CZ9902688A3 - Preparation and use of water-soluble polymers with attached functional groups derived from amides, esters and ethers such as ceramic dispersants and binding agents - Google Patents

Abstract

The present invention relates to the preparation and use of water-soluble polymers as binders for dispersing and bonding ceramic materials in an aqueous medium. For dispersing and bonding different classes water-soluble polymers are used with functional groups based on amides, esters and ethers

Description

Preparation and use of water-soluble polymers with attached functional groups derived from amides, esters and ethers as ceramic dispersing agents and binders.

Technical field

Methods of dispersion and bonding of ceramic materials in aqueous media are described. These methods use water-soluble polymers that have functional groups derived from amides, esters and ethers to disperse and bond different classes of ceramic materials.

BACKGROUND OF THE INVENTION

Ceramic materials are commonly prepared by mixing powdered ceramic oxides such as magnesium, aluminum, titanium, and zirconium oxides into a slurry together with other additives such as dispersing agents and binders. Spray drying of the slurry produces ceramic particles. These particles are compressed into a unit, called "unburned ceramics". At this point, the whole has the desired shape and is then subjected to a high-temperature treatment, which is called firing. The firing process converts the unburnt ceramic into a coherent “burnt ceramic”, which has an almost monolithic, polycrystalline ceramic structure.

The binder serves to keep the parts of the unburnt ceramics in the desired shape after compression. It can also provide humidification when compressing ceramic parts. In a preferred embodiment, the binder is completely burned or vaporized during firing and leaves no trace in the fired ceramic.

- 2 · · · · · · · · · · · · · · · · · · · ·

By fulfilling or not fulfilling these functions, the binders can appreciably affect the properties of the resulting fired ceramic.

In common practice, polyvinyl alcohols are commonly used as ceramic binders. Furthermore, copolymers of polyethylene oxides and ethylene vinyl acetate are used for some materials, such as granulated silica gel.

For example, polymeric binders containing copolymers of hydrolyzed copolymers made from monomers and having ester or amide functional groups, polyvinylformamide, or a vinyl alcohol / vinylamine copolymer are disclosed in U.S. Pat. Nos. 5358911, 54877855 and 5525665.

Further, the use of polymers has been described in U.S. Pat. Nos. 4680339, 4731419, 4885345 and 5084520. Their use as dispersing agents in water treatment, scale inhibitors in industrial and natural waters, flocculants, precipitating agents and thickeners has been described, but their use in joining and dispersing ceramics has not been described.

Although commercially available binders are sufficient for many applications, there is still a need for improved binders that provide even more strength and / or density to unburned ceramic materials. Greater strength will limit the breakability of the unburnt ceramic when handled and is generally related to the higher quality of the fired ceramic. Preferably, these improved binders should be cheaper and also have a wider use than the binders hitherto known.

Spray drying is an evaporation process during which a slurry containing both liquid and

- 3 non-volatile solid component, liquid component removed. The fluid is evaporated by direct contact with the drying medium, usually air, in an extremely short retention time, such as from about 3 to 30 seconds. The primary factors governing the drying process are the size, size distribution and shape of the dried part, density and viscosity of the casting slurry, temperature, time of placement and moisture of the product.

The viscosity of the casting slurry must comply with the handling and spray drying requirements. Although the properties of the spray drier can be adjusted to accommodate materials of different viscosities, larger ceramic portions can be made from more viscous slurries.

Those skilled in the art are familiar with the spray drying process used in the manufacture of ceramic materials and will be able to optimize spray drying control factors for best results. Alternatively, the spray-drying process may be replaced by other well known processes, such as granulation, stripping or dipping of coarse stoneware.

Spray-drying the slurry produces pellet-dry, free-moving dust particles containing the ceramic material, binder and other possible materials described above. These dry particles are generally spherical in shape and have a radius of 50 to 300 microns. Typically, 0.5 to 8 percent of the binder attached to the dry ceramic powder particles is present in these dry particles.

During granulation, a mixture of dry powder or dry powders is mixed and rolled, usually in a barrel-shaped device.

• ···· · · · * tvaru tvaru tvaru tvaru tvaru tvaru tvaru tvaru Water and / or binder solution is injected into the mixing powder, causing small particles to agglomerate into larger granules. The size of the granules is controlled by the amount of material injected into the powder and the rate at which it is injected. The granulated powder can be sieved to the desired size and compressed to a certain shape by compression that precedes firing. Another possibility is that the granules themselves should be the desired product and in this case they are fired straight.

For the production of thin plates for the computer industry, tape casting is commonly used. In this process, a thick layer of ceramic casting slurry, a dispersing agent and a binder are first prepared. The slurry spreads on a smooth surface, such as a mylar or plastic plate. The thickness of the resulting slurry layer is controlled by slipping the slurry under the blade to smooth the slurry surface and scrape off excess material. The slurry tape is dried to make the slurry plastic, then sliced and shaped as desired. The binder volume in the strip casting process is very high, usually about 15 to 20 weight percent of the ceramic powder mass.

In fluidized bed spray drying, small so-called seed particles are placed in the distillation apparatus, and then hot air is blown into the seed powder, causing the particles to float freely in the distillation apparatus. Then a ceramic slurry is sprayed on the seed particles from above, causing them to grow. When the particles have grown to a sufficient size, they are exhausted from the dryer, after which new seed particles are inserted. This process can produce a powder usable in the next processing process, or it can also be the final product itself.

- 5 yourself. In such a case, it is subsequently fired to form the final ceramic.

The dried particles are then joined to form a compact, unburned ceramic structure. Preferably, the particles should be joined by pressing in presses having an internal volume which roughly corresponds to the shape that the resulting fired ceramic product should have. Alternatively, the particles may be bonded by rolling or other well known bonding methods. The spray-dried mixture of powder, binder and possible other additives and lubricants is relatively free-formable so that it can be inserted into the press and is able to adapt to its shape.

Inside the press, the particles are subjected to a pressure which is usually in the range of 350 - 3500 kg / cm ² . Compressing the particles produces a compact structure, called unburned ceramic, which retains its shape when removed from the press.

One of the techniques used to spray-dry or granulated material is rolling, which is that the dry powder is drawn between two rolls. Ceramic plates of different thickness and width are obtained in this way. These plates can be cut to the desired shape and fired to form the resulting ceramic article. This process is usually used in the manufacture of ceramic plates for the computer industry.

Dry compression involves filling the shaped press by spray drying with dried or granulated powder and compressing it with high pressure. The compression is accomplished by means of movable pistons located at the top and / or bottom of the cavity.

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This process can be used to produce relatively complex shapes in one single molding step. The resulting ceramic body is removed from the press and fired to form the final ceramic product.

Isostatic compression is similar to dry compression in that the ceramic powder is compressed within the cavity of the press. However, in isostatic compression, either the entire or at least a portion of the press wall consists of a resilient material. After filling the cavity of the press with powder, the press is immersed in a pressure chamber filled with fluid and by means of a press the press of the press and the connection of the powder are achieved. Unlike dry compression, no moving parts are used. Isostatic compression is commonly used in the manufacture of bulky or very long objects to limit the likelihood of cracking or peeling of the resulting unburned ceramic body.

Extrusion involves extruding a concentrated, plastic ceramic slurry through an opening having the shape and size of the desired ceramic article. This process is typically used in the manufacture of ceramic pipes or objects of similar shape. The slurry used is prepared from a dry powder mixed with water, organic binders, lubricants and a precipitating agent. This slurry is usually pre-dried in a filter press or similar device to remove water and to concentrate the slurry to a degree that is plastic. This material is then forced through a press which is controlled by either a piston or a screw. After extrusion, the material is shortened to the desired length, dried and fired.

The beading is commonly used in the manufacture of white ceramics for extruding or molding

- 7 4 · · 4 4 * ceramic slurries. The slurry piece is usually placed on a rotating wheel and formed into rollers by the rollers and / or the blade of the knife. This body is then dried and fired.

Another method of forming ceramics, which is used in the manufacture of parts of a particular unit, is soaking coarse stoneware. In this process, a concentrated ceramic slurry (coarse coating) is poured into a mold having the shape of a desired ceramic body therein. The slurry used must be very concentrated to avoid particle deposition and / or excessive precipitation or loss of volume or weight during drying. At the same time, however, it must be sufficiently fluid to perfectly fill the entire interior of the mold and to allow air bubbles to escape. The presence of the polymeric binder will add strength to the body and limit breakage in mold removal and handling prior to firing.

Heating the compact structure removes evaporable materials such as water and burns organic materials as binders or other additives. When a sufficiently high temperature is reached, the particles of the structure begin to bond (but do not fully bond) and firmly bond to each other, thereby forming a relatively strong fired ceramic having approximately the desired shape.

The slurry can be dried, for example, by spray-drying to form pellet-dry portions. These portions should preferably be compressed to form a cohesive, unburnt ceramic structure and then heated to form a fired ceramic. In addition, the particles may •

- 8 - · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · known procedures.

Although commercially available binders are sufficient for many applications, there is still a need for improved binders that provide even more strength and / or density to unburned ceramic materials. Greater strength will limit the breakability of the unburnt ceramic when handled and is generally related to the higher quality of the fired ceramic. Preferably, these improved binders should be cheaper and also have a wider use than the binders hitherto known.

The invention also relates to a process for dispersing ceramic materials, in particular to a process for dispersing one or more ceramic materials in an aqueous medium using a polymeric dispersing agent formed from acid-containing monomers and hydroxyl-functional monomers.

Ceramic materials are often used in the production of light, solid and thermally and chemically resistant products. Because of the difficulty of handling solid ceramic materials, it is desirable that they be in the form of a water dispersion. However, aqueous dispersions of ceramic materials are often unstable and precipitate upon standing, dispersion becomes sticky and becomes inhomogeneous, making handling difficult. Cartons can also damage pipes, pumps, and other mechanical devices designed to handle dispersions. By using dispersing agents, these problems can be avoided while increasing the strength and density of the ceramic articles produced, in particular articles made by dry compression, soaking of coarse stoneware and strip peeling.

