EP3818025A1

EP3818025A1 - Composition for flowable fire-resistant materials

Info

Publication number: EP3818025A1
Application number: EP19732065.8A
Authority: EP
Inventors: Adolf FAERBERBOECK; Konrad Wutz; Alexander ASSMANN; Torben Gaedt
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2018-07-06
Filing date: 2019-06-25
Publication date: 2021-05-12
Also published as: CN112351964A; JP7315595B2; KR20210027460A; US11542200B2; WO2020007664A1; US20210261463A1; JP2021530418A

Abstract

The present invention relates to a composition for flowable fire resistant materials comprising calcium aluminate cement, a filler, a flow agent in the form of a copolymer, which comprises polyether side chains, and a retarder, which contains at least one acid. The invention also relates to an article which comprises said composition.

Description

Composition for flowable refractory masses

The present invention relates to a composition for flowable refractory compositions comprising calcium aluminate cement, a filler, a flow agent in the form of a copolymer which comprises polyether side chains, and a retarder which contains at least one acid. The present invention also relates to an article which comprises said composition.

Flow agents and solidification retarders are organic or inorganic additives that increase the water demand of unshaped refractory materials, especially so-called

Castables, belittling. Such flow agents are characterized by the fact that they either improve the processability of the refractory mass at the same water content or that they can be used to reduce the water addition and maintain the consistency of the mass to a low water value.

Refractory materials containing aluminate cement are those in which a calcium aluminate cement (synonymous names: alumina cement, alumina cement or high alumina cement) acts as the hydraulic binder. The basis of these cements are AhOs-rich calcium or barium aluminates, the AhOs content being at least 35%. When classifying the cement content, the content of CaO as a hydrating element is decisive.

For hydraulic binder compositions and in particular those containing calcium aluminate cement, the use of boric acid and boric acid derivatives as retarding agents has proven successful. Binder compositions which contain boric acid as a solidification retardant can be shaped for a long time and are easy to process, while the strength values of the molded articles produced remain at a high level.

According to current EC legislation (REACH), however, boric acid and boric acid esters have been classified as harmful to health. Preparations are therefore to be labeled as toxic with a boron content of 1%, which corresponds to 5.5% boric acid or 8.5% borax, with the hazard warnings "May impair reproduction" and "May damage the unborn child". Due to these increasing requirements and in order to avoid hazards when using hydraulic binders, the use of boric acid-free solidification retarders is preferable.

There is therefore a need for solidification retarders for cementitious hydraulic binders, in particular for flowable refractory compositions which do not contain boric acid or boric acid derivatives.

For example, WO 2015/036262 describes liquefaction systems for binder compositions which, instead of boric acid, contain mixtures of trisodium citrate, Contain polycarboxylic acid esters and sulfonic acids as solidification retarders. The

However, the binder compositions described are cement-free.

From EP 1 535 887 A1, binder compositions for refractory materials based on calcium aluminate cement are known which contain freezing agents which are free from boric acid. However, the processing of these compositions requires a relatively high amount of mixing water, which has a negative effect on the strength and durability of the resulting refractory material. In order to convert building material mixtures, in particular those based on inorganic binders, into a ready-to-use, processable form, considerably more mixing water is generally required than for the subsequent one

Hydration or hardening process would be necessary. The proportion of voids in the structure formed by the excess, later evaporating water leads to a significantly deteriorated mechanical strength, durability and durability.

In order to reduce this excess water content at a given processing consistency and / or to improve the processability at a given water / binder ratio, additives are used, which are generally referred to in water chemistry as water reducing or flow agents. As such agents, especially polycondensation products based on naphthalene or alkylnaphthalenesulfonic acids or melamine-formaldehyde resins containing sulfonic acid groups are known. The binder composition described in EP 1 535 887 A1 contains a condensate of β-naphthalenesulfonate and formalin as a flow agent. However, as indicated above, the amount of mixing water required is not satisfactory.

It was therefore an object of the present invention to provide a cement-containing, in particular calcium-aluminate-cement, binder composition for refractory materials which is free of boric acid and boric acid derivatives and at the same time is characterized by good flow behavior and high strength values with a minimum amount of mixing water.

This task was solved by a composition for flowable refractory masses comprehensively

i) calcium aluminate cement,

ii) at least one filler,

iii) at least one flow agent which contains at least one copolymer which comprises a main chain and polyether side chains, and

iv) at least one retarder which contains at least one acid.

