EP1904418A2 - Utilisation de polymeres contenant des carboxylates comme additifs dans des matieres ceramiques - Google Patents

Utilisation de polymeres contenant des carboxylates comme additifs dans des matieres ceramiques

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Publication number
EP1904418A2
EP1904418A2 EP06764036A EP06764036A EP1904418A2 EP 1904418 A2 EP1904418 A2 EP 1904418A2 EP 06764036 A EP06764036 A EP 06764036A EP 06764036 A EP06764036 A EP 06764036A EP 1904418 A2 EP1904418 A2 EP 1904418A2
Authority
EP
European Patent Office
Prior art keywords
units
acrylic acid
meth
skeleton
clay
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06764036A
Other languages
German (de)
English (en)
Inventor
Joachim Pakusch
Marcus Guzmann
Thorsen Wiedemann
Stefan Becker
Marco Schmidt
Thomas GÖTZ
Gregor Brodt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1904418A2 publication Critical patent/EP1904418A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/04—Clay; Kaolin
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63424—Polyacrylates; Polymethacrylates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/6344—Copolymers containing at least three different monomers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6021—Extrusion moulding
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/61—Mechanical properties, e.g. fracture toughness, hardness, Young's modulus or strength
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F220/66—Anhydrides

Definitions

  • the present invention relates to the use of homopolymers or copolymers of (meth) acrylic acid or copolymers of C 3 -C 40 monoolefins with ethylenically unsaturated CU-Ce-dicarboxylic anhydrides as additives in ceramic compositions, in particular in loam and clay for the production of Building ceramics, such as bricks and roof tiles as well as ceramic masses containing these additives.
  • Clay is an earthy mineral aggregate consisting predominantly of hydrous aluminum silicates which are plastically deformable when wet, rigid in the dry state and become glassy when heated.
  • clay As a clastic sediment, clay is a mixture of various minerals, mainly composed of clay minerals, aluminum hydrosilicates and hydrates, quartz, feldspar, gypsum, etc.
  • Clay minerals essentially comprise kaolinite, halloysite, montmorillonite, illite and chlorite. Clay is plastically deformable in the wet state, rigid in the dry state and becomes transparent when heated.
  • the clay or clay is mined according to its occurrence, and transported to brickworks for further processing into bricks.
  • water is added to adjust the moisture content or to increase plasticity, and the clay / clay is then temporarily stored for swelling.
  • the raw material is then ground to achieve a small particle size, typically less than 1mm, as a rule.
  • a moisture content of, for example, 20% is set with water so that the material becomes plastically processable.
  • Additives or the polymers according to the invention can also be added in this step.
  • the polymers according to the invention lead to increased plasticity as well as increased mechanical strength of the dried products.
  • the additivated clay is then extruded by molding. This is followed by drying at temperatures greater than 100 ° C. Optionally, the moldings are then engobed or coated. Then the firing process takes place at temperatures up to 110o 0 C. After firing, the finished products are cooled.
  • WO 01/09058 discloses a mixture containing clay, water and a tannin or a tannin derivative and a method for producing bricks using the claimed mixture.
  • JP 10-194844 describes the production of ceramic shaped bodies, containing not only clay but also cement using maleic acid copolymers.
  • US 4,148,662 and GB 2041950 disclose a mixture for the production of bricks as well as a method for producing bricks using water-soluble anionic polyelectrolytes.
  • the water content is a critical size. If the water content is too high, the bricks may deform during stacking, resulting in long drying times and undesirable shrinkage during the drying process. By far, the mechanical stability of the dried products is relatively low, so that easily damage occurs and thus the committee is increased.
  • Object of the present invention was therefore to reduce the water content of clay or clay to achieve the plastic processability and increasing the mechanical strength of the dried molded body.
  • (Meth) acrylic acid copolymer is 100 wt .-% or of
  • Another object of the invention are ceramic compositions containing these additives, in particular clay and clay tiles containing these additives.
  • the term (meth) acrylic acid copolymers means methacrylic acid polymers, acrylic acid polymers and mixed polymers of methacrylic acid and acrylic acid.
  • the polymer according to the invention comprises a polyacrylic acid skeleton.