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0

Polymers used as dispersing agents for ceramic materials are known. Conventional dispersing agents for ceramic materials include polymers formed from acid-containing monomers, such as polymerized acrylic acid or polymerized polymethacrylic acid. For example, anionic polymers made by hydrolyzing a maleic anhydride trimmer, N-vinylpyrrolidinone and a vinyl component selected from the group consisting of acrylic acid, methyl methacrylate, and butyl vinyl ether are disclosed in U.S. Pat. Further, polymer dispersing agents which consist of 5-95 weight percent of one or more hydroxyl functional monomers and 95-5 weight percent of one or more acid-containing monomers are described in U.S. Pat. The hydroxyl functional monomer is selected from the group consisting of hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, allyloxyethanol, allylpropoxylate, vinyl acetate, 1-butene-3,4-diol and 3-allyloxypropane. -diol.

Further, imidized acrylic polymers have been described as being useful for increasing the spreadability of cementitious compositions in U.S. Pat. No. 5393343.

These polymers are sufficient to disperse some ceramic materials. However, dispersion of certain ceramic materials is more difficult and conventional polymeric dispersing agents are insufficient. Ceramic materials exhibiting partial difficulty in forming dispersions include nitrides such as boron nitride. U.S. Pat. No. 5209885 discloses a silica nitride dispersion using a graft copolymer comprising

Polyoxyalkylene backbone and polyacrylate side chains.

The present invention seeks to provide a method for dispersing ceramic materials, including materials known to be difficult to disperse.

SUMMARY OF THE INVENTION

Methods of dispersion and bonding of ceramic materials in an aqueous environment are described. These methods utilize water-soluble polymers with attached functional groups derived from amides, esters and ethers to disperse and bond ceramic materials of various classes.

Each of the five groups of polymers described herein may also have use in mine work, for example, to reduce air dust and sludge flocculation; in the treatment of cooling water, for example to reduce corrosion and scale formation, for example to limit the deposition of calcium carbonate or calcium phosphite; when working with ceramics, for example in the processing of unfired ceramics or in the process of forming gypsum tile cores; in the preparation of gypsum slurry and for the suppression of reverse osmosis such as desalination; in oil mining, for example additives to prevent emulsion reversal and, for example, to reduce the deposition of barium sulfate and calcium carbonate; in the treatment of paper and paper, for example as deposit restrictors, sizing agents, dry-strength additives, separators and as preparations used in the separation of liquids and solids. These structures can also be used, inter alia, as dispersing agents, flocculants, precipitating agents and thickeners.

4

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Φ Φ Φ ·

4 4 ·

444 444 • Φ

4 4 4

The invention relates to polymeric binders and their use in the preparation of ceramic materials. This method can be used to make fired ceramic materials from ceramic powder. Suitable powders include, but are not limited to: aluminum oxide, silica nitride, aluminum nitride, silicon carbide, silica, magnesium oxide, lead oxide, zirconia, titanium dioxide, and neodymium oxide. Aluminum oxide is particularly recommended. The powder particles may have a mean size ranging from a few nanometers to about 1/2 millimeter. Powders with a particle size in the range of about 0.5 to 10 microns are recommended.

Mixing the ceramic powder with an aqueous solution containing the polymer results in a ceramic slurry. Preferably, deionized water should be used to prepare the slurry. The slurry may also contain lubricants, emollients, and other additives such as dispersing or anti-foam agents.

It is also known that ceramic properties such as (but not limited to) firing density, surface quality or milling or rolling properties can be varied as desired by varying the ratio of the various monomers in the copolymer, the degree of hydrolysis of the copolymer, and the molecular weight of the polymer. used in the binder mixture.

Several factors may affect the amount of polymer dispersant required to produce the ceramic dispersion. Due to the wide range of ceramic materials that can be used for individual purposes and the fact that many different uses may require different levels of solids contained, the amount of dispersant can

99

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999 9999

99

9 9 9

9 9 9

999 999 ·

9 to 9, in the range of 0.01 to 3 weight percent, based on the weight of the powder. For example, the morphology of the ceramic material may affect the value of the optimum amount of dispersant. In general, the closer the particles are to the shape of a perfect sphere, the less dispersant is required. Also, the surface area of the ceramic material can affect the optimum amount of dispersant. The larger the surface area of the ceramic material, the more dispersant is usually required.

Also, the ionic strength (or water hardness) of the dispersion can affect the optimum amount of the dispersant. The ionic strength can be controlled, for example, by using distilled, deionized, partially distilled or partially deionized water, by controlling the amount of contaminants present in solution together with its various components, or by adding or admixing one or more chelating agents to the solution. Preferably, the hardness of the water used in the solution relative to the amount of polyvalent cations should not exceed about 600 parts Ca ²⁺ per million, preferably when it does not exceed 500 parts per million. Generally, the higher the pH of the solution, the less amount of dispersant is required. For purposes of the present invention, it is recommended that the pH is not less than 6. The polymeric dispersing agent of the present invention is particularly effective at a pH of from 8 to 11.

Ceramic materials useful in forming the solution of the present invention include oxide, nitride and carbonate ceramics; specifically: aluminum oxide, aluminum nitride, lead titanite, boron nitride, silicon, silicon carbonate, sialon, zirconium nitride, zirconium carbonate, zirconium boride, tungsten carbonate, stannous oxide, ruthenium oxide, • 9

Yttrium, magnesium oxide, calcium oxide, chromium oxide, ferromagnetic oxides and mixtures thereof.

As has been said here, "ceramic materials" include ferromagnetic oxides, in short ferrites. Ferrite classes include spinel ferrites, which are oxides having the general formula MO. Fe 2 C> 3, where "M" is a divalent metal ion or ion mixture. Examples of spinel ferrites are Fe3O ₄ NiFe2O and _fourth Another class of ferrites are orthopherites whose general formula is MFeO3.MCoO3, or Mh / lnCty where “M” is La, Ca, Sr, Ba, Y or some rare earth ion. Another class of ferrites are hexagonal ferrites having the general formula AB ₁₂₀ O ₁₉ when A is a divalent metal and B is a trivalent metal. An example of a hexagonal ferrite is PbFe ₁₂ Oig.

The term clays as used herein are materials used in the manufacture of sanitary engineering such as kaolin.

The polymers described herein for use in the present invention should have a molecular weight in the range of 1000 to 1000000. Preferably, the molecular weight should be in the range of 5000 to 100000. For the polymers defined herein, the number of monomer units defined by formulas I IV should be between 5% and 75% of the total number of monomer units in the polymer. In a preferred embodiment, the number of monomer units defined by formulas I-IV should exceed 30% of the total number of monomer units in the polymer.

Classes of polymers described herein include amide, ester, and ether monomer units with attached functional groups. These pendant groups give the polymer favorable properties when used as a binder of ceramic materials.

- 14 4 4 · · 44 4 44 44

4 444 4 4 44 4

44 «4 · 4 4 4

44 4 4 444444

4 4 4 4 4 5

444 44 444 4444

The polymers are formed by polymerization using certain monomers, for example those formed by copolymerization of acrylic acid with a polyethylene glycol methacrylate comonomer. The polymer thus prepared will consist of a hydrophilic backbone and pendant groups composed of polyethylene glycol. The pendant groups may also be attached to the polymer after polymerization. For example, polyacrylic acid may be aminated with an ethyleneoxy or propoxylated amine, such as available from Texaco under the tradename Jeffamine, to form a hydrophilic backbone and ethylene oxide or propylene oxide pendant groups. During the amination process, cyclic imide structures may form on the polymer backbone between two adjacent carboxylate or carboxyamide groups. These imide structures are not expected to have an adverse effect on the utility of polymers as processing aids in ceramics.

The present invention provides a ceramic binder comprising a water-soluble polymer having:

A) monomer units of the formula

R ⁵ R ⁶

-C-CHC = O

NR ¹ (11HR ² CHR ³ H ² -tyCHR ² CHR ³ Het ² ty-R ⁴

- 15 99 9 ·· ·· ··

9 9 9 9 9 9 4 9 4

4 9 4 9 4 9 4 449 4999 94 9 where R ¹ belongs to the group consisting of hydrogen and C 1 -C 3 alkyl p and q are integers from the interval 1-10; R ² and R ³ belongs to the group consisting of hydrogen and Ci - C3 alkyl; Het ¹ and Het ² belong to the group comprising oxygen and nitrogen, R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate and C 4 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C 3 alkyl, and cycloalkyl groups of 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring; and

B) a monomer unit belonging to the group consisting of acrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinyl sulfonic acid, styrene sulfonate, N-tert. butylacrylamide, butoxymethylacrylamide, Ν, dim-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, maleic acid and combinations thereof.

For this purpose, the monomers described above may be in both salt and acid form.

In a preferred embodiment, the binder has the formula to which p = 1; q = 1; R ^2, R ^3, R ^4, R ⁵ and R ⁶ are hydrogen; Het ¹ and Het ² are oxygen in the formula 1 of step A; the monomer units of step B are acrylic acid and acrylamide.

Also provided is an unburned, preliminary ceramic material comprising a mixture of:

A. ceramic powder belonging to the group consisting of alumina, aluminum nitrate, silicon carbonate, silica, magnesium oxide, lead oxide, zirconia, titanium dioxide, talc,

- 16 • »4 ·· ··· 4 4 4 4 4 4 * · 4 4 ·· • · 4 4 4 4 4 4 4 • 4 · 4 4 4 4

444 44 444 4444 4 · · * barium titanite, lead-zirconium titanite, clays, ferrites, yttrium oxide, zinc oxide, tungsten carbonate, sialon, neodymium oxide and combinations thereof and

B. a water-soluble polymer having: i) a monomer unit of the formula

R ⁵ R ⁶

-C-CHC = O

AND

NR ¹ (CHR ² CHR ³ Het ¹ HpHCHR ² CHR ³ Het ² jq-R ⁴ where R ¹ belongs to the group consisting of hydrogen and C 1 -C 3 alkyl; and p and q are integers from 1-10; R ² and R ³ include the group consisting of hydrogen and C - C3 alkyl, Het ¹ and Het ² belongs to the group comprising oxygen and nitrogen, R ⁴ belongs to the group consisting of hydrogen, phosphate, sulfate and C4 - C2o alkyl; R ⁵ and R ⁶ belongs to group consisting of hydrogen, carboxyl, C - C3 alkyl, and cycloalkyl groups having 1-6 carbon atoms formed by combining R ⁵ and R ⁶ in the ring, and ii) a monomer unit belongs to the group consisting of acrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethyl acrylamide,,, Ν-dimethylacrylamide, monosodium salts of acid

- 17 • 99 · 94 94 · 9 99 99 9999

999 9 9 9999

9 9 9 · 9 9 999 994

9 9 9 9 9

994 »4 999 9999 99 44 acrylamidomethylpropanesulfonic acid, vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, maleic acid and combinations thereof.

