropwise adding 20 g of 7.5 wt% sodium persulfate solution into the mixed solution H1 at the speed of 10 drops/min under the stirring speed of 70 ℃ and 250r/min, gradually raising the temperature, keeping the temperature of the solution at 80-105 ℃ for reaction for 1 hour after the dropwise adding is finished, then dropwise adding the rest 20 g of 7.5 wt% sodium persulfate solution at the speed of 15 drops/min, reacting at 80-105 ℃ for 2 hours after the dropwise adding is finished, adding 1 g of 10 wt% sodium phosphite solution, and cooling to obtain 341 g of PJ6 solution of the polymer debonder, wherein the solid content is 33.31 wt% (including potassium chloride, reducing agent, initiator, chain transfer agent and the like).
Examples 2 to 7:
(1) 60 g (containing 18.1 g of DTIII and 3.0 g of potassium chloride) of the DTIII solution prepared in example 1, 30 g (containing 8.8 g of DTII and 1.76 g of sodium chloride) of the DTII solution, 63.1 g of sodium methacrylate, 10 g of dipotassium maleate, 76.9 g of tap water and 60 g of 10 wt% potassium hypophosphite solution are mixed and stirred to obtain 300 g of mixed solution H1;
(2) dropwise adding 20 g of 7.5 wt% sodium persulfate solution into the mixed solution H1 at the speed of 10 drops/min under the stirring speed of 70 ℃ and 250r/min, gradually raising the temperature, keeping the temperature of the solution at 80-105 ℃ for reaction for 1 hour after the dropwise adding is finished, then dropwise adding the rest 20 g of 7.5 wt% sodium persulfate solution at the speed of 15 drops/min, reacting at 80-105 ℃ for 2 hours after the dropwise adding is finished, adding 1 g of 10 wt% sodium phosphite solution, and cooling to obtain 341 g of polymer debonder PJ7 solution, wherein the solid content is 33.40 wt% (including potassium chloride, sodium chloride, reducing agent, initiator, chain transfer agent and the like).
Table 1 shows the composition of the polymer debonder monomer and the radical oxidation-reduction system used in the above examples.
Table 1: example 2 Polymer debonder monomer and Oxidation-reduction System composition
Figure BDA0002579258890000091
Figure BDA0002579258890000101
EXAMPLE 3 Properties of Polymer debonder
(1) Change in viscosity
The polymer degelling agent solution prepared in example 2 was diluted with an appropriate amount of water to an initial viscosity at 25 ℃ when the polymer degelling agent content (excluding chloride salt) was 30 wt%, and then stored in a sealed state, and after 9 months at room temperature, viscosity test was performed to observe the change in viscosity. The test results are then listed in table 2.
Table 2: viscosity (25 ℃) of the polymer debonder solution (30 wt%, not counting chloride salt)
Figure BDA0002579258890000102
As can be seen from Table 2, the polymer debonder solution prepared by the method has no easily hydrolyzed ester bond and other groups on the main chain of the polymer molecules, almost no change in viscosity after being placed at room temperature for 9 months in a sealing manner, and has good storage stability. Preparation of polymer solutions in example 2In the case of the gel, the reducing agent containing P not only plays a role of a reducing agent in free radical redox to initiate into free radicals, but also can generate chain transfer and termination effects, and continuously participates in the reaction at a higher temperature to enter a polymer main chain to form-P (O) (OM)5) -a bond (see equation 3). When PJ1 is prepared, the dosage of the P-containing reducing agent is only 1.5 wt% of the total monomer amount, the chain transfer is less, the chain growth of the formed polymer is large, the molecular weight is maximum, and the viscosity of the polymer solution is the highest and is 210.5 cP; while the P-containing reducing agent was used in the maximum amount of 10 wt% of the total monomer in the preparation of PJ2, the other conditions were almost the same as in the preparation of PJ1, which gave the highest chain transfer ratio, the lowest molecular weight of the polymer, and the lowest viscosity of 72.1 cP.
