CN111454065A - N, P, Si compound organic-inorganic composite ceramic dispergator - Google Patents
N, P, Si compound organic-inorganic composite ceramic dispergator Download PDFInfo
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- CN111454065A CN111454065A CN202010202552.6A CN202010202552A CN111454065A CN 111454065 A CN111454065 A CN 111454065A CN 202010202552 A CN202010202552 A CN 202010202552A CN 111454065 A CN111454065 A CN 111454065A
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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
- C04B35/632—Organic additives
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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
- C04B35/6303—Inorganic additives
- C04B35/6306—Binders based on phosphoric acids or phosphates
- C04B35/6313—Alkali metal or alkaline earth metal phosphates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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
- C04B35/6303—Inorganic additives
- C04B35/6316—Binders based on silicon compounds
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63424—Polyacrylates; Polymethacrylates
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Abstract
The invention discloses an N, P, Si compound organic-inorganic composite ceramic debonder, belonging to the technical field of ceramic auxiliary agent fine chemical industry, which comprises the following effective components:
the micromolecule contains N methylene phosphonate,
Polyacrylate salt,
Polyphosphate or/and metaphosphate,
Silicate (M)2O·nSiO2) Or/and metasilicate to form solid dispergator, or the effective component and
Description
Technical Field
The invention relates to the technical field of ceramic auxiliary agent fine chemical industry, in particular to an N, P, Si compound organic-inorganic composite ceramic dispergator.
Background
The ceramic debonder (also called water reducing agent) is used as one of the ceramic additives, and has the main functions of destroying the flocculation structure of ceramic slurry particles, so that the slurry still has better dispersibility and lower viscosity under the condition of lower water content, is convenient to operate and form, and can play a certain role in energy conservation and consumption reduction. The ceramic dispergator can be widely applied to the ceramic production process of mud making, pulp grinding, glaze making and the like in the ceramic industry.
The inorganic dispergator is the dispergator with the largest use amount in the ceramic industry, and the water glass has low price, is the most common inorganic ceramic dispergator in the ceramic industry, is commonly used for the dispersion and dispergation of ceramic slurry, keeps certain fluidity of the slurry and is convenient to operate and form. However, the inorganic dispergator is influenced by factors such as molecular structure, relative molecular mass and the like, has poor water reducing effect and narrow dispergation range, can obtain better fluidity when the addition amount is larger (more than 0.5wt percent), and has larger contact with ceramic slurry. Particularly for ceramic slurry with high content of alumina and the like or ceramic slurry with certain impurities or metal ions mixed by other natural factors, environmental pollution and human factors, the slurry dispergation is often disabled by the water glass or polyphosphate of the single inorganic dispergator with low doping amount, the polyphosphate of the single inorganic dispergator has low solubility in water, is easy to hydrolyze, has poor adaptability to slurry of different materials and production areas, and brings great uncertainty to production.
Disclosure of Invention
The invention aims to provide an N, P, Si compound organic-inorganic composite ceramic debonder, which solves the problems that the inorganic debonder provided in the background art is influenced by factors such as molecular structure, relative molecular mass and the like, has poor water reducing effect, has a relatively wide debonding range, has large contact with ceramic slurry, has low solubility of polyphosphate in water, is easy to hydrolyze, has poor adaptability to slurry of different materials and production areas, brings great uncertainty to production, and is easy to crack or shatter ceramic products at high doping amount after a slurry blank is fired at high temperature.