In a preferred embodiment, the binder has the formula to which p = 1; q = 1; R ^2, R ^3, R ^4, R ⁵ and R ⁶ are hydrogen; Het ¹ and Het ² are oxygen in the formula 1 of step A; the monomer units in step B are acrylic acid and acrylamide.

There is also provided a method of preparing a ceramic material comprising the steps of:

A) mixing the ceramic powder with an aqueous solution containing a water-soluble polymer to form a slurry; said water-soluble polymer has:

i) a monomer unit of the formula

R ⁵ R ⁶

C-CHI, c = o

NR (CH ² CHR ³ Het ¹ - ^ CHR ² CHR ³ Het ² - ^ - R ⁴ where R ¹ belongs to a group containing hydrogen and C 1 -C 3 alkyl; and p and q are integers from the range 1-10; R ² and R R ³ belongs to the group comprising hydrogen and C 1 -C 3 alkyl; Het ¹ and Het ² belong to the group containing oxygen and nitrogen, R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate and C ₄ -C ₂ alkyl; R ⁵ and R ⁶ belongs to the group consisting of hydrogen, carboxylate, C ₁ -C ₃ alkyl, and cycloalkyl groups of 1 to 6 carbon atoms, formed by the combination of R ⁵ and R 6 ⁶ in a circle, and ii) a monomer unit belongs to the group consisting of acrylic acid, acrylamide, maleic anhydride, ithakonové acid, vinyl sulfonic acid, styrene sulfonate, N-tert-butylacrylamide, butoxymethylacrylamide, Ν, Ν-dimethylacrylamide, N -acrylamidomethylpropanesulfonic acid, vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, maleic acid and a combination of uv edeného;

B) drying the slurry by a process selected from the group consisting of fluidized bed spray drying and spray drying to form particles comprising said copolymer;

C) joining the particles by a process selected from the group consisting of dry pressing, rolling and isostatic compression to form a compact structure;

and

D) heating the compact structure to form a fired ceramic material.

Said water-soluble polymer preferably has the formula p = 1; q = 1; R ^2, R ^3, R ^4, R ⁵ and R ⁶ are hydrogen; Het ¹ and Het ² are oxygen in the formula I of step i; the monomer units of step ii are acrylic acid and acrylamide.

- 19 ·· · ··

Further, in practice of the present invention, the particles should be made by granulation, and the method of joining the particles to form a compact structure should belong to the group comprising dry compression and isostatic compression.

Other ceramic manufacturing processes useful in the present invention include extrusion, machine dialing, strip casting and slurry casting.

Also provided is a ceramic binder comprising a water-soluble polymer having:

A) a monomer unit of the formula

R ⁵ R ⁶

-C-CHC = Q

O (CHR ² CHR ³ O) pR ⁴ where p is an integer from 1-10; R ² and R ³ belongs to the group consisting of hydrogen and C - C3 alkyl; R ⁴ belongs to the group consisting of hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C 3 alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by the combination of R ⁵ and R ⁶

- 20 • · • · * · 99 9999 • · • · · · in the ring, except that p = 1, R ^2, R ^3, R ^4, R ⁵ and R ⁶ are not all hydrogen with the exception that p = 1, R ⁵ is not methyl; and

B) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinyl sulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salt acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

For this purpose, the monomers described above may be in both salt and acid form.

Also provided is an unburned, preliminary ceramic material comprising a mixture of:

A. ceramic powder belonging to the group consisting of alumina, aluminum nitrate, silica, silica, magnesium, lead, zirconium, titanium dioxide, talc, barium titanite, lead-zirconium titanite, clays, ferrite, yttrium oxide, zinc oxide, tungsten carbonate, sialon, neodymium oxide and combinations thereof; and

B. a water-soluble polymer having: i) a monomer unit of the formula

- From I - ··· ·· ··· ···· ·· ··

R ⁵ R ⁶

I I

-c-CH-C = ^O11

O (CHR ² CHR ³ 0) ρ ^Κ-4 wherein p is an integer from 1-10; R ² and R ³ belongs to the group consisting of hydrogen and Ci - C3 alkyl; R ⁴ belongs to the group consisting of hydrogen, phosphate, sulfate and C 1 - 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C ₃ alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring, except that p = 1, R ² R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; and ii) a water-soluble monomer unit, consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

A method of preparing a ceramic material is also provided, which comprises the following steps:

A) mixing the ceramic powder with an aqueous solution containing a water-soluble polymer to form a slurry; said water-soluble polymer has:

(i) monomer unit of the formula:

RR ⁶

I I

-C - CH

C = 0

O

II (CHR ² CHr 'Ob — r ⁴ where p is an integer from 1-10; R ² and R ³ belong to the group comprising hydrogen and C 1 -C 3 alkyl; R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C ₁ -C ₃ alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring, except that that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl, and ii) a water-soluble monomer unit belonging to the group consisting of from acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, N-vinyl alcohol; a combination of said.

B) drying the slurry by a process selected from the group consisting of fluid bed spray drying and spray drying to form particles comprising said copolymer;

- 23 • φ φ · φ φ φ φ φ φ φ φ

C) joining the particles by a process selected from the group consisting of dry pressing, rolling and isostatic compression to form a compact structure; and

D) heating the compact structure to form a fired ceramic material.

Further, in practice of the present invention, the particles should be made by granulation, and the method of joining the particles to form a compact structure should belong to the group comprising dry compression and isostatic compression.

Other ceramic manufacturing processes useful in the present invention include extrusion, machine dialing, strip casting and slurry casting.

Also provided is a method of dispersing one or more ceramic materials in an aqueous medium, comprising using a polymer dispersant of a volume preferred for dispersion; the agent comprises a water-soluble polymer having:

A) a monomer unit of the formula

R ⁵ R ⁶

-C-CH

O (CHR ² CHR ³ where ρ is an integer from 1-10; R ² and R ³ belong to the group comprising hydrogen and C 1 -C 3 alkyl; R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate and C 1 -C 20 R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C 3 alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to the ring, except that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl;

B) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salt acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

Further, one or more of ceramic materials may be selected from the group consisting of alumina, aluminum nitrate, lead titanite, boron nitrate, silicon, silica carbonate, sialon, zirconium nitrate, zirconium carbonate, zirconium boron, boron carbonate, tungsten carbonate, tungsten boride, stannous oxide, ruthenium oxide, yttrium oxide, magnesium oxide, calcium oxide and ferrites.

Also disclosed is an aqueous dispersion of a ceramic material produced by the process described above.

The invention further provides a binder for ceramic materials comprising a water-soluble polymer having:

- 25> · 0 0 · 0 • 00 0 0 00 «• 0 0 0 0 0 0 0 0 000 000 *

0 · ·

000 0000 00

A) a monomer unit of the formula

R ⁵ R ⁶

-C-CHCH ₂ | ¹¹¹ O (CHR ³ CHR ³ O) p - R ⁴ where p is an integer from 1-10; R ² and R ³ belongs to the group consisting of hydrogen and Ci - C3 alkyl; R ⁴ is hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C ₃ alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to the ring, except that p = 1, R ² R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; and

B) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinyl sulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salt acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

For this purpose, the monomers described above may be in both salt and acid form.

Ttt ttt # ttt tt tt tt tt tt

Tβ ··· ·· ·· ““ «« tt tttt ··· ♦♦ ·· ·· ··

Also provided is an unburned, preliminary ceramic material comprising a mixture of:

A. ceramic powder belonging to the group consisting of alumina, aluminum nitrate, silica, silica, magnesium, lead, zirconium, titanium dioxide, talc, barium titanite, lead-zirconium titanite, clays, ferrite, yttrium oxide, zinc oxide, tungsten carbonate, sialon, neodymium oxide and combinations thereof; and

B. a water-soluble polymer having: i) a monomer unit of the formula

R ⁵ R ⁶

I I

-c-CHCH ₂

III o

(CHR ² CH ³ O) R ⁴ where p is an integer from 1-10; R ² and R ³ belongs to the group consisting of hydrogen and C - C3 alkyl; R ⁴ is hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxy, C 1 -C 3 alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring, except that p = 1, R ² R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; and

- 27 • 44 · 4 9 • 9 9

9 *

4 9

448 94 • 4944

99

4 »4

4 4 4

999 444

Ii) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethyl acrylamide, N, N- dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

A method of preparing a ceramic material is also provided, which comprises the following steps:

A) mixing the ceramic powder with an aqueous solution containing a water-soluble polymer to form a slurry; said water-soluble polymer has:

i) a monomer unit of the formula

R ⁵ R ⁶

-C-CHCH _Z << 1

O (CHR ² CHR ³ O / P-R ⁴ where p is an integer from 1-10; R ² and R ³ belongs to the group consisting of hydrogen and C-ι - 3 alkyl; R ⁴ is one of the group consisting of hydrogen , phosphate, sulfate and C ₁ -C ₂ alkyl; R ⁵ and R ⁶ are hydrogen, carboxylate, C 1 -C 3 alkyl, and a C 1 -C 6 cycloalkyl group formed by the combination of R ⁵ and R ⁶ • 9

- 28 9 9 9 9 · 99 9 ···

9 9

To the ring, except that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; and ii) a water-soluble monomer unit, consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

B) drying the slurry by a process selected from the group consisting of fluid bed spray drying and spray drying to form particles comprising said copolymer;

C) joining the particles by a process selected from the group consisting of dry pressing, rolling and isostatic compression to form a compact structure; and

D) heating the compact structure to form a fired ceramic material.