  • terelactone units are understood as meaning units of the following structure:
  • Homopolymers of acrylic acid and methacrylic acid are known. They are prepared, for example, by polymerizing acrylic acid or methacrylic acid in aqueous solution in the presence of polymerization initiators and optionally polymerization regulators at temperatures of 50 to 150 ° C. At temperatures above 100 ° C, it is necessary to carry out the polymerization in pressure equipment.
  • the molecular weights of the polyacrylic acids and polymethacrylic acids to be used according to the invention are from 500 to 100 000 g / mol and are preferably in the range from 800 to 40 000 g / mol.
  • copolymers of acrylic acid and methacrylic acid which may contain the two monomers in any ratio, use according to the invention.
  • the molecular weight range of the copolymers of acrylic acid and methacrylic acid corresponds to that of the homopolymers.
  • the novel polymers (a) may additionally comprise units (iv) of other ethylenically unsaturated monomers copolymerizable with (meth) acrylic acid.
  • Suitable monomers for this purpose are, for example, monoethylenically unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylene malonic acid and citraconic acid.
  • Further copolymerizable monomers are C 1 to C 4 alkyl esters of monoethylenically unsaturated carboxylic acids, such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate.
  • alkylpolyethylene glycol (meth) acrylates which are derived from polyalkylene glycols having 2 to 50 ethylene glycol units, monoallyl ethers of polyethylene glycols having 2 to 50 ethylene glycol units and allyl alcohol.
  • Suitable monomers are acrylamide, methacrylamide, N-vinylformamide, styrene, acrylonitrile, methacrylonitrile and / or monomers carrying sulfonic acid groups and also vinyl acetate, vinyl propionate, allyl phosphonate, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-one.
  • the basic monomers such as dimethylaminoethyl methacrylate can be used for example in the form of the free bases, as salts with strong acids such as hydrochloric acid, sulfuric acid or phosphoric acid or in the form of quaternized compounds as comonomers.
  • the above-mentioned acid group-containing monomers can be used in the form of the free acids or as salts, for example the sodium, potassium or ammonium salts in the polymerization.
  • polymers according to the invention are present in neutralized form.
  • sulfonic acid monomers or their salts can also be copolymerized directly.
  • the sulfonic acid monomers are preferably selected from the group consisting of 2-acrylamidomethyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, S-methacrylamido-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3 - (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and their water-soluble salts.
  • the (meth) acrylic acid copolymer of the present invention may have at least one unit bonded to the poly (meth) acrylic acid skeleton selected from the group consisting of isobutene units, terelactone units and isopropanol units.
  • isobutene units When isobutene units are contained in the polymer of the present invention, their amount is, for example, 0.5 to 3.0 mol%. In further embodiments, the amount of isobutene units present may be 0.8 to 2.5 mole% or 1.0 to 2.0 mole%.
  • the terelactone units can be present both terminally and in the polymer chain.
  • the (meth) acrylic acid copolymers according to the invention may additionally have at least one of the following structural units:
  • the amide units based on aminoalkylsulfonic acids can be derived from any aminoalkylsulfonic acid.
  • Particularly suitable aminoalkylsulfonic acids are those having 2 to 12, preferably 4 to 10 carbon atoms.
  • the amino groups may be primary, secondary or tertiary.
  • the aminoalkylsulfonic acids may, for example, have hydroxyl or alkoxy groups or halogen atoms.
  • the alkyl groups may be unsaturated or preferably saturated, straight or branched or closed to the ring.
  • the amino groups may be located within the chain of aminoalkyl groups or as side or terminal substituents. They may also be part of a preferably saturated heterocyclic ring.
  • the (meth) acrylic acid copolymer according to the invention contains the structural unit (II) based on aminoethanesulfonic acid (taurine):
  • the sulfonate moieties of the (meth) acrylic acid copolymers can be saturated with any counterion.
  • the counterion is selected from the group consisting of protons, alkali ions or ammonium ions.
  • the sulfoalkylamide structural units are preferably randomly distributed in the (meth) acrylic acid copolymer.
  • polymers (a), groups (i) and (iii) (polymer A) or (ii) and (iii) (polymer B) of the invention are prepared by the following process steps:
  • This process is suitable, for example, for the preparation of the (meth) acrylic acid copolymers according to the invention described above.