Figure BDA0002579258890000111
Reaction formula 3: monomer reaction initiated by P-containing reducing agent and chain initiator
Table 3: functional group composition of polymer debonder
Figure BDA0002579258890000121
Although the total amount of maleic acid salt and maleic anhydride monomers which are used for preparing PJ4 and PJ6 and have poor free radical copolymerization reactivity with acrylic monomers is higher and reaches 23 wt%, polymers with certain molecular weight can be obtained after the free radical reaction due to good copolymerization performance with styrene monomers, and the viscosities of PJ4 and PJ6 with the content of 30 wt% respectively reach 83.8cP and 78.7 cP.
Table 3 shows the calculated functional group composition of the prepared polymer debonder and sodium polyacrylate based on the monomer composition and the addition amount of the P-containing reducing agent, including total carboxylic acid anions (COO)-) The polydentate carboxylic acid anions (containing N carboxylic acid anions and butylene dicarboxylic acid anions) and the hypophosphorous acid bond anions (P (O) -O) with strong chelating function-]-)。
(2) And (3) testing the dispergation performance:
the polymer debonder prepared in example 2 was added to ceramic clay and water of different water quality (including 100 wt% tap water, 20 wt% ceramic reuse water (available from fujiu jew ceramics, which mainly contains three metal ions of high-valent calcium, magnesium and aluminum) +80 wt% tap water) at a rate of 0.2 wt% of the debonder solid (excluding chloride salt)/dry clay (GF-M250, the same applies below) at 25 ℃ of room temperature, respectively, so that the total water content of the slurry was 0.34 and 0.37, respectively, and after grinding for 10 minutes, the fluidity at 25 ℃ of room temperature was measured by using a paint 4 cup, and the experimental results are shown in table 4.
Comparative example 1 (sodium polyacrylate): sodium acrylate (average molecular weight of 3000) was added to a mixture of ceramic clay and water of different water qualities (including 100 wt% tap water, 20 wt% ceramic reuse water (Fushan gold Italy ceramic Co.) +80 wt% tap water) in a proportion of 0.2 wt% of dispergator solid/dry clay (ceramic clay Silicoidaceae GF-M250, the same applies hereinafter) so that the total water content of the slurry was 0.34 and 0.37, respectively, and after grinding for 10 minutes, the change in viscosity of the slurry at room temperature of 25 ℃ was measured by coating 4 cups. The test results are then listed in table 4.
As shown in an experimental test result table 4, the N, P atom-containing polymer dispergator prepared by the invention has outstanding storage stability, and after being sealed and placed for 9 months at room temperature, the initial viscosity and the viscosity change after standing for 5 minutes of ceramic slurry under different water quality conditions are very small under the same slurry water content, the thixotropy of the ceramic slurry (the ratio of the viscosity after standing for 5 minutes to the initial viscosity) is small, the change is very small, and the dispergation performance of the dispergator is stable. It can also be seen from table 4 that although the sodium polyacrylate contains a large amount of carboxylic acid anions (as high as 46.81 wt%), the peptizing performance of the ceramic slurry was good under the condition of tap water quality without ceramic reuse water, the initial fluidity was poor under the condition of water quality containing 20 wt% of ceramic reuse water, and a part of the ceramic slurry did not flow out after standing for 5 minutes, and the peptizing performance was poor. The polymer dispergator prepared by the invention contains a large number of groups which are stable to chelating of high-valence metal ions, and has outstanding dispergation performance on ceramic slurry containing ceramic reuse water quality.
Table 4: dispergation performance of polymer dispergator on ceramic slurry of different water quality (25 ℃ C.)