Further, in practice of the present invention, the particles should be made by granulation, and the method of joining the particles to form a compact structure should belong to the group comprising dry compression and isostatic compression.

• ·

Other ceramic manufacturing processes useful for the purposes of this invention include extrusion, machine dialing, strip casting and slurry casting.

Also provided is a method of dispersing one or more ceramic materials in an aqueous medium, comprising using a polymer dispersant of a volume preferred for dispersion; the agent comprises a water-soluble polymer having:

A) a monomer unit of the formula

R ⁵ R ⁶

I I

-C-CH ₂

III o

(chr ² chr ³ <% - r ⁴ where p is an integer from 1-10; R ² and R ³ belong to the group comprising hydrogen and C 1 -C 3 alkyl; R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C ₃ alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring, except that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl;

B) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate,

- 30 9

9999

99 9 9 9

999 999

9

99

N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

Further, one or more of ceramic materials may be selected from the group consisting of alumina, aluminum nitrate, lead titanite, boron nitrate, silicon, silica carbonate, sialon, zirconium nitrate, zirconium carbonate, boron carbonate, tungsten carbonate, stannous oxide, ruthenium oxide, yttrium oxide, magnesium oxide, calcium oxide and ferrites.

zirconium, tungsten, boride boride

Also disclosed is an aqueous dispersion of a ceramic material produced by the process described above.

The invention further provides a binder for ceramic materials comprising a water-soluble polymer having:

A) a monomer unit of the formula

R ⁵ R ⁶

-C-CH

C = O

NR ¹ (CH ₂ ) _p

OR ⁴

IV wherein R ¹ belongs to the group consisting of hydrogen and C ₁ -C ₃ alkyl; p is an integer from 1-10; R ⁴ belongs to the group consisting of hydrogen,

- 31 ta and ta ta ta phosphate, sulfate and C 1 -C ₂ alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C 3 alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring; and

(B) a unit of measurement consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulphonic acid, styrene sulphonate, N-tert-butyl acrylamide, butoxymethylacrylamide, Ν, dim-dimethylacrylamide and monosodium salt of acrylic acid , vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, maleic acid and combinations thereof.

For this purpose, the monomers described above may be in both salt and acid form.

In a preferred embodiment, the binder has a structure wherein p = 2, R ¹ , R ⁴ , R ⁵ and R ⁶ are hydrogen in the formula IV of step A and the monomer units in step B are acrylic acid and acrylamide.

Further, the binder may have a structure wherein p = 3, R ¹ , R ⁵ and R ⁶ are hydrogen in formula IV of step A and R ⁴ is methyl and the monomer units in step B are acrylic acid and acrylamide.

Further, monomer units with N-suspended polyoxide groups as well as the alkyl oxide groups described above may also be effective for the purposes of the present invention. For example, polyhydroxide groups suspended on N, as well as alkyl derivatives having dihydroxy or trihydroxy groups, as well as alkyl groups.

- 32 4 44

4 4 4 4 4

4 4 4 ··

4 4 4 4 · ···

4 4 4 4 · · ··· 44 444 4444 4 · · * derivatives, part containing diether or triether moieties, can be equally effective.

Also provided is an unburned, preliminary ceramic material comprising a mixture of:

A. ceramic powder belonging to the group consisting of alumina, silicate, aluminum nitrate, silicate, silicon dioxide, silicon dioxide, lead oxide, zirconia, titanium dioxide, talc, barium titanite, lead-zirconium titanite, clays, ferrites, yttrium oxide, zinc oxide, tungsten carbonate, sialon, neodymium oxide and combinations thereof;

B. a water-soluble polymer having: i) a monomer unit of the formula

IV wherein R ¹ belongs to the group consisting of hydrogen and C 1 - (

R ⁵ R ⁶

-C-CHC = O

NR ⁴ (CH ₂ ) _p

^OR4 ₃ alkyl; p is an integer from 1-10; R ⁴ is hydrogen, phosphate, sulfate and C 1 -C ₂ alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C 3 alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring; and

- 33 • · · · · · · · · · · · · · · · · · · · · · · φ · φ · φ · φφφφφφφφφφφφφφφφφφφφ φ φφφφφφ (ii) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulphonic acid, styrene sulphonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N- dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

In a preferred embodiment, the binder has a structure wherein p = 2, R ¹ , R ⁴ , R ⁵ and R ⁶ are hydrogen in the formula IV of step A and the monomer units in step B are acrylic acid and acrylamide.

Further, the binder may have a structure wherein p = 3, R ¹ , R ⁵ and R ⁶ are hydrogen in formula IV of step A and R ⁴ is methyl and the monomer units in step B are acrylic acid and acrylamide.

A method of preparing a ceramic material is also provided, which comprises the following steps:

A) mixing the ceramic powder with an aqueous solution containing a water-soluble polymer to form a slurry; said water-soluble polymer has:

i) a monomer unit of the formula

R ⁵ —r

C = O

NR ¹ iv <ch ₂ ) _p

OR ⁴

R ⁶

AND

-CH

00

9 * 0

9 ··

0

0 ·· 0900

- 33 0 0

90

0 9 9

0 0 0

900 900

Wherein R ¹ belongs to the group consisting of hydrogen and C 1 -C 3 alkyl; p is an integer from 1-10; R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate and (%-C 20 alkyl; R ⁵ and R ⁶ belong to the group comprising hydrogen, carboxylate, C ₁ -C ₃ alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed combining R ⁵ and R ⁶ in the ring; and ii) a water-soluble monomer unit, belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithakonové acid, vinyl sulfonic acid, styrene sulfonate, N-tert-butylacrylamide, butoxymethylacrylamide, Ν, Ν-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

B) drying the slurry by a process selected from the group consisting of fluid bed spray drying and spray drying to form particles comprising said copolymer;

C) joining the particles by a process selected from the group consisting of dry pressing, rolling and isostatic compression to form a compact structure; and

D) heating the compact structure to form a fired ceramic material.

35 35 35 35 35 35 · 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 φφφ ·· φφφ φφφφ ΦΦ · Φ

In a preferred embodiment, the binder has a structure wherein p = 2, R ¹ , R ⁴ , R ⁵ and R ⁶ are hydrogen in the formula IV of step A and the monomer units in step B are acrylic acid and acrylamide.

Further, the binder may have a structure wherein p = 3, R ¹ , R ⁵ and R ⁶ are hydrogen in formula IV of step A and R ⁴ is methyl and the monomer units in step B are acrylic acid and acrylamide.

Further, in practice of the present invention, the particles should be made by granulation, and the method of joining the particles to form a compact structure should belong to the group comprising dry compression and isostatic compression.

Other ceramic manufacturing processes useful in the present invention include extrusion, machine dialing, strip casting and slurry casting.

Also provided is a method of dispersing one or more ceramic materials in an aqueous medium, comprising using a polymer dispersant of a volume preferred for dispersion; the agent comprises a water-soluble polymer having:

A) a monomer unit of the formula

NR *

I (CH ₂ \

AND

OR ⁴ wherein R ¹ belongs to the group consisting of hydrogen and C 1 -C ₃ alkyl; p is an integer from 1-10; R ⁴ belongs to the group consisting of hydrogen,

Phosphate, sulfate and C ₁ -C ₂ alkyl; R ⁵ and R ⁶ belong to the group comprising hydrogen, carboxylate, C 1 -C ₃ alkyl, and a cycloalkyl group of 1 to 6; carbon atoms formed by the coupling of R ⁵ and R ⁶ into a ring;

B) a monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulphonic acid, styrene sulphonate, N-tert-butyl acrylamide, butoxymethylacrylamide, Ν, dim-dimethylacrylamide and monosodium salt of acrylic acid , vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof.

In a preferred embodiment, the binder has a structure wherein p = 2, R ¹ , R ⁴ , R ⁵ and R ⁶ are hydrogen in the formula IV of step A and the monomer units in step B are acrylic acid and acrylamide.

Further, the binder may have a structure wherein p = 3, R ¹ , R ⁵ and R ⁶ are hydrogen in formula IV of step A and R ⁴ is methyl and the monomer units in step B are acrylic acid and acrylamide.

Further, one or more of the ceramic materials may be selected from the group consisting of alumina, silica nitrate, aluminum nitrate, lead titanite, boron nitrate, silicon, silica carbonate, sialon, zirconium nitrate, zirconium carbonate, zirconium boron, boron carbonate, tungsten carbonate, tungsten boride, stannous oxide, ruthenium oxide, yttrium oxide, magnesium oxide, calcium oxide and ferrites.

This process also includes aqueous dispersion of the ceramic material.

- 37 · · · 9 9 · ···

995 9 · 4994

9 9 · 9 999999 9 9 9 9

999 99 999 9 · 99 99 99

The following examples are provided to describe the recommended specific uses of the invention and are not intended to limit the scope of the invention in any way unless expressly provided in the claims appended hereto.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Synthesis of a copolymer of ammonium acrylate and N-hydroxyethyoxyethylacrylamide was performed with the following reactants in the following amounts:

Reactant Quantity (g)

Poly (AA), 25.6% by weight in water 100.00 Ethoxyethanolamine 11.92

Ammonium hydroxide, 29% by weight 2.51

To prepare the polymer, Poly (acrylic acid) (polyacrylic acid solution, 25.6 weight percent, pH = 3.8, 16000 MW) was added to the beaker cooled in an ice bath. Ethoxyethanolamine, commercially available from Huntsman Petrochemical Co. of Houston, Texas, was then added dropwise to the solution of poly (acrylic acid) and water with vigorous stirring. The mixture was then stirred for an additional 15 minutes. The pH of the reaction mixture was measured using water-moistened pH papers, and a base was added to stabilize the pH at a value close to 5. The reaction mixture was then transferred to a 300 ml Parr reactor at a pressure of at least 56245.6 g / cm ² . The reactor was then sealed and purged with nitrogen for 60 minutes. Then the Parr reactor was slowly heated to 160 ° C (or in some cases less) and held at that temperature for 8 (or in some cases more) hours. Then the reactor was cooled to room temperature and the pressure was released and the product was removed and stored.