  • the process step (1) is performed at temperatures of preferably 100 to 200 0 C, particularly preferably 105 to 135 ° C, in particular 120 to 125 ° C is performed.
  • Process step (1) is preferably carried out in a closed reaction vessel, for example an autoclave.
  • the pressure in process step (1) thus generally results from the vapor pressure (autogenous pressure) of water or, if appropriate, isopropanol or isopropanol / water mixtures at the abovementioned temperatures. independence this may possibly also be carried out under additional pressure or under reduced pressure.
  • Process step (1) can be carried out in isopropanol or in at least 20% by weight, particularly preferably at least 25% by weight, in particular at least 30% by weight, of isopropanol-containing aqueous solutions.
  • the radical polymerization of the monomers is preferably carried out using hydrogen peroxide as an initiator.
  • hydrogen peroxide as an initiator.
  • all compounds which form radicals under the reaction conditions for example peroxides, hydroperoxides, peroxydisulfates, peroxodicarboxylic acids, peroxycarboxylic acid esters and / or azo compounds, can also be used as polymerization initiators.
  • additional monomers can be used in process step (1) of the process according to the invention, for example, with (meth) acrylic acid copolymerizable ethylenically unsaturated monomers.
  • Suitable comonomers are, for example, monoethylenically unsaturated carboxylic acids, such as maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid and citraconic acid.
  • Further copolymerizable monomers are C 1 - to C 4 -alkyl esters of monoethylenically unsaturated carboxylic acids, such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate.
  • alkylpolyethylene glycol (meth) acrylates which are derived from polyalkylene glycols having 2 to 50 ethylene glycol units, monoallyl ethers of polyethylene glycols having 2 to 50 ethylene glycol units and allyl alcohol.
  • Further suitable monomers are acrylamide, methacrylamide, N-vinylformamide, styrene, acrylonitrile, methacrylonitrile and / or monomers carrying sulfonic acid groups and also vinyl acetate, vinyl propionate, allyl phosphonate, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-one.
  • methylimidazoline diallyldimethylammonium chloride, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.
  • the basic monomers such as dimethylaminoethyl methacrylate can be used for example in the form of the free bases, as salts with strong acids such as hydrochloric acid, sulfuric acid or phosphoric acid or in the form of quaternized compounds as comonomers.
  • the abovementioned monomers containing acid groups can be used in the form of the free acids or as salts, for example the sodium, potassium or ammonium salts, in the polymerization.
  • the proportion of (meth) acrylic acid in the polymer B is 75 to 95 wt .-%, preferably 80 to 90 wt .-%, particularly preferably 82.5 to 87.5 wt .-%.
  • the proportion of units based on isopropanol in the polymer B is then preferably from 5 to 25% by weight, particularly preferably from 10 to 20% by weight, in particular from 12.5 to 17.5% by weight.
  • the polymer B obtainable by process step (1) of the process according to the invention optionally has isobutene units in an amount of preferably 0.5 to 3.0 mol%, particularly preferably 0.8 to 2.5 mol%, in particular 1, 0 to 2 , 0 mol%, on.
  • the isobutene units may optionally be arranged terminally in the polymer B.
  • the polymer B contains terephthalone units which are arranged terminally or in the polymer chain of the polymer B.
  • the polymer B contains both isobutene units and terelactone units.
  • the preparation process may preferably be carried out such that the (meth) acrylic acid copolymer has sulfonate groups with a counterion selected from the group consisting of protons, alkali ions or ammonium ions.
  • a counterion selected from the group consisting of protons, alkali ions or ammonium ions.
  • the sulfonate moieties of the (meth) acrylic acid copolymers can be saturated with any counterion.
  • the polymers A and B obtainable according to process step (1) are preferably obtained in a polymer solution which has a solids content of preferably 10 to 70%, particularly preferably 30 to 60%, in particular 40 to 55%.
  • the polymer solution containing the polymer A and B is at a pH of preferably from 2.0 to 9.0, particularly preferably 4.0 adjusted to 7.5, in particular 4.5 to 6.5.
  • all bases are suitable for this purpose, but preferably aqueous solutions of alkali metal hydroxides, for example aqueous sodium hydroxide solution, are used.