In order to achieve the purpose, the invention provides the following technical scheme: an N, P, Si compound organic-inorganic composite ceramic debonder comprises the following raw materials:
the total weight of the above components (excluding water of crystallization) is 100 wt%, wherein M ═ Na, K, 3> n >1, and M ═ 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;
the micromolecule contains N methylene phosphonate which is at least one of sodium salt and potassium salt and comprises amino trimethylene phosphonate, ethylene diamine tetra methylene phosphonate, diethylene triamine pentamethylene phosphonate, N-2 hydroxyethyl-N-dimethyl methylene phosphonate, ethoxyethyl diamine tetra methylene phosphonate, 1, 3-diamine-2-propanol tetra methylene phosphonate, (2-hydroxy) ethoxy ethylamine dimethyl methylene phosphonate, piperazine dimethyl methylene phosphonate, aminoethyl piperazine trimethyl methylene phosphonate, glycine dimethyl methylene phosphonate, hydroxymethyl glycine dimethyl methylene phosphonate, glutamic dimethyl methylene phosphonate, formamido methyl methylene phosphonate, acetamido methyl methylene phosphonate or ureido tetramethyl methylene phosphonate;
the raw materials are prepared into N, P, Si compound organic-inorganic composite ceramic dispergator.
Preferably, the polyacrylate is sodium salt or potassium salt and has a molecular weight of
In the meantime.
Preferably, the polyphosphate is sodium salt and potassium salt, and comprises tripolyphosphate, pyrophosphate or polyphosphate.
Preferably, the metaphosphate is sodium salt or potassium salt, including trimetaphosphate and hexametaphosphate.
Preferably, the silicate is water-soluble sodium salt and potassium salt, and comprises solid or liquid sodium water glass and potassium water glass.
Preferably, the metasilicate is sodium salt and potassium salt, and comprises metasilicate pentahydrate, metasilicate hexahydrate and metasilicate nonahydrate.
Preferably, the preparation method of the N, P, Si compound organic-inorganic composite ceramic dispergator from the raw materials comprises the following preparation methods:
(1) will be provided with
Small molecule powder containing N methylene phosphonate,
Polyacrylate powder,
Polyphosphate or/and metaphosphate powder,
Silicate or/and metasilicate powder (not containing crystal water) are uniformly mixed to obtain 100 wt% of solid dispergator;
alternatively, (2) 100 wt% of the solid dispergator obtained in (1) above was added
Dissolving the water by weight to prepare a liquid water solution type ceramic debonder;
or, (3) mixing the solid or aqueous solution of the components according to
Small molecule containing N methylene phosphonate powder,
Polyacrylate salt,
Polyphosphate or/and metaphosphate,
Silicate or/and metasilicate (not containing crystal water) and the total amount of water is the total amount of effective components
The water is mixed, stirred and dissolved to prepare the liquid water solution type ceramic debonder.
Compared with the prior art, the invention has the beneficial effects that:
1) compared with the blank inorganic debonder silicate water glass and metasilicate, the prepared organic-inorganic composite ceramic debonder has obvious debonding effect on ceramic slurry at low consumption and low water content, shows outstanding fluidity and dispersion water-reducing effect, has small fluidity loss after being placed, small thixotropy and easy molding, and ensures that the surface of a ceramic product fired at high temperature is flat and has no defects of cracks and the like; the blank inorganic debonder silicate waterglass and metasilicate have still unobvious debonding effect at higher consumption and higher water content, are large in touch, inconvenient to operate and form, and have the defects of uneven surface or cracks and the like of a formed and fired ceramic product;
2) the prepared organic-inorganic composite ceramic dispergator has the advantages that with the increase of the proportion of N methylene phosphonate and polyacrylate contained in organic micromolecules, the dispergation effect is obviously enhanced, the initial viscosity of the ceramic slurry is reduced, the fluidity loss after the ceramic slurry is placed is reduced, and the thixotropy is reduced. The dosage is low, the dispersion and dispergation effects are outstanding, the touch becomes small, and the molding is easy; the water reducing effect is obvious, and a large amount of energy can be saved; few influencing factors, small defects of high-temperature sintered products and high yield.