¹³ C nuclear magnetic resonance confirmed the construction of the product. The N-hydroxyethoxyethyl acrylamide content was 21 mole percent, 100% being the total number of all monomer units in the polymer, representing both the secondary amide and imide monomer units. The molecular weight of the polymer was 24,000.

Example 2

Synthesis of ammonium acrylate tertiary polymer and N-hydroxyethyoxyethylacrylamide was performed with the following reactants in the following amounts:

Reactant Quantity (g)

Poly (NH4AA / AcAm) aqueous solution,

50/50 mol%,

38.2% by weight, 300.00

Ethoxyethanolamine 114.00

In the preparation of the polymer, Poly (NH 4 AA / AcAm) (acrylate / acrylamide copolymer in a molar ratio of 1: 1, 38.2 weight percent, pH = 5.5, 33000 MW) was placed in an ice bath beaker. Ethoxyethanolamine, which is commercially available from Huntsman Petrochemical, was added dropwise with vigorous stirring (pH = 10.1).

- 39 · · 39 39 39 39 39 39 39 39 39 39 39 39 39 39 39 39 39 39 39 39 39

Co., Houston, Texas, USA. The mixture was then stirred for an additional 15 minutes. The pH of the reaction mixture was measured using water-moistened pH papers. The reaction mixture was then transferred to a 300 ml Parr reactor at a pressure of at least 56245.6 g / cm ² .

The reactor was then sealed and purged with nitrogen for 60 minutes.

The Parr reactor was then slowly warmed to 138 ° C and held at this temperature for 14 hours. Then the reactor was cooled to room temperature and the pressure was released and the product was removed and stored.

¹³ C nuclear magnetic resonance confirmed the construction of the product. The N-hydroxyethoxyethyl acrylamide content was 33.3 mole percent, 100% being the total mole volume of all monomer units in the polymer, representing both the secondary amide and imide monomer units. The molecular weight of the polymer was 35,000 and the molar ratio of N-hydroxyethoxyethyl acrylamide / acrylic acid / acrylamide was 33/41/26.

Example 3

Synthesis of sodium tertiary acrylate / acrylamide / N-hydroxyethyoxyethylacrylamide was performed with the following reactants in the following amounts:

Reactant

Quantity (g)

Poly solution (NaAA / AcAm),

50/50 mole%, weight%, in water

100.00

- 40

Ethoxyethanolamine 32.00

Sulfuric acid (95%) 11.5

To prepare the polymer, Poly (NaAA / AcAm) (sodium acrylate / acrylamide copolymer in a molar ratio of 1: 1, 32 weight percent, pH = 5.2, 11000 MW) was placed in an ice bath beaker. Ethoxyethanolamine, commercially available from Huntsman Petrochemical Co. of Houston, Texas, was then added dropwise with vigorous stirring (pH = 10.1). The mixture was then stirred for an additional 15 minutes. Using the water-moistened pH papers, the pH of the reaction mixture was measured, and sulfuric acid was added to stabilize the pH at 5.6. The reaction mixture was then transferred to a 300 ml Parr reactor at a pressure of at least 56245.6 g / cm ² . The reactor was then sealed and purged with nitrogen for 60 minutes. The Parr reactor was then slowly heated to 138 ° C and held at that temperature for 12 hours. Then the reactor was cooled to room temperature and the pressure was released and the product was removed and stored.

Nuclear Magnetic Resonance Imaging confirmed the ¹³ C construction of the product. The content of N-hydroxyethoxyethyl acrylamide was 33 mole percent, 100% being the total mole volume of all monomer units in the polymer, representing both the secondary amide and imide monomer units. The molecular weight of the polymer was 12,000 and the molar ratio of N-hydroxyethoxyethyl acrylamide / acrylic acid / acrylamide (including 3% imide monomer units) was 33/42/22.

Example 4

- 41 · · · 41 41 41 41 41 41 41 41 41 41 41 41 41 41 41

The synthesis of sodium tertiary acrylate / acrylamide / N-methoxypropyl acrylamide was performed with the following reactants in the following amounts:

Reactant Quantity (g)

Poly solution (NaAA / AcAm),

50/50 mole%, weight%, in water 100.00

Methoxypropylacrylamide 23.32

Sulfuric acid (95%) 11.23

To prepare the polymer, Poly (NaAA / AcAm) (sodium acrylate / acrylamide copolymer in a molar ratio of 1: 1, 32 weight percent, pH = 5.2, 11000 MW) was placed in an ice bath beaker. Methoxypropylacrylamide, which is commercially available from Aldrich Chem, was added dropwise with vigorous stirring (pH = 10.1). Co., Milwaukee, Wisconsin, USA. The mixture was then stirred for an additional 15 minutes. Using the water-moistened pH papers, the pH of the reaction mixture was measured, and sulfuric acid was added to stabilize the pH at 5.6. The reaction mixture was then transferred to a 300 ml Parr reactor at a pressure of at least 56245.6 g / cm ² . The reactor was then sealed and purged with nitrogen for 60 minutes. The Parr reactor was then slowly heated to 138 ° C and held at that temperature for 12 hours. Then the reactor was cooled to room temperature and the pressure was released and the product was removed and stored.

¹³ C nuclear magnetic resonance confirmed the construction of the product. The methoxypropyl acrylamide content was 34.2 mole percent, 100% being the total mole volume of all monomeric

- 42 · · · 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 ·· ·· ·· units in the polymer. The molecular weight of the polymer was 11,000 and the molar ratio of N-methoxypropylacrylamide / acrylic acid / acrylamide (including 6% imide monomer units) was 34/41/17.

Example 5

The synthesis of sodium tertiary acrylate / acrylamide / N-hydroxyethylaminomethyl acrylamide was performed with the following reactants in the following amounts:

Reactant

Quantity (g)

Poly (NaAA / AcAm) solution, 50/50 mol%, weight%

Amine ethylamine ethanol

Sulfuric acid (95%)

100.00

23.32

11.23

In the preparation of the polymer, Poly (NaAA / AcAm) (sodium acrylate / acrylamide copolymer in a molar ratio of 1: 1, 24 weight percent, pH = 3.5, 15000 MW) was placed in an ice bath beaker. Then, aminethylaminethanol, commercially available from Aldrich Chem, was added dropwise with vigorous stirring (pH = 10.1). Co., Milwaukee, Wisconsin, USA. The mixture was then stirred for an additional 15 minutes. Using the water-moistened pH papers, the pH of the reaction mixture was measured, and sulfuric acid was added to stabilize the pH at 5.6. The reaction mixture was then transferred to a 300 ml Parr reactor at a pressure of at least 56245.6 g / cm ² . The reactor was then sealed and purged with nitrogen for 60 minutes. The Parr reactor was then slowly warmed to 138 ° C and

Held at this temperature for 14 hours. Then the reactor was cooled to room temperature and the pressure was released and the product was removed and stored.

¹³ C nuclear magnetic resonance confirmed the construction of the product. The hydroxyethylaminomethyl acrylamide content was 46 mole percent, 100% being the total mole volume of all monomer units in the polymer, representing both the secondary amide and imide monomer units. Polymer

also included weight of polymer 51% of units was 15000. acid acrylic. Molecular Example 6 Synthesis tertiary polymer acrylate sodium /

of acrylamide / N-hydroxyethyoxyethylaminomethyl acrylamide was carried out with the following reactants in the following amounts:

Reactant

Quantity (g)

Poly (AcAm) solution, wt% 50.00

Aminethyoxyethanol 12.9

Deionized water 50.0

Sulfuric acid (95%) 6.1 _ 44 · # · · 9 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ♦ ····· ·· ··

To prepare the polymer, Poly (AcAm) (manufactured by Aldrich Chem. Co., Milwaukee, Wisconsin, USA; 50 weight percent, 10000 MW) was placed in an ice bath beaker. Aminethyoxyethanol, which is commercially available from Huntsman Petrochemical Co., Houston, Texas, USA, was added dropwise with vigorous stirring (pH = 10.1). The mixture was then stirred for an additional 15 minutes. Using the water-moistened pH papers, the pH of the reaction mixture was measured, and sulfuric acid was added to stabilize the pH at 5.6. The reaction mixture was then transferred to a 300 ml Parr reactor at a pressure of at least 56245.6 g / cm ² . The reactor was then sealed and purged with nitrogen for 60 minutes. The Parr reactor was then slowly warmed to 138 ° C and held at this temperature for 14 hours. Then the reactor was cooled to room temperature and the pressure was released and the product was removed and stored.

¹³ C nuclear magnetic resonance confirmed the construction of the product. The N-hydroxyethyoxyethylacrylamide content was 19.6 mole percent, 100% being the total mole volume of all monomer units in the polymer, representing both the secondary amide and imide monomer units. The polymer also contained 51% acrylic acid units. The molecular weight of the polymer was 15000 molar ratio of acrylic acid / acrylamide / N-hydroxyethyoxyethylacrylamide was 32/44/20.

Example 7

The synthesis of the tertiary acrylic acid / acrylamide / N-hydroxyethylacrylamide polymer in a 33/50/17 molar ratio was as follows: To 100 g of AA / AcAm copolymers in a 52/48 molar ratio (42.7% reactive polymer, average molecular weight 34100)

- 45 • * 4 4

9 4 4

444 444

4

4 * 44 in a Parr reactor was added 17.4 g of ethanolamine. The pH was then adjusted to 5-5.5 by the addition of 8.32 g of 36% hydrochloric acid. Then the solution was purged with nitrogen for 1 hour and held at 138-142 ° C for about 8 hours. The results of nuclear magnetic resonance analysis revealed that the composition of this tertiary polymer was 38/52/10 N-hydroxyethylacrylamide / AA / AcAm. The average molecular weight of the product was 128,000, indicating that the polymer is slightly crosslinked. 50% NaOH solution (19.24 g) with a pH <11.39 was added dropwise to half the product volume with stirring. Then the solution was further stirred at room temperature for 3.5 hours. The pH was adjusted to a value close to 7 by the addition of 36% hydrochloric acid. The average molecular weight was 42,600. The results of nuclear magnetic resonance analysis revealed that this product is a tertiary polymer of N-hydroxyethylacrylamide / acrylic acid / acrylamide in a 33/50/17 ratio.