  • the amidation (process step (2)) is preferably carried out under a protective gas atmosphere, for example using argon or nitrogen.
  • the process step (2) of the preparation process is preferably carried out at temperatures of 140 to 250 0 C, more preferably 165 to 200 0 C, in particular 175 to 185 ° C, performed.
  • the molar ratio of monomer units in polymer A and B to aminoalkanesulfonic acid is preferably 15 to 1 to 2 to 1, more preferably 11 to 1 to 3 to 1, in particular 8 to 1 to 4 to 1.
  • the pressure in process step (2) is preferably 1 to 25 bar, more preferably 5 to 17 bar, in particular 7 to 13 bar.
  • the (meth) acrylic acid copolymer resulting from process step (1) preferably has at least one of the following structural units based on isopropanol:
  • the (meth) acrylic acid copolymer obtainable according to the preparation process particularly preferably has isobutene units and / or terelactone units.
  • the isobutene units are preferably arranged terminally in the (meth) acrylic acid copolymer, while the terelactone units can be present both terminally and in the polymer chain.
  • the (meth) acrylic acid copolymer B obtainable by the present invention preferably has a weight-average molecular weight of 500 to 20,000 g / mol, more preferably 1,000 to 15,000 g / mol, especially 1,500 to 10,000 g / mol.
  • aminoethylsulfonic acid is used as the aminoalkylsulfonic acid, so that the polymer resulting from process step (2) has units based on aminoethylsulfonic acid.
  • any other aminoalkylsulfonic acids can also be used. In this regard, reference is made to the above statements.
  • the copolymers (b) are known, for example, from DE-05 3 730 885. They are obtained by copolymerizing the monomers of group (i) with the monomers of group (ii) at temperatures of 80 to 300 0 C by a mass.
  • Suitable monoolefins having 3 to 40 carbon atoms are, for example, 2-propene, isobutene, n-octene-1,2,4,4-trimethylpentene-1,2,4,4-trimethylpentene-2,2-diisobutene, which is technically a mixture of isomers about 80% by weight of 2,4,4-trimethylpentene-1 and about 20% by weight of 2,4,4-trimethylpentene-2, 4,4-dimethylhexene-1, decene-1, dodecene-1 , Tetradecene-1, hexadecene-1, octadecene-1, C 2 o-olefin-1, C 22 -olefin-1, C 24 -olefin-1, C 20 - to C 24 -olefin-1, C 24 - to C 28 -olefin-1, C 30 -olefin-1, C 35 -olefin-1 and C 40 o
  • the olefins or mixtures of olefins are commercial products. Besides the straight-chain olefins, cyclic olefins such as cyclooctene are also suitable.
  • the olefins may contain minor amounts of inert organic hydrocarbons, eg, up to about 5% by weight, as produced.
  • the olefins are commonly used in the commercial grade. You do not need to be subjected to any special cleaning.
  • the preferred olefins are alpha-olefins having chain lengths between C 4 and C 24, as component (ii) of the copolymers are monoethylenically unsaturated C 4 - to C 8 - dicarboxylic into consideration, for example, maleic anhydride, itaconic anhydride, methyl saconklareanhydrid, citraconic anhydride, methylenemalonic and mixtures with each other. Of the anhydrides mentioned, maleic anhydride is preferably used.
  • the copolymers contain from 40 to 60 mol% monoolefins and 60 to 40 mol% of said dicarboxylic anhydrides copolymerized and have a molecular weight of 500 to 20,000, preferably 800 to 12,000 g / mol. They are obtainable by polymerizing the monomers (i) and (ii) in a molar ratio of 1.1: 1 to 1: 1. Preferably, the monomers (i) and (ii) are polymerized in a molar ratio of 1: 1 or use only a 1 wt .-% excess of monomers of component (i).
  • the monomers of groups (i) and (ii) form alternating copolymers which contain the monomers (i) and (ii) in copolymerized form at 50 mol% in each case at high molecular weights.
  • the copolymers depending on the nature of the end groups, there may be a deviation from the molar ratio in the frame indicated above, for example if the copolymer chain starts with the monomer (i) and also terminates with the monomer (i).