Detailed Description
The described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: an N, P, Si compound organic-inorganic composite ceramic dispergator comprises the following raw materials:
the total weight of the above components (excluding water of crystallization) is 100 wt%, wherein M ═ Na, K, 3> n >1, and M ═ 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;
the micromolecule contains N methylene phosphonate which is at least one of sodium salt and potassium salt and comprises amino trimethylene phosphonate, ethylene diamine tetra methylene phosphonate, diethylene triamine pentamethylene phosphonate, N-2 hydroxyethyl-N-dimethyl methylene phosphonate, ethoxyethyl diamine tetra methylene phosphonate, 1, 3-diamine-2-propanol tetra methylene phosphonate, (2-hydroxy) ethoxy ethylamine dimethyl methylene phosphonate, piperazine dimethyl methylene phosphonate, aminoethyl piperazine trimethyl methylene phosphonate, glycine dimethyl methylene phosphonate, hydroxymethyl glycine dimethyl methylene phosphonate, glutamic dimethyl methylene phosphonate, formamido methyl methylene phosphonate, acetamido methyl methylene phosphonate or ureido tetramethyl methylene phosphonate;
the raw materials are prepared into N, P, Si compound organic-inorganic composite ceramic dispergator.
Further, the polyacrylate is sodium salt or potassium salt, and has molecular weight of
In the meantime.
Further, the polyphosphate is sodium salt, potassium salt, including tripolyphosphate, pyrophosphate or polyphosphate.
Further, the metaphosphate is sodium salt and potassium salt, including trimetaphosphate and hexametaphosphate.
Further, the silicate is water-soluble sodium salt and potassium salt, including solid or liquid sodium water glass and potassium water glass.
Further, the metasilicate is sodium salt and potassium salt, including metasilicate pentahydrate, metasilicate hexahydrate and metasilicate nonahydrate.
Further, the preparation method of the N, P, Si compound organic-inorganic composite ceramic dispergator from the raw materials comprises the following preparation methods:
(1) will be provided with
Small molecule powder containing N methylene phosphonate,
Polyacrylate powder,
Polyphosphate or/and metaphosphate powder,
Silicate or/and metasilicate powder (not containing crystal water) are uniformly mixed to obtain 100 wt% of solid dispergator;
alternatively, (2) 100 wt% of the solid dispergator obtained in (1) above was added
Dissolving by weight of water to prepare a liquid water solution type ceramic debonder;
alternatively, the first and second electrodes may be,(3) mixing the solid or aqueous solution of the components according to
Small molecule containing N methylene phosphonate powder,
Polyacrylate salt,
Polyphosphate or/and metaphosphate,
Silicate or/and metasilicate (not containing crystal water) and the total amount of water is the total amount of effective components
The water is mixed, stirred and dissolved to prepare the liquid water solution type ceramic debonder.
Example 1
15 parts by weight of ethylenediamine tetramethylene sodium phosphonate powder and 160.25 parts by weight of hexahydrate sodium metasilicate powder (85 parts by weight of sodium metasilicate) are uniformly mixed to obtain 175.25 parts by weight of the solid organic-inorganic composite dispergator. Then a certain proportion of the slurry was added to a certain amount of aqueous ceramic slurry, after grinding for 10 minutes, the initial viscosity of the slurry and its change in fluidity were measured at room temperature of 25 ℃, the slurry was sintered at high temperature of 1200 ℃ after molding, and the surface condition of the product was observed, and the results are shown in table 1.
Example 2
30 parts by weight of amino trimethylene sodium phosphonate powder, 10 parts by weight of potassium tripolyphosphate, 120 parts by weight of potassium silicate water glass solution (modulus is 2.5, concentration is 50 wt%) and 240 parts by weight of water are uniformly mixed to obtain 400 parts by weight of liquid organic-inorganic composite debonder with content of 25 wt%. Then, a predetermined amount of the slurry was added to a predetermined amount of aqueous ceramic slurry, and after grinding for 10 minutes, the initial viscosity and the change in fluidity of the slurry were measured at room temperature of 25 ℃, after molding, the slurry was sintered at a high temperature of 1200 ℃, and the surface condition of the product was observed, and the results are shown in Table 1.