Example 8

Synthesis of tertiary polymer

N-hydroxyethylacrylamide / acrylic acid / acrylamide in a 33/51/14 molar ratio was carried out as follows: To 100 g of AA / AcAm copolymer in a 52/48 molar ratio (42.7% polymer are active, average molecular weight is 34100) in a Parr reactor, 25.3 g of ethanolamine was added. Then the solution was purged with nitrogen for 1 hour and held at 136-138 ° C for 7 hours. The pH was then added by adding 18.8 g of 36% acid

• 44 44 «44« 44 44 4

4 4 4 4 4

4 444444

4 «4 • 44 4444 44 44.

hydrochloric acid adjusted to about 5.3. To the stirred solution was added dropwise 37 g of 50% NaOH pH <12. After the solution was stirred for an additional 5 hours, the pH was adjusted to 8.5 with 36% hydrochloric acid. The results of nuclear magnetic resonance analysis showed that the composition of this tertiary polymer was 35/51/14 N-hydroxyethylacrylamide / AA / AcAm. The average molecular weight of the product was 31000.

Example 9

The following experimental procedure was carried out to determine the dispersibility of the polymers. 1500 g of suspension was prepared to 80 weight percent alumina powder (99.5% calcined alpha alumina, manufactured by Alcan, C90 LSB Alumina) in water, using 0.25 weight percent (polymer / powder) of the test polymer.

Each suspension was crushed in a small 1 liter porcelain ball mill using 1500 g of grinding medium. Then the resulting suspension was filtered through a 60 mesh screen and the Brookfield viscosity was measured with an LVT viscometer using thread # 2. For comparison purposes, a conventional, commercially available alumina additive polymer was used. Polymer B is ammonium polymethacrylate available from R.T. Vanderbilt Co., Norwalk, Connecticut, USA. Polymer A is a polymer synthesized according to the procedure of Example no. 2.

The viscosity of the slurry must be appropriate to its handling and spray drying. Although the spray drier and operating conditions may be modified to handle slurries of various types.

4 4 4

4444 44 44

viscosities, the use of a more viscous slurry will result in larger particle sizes. There will be larger gaps between the larger resultant particles, thereby reducing the strength or cohesion of the slurry. The binder contributes to the viscosity of the slurry dispersion medium by its advantages such as molecular weight, solubility, solution conformation and possible incompatibility with the combination of powder and dispersant. Since a lower viscosity is more suitable for use in ceramic works, the results in Table I show that the polymer prepared according to the procedure of Example 2 is preferable to the conventional treatment.

- 48 tata tata tata tata tata tata tata tata

TABLE I

Dispersion in alumina

Polymer Brookfield viscosity (cP) 6 rpm 12 rpm 30 rpm 60 rpm AND 100 ALIGN! 88 70 65 (B) 300 225 160 105

Example 10

The polymers were also tested to determine the effect of slurry viscosity depending on the type of binder according to the following procedure. The deflocculated slurry was prepared according to the procedure of Example 9. To each sample of the slurry so prepared was added a polymer treatment to be tested in an amount such that the polymer was 4% by weight (relative to the powder). Thereafter, each slurry containing the binder was stirred for 1 hour with a propeller stirrer at 800 rpm. If necessary, deionized water was added to achieve the powder solids shown in the tables. Finally, the slurry viscosity was measured by the method of Example 9.

The results in Table II show that, although the binder composition has been altered, the polymers described or otherwise mentioned in the present invention exhibit lower slurry viscosity than previously available polymers. In Table II, polymer C is polyvinyl alcohol having a molecular weight ranging from 30,000 to 50,000 and is 88% hydrolyzed. It is available from Air Products of Allentown, Pa., USA. Polymer A is a polymer synthesized according to the procedure of Example 2. For each tested

The polymer was used in an amount corresponding to four percent by weight, and the viscosity was measured at 3.14 sec- ¹ .

TABLE II

Slurry viscosity in relation to binder type

Weight percent solids in the slurry BFV ¹ polymer C slurry (cP) BFV ¹ polymer A slurry (cP) 76.4 > 10000 440 74.8 8200 170 72 840 20 May 70 360 -

= Brookfield viscosity

Example 11

The copolymer synthesized as described in Example 2 above was tested as a binder of alumina particles commonly used in the manufacture of ceramic materials.

The slurry preparation procedure described in Example 10 was used in this Example to further investigate the properties of the binders.

The ground slurry was spray dried in a Yamato DL-41 laboratory spray dryer. The operating conditions of the dryer were: inlet air temperature: 250 ° C, spray air setting: 1.2, dosing pump setting: 5, drying air dosing rate: 0.7 m ³ / min. A dry powder was formed, which was then renewed, sieved and stored overnight in a chamber with an internal relative humidity of 20%.

- 50 • 0 00

0 9 ·

999 900

0

00

The sieved powder was compressed into nine pellets in a Carver laboratory press, three pellets pressed under 351535 g / cm ² , the other three under 1054605 g / cm ² and the remaining three under 1757675 g / cm ² . The pellets had an average of 28.7 mm in diameter and 5-6 mm in height. The other dimensions and weight of the pellets were also measured, and the pellets were crushed to determine the force required to break them. The average compressive strength (PPT) of each pellet was determined from the force required to break the pellets and their dimensions. The PPT averages for each of the three pellet groups are presented below in Table III.

The average compressive strength of the unburned body is significant for ceramic work for the following reasons. The central function of the binder is to keep the compressed shape together after compression. The method used to determine a suitable strength after molding is to determine the average compressive strength, or PPT, in the diameter of the cylindrical section. PPT is in fact a measure of tensile strength. The unit of measurement of the permissible pressure deviation is megapascal (MPa). Rounded PPT values of unburned bodies range from 0.3 to 3.0 MPa. Polymer A is a polymer prepared according to the procedure set forth in Example 2. Polymer C is a conventional additive as described in Example 10. Therefore, since a higher PPT value indicates greater binder performance, Table III shows that the polymers of the present invention, are more effective than conventional forms. D is another additive often used in ceramic work with these polymers.

Since greater strength is a desirable property, the results presented in Table III demonstrate that the polymers presented in this invention are also more advantageous in this respect, as evidenced by the fact that the numbers obtained are higher than those obtained with conventional forms.

4 9 9 9 9 9 9 9 9 9 9 9 9 9

Cd 9 9 9 9 99999 “Ol” 9 9 9 · 9 9 999 999 999 • 9 9 9 9 9 9

999 99 999 9999 99 ··

Another important measure of the advantage of using a polymer when working with ceramics is the springing characteristics, for the following reasons. After pressing, the resulting compacted part must be easily removable from the press, be as dense as possible and must not suffer any significant dimensional difference from the shape of the press. Chemical additives have a major influence on the resulting slipperiness of the body. The compressed powder is equalized to release pressure when removed from the press by expanding. This phenomenon is called springing and is undesirable in terms of dimensional accuracy, as well as density and strength. For this example, D is used as a plasticizer and plasticizer. It is important to maintain the shape of the mesh, as significant expansion of the body could cause layering failures or unwanted density gradients. Thus, the lower back-expansion values obtained with the polymers of the present invention demonstrate that these polymers are more advantageous than conventional ones.

The required pressure to be removed from the press was also measured. The same test equipment as described above was used except that after pressing the pellet, a piston was used at the bottom of the device, or a force was applied inside the press. Lower pressure is more desirable. The pressure required for the polymers of the present invention was lower than for the polymers commonly used in ceramics.

- 52 44 44

445 44 * • ·

4 ·

TABLE III

Comparison of properties of unburned bodies

Polymer AND C A + D ¹ C + D ¹ A + D ² C + D ² Pressure Average compressive strength of unburned body (Mpa) 5000 0.64 0.20 0.55 0.45 0.45 0.38 15000 1.76 0.98 1.24 1.01 1.04 0.79 25000 2.42 1.19 1.79 1.30 1.31 0.91 Raw pellet density (g / cm ^J ) 5000 2.28 2.09 2.30 2.23 2.33 2.34 15000 2.52 2.38 2.51 2.43 2.54 2.50 25000 2.60 2.43 2.61 2.51 2.60 2.57 Percent expansion of raw cheese h bodies after removal from the press 5000 0.06 0.22 -0.02 0.19 0.11 0.12 15000 0.11 0.22 0.12 0.19 0.14 0.18 25000 0.16 0.23 0.14 0.19 0.15 0.18 Pressure to remove from press (PSI) 5000 0.00 7.93 0.96 29.16 7.46 22.47 15000 19.86 49.37 26.57 73.94 39.08 64.57 25000 41.30 77.87 42.12 101.14 59.48 92.00

D ¹ = polyethylene oxide propylene oxide ether, cross-linked 1,2-ethanediyldine trilotetrakispropanol (0,8% by weight)

D ² = same as D ¹ , 3.0% by weight

- 53 • 4 44 44 · 4 4 4 4

4,444,444

4 4

4444 44 44

Example 12

The procedures used in Example 11 were used to obtain the results of Table IV. In contrast to the previous example, where a pressure spectrum is used, the properties are summarized here using a single density example. The pressure required to achieve such density is also recorded in the table. Polymers A, C and D are defined as in the previous example. Even when measured with constant density compressed pellets, the polymers of the present invention provide better properties than the polymers hitherto commonly used in ceramics.