  • the bulk polymerization is carried out at temperatures of 80 to 300, preferably from 120 to 200 0 C, wherein the lowest to be selected polymerization temperature is preferably at least about 20 0 C above the glass transition temperature of the polymer formed.
  • the polymerization conditions are selected. Polymerization at high temperatures gives copolymers with low molecular weights, while at lower polymerization temperatures polymers with higher molecular weights are formed.
  • the amount of the polymerization initiator also has an influence on the molecular weight. It generally requires from 0.01 to 5 wt .-%, based on the monomers used in the polymerization, of radical-forming polymerization initiators.
  • the monomers (i) and (ii) can also be copolymerized at temperatures above 200 ° C., even in the absence of polymerization initiators, ie it is not absolutely necessary to use initiators because the monomers (i) and (ii) are at temperatures above 200 ° C radically polymerize even in the absence of initiators.
  • Suitable polymerization initiators are, for example, di-tertiary-butyl peroxide, acetylcyclohexanesulfonyl peroxide, diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tertiary butyl pheodecanoate, 2,2 "azobis (4-methoxy-2,4-dimethylvaleronitrile), tertiary butyl perpivalate, tertiary butylper-2-ethyl-hexanoate, tertiary-butylpermaleinate, 2,2 "-azobis (isobutyronitrile), bis (tertiary-butylperoxy) cyclohexane, tertiary-butylperoxy-isopropylcarbonate, tertiary-butyl-peracetate, di-tertiary
  • the initiators can be used alone or mixed with each other. In the bulk polymerization, they are preferably introduced into the polymerization reactor separately or in the form of a solution or dispersion in the monoolefin.
  • redox coinitiators may also be used in the copolymerization, for example benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals, such as copper, cobalt, iron, manganese, nickel and chromium.
  • the concomitant use of redox coinitiators makes it possible to carry out the polymerization at a lower temperature.
  • the amounts of redox coinitiators commonly used are about 0.1 to 2000, preferably 0.1 to 1000 ppm, based on the amounts of monomers used.
  • the monomer mixture is polymerized at the lower limit of the temperature range to be used for the polymerization and then polymerized at a higher temperature, it is expedient to use at least two different initiators which decompose at different temperatures, so that one at each temperature interval sufficient concentration of radicals is available.
  • regulators can be used for this purpose, for example C 1 - to C 4 -aldehydes, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, tert-butylmercaptan, n-dodecylmercaptan and tertiary-dodecylmercaptan ,
  • the polymerization regulators are generally used in amounts of from 0.1 to 10% by weight, based on the monomers.
  • the copolymerization is carried out in customary polymerization apparatuses, for example a pressure-tight vessel provided with a stirrer, in pressure-tight stirred tank cascades or in a tubular reactor.
  • a pressure-tight vessel provided with a stirrer
  • pressure-tight stirred tank cascades or in a tubular reactor.
  • the copolymerization of the olefins and the anhydrides takes place in a molar ratio in the absence of solvents.
  • the copolymerization can be carried out continuously or batchwise.
  • the olefin or a mixture of different olefins can be initially charged in the reactor and heated to the desired polymerization temperature with stirring.
  • the ethylenically unsaturated dicarboxylic acid anhydride is metered in. If an initiator is used, it is added to the reaction mixture, preferably separately or dissolved in an olefin coming to polymerization. The polymerization is, if it is used, either separately or dissolved in an olefin dissolved added to the polymerizing mixture.
  • the acid anhydrides in particular maleic anhydride, are preferably added to the reaction mixture in the form of a melt. The temperature of the melt is about 70 to 90 ° C.
  • the olefin is used in excess in the copolymerization, for example in a 10% excess, it may without difficulty from the reaction mixture with the aid of a distillation after completion of the copolymerization, preferably under reduced pressure, be removed from the copolymer melt.
  • the copolymerisatschmelze is then conveniently further processed directly.
  • the copolymers thus prepared, after cooling to room temperature or preferably in the form of the melt, which has a temperature in the range of 80 to 180 0 C, preferably 90 to 150 0 C, solvolysiert.
  • the solvolysis of the anhydride groups of the copolymers consists in the simplest case in a hydrolysis and subsequent neutralization.
  • the copolymers obtainable by bulk polymerization can also be solvolyzed by the addition of primary and / or secondary amines.