Example 3
50 parts by weight of diethylenetriamine penta (methylene phosphonic acid) sodium powder, 10 parts by weight of sodium tripolyphosphate and 93.11 parts by weight of sodium metasilicate nonahydrate powder (40 parts by weight of sodium metasilicate) are uniformly mixed to obtain 153.11 parts by weight of the solid organic-inorganic composite dispergator. Then, a certain proportion of the slurry was added to a certain amount of aqueous ceramic slurry, after grinding for 10 minutes, the initial viscosity and the change in fluidity of the slurry were measured at room temperature of 25 ℃, the slurry was sintered at high temperature of 1200 ℃ after molding, and the surface condition of the product was observed, and the results are shown in table 1.
Example 4
50 parts by weight of glycine dimethylidene sodium phosphonate powder, 3 parts by weight of sodium polyacrylate (average molecular weight of 9500), 10 parts by weight of potassium tripolyphosphate and 64.30 parts by weight of sodium metasilicate pentahydrate powder (37 parts by weight of sodium metasilicate) are uniformly mixed to obtain 127.30 parts by weight of the solid organic-inorganic composite dispergator. Then a certain proportion of the slurry is added into a certain amount of water-containing ceramic slurry, after grinding for 10 minutes, the initial viscosity and the fluidity change of the slurry are measured at the room temperature of 25 ℃, the slurry is sintered at the high temperature of 1200 ℃ after forming, the surface condition of the product is observed, and the results are listed in table 1.
Example 5
20 parts by weight of an ethylenediamine tetramethylene potassium phosphonate aqueous solution (30 wt%), 30 parts by weight of sodium polyacrylate (average molecular weight 1500) powder, 4 parts by weight of potassium pyrophosphate powder, 40 parts by weight of solid sodium silicate glass (modulus 1.5), 37.70 parts by weight of sodium metasilicate hexahydrate powder (20 parts by weight of sodium metasilicate) and 118.3 parts by weight of water are mixed and stirred uniformly to obtain 250 parts by weight of a 40% liquid organic-inorganic composite dispergator. Then a certain proportion of the slurry was added to a certain amount of aqueous ceramic slurry, the initial viscosity of the slurry and the change in fluidity thereof were measured, the slurry was sintered at a high temperature of 1200 ℃ after molding, the surface condition of the product was observed, and the results are shown in Table 1.
Example 6
Uniformly mixing 50 parts by weight of amino trimethylene phosphonic acid sodium, 30 parts by weight of sodium polyacrylate (average molecular weight 1500) powder, 10 parts by weight of potassium tripolyphosphate and 17.38 parts by weight of sodium metasilicate pentahydrate powder (10 parts by weight of sodium metasilicate), adding 392.62 parts by weight, stirring and dissolving to obtain the liquid organic-inorganic composite dispergator with the content of 20 wt%. Then a certain proportion of the slurry was added to a certain amount of aqueous ceramic slurry, the initial viscosity of the slurry and the change in fluidity thereof were measured, the slurry was sintered at a high temperature of 1200 ℃ after molding, the surface condition of the product was observed, and the results are shown in Table 1.
Table 1: test results of various dispergents on fluidity and sintering test of ceramic slurry
As can be seen from the results of fluidity tests and sintering tests shown in Table 1, compared with silicate waterglass and metasilicate which are used as blank inorganic debonding agents, the organic-inorganic composite ceramic debonding agent prepared by the invention has an obvious debonding effect on ceramic slurry at a low dosage of 0.15 wt%, the ceramic slurry shows outstanding fluidity at a low water content of 33 wt%, and the ceramic slurry has the advantages of small fluidity loss after being placed, small thixotropy and easy molding, and the surface of a ceramic product fired at high temperature is flat and has no defects such as cracks; the ungluing effect of the blank inorganic debonder silicate waterglass and metasilicate is still not obvious when the dosage is 0.3 wt% and the higher water content is 37 wt%, the surface of the formed and fired ceramic product is not flat, the debonder can be debonded when the dosage of the debonder is increased to 0.75 wt%, but the fluidity loss after the ceramic product is placed is large, the thixotropy is large, and the surface of the product fired at high temperature has the defects of cracks and the like.