TABLE IV

Comparison of properties of unburned bodies with density 2,4 g / ml

Polymer Necessary pressure (DOGS) PPT (MPa) % retroactive expansion Extraction pressure (DOGS) AND 10000 1,22 0.08 10 C 19200 1.1 0.23 63 A + D ¹ 9700 0.94 0.04 13 C + D ¹ 13300 0.88 0.19 67 A + D ² 8200 0.65 0.12 18 C + D 8800 0.56 0.14 39

^{1 1} = Polyethylene oxide propylene oxide ether, crosslinked with 1,2-ethanediyldine trilotetrakispropanol (0,8% by weight)

D ² = same as D ¹ , 3,0% by weight

It is possible to make changes in the composition, workflow and configuration of the process described in the present invention without departing from its concept and scope as defined in the following claims:

Claims (36)

A binder of ceramic materials comprising a water-soluble polymer having: A) a monomer unit of the formula R ⁵ R ⁶ -C-CHc = o I, NR ¹ (CHR ² CHR ³ Het-y (CHR ² CHR ³ Het ² R ⁴ -R ⁴ where R ¹ belongs to the group consisting of hydrogen and C 1 -C 3 alkyl; paq are integers from the range 1-10; R ² and R ³ belongs to the group comprising hydrogen and C 1 -C 3 alkyl, Het ¹ and Het ² belong to the group comprising oxygen and nitrogen, R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate and C 4 -C 20 alkyl; R ⁵ and R ⁶ belongs to the group consisting of hydrogen, carboxylate, C 1 -C 3 alkyl, and cycloalkyl groups of 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ into a ring; B) a monomer unit belonging to the group consisting of acrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, Ν, Ν-dimethylacrylamide, monosodium salt of acrylamidomethylpropropanol vinyl acetate, N-vinylpyrrolidone, maleic acid and combinations thereof. - 55 44 4 44 44 4444 44 4 44 ··· • 4 4 4 4 4 444 444 _ 4 4 4 4 4 4 444 44 444 444 The binder of claim 1, wherein p = 1; q = 1; R ^2, R ^3, R ^4, R ⁵ and R ⁶ are hydrogen; Het ¹ and Het ² are oxygen in the formula 1 of step A; the monomer units of step B are acrylic acid and acrylamide. 3. Unburned, pre-ceramic material containing a mixture of: A. ceramic powder belonging to the group consisting of alumina, aluminum nitrate, silica, silica, magnesium, lead, zirconium, titanium dioxide, talc, barium titanite, lead-zirconium titanite, clays, ferrite, yttrium oxide, zinc oxide, tungsten carbonate, sialon, neodymium oxide and combinations thereof; and B. a water-soluble polymer having: i) a monomer unit of the formula R ⁵ R ⁶ -C-CHC = O NR ¹ (CHR ² CHR ³ Het - ie CHR ² CHR ³ Het ² - ^ - R ⁴ where R ¹ belongs to a group containing hydrogen and C 1 -C 3 alkyl; and p and q are integers from the range 1-10; R ² and R ³ belongs to the group comprising hydrogen and C 1 -C 3 alkyl; Het ¹ and Het ² belong to the group comprising oxygen and nitrogen, R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate and C 4 -C 20 alkyl; R ⁵ and R ⁶ include to group, - 56 containing hydrogen, carboxylate, C 1 -C ₃ alkyl, and cycloalkyl groups of 1 to 6 carbon atoms, formed by linkage R ⁵ and R ⁶ ring; and (ii) a monomer unit belonging to the group consisting of acrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, Ν, Ν-dimethylacrylamide, monosodium salt of acrylamidomethylpropyl; , vinyl acetate, N-vinylpyrrolidone, maleic acid and combinations thereof. The water-soluble polymer of claim 3, wherein p = 1; q = 1; R ^2, R ^3, R ^4, R ⁵ and R ⁶ are hydrogen; Het ¹ and Het ² are oxygen in the formula 1 of step A; the monomer units of step B are acrylic acid and acrylamide. 5. A method of preparing a ceramic material comprising the steps of: A) mixing the ceramic powder with an aqueous solution containing a water-soluble polymer to form a slurry; said water-soluble polymer has: i) a monomer unit of the formula R ⁵ R ⁶ -C-CH c = o NR ¹ (CHR ² CHR ^? Het-f _F tCHR ² CHR ³ Het ² t54 < ⁴ - 57 / ^ 99-Μξ ························ Wherein R ¹ belongs to the group consisting of hydrogen and C 1 -C ₃ alkyl, and p and q are integers from the range 1-10; R ² and R ³ belongs to the group consisting of hydrogen and Ci - C ₃ alkyl; Het ¹ and Het ² belong to the group comprising oxygen and nitrogen, R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate and C 4 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C ₃ alkyl, and cycloalkyl groups of 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring; and (ii) a monomer unit belonging to the group consisting of acrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, Ν, Ν-dimethylacrylamide, monosodium salt of acrylamidomethylpropyl; , vinyl acetate, N-vinylpyrrolidone, maleic acid and combinations thereof; B) drying the slurry by a process selected from the group consisting of fluid bed spray drying and spray drying to form particles comprising said copolymer; C) joining the particles by a process selected from the group consisting of dry pressing, rolling and isostatic compression to form a compact structure; and D) heating the compact structure to form a fired ceramic material. / W-cZAfZ'··································· The water-soluble polymer of claim 5, wherein p = 1; q = 1; R ^2, R ^3, R ^4, R ⁵ and R ⁶ are hydrogen; Het ¹ and Het ² are oxygen in the formula I of step i; the monomer units of step ii are acrylic acid and acrylamide. The method of claim 5, wherein the particles are made by granulation and the method of joining the particles to form a compact structure should belong to the group comprising dry compression and isostatic compression. A ceramic binder comprising a water-soluble polymer having: A) a monomer unit of the formula R ⁵ R ⁶ -C-CHC-O (CH ² CHR ³ O) _r -R ⁴ where p is an integer from 1-10; R ² and R ³ belongs to the group consisting of hydrogen and C - C3 alkyl; R ⁴ belongs to the group consisting of hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C 3 alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to the ring, except that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; and - 59 «··································· ·· ·· Β) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salt acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. 9. Unburned, pre-ceramic material containing a mixture of: A. ceramic powder belonging to the group consisting of alumina, aluminum nitrate, silica, silica, magnesium, lead, zirconium, titanium dioxide, talc, barium titanite, lead-zirconium titanite, clays, ferrite, yttrium oxide, zinc oxide, tungsten carbonate, sialon, neodymium oxide and combinations thereof; and B. a water-soluble polymer having: i) a monomer unit of the formula R ⁵ R ⁶ I I C = CHc = O I o (CHR ² CHR ³ OlfT-R ⁴ 7X W? - 60 where p is an integer from 1-10; R ² and R ³ belongs to the group consisting of hydrogen and Ci - C3 alkyl; R ⁴ belongs to the group consisting of hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C 3 alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring, except that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; and ii) a water-soluble monomer unit, consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. A method of preparing a ceramic material, comprising the steps of: A) mixing the ceramic powder with an aqueous solution containing a water-soluble polymer to form a slurry; said water-soluble polymer has: i) a monomer unit of the formula R ⁵ R ⁶ I I -C-CHC = O I ¹¹ o (CHrWo ^ - 61 kde· kde kde kde p p p p p p p p p p p p where p is an integer from 1-10; R ² and R ³ belongs to the group consisting of hydrogen and Ci - C3 alkyl; R ⁴ belongs to the group consisting of hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C 3 alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to the ring, except that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; and ii) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. B) drying the slurry by a process selected from the group consisting of fluid bed spray drying and spray drying to form particles comprising said copolymer; C) joining the particles by a process selected from the group consisting of dry pressing, rolling and isostatic compression to form a compact structure; and D) heating the compact structure to form a fired ceramic material. - 62 • φ φ φ φφφ φφφ The method of claim 10, wherein the particles are made by granulation and the method of joining the particles to form a compact structure should belong to the group comprising dry compression and isostatic compression. A method of dispersing one or more ceramic materials in an aqueous medium, comprising using a polymer dispersant of a volume preferred for dispersion; the agent comprises a water-soluble polymer having: R ⁵ R ⁶ A monomeric unit of the formula: -C-CHC '= O II O (CHR ² CHR ³ O-R ⁴ where p is an integer from 1-10; R ² and R ³ belong to the group consisting of hydrogen and C 1 -C 3 alkyl; R ⁴ belongs to the group comprising hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ are hydrogen, carboxylate, C 1 -C ₃ alkyl, and a C 1 -C 6 cycloalkyl group formed by joining R ⁵ and R ⁶ into a ring, except that that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; B) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butylacrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salt of acrylamidomethyl-63-l / 1999 0 00 0 000 0 0 0 0 0 0 00 00 0 0 0 0 0 0 0 000 00 000 0000 00 00 propanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. The method of claim 12, wherein one or more of ceramic materials is selected from the group consisting of alumina, aluminum nitrate, lead titanite, boron nitrate, silicon, silica carbonate, sialon, zirconium nitrate, zirconium carbonate, zirconium boride, boron carbonate, tungsten carbonate, tungsten boride, stannous oxide, ruthenium oxide, yttrium oxide, magnesium oxide, calcium oxide and ferrites. An aqueous dispersion of a ceramic material produced by the process of claim 12. A binder for ceramic materials comprising a water-soluble polymer having: A) a monomer unit of the formula R ⁵ R ^b -C-CHCH ₂ I ^IH O (CHR ¹ CHR ³ O> p - R ⁴ where p is an integer from 1-10; R ² and R ³ belong to the group containing hydrogen and C 1 -C 3 alkyl; R ⁴ belongs to the group containing hydrogen, phosphate , sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ are hydrogen, carboxylate, C ₁ -C ₃ alkyl, and cycloalkyl; - 64 99 4 · ·· »· 9 9 9 9 9 9,999,999 9 9 9 9 9999 9 9 99 a group having 1 to 6 carbon atoms, formed by joining R ⁵ and R ⁶ into a ring, except that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception of that p = 1, R ⁵ is not methyl; and B) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinyl sulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salt acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. 