  • the solvolysis is carried out with such amounts of amines that 10 to 50% of the copolymerized from the copolymerized monomers (ii) in total resulting in a complete hydrolysis carboxyl groups are amidated. After the formation of half-amide groups in the copolymer, the neutralization takes place. It is carried out so far that at least 10% of the carboxyl groups of the copolymer obtained in the bulk polymerization are neutralized.
  • alkali metal salts of ⁇ -aminocarboxylic acids the alkali metal salts of sarcosine being very particularly advantageous.
  • the solvolysis by means of salts of aminocarboxylic acids is expediently carried out in an aqueous medium.
  • the solvolysis is carried out with such amounts of aminocarboxylates that 10 to 50% of the polymerized from the copolymerized monomers (ii) in total in a complete hydrolysis
  • Carboxyl groups are amidated. After the formation of half-amide groups in the copolymer, the neutralization takes place. It is carried out to the extent that at least 10% of the carboxyl groups of the copolymer obtained in the bulk polymerization are neutralized.
  • the solvolysis can also be carried out by adding alcohols to a melt of the copolymers obtainable in the bulk polymerization. You bet with it such amounts of alcohol that 10 to 50% of the total of the polymerized dicarboxylic acid units resulting carboxyl groups are esterified. Subsequently, a neutralization is carried out in which at least 10% of the total resulting from the anhydride-containing copolymer carboxyl groups are neutralized.
  • Suitable neutralizing agents are, for example, ammonia, amines, alkali metal and alkaline earth metal bases, for example sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide, calcium hydroxide, barium hydroxide and all amines which are also used for amidation of the copolymers.
  • the neutralization is preferably carried out by adding aqueous sodium hydroxide solution to the copolymer.
  • the neutralization of the anhydride-containing copolymers is carried out at least to such an extent that water-dispersible copolymers are obtained.
  • This degree of neutralization is at least 10% of the carboxyl groups formed in total from the anhydride groups.
  • the degree of neutralization is also dependent on the chain length of the particular olefin used in component (a).
  • a copolymer of a C 30 olefin and maleic anhydride is neutralized to at least 75%, while, for example, a copolymer of a C 2o / C 24 - olefin and maleic anhydride at a degree of neutralization of 50 % of the carboxyl groups formed from this copolymer are already readily dispersible in water.
  • amide formation can be used ammonia and primary and secondary amines.
  • the amide formation is preferably carried out in the absence of water by reaction of the anhydride groups of the copolymer with ammonia or the amines.
  • the suitable primary and secondary amines may have 1 to 40, preferably 3 to 30, carbon atoms.
  • Suitable amines are, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, dimethylamine, Diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-isobutylamine, dihexylamine, di-cyclohexylamine, di-methylcyclohexylamine, di-2-ethylhexylamine, di-n-octylamine, di-isotridecylamine, di-n-butylamine.
  • morpholine is used.
  • Suitable alcohols may contain 1 to 40, preferably 3 to 30, carbon atoms.
  • Primary, secondary and tertiary alcohols can be used. It is possible to use both saturated aliphatic alcohols and unsaturated alcohols, such as oleyl alcohol.
  • alcohols having 4 to 24 carbon atoms such as n-butanol, isobutene Tanol, amyl alcohol, 2-ethylhexanol, tridecanol, tallow fatty alcohol, stearyl alcohol, C9 / n- oxo, Ci 2 / i 5 oxo alcohol, C 2 / i 4 -alpha and Ci 6 / i 8 -alpha.
  • the hydrolysis of the remaining anhydride groups of the copolymer is carried out.
  • the hydrolysis of the remaining anhydride groups of the copolymer can also be carried out simultaneously with the still required partial neutralization by adding an aqueous base to the partially amidated or esterified and still containing anhydride copolymer.
  • the amount of water and bases is chosen so that the concentration of the copolymer dispersion or solution is preferably from 20 to 55% by weight.
  • the pH of the ready-to-use agents is in the range of about 4 to 10.
  • ceramic masses is meant, for example, building ceramics, such as clay and clay tiles, for masonry and roof (clay bricks, clay roof tiles).