Figure BDA0002579258890000131
Figure BDA0002579258890000141
In addition, the viscosity of the solution of the dispergator PJ1 prepared by the invention is the largest, the molecular weight of the polymer is the largest, and when the solution is added into ceramic slurry with the same water content, the viscosity of the ceramic slurry is the largest, the fluidity is the worst, and the dispergation effect is the worst; under the condition of tap water (low content of high-valence metal ions), the viscosity of the ceramic slurry added with the same dosage of dispergator is along with the COO in the polymer dispergator-The increase of the total content is reduced, such as from PJ7(37.82) → PJ6(40.54) → PJ2(42.86) → PJ3(43.09) → PJ4(43.22) → PJ5(44.51 wt%), the initial viscosity of the ceramic slurry is from 28.16 → 27.35 → 26.91 → 26.57 → 26.03 → 25.29s, and the viscosity change tendency after standing for 5 minutes is also the same; however, in the water quality of ceramic reuse water containing a large amount of high-valence metal ions, the viscosity of the ceramic slurry changes due to the influence of the high-valence metal ions, and the groups capable of chelating the high-valence metal ions in the polymer debonder molecules (butene dicarboxylic acid anions: (b) (b))-OOC-CHCH-COO-In COO-Calculated as COO), aminocarboxylic acid anion (calculated as COO)-Meter), phosphorous acid bonded negative ion (- [ P (O) -O)-]-) are closely related. The total content of carboxylic acid anions in the PJ4 is 43.22 wt%, the contents of N-containing carboxylic acid anions, butylene dicarboxylic acid anions and hypophosphorous acid anions are respectively 8.30, 14.29 and 3.36 wt%, the sum is the highest, and the dispergation performance of the PJ4 on ceramic slurry containing 20 wt% of ceramic reuse water is the best; secondly, PJ6, wherein the total content of carboxylic acid anions is 40.54 wt%, and the contents of N-containing carboxylic acid anions, butylene dicarboxylic acid anions and hypophosphorous acid bond anions are respectively 9.96, 11.82 and 2.92 wt%; the content of PJ5(44.51 wt%) with highest total carboxylic acid anion content is respectively 6.63, 7.02 and 3.53 wt% of N carboxylic acid anion, butylene dicarboxylic acid anion and hypophosphorous acid bond anion, and the sum of the contents is slightly lower.
In summary, the polymer dispergator prepared by the invention not only has good stability of the viscosity of the dispergator solution, but also keeps good stability of dispergation performance of ceramic slurry under different water quality conditions, and keeps outstanding dispergation performance of ceramic slurry containing ceramic reuse water.
Example 4: properties of composite dispergator
(1) The selection of 4 of the preferred polymer debonders of example 3, PJ3, PJ4, PJ6, PJ5, were combined with an inorganic debonder sodium water glass (modulus 2.2) according to 40: 60 (active solids basis), with sodium tripolyphosphate in a ratio of 95: 5 (calculated by effective solids) at room temperature, compounding to prepare the compound N, P hybrid liquid debonder, wherein the effective solid content of the liquid hybrid debonder is 30 wt%, and observing the change of the viscosity (25 ℃) of the compound debonder along with time. The results of the viscosity change test of the liquid composite debonder are then set forth in table 5.
(2) The prepared liquid composite debonder is respectively taken, and added into ceramic soil and water with different water qualities (comprising a mixture of 100 wt% of tap water, 20 wt% of ceramic reuse water (Fushan gold Italy ceramic company) +80 wt% of tap water) according to the proportion of 0.2 wt% of solid (excluding chloride salt)/dry soil (ceramic clay silica ratio family GF-M250, the same below) of the composite debonder, so that the total water content of the slurry is 0.34 and 0.37 respectively, and after grinding for 10 minutes, the viscosity change of the slurry at room temperature of 25 ℃ is tested by coating 4 cups. The test results are then listed in table 6.
(3) Comparative example 2 (liquid inorganic debonder water glass): water glass (sodium water glass, modulus 2.2, solid content 50 wt%) was added to ceramic clay and water of different water quality (including a mixture of 100 wt% tap water, 20 wt% ceramic reuse water (Fushan gold Italy ceramic Corp) +80 wt% tap water) in a proportion of 0.4 wt% of debonder solid/dry clay (ceramic Clapsidae GF-M250, hereinafter the same) so that the total water content of the slurry was 0.37, and after grinding for 10 minutes, the change in viscosity of the slurry at room temperature 25 ℃ was measured with 4 cups. The test results are then listed in table 6.