16. Unburned, pre-ceramic material containing a mixture of: A. ceramic powder belonging to the group consisting of alumina, aluminum nitrate, silica, silica, magnesium, lead, zirconium, titanium dioxide, talc, barium titanite, lead-zirconium titanite, clays, ferrite, yttrium oxide, zinc oxide, tungsten carbonate, sialon, neodymium oxide and combinations thereof; and B. a water-soluble polymer having: i) a monomer unit of the formula R ³ R ⁶ -C-CHCH _X III o (CHR ² CHR ³⁰ ) pR ⁴ - 65 where p is an integer from 1-10; R ² and R ³ belongs to the group consisting of hydrogen and Ci - C3 alkyl; R ⁴ belongs to the group consisting of hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C ₃ alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to the ring, except that p = 1, R ² R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; and ii) a water-soluble monomer unit, consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. 17. A method of preparing a ceramic material comprising the steps of: A) mixing the ceramic powder with an aqueous solution containing a water-soluble polymer to form a slurry; said water-soluble polymer has: i) a monomer unit of the formula - 66 R ⁵ R ⁶ ta · ata ata t ata ata ata ata ata ata ata ata ata ata ata ata ata ata ata ta ta ta ta · · · · ···················································· -C -C CH _Ž III (CHR ³ CHR ³ O ⁴ - R ⁴ where p is an integer from 1-10; R ² and R ³ belong to the group containing hydrogen and C 1 -C 3 alkyl; R ⁴ belongs to the group containing hydrogen, phosphate , sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ are hydrogen, carboxylate, C 1 -C 3 alkyl, and a C 1 -C 6 cycloalkyl group formed by joining R ⁵ and R ⁶ into a ring, except that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl, and (ii) a water-soluble monomer unit belonging to the group consisting of: It consists of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulphonic acid, styrene sulphonate, N-tert-butyl acrylamide, butoxymethylacrylamide, Ν, dim-dimethylacrylamide, monosodium salts of acrylamidomethyl-vinylpropanesulphone, a combination of said. B) drying the slurry by a process selected from the group consisting of fluid bed spray drying and spray drying to form particles comprising said copolymer; C) joining the particles by a process selected from the group consisting of dry pressing, rolling and γι / t * · · · · · · · · · · · · · · · · · · · · · · · · Compact isostatic compression to form a structure; and D) heating the compact structure to form a fired ceramic material. The method of claim 17, wherein the particles are made by granulation, and the method of joining the particles to form a compact structure should belong to the group comprising dry compression and isostatic compression. A method of dispersing one or more ceramic materials in an aqueous medium, comprising using a polymer dispersant of a volume preferred for dispersion; the agent comprises a water-soluble polymer having: A) a monomer unit of the formula R ⁵ R ⁶ -C-CHCH ₂ I III O (CHR ² CHR ³ o ¹ -r ⁴ where p is an integer from 1-10; R ² and R ³ belong to the group containing hydrogen and C ₁ -C ₃ alkyl; R ⁴ belongs to the group containing hydrogen, phosphate , sulfate and C 1 -C 20 alkyl, R ⁵ and R ⁶ are hydrogen, carboxylate, C 1 -C ₃ alkyl, and a C 1 -C 6 cycloalkyl group formed by the combination of R ⁵ and R ⁶ - 68 • 999 » 99 99 9 «9 9 9 9 9,999,999 99 99 to the ring, except that p = 1, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are not all hydrogen and with the exception that p = 1, R ⁵ is not methyl; and B) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinyl sulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, N, N-dimethylacrylamide, monosodium salt acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. The method of claim 19, wherein one or more of ceramic materials is selected from the group consisting of alumina, aluminum nitrate, lead titanite, boron nitrate, silicon, silica carbonate, sialon, zirconium nitrate, zirconium carbonate, zirconium boride, boron carbonate, tungsten carbonate, tungsten boride, stannous oxide, ruthenium oxide, yttrium oxide, magnesium oxide, calcium oxide and ferrites. An aqueous dispersion of a ceramic material produced by the process of claim 19. A binder for ceramic materials comprising a water-soluble polymer having: A) a monomer unit of the formula - 69 R ⁵ i CH99 99 9 · «* • 999 999 9 9 99 99 c = o _lv NR * I (CH ₂ ) _p OR ⁴ wherein R ¹ belongs to the group consisting of hydrogen and C 1 -C 3 alkyl; p is an integer from 1-10; R ⁴ belongs to the group consisting of hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C ₃ alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring; and (B) a unit of measurement consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulphonic acid, styrene sulphonate, N-tert-butyl acrylamide, butoxymethylacrylamide, Ν, dim-dimethylacrylamide and monosodium salt of acrylic acid , vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, maleic acid and combinations thereof. The binder of claim 22, wherein p = 2, R ¹ , R ⁴ , R ⁵ and R ⁶ in the formula IV of step A are hydrogen and the monomer units in step B are acrylic acid and acrylamide. The binder of claim 22, wherein p = 3, R ¹ , R ⁵ and R ⁶ in the formula IV of step A are hydrogen and R ⁴ is methyl and the monomer units in step B are acrylic acid and acrylamide. 25. Unburned, pre-ceramic material containing a mixture of: 99 99 99 9 9 9 9 9 0 0 9 9 0 • 9 9 * 9 900 9 0 9 * 909 · 0 «00 A. ceramic powder belonging to the group consisting of alumina, silicate, aluminum nitrate, silicate, silicon dioxide, magnesium oxide, lead oxide, zirconia, titanium dioxide, talc, barium titanite, lead-zirconium titanite, clays, ferroalloys , yttrium oxide, zinc oxide, tungsten carbonate, sialon, neodymium oxide and combinations thereof and B. a water-soluble polymer having: i) a monomer unit of the formula R ⁵ NO I I -C-CH ₁ c = o (CH ₂ ) _p OR ⁴ wherein R ¹ belongs to the group consisting of hydrogen and C 1 -C 3 alkyl; p is an integer from 1-10; R ⁴ is hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C ₁ -C ₃ alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring; and (ii) a water-soluble monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate; - 71 pi / 4 * · 43 ·· 43 4 4 4 4 4 4 4 · 4 · 444 444 4 4 4 4 444 4444 4 4 94 N-tert-butylacrylamide, butoxymethylacrylamide, Ν, Ν-dimethylacrylamide, monosodium salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. The water-soluble polymer of claim 25, wherein p = 2, R ¹ , R ⁴ , R ⁵ and R ⁶ are hydrogen in the formula IV of step i and the monomer units in step ii are acrylic acid and acrylamide. The water-soluble polymer of claim 25, wherein p = 3, R ¹ , R ⁵ and R ⁶ are hydrogen in formula IV of step i and R ⁴ is methyl and the monomer units in step B are acrylic acid and acrylamide. 28. A method of preparing a ceramic material comprising the steps of: A) mixing the ceramic powder with an aqueous solution containing a water-soluble polymer to form a slurry; said water-soluble polymer has: i) a monomer unit of the formula R ⁵ R ⁶ -C-CHC = O IV NR ¹ (CH ₂ ) _p OR ⁴ - 72 99 99 99 9 9 999 999 9 9 Wherein R ¹ belongs to the group consisting of hydrogen and C 1 -C 3 alkyl; p is an integer from 1-10; R ⁴ is hydrogen, phosphate, sulfate and C 1 -C 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, CH-C 3 alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring; and (ii) a water-soluble monomer unit, consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulfonic acid, styrene sulfonate, N-tert-butyl acrylamide, butoxymethylacrylamide, Ν, Ν-dimethylacrylamide, monosodium acrylamide salts of acrylamidomethylpropanesulfonic acid, vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. B) drying the slurry by a process selected from the group consisting of fluid bed spray drying and spray drying to form particles comprising said copolymer; C) joining the particles by a process selected from the group consisting of dry pressing, rolling and isostatic compression to form a compact structure; and D) heating the compact structure to form a fired ceramic material. The water-soluble polymer of claim 28, wherein p = 2, R ¹ , R ⁴ , R ⁵ and R ⁶ are hydrogen in the formula IV of step i and the monomer units in step B are acrylic acid and acrylamide. - 73 · · 73 73 73 73 73 t t t t t t t t t t The water-soluble polymer of claim 28, wherein p = 3, R ¹ , R ⁵ and R ⁶ are hydrogen in formula IV of step i and R ⁴ is methyl and the monomer units in step ii are acrylic acid and acrylamide. The method of claim 28, wherein the particles are produced by granulation and the step of joining the particles to a compact structure is selected from the group consisting of dry compression and isostatic compression. A method of dispersing one or more ceramic materials in an aqueous medium, comprising using an effective amount of a polymer dispersing agent of a volume, the agent comprising a water-soluble polymer having: A) a monomer unit of the formula R ⁵ R ⁶ C-CHC = O NR ^11v (CH ₂ ) _p OR ⁴ wherein R ¹ belongs to the group consisting of hydrogen and C 1 -C 3 alkyl; p is an integer from 1-10; R ⁴ belongs to the group consisting of hydrogen, phosphate, sulfate and C 1 - 20 alkyl; R ⁵ and R ⁶ belong to the group consisting of hydrogen, carboxylate, C 1 -C ₃ alkyl, and a cycloalkyl group having 1 to 6 carbon atoms, formed by linking R ⁵ and R ⁶ to a ring; and - 74 tt tttt ·· · ttt tt tt tt ttt tttt tttt ttttt ttttt ttt tttt B) a monomer unit belonging to the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic anhydride, ithaconic acid, vinylsulphonic acid, styrene sulphonate, N-tert-butyl acrylamide, butoxymethylacrylamide, Ν, dim-dimethylacrylamide and monosodium salt of acrylic acid , vinyl alcohol, N-vinylpyrrolidone, maleic acid and combinations thereof. The water-soluble polymer of claim 32, wherein p = 2, R ¹ , R ⁴ , R ⁵ and R ⁶ are hydrogen in the formula IV of step A and the monomer units in step B are acrylic acid and acrylamide. The water-soluble polymer of claim 32, wherein p = 3, R ¹ , R ⁵ and R ⁶ are hydrogen in Formula IV of Step A and R ⁴ is methyl and the monomer units in Step B are acrylic acid and acrylamide. The method of claim 32, wherein one or more of ceramic materials is selected from the group consisting of alumina, silica nitrate, aluminum nitrate, lead titanite, boron nitrate, silicon, silica carbonate, sialon, zirconium nitrate, zirconium carbonate, zirconium boride, boron carbonate, tungsten carbonate, tungsten boride, stannous oxide, ruthenium oxide, yttrium oxide, magnesium oxide, calcium oxide and ferrites. An aqueous dispersion of a ceramic material prepared by the process of claim 32.