  • the additive to be used according to the invention may be added in the form of its aqueous solution shortly before or during extrusion (injection in the extruder) in the course of the production process for the ceramic masses. It is added in amounts of 0.01% to 5%, preferably 0.1 to 1%, based on the solids content of the clay.
  • the additives according to the invention can also be used in combination with other additives suitable for reducing the water content, for example tannins or tannin derivatives, as described in WO 01/09058.
  • the percentages in the examples are by weight unless otherwise specified.
  • the molecular weights of the copolymers were determined by gel permeation chromatography using tetrahydrofuran as eluant and narrow fractions of polystyrene for calibration.
  • Feed 1 186.70 g of maleic anhydride (as a melt in a heatable dropping funnel)
  • Feed 2 9.40 g of tert-butyl peroctoate dissolved in 70.60 g of 2,4,4-trimethyl-1-pentene
  • Example 6 In a 2 l reactor, 250 g of water and 3.0 g of 50% phosphorous acid are initially charged under an atmosphere of nitrogen to an internal temperature of 100 0 C. At this temperature, feed 5 simultaneously gives 517 g of acrylic acid within 4 hours, Through feed 2 76.0 g of 7% sodium peroxodisulfate within 4.5 hours and fed by feed 3 44.5 g of mercaptoethanol within 3.75 hours. Then it is cooled to 80 0 C. Dissolved azobis (2-methypropionamidine) dihydrochloride in water and polymerization 16,25g then for 1 hour - within 30 minutes 0.43 g 2,2 'is subsequently feed.
  • azobis (2-methypropionamidine) dihydrochloride in water and polymerization 16,25g then for 1 hour - within 30 minutes 0.43 g 2,2 'is subsequently feed.
  • Example 7 In a 2 l reactor, 200 g of water and 2.7 g of 50% phosphorous acid are initially charged under an atmosphere of nitrogen to an internal temperature of 99 ° C. At this temperature, feed 428 g of acrylic acid within 5 hours, feed 2 61.3 g of 7% strength sodium peroxodisulfate within 5.25 hours and feed 3 54 g of mercaptoethanol are fed in within 4.75 hours simultaneously. The mixture is stirred for 15 minutes at 99 ° C and then cooled to 80 ° C. 0.87 g of 2,2'-azobis (2-methypropionamidine) dihydrochloride dissolved in 15.3 g of water are then added through feed 4 within 30 minutes and then polymerized for 1 hour.
  • 2,2'-azobis (2-methypropionamidine) dihydrochloride dissolved in 15.3 g of water are then added through feed 4 within 30 minutes and then polymerized for 1 hour.
  • the kettle is charged with 48.29 g of deionized water, 344.19 g of isopropanol and 31.16 g of hydrogen peroxide solution (30% strength).
  • the boiler is rendered inert with nitrogen and sealed pressure-tight after pressure equalization.
  • the mixture is heated to (220 rpm) at 120 0 C with stirring.
  • Feed 1 consists of 431.00 g of isopropanol and 745.50 g (10.35 mol) of acrylic acid.
  • Feed 2 consists of 47.80 g of hydrogen peroxide solution (30%) and 127.17 g of deionized water.
  • the feeds are fed in separately. Feed 1 within 6 hours and feed 2 within 7 hours.
  • the polymerization temperature is 120 ° C. After the end of the feed 2, the reaction mixture is cooled and drained.
  • the isopropanol is removed by simple distillation. During the distillation, 341.26 g of deionized water are added. Subsequently, the pH is adjusted to 4.5 with 50% sodium hydroxide solution and the product is diluted with a further 500 ml of water.
  • a polymer is prepared from acrylic acid (process step (a)).
  • the K values of the polymers were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 48-64 and 71-74 (1932) in aqueous solution at a pH of 7, a temperature of 25 ° C. and a polymer concentration of Sodium salt of the polymers of 1 wt .-% determined.
  • Section 1 Since the ball leaves an immersion channel when immersed in the sample, a short section (section 1) has been inserted, which moves the ball away from the point of immersion. After that, a break (Section 2) was introduced, which proved to be useful in restoring structures that may have been destroyed by immersion and movement in Section 1.
  • the clay used for the experiments shown below comes from a mine
  • the torque of the extruder shaft and the radial pressure at the extruder head (mouthpiece) were determined. The lower the torque and the pressing pressure, the higher the plasticity of the additoned clay.