Tripolyphosphate, hexametaphosphate and polyphosphate are low in solubility in water and easy to separate out along with the change of environmental temperature, and cannot be independently prepared into a liquid debonding agent.
As shown in the experimental test result table 5, the compound debonder prepared by the method has no precipitation after being placed for a long time. Although the alkali of the water glass is strong, the alkali of the compound debonder prepared from the water glass is also strong, but the debonder also has outstanding storage stability, and the viscosity change is very small after the debonder is placed at room temperature for 9 months in a sealing manner; the viscosity change of the debonder compounded with the sodium tripolyphosphate is small.
Table 5: viscosity change results of liquid composite debonder
Figure BDA0002579258890000161
As can be seen from the experimental test results shown in Table 6, the compound dispergator prepared by the invention also has outstanding storage stability, the initial viscosity of the ceramic slurry under different water quality conditions and the viscosity change after standing for 5 minutes are both very small under the same slurry water content after being sealed and placed for 9 months at room temperature, the thixotropic change of the ceramic slurry (the ratio of the viscosity after standing for 5 minutes to the initial viscosity) is also very small, and the dispergator has stable dispergation performance. While pure inorganic water glass has poor peptizing performance on the ceramic slurry (0.37 water content) under the condition of 0.4 percent of low doping amount.
Table 6: dispergation performance (25 ℃) of liquid composite dispergator on ceramic mud with different water qualities in storage time
Figure BDA0002579258890000171
Therefore, the polymer dispergator without easily hydrolysable groups and the liquid compound dispergator compounded with the inorganic dispergator, which are prepared by the invention, have outstanding storage stability, maintain excellent dispergation performance on ceramic slurry under different water quality conditions, and have outstanding dispergation performance on ceramic slurry containing ceramic reuse water.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A polymer debonder, characterized by the following structural formula:
Figure FDA0002579258880000011
2. the method of preparing a polymer debonder of claim 1, comprising the steps of:
(1) mixing and stirring an amino acid salt substituted styrene monomer or a solution thereof with (methyl) acrylate, maleic anhydride or/and maleate, a P-containing reducing agent solution and water uniformly to obtain a mixed solution H1;
(2) dropwise adding the initiator solution into the mixed solution H1 under stirring, and adding a chain terminator solution after the free radical polymerization reaction under the heating condition to obtain a polymer dispergator;
the amino acid salt substituted styrene monomer has a structure shown in the following formula (II) and/or (III):
Figure FDA0002579258880000012
3. the method according to claim 2, wherein the amino acid salt-substituted styrene-type monomer solution is prepared as follows:
dissolving iminodiacetate or iminodisuccinate in water, adding a mixed solution of p-chloromethyl styrene and a water-soluble organic solvent under stirring, adding a strong alkali aqueous solution, continuously stirring for reacting for 2-4 hours, heating to 40-50 ℃, reacting for 2-4 hours, and cooling to obtain the amino acid salt substituted styrene type monomer solution;
the mol ratio of the iminodiacetate or iminodisuccinate to the p-chloromethyl styrene to the strong base is 1:1: 1;
the strong base is one or more than two of sodium hydroxide, potassium hydroxide, sodium alkoxide and potassium alkoxide.
4. The method according to claim 2, wherein the total content of the water-soluble organic solvent and water in the monomer solution of step (1) is not more than 80 wt%, wherein the content of the water-soluble organic solvent is not more than 30 wt%; the water-soluble organic solvent is one or two of dimethylformamide and dimethylacetamide.