While there have been shown and described the fundamental principles and essential features of the invention and advantages thereof, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof; the present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. An N, P, Si compound organic-inorganic composite ceramic dispergator, which is characterized in that: the raw materials comprise the following components:
the total weight of the above components (excluding water of crystallization) is 100 wt%, wherein M ═ Na, K, 3> n >1, and M ═ 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10;
the micromolecule contains N methylene phosphonate which is at least one of sodium salt and sylvite, and comprises amino trimethylene phosphonate, ethylene diamine tetra methylene phosphonate, diethylene triamine pentamethylene phosphonate, N-2 hydroxyethyl-N-dimethyl methylene phosphonate, ethoxyethyl diamine tetra methylene phosphonate, 1, 3-diamine-2-propanol tetramethylene phosphonate, (2-hydroxy) ethoxy ethylamine dimethyl methylene phosphonate, piperazine dimethyl methylene phosphonate, aminoethyl piperazine trimethyl methylene phosphonate, glycine dimethyl methylene phosphonate, hydroxymethyl glycine dimethyl methylene phosphonate, glutamic acid dimethyl methylene phosphonate, formamido monomethyl methylene phosphonate, acetamido-monomethyl methylene phosphonate or ureido tetramethyl methylene phosphonate;
the raw materials are prepared into N, P, Si compound organic-inorganic composite ceramic dispergator.
2. The N, P, Si Compound organic-inorganic composite ceramic debonder of claim 1, wherein: the polyacrylate is sodium salt or potassium salt and has a molecular weight of
In the meantime.
3. The N, P, Si Compound organic-inorganic composite ceramic debonder of claim 1, wherein: the polyphosphate is sodium salt and potassium salt, and comprises tripolyphosphate, pyrophosphate or polyphosphate.
4. The N, P, Si Compound organic-inorganic composite ceramic debonder of claim 1, wherein: the metaphosphate is sodium salt and potassium salt, including trimetaphosphate and hexametaphosphate.
5. The N, P, Si Compound organic-inorganic composite ceramic debonder of claim 1, wherein: the silicate is water soluble sodium salt and potassium salt, including solid or liquid sodium water glass and potassium water glass.
6. The N, P, Si Compound organic-inorganic composite ceramic debonder of claim 1, wherein: the metasilicate is sodium salt and sylvite, including metasilicate pentahydrate, metasilicate hexahydrate and metasilicate nonahydrate.
7. The N, P, Si Compound organic-inorganic composite ceramic debonder of claim 1, wherein: the preparation method of the N, P, Si compound organic-inorganic composite ceramic dispergator from the raw materials comprises the following steps:
(1) will be provided with
Small molecule powder containing N methylene phosphonate,
Polyacrylate powder,
Polyphosphate or/and metaphosphate powder,
Silicate or/and metasilicate powder (not containing crystal water) are uniformly mixed to obtain 100 wt% of solid dispergator;
alternatively, (2) 100 wt% of the solid dispergator obtained in (1) above was added
Dissolving by weight of water to prepare a liquid water solution type ceramic debonder;
or, (3) mixing the solid or aqueous solution of the components according to
Small molecule powder containing N methylene phosphonate,
Polyacrylate salt,
Polyphosphate or/and metaphosphate,
Silicate or/and metasilicate (not containing crystal water) and the total amount of the active ingredients is calculated according to the total amount of the silicate or/and metasilicate and the total amount of the crystal water
Mixing and stirring the mixture by times of water to dissolve the mixture to prepare the liquid water solution type ceramic debonder.
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| CN112960985A (en) * | 2021-01-22 | 2021-06-15 | 佛山市山有海科技有限公司 | Liquid dispergation reinforcing agent and preparation method thereof |
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| CN110028642A (en) * | 2018-12-19 | 2019-07-19 | 江苏苏博特新材料股份有限公司 | A kind of sulfamate polymeric dispersant and preparation method thereof and its application in ceramic slurries |
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Application publication date: 20200728 |