  • the copolymers also cause an increase in plasticity. As well as an increase in the BZF.
  • AS acrylic acid
  • MSA maleic anhydride
  • DIB diisobutene
  • IB isobutene
  • BZF bending tensile strength
  • the addition of polyacrylates to the clay allows processing by means of extruders for the production of moldings even at reduced water content.
  • the non-polymer additivated clay sample could no longer be processed in the extruder at a moisture content of less than 19.4%.
  • the results are shown below.
  • the polyacrylates were additized in the respective experiment with 0.2 wt .-% based on the dry content of the clay.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Press-Shaping Or Shaping Using Conveyers (AREA)

Abstract

La présente invention concerne l'utilisation d'homopolymères ou de copolymères de l'acide (méth)acrylique ou de copolymères de mono-oléfines C<SUB>3</SUB>-C<SUB>40</SUB> avec des anhydrides de l'acide dicarboxylique C<SUB>4</SUB>-C<SUB>6</SUB> éthyléniquement insaturés comme additifs dans des matières céramiques, en particulier dans l'argile ou la glaise pour produire de la céramique de bâtiment, notamment des briques et des tuiles. L'invention concerne également des matières céramiques contenant ces additifs.
EP06764036A 2005-07-14 2006-07-04 Utilisation de polymeres contenant des carboxylates comme additifs dans des matieres ceramiques Withdrawn EP1904418A2 (fr)

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DE102005033518A DE102005033518A1 (de) 2005-07-14 2005-07-14 Verwendung von carboxylathaltigen Polymeren als Additive in keramischen Massen
PCT/EP2006/063832 WO2007006683A2 (fr) 2005-07-14 2006-07-04 Utilisation de polymeres contenant des carboxylates comme additifs dans des matieres ceramiques

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JP5328667B2 (ja) * 2006-12-08 2013-10-30 ビーエーエスエフ ソシエタス・ヨーロピア アルコキシ基を有する重合可能なカルボン酸エステルの製造方法
RU2360887C1 (ru) * 2007-12-11 2009-07-10 Попова Елена Алексеевна Керамическая масса для получения кирпича и способ его изготовления
DE102008035508A1 (de) * 2008-07-30 2010-02-04 Novokeram Gmbh Keramisches Formteil und Herstellverfahren
EP3363879A3 (fr) * 2014-01-29 2018-10-03 Basf Se Carburants diesel contenant des additifs à base d'acide polycarboxique

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US4148662A (en) * 1977-11-01 1979-04-10 American Colloid Company Brick composition and method therefor

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US3061564A (en) * 1959-03-18 1962-10-30 Rohm & Haas Shellac copolymers and compositions and methods for making them
DE59101468D1 (de) * 1990-02-21 1994-06-01 Basf Ag Thermoplastische Massen für die Herstellung keramischer Formkörper.
DE69321828T2 (de) * 1993-07-21 1999-04-15 Kao Corp Rohstoffzusammensetzung für keramische Werkstoffe und Verfahren zu seiner Herstellung
US5976240A (en) * 1997-09-08 1999-11-02 North American Refractories Co. Refractory system including reactive metakaolin additive
ATE280741T1 (de) * 2001-06-02 2004-11-15 Cognis Iberia Sl Wässrige rohstoffzusammensetzungen für keramische werkstoffe
JP2005060208A (ja) * 2002-11-08 2005-03-10 Murata Mfg Co Ltd 水溶性アクリルバインダおよびその製造方法、セラミックスラリー組成物およびその製造方法、ならびに積層セラミック電子部品およびその製造方法

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US4148662A (en) * 1977-11-01 1979-04-10 American Colloid Company Brick composition and method therefor

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WO2007006683A3 (fr) 2007-10-11
CA2615234A1 (fr) 2007-01-18
RU2413700C9 (ru) 2012-03-20
RU2008104960A (ru) 2009-08-20
RU2413700C2 (ru) 2011-03-10
BRPI0613035A2 (pt) 2016-11-29
DE102005033518A1 (de) 2007-01-18
WO2007006683A2 (fr) 2007-01-18
CN101263094A (zh) 2008-09-10
US20090105390A1 (en) 2009-04-23

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