5. The method according to claim 2, wherein the (meth) acrylate is one or more of sodium acrylate, potassium acrylate, sodium methacrylate, and sodium potassium methacrylate;
the maleate is one or more than two of monopotassium maleate, monosodium maleate, dipotassium maleate and disodium maleate;
the P-containing reducing agent is one or more than two of sodium hypophosphite, potassium hypophosphite and ammonium hypophosphite;
the initiator is one or more than two of sodium persulfate, potassium persulfate and ammonium persulfate;
the chain terminator is one or more than two of potassium phosphite, sodium phosphite and phosphorous acid.
6. The preparation method of claim 2, 3, 4 or 5, wherein the amount of the (meth) acrylate is 40-80 wt% of the total amount of the monomers used in the polymer debonder;
the total using amount of the maleate or/and the maleic anhydride is 5-30 wt% of the total amount of the monomers used by the polymer dispergator;
the amount of the amino acid salt substituted styrene type monomer is 8-32 wt% of the total amount of the monomers used in the polymer dispergator;
the initiator accounts for 0.8-4 wt% of the total amount of all the polymerization monomers;
the P-containing reducing agent accounts for 1-12 wt% of the total amount of all the polymerized monomers;
the amount of the chain terminator is 0.08-0.5 wt% of the total amount of all the polymerization monomers;
the total amount of water and the organic solvent in the mixed solution H1 is 80-50 wt% of the total amount of the mixed solution H1.
7. The method of claim 6, wherein the concentration of the P-containing reducing agent solution is 5 to 20 wt%, the concentration of the initiator solution is 1 to 10 wt%, and the concentration of the chain terminator solution is 2 to 20 wt%; the dropping speed of the initiator solution is 7-15 drops/min.
8. The preparation method according to claim 2, 3, 4 or 5, wherein in the step (2), 1/2-2/3 of initiator solution is firstly dropwise added into the mixed solution H1 at the temperature of 60-80 ℃ and the stirring speed of 70-300 r/min, the temperature of the solution is kept at 80-105 ℃ after the dropwise addition, the reaction is carried out for 1-2 hours, then the rest of initiator solution is dropwise added, the reaction is carried out at 80-105 ℃ for 1-2 hours after the dropwise addition, a chain terminator solution is added, and the solution is cooled to obtain the dispergator solution.
9. The composite dispergator is characterized by comprising the polymer dispergator and an inorganic dispergator in claim 1, wherein the solid content of the composite dispergator is 20-50 wt%.
10. The composite debonder of claim 9, wherein the inorganic debonder is water glass, sodium tripolyphosphate, sodium hexametaphosphate, or sodium polyphosphate, and the amount of inorganic debonder solids is 5-500 wt% of the amount of polymer debonder solids.
CN202010662838.2A 2020-07-10 2020-07-10 Polymer debonder and preparation method thereof Withdrawn CN111777708A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113354108A (en) * 2021-05-12 2021-09-07 深圳市点石源水处理技术有限公司 Modified S-carboxyethyl thiosuccinic acid and preparation method and application thereof
CN113549478A (en) * 2021-08-13 2021-10-26 肇庆市欧陶新型材料有限公司 Multi-component copolymer composite dispersant for ceramic phenolic water coal water slurry and preparation method thereof
CN115073187A (en) * 2022-07-01 2022-09-20 江西雄瓷科技有限公司 Preparation method of compound liquid debonder

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113354108A (en) * 2021-05-12 2021-09-07 深圳市点石源水处理技术有限公司 Modified S-carboxyethyl thiosuccinic acid and preparation method and application thereof
CN113354108B (en) * 2021-05-12 2022-04-26 深圳市点石源水处理技术有限公司 Modified S-carboxyethyl thiosuccinic acid and preparation method and application thereof
CN113549478A (en) * 2021-08-13 2021-10-26 肇庆市欧陶新型材料有限公司 Multi-component copolymer composite dispersant for ceramic phenolic water coal water slurry and preparation method thereof
CN115073187A (en) * 2022-07-01 2022-09-20 江西雄瓷科技有限公司 Preparation method of compound liquid debonder

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