It has surprisingly been found here that a composition which chains calcium aluminate cement, a polymeric flow agent with polyether sides and comprises an acid as retarder has good flow behavior and requires a small amount of mixing water for processing. It has been shown that plasticizers based on lignin sulfonate, melamine sulfonate and naphthalene sulfonate are used in the copolymers according to the invention are clearly inferior to their effectiveness. The flowability is particularly to be emphasized in connection with the fact that the composition is preferably a refractory composition, in particular a free-flowing, refractory composition. Preferably, the composition contains less than 3.0% by weight of Portland cement, more preferably less than 2.0% by weight, particularly preferably less than 1.0% by weight, based on the total weight of the composition.

According to a further preferred embodiment of the present invention, the main chain exists

i) at least one structural unit, which consists of a carbon chain with at least 16 carbon atoms,

or

ii) at least one structural unit which consists of a (CCO) _n chain, where n is a number of at least 5,

or

iii) from at least one structural unit which comprises an aromatic or a heteroaromatic.

According to a further preferred embodiment of the present invention, the polyether side chains of the at least one copolymer are polyether side chains of the structural unit (I)

^* -U- (C (0)) _k -X- (AlkO) zW (I) where

^* indicates the binding site to the polymer,

U stands for a chemical bond or an alkylene group with 1 to 8 C atoms, which is unsubstituted or with at least one group from the series carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy , Sulfinoalkyloxy and phosphonooxy is substituted,

X represents oxygen, sulfur or a group NR ¹ ,

k is 0 or 1,

z stands for an integer whose average, based on the polymer in

Ranges from 3 to 300,

Alk represents C2-C4-alkylene, where Alk within the group (Alk-0) _z

can be the same or different,

W represents a hydrogen, a C ₁ -C ₆ -alkyl or an aryl radical or

the group Y-F means where

Y represents a linear or branched alkylene group with 2 to 8 carbon atoms,

that can wear a phenyl ring,

F for a 5- to 10-membered bonded via nitrogen

Nitrogen heterocycle, which as ring members, in addition to the nitrogen atom and carbon atoms, 1, 2 or 3 additional heteroatoms, selected from oxygen, nitrogen and sulfur,

where the nitrogen ring members can have a group R ² , and where 1 or 2 carbon ring members can be present as a carbonyl group,

R ^{1 represents} hydrogen, Ci-C4-alkyl or benzyl, and

R ^{2 represents} hydrogen, Ci-C ₄ alkyl or benzyl.

According to a further preferred embodiment of the present invention, the at least one copolymer comprises at least one group from the group consisting of carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and

Phosphonooxy.

According to a further preferred embodiment of the present invention, the at least one copolymer is a polycondensation product containing

(II) a structural unit containing an aromatic or heteroaromatic and the polyether group, and / or

(III) a phosphated one containing an aromatic or heteroaromatic

Structural unit.

The structural units (II) and (III) are particularly preferably represented by the following general formulas

(l l)

AU- (C (0)) _k -X- (AlkO) _z -W with

A is the same or different and is represented by a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 carbon atoms in the aromatic system, the other radicals having the meaning given for structural unit (I);

With

D the same or different and represented by a substituted or

unsubstituted aromatic or heteroaromatic compound with 5 to 10 carbon atoms in the aromatic system with E the same or different and represented by N, NH or O with

m = 2 if E = N and m = 1 if E = NH or O with

R ³ and R ⁴ independently of one another, the same or different, and represented by a branched or unbranched Ci to C-io-alkyl radical, C5 to Cs cycloalkyl radical, aryl radical, heteroaryl radical or H with b

the same or different and represented by an integer from 0 to 300.

According to a further preferred embodiment of the present invention, the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, sulfonic acids, metal salts and mixtures thereof.

The metal salts are preferably aluminum salts.

According to a further preferred embodiment of the present invention, the at least one acid is a sulfonic acid of the formula (VII)

R ¹⁷ - (CH ₂ ) p-S0 ₃ Ma (VII) where

R17 is a branched or unbranched Ci-C ₂ o-alkyl radical, a C ₆ -Cio-aryl radical which may be unsubstituted or substituted by one or more branched or unbranched Ci-C2o-alkyl radicals, NR ¹⁸ R ¹⁹ or a substituent of the formula (VIII) stands

R ¹⁸ and R ^{19 can,} independently of one another, be the same or different and represent hydrogen or branched or unbranched Ci-C2o-alkyl radicals,

R ²⁰ and R ^{21 are} independently hydrogen or a branched or unbranched

Ci-C2o-alkyl radicals,

V stands for -O- or -NH-,

R ^{22 represents} hydrogen or methyl,

p stands for a number between 0 and 10,

M for hydrogen, a metal cation or an ammonium cation, and a stand for 1 or 1 / valence of the metal cation.

According to a further preferred embodiment of the present invention, the composition comprises

i) 1.0 to 20.0% by weight of calcium aluminate cement,

ii) 60.0 to 98.99% by weight of the at least one filler,

iii) 0.01 to 3.0 wt .-% of the at least one eluent, which is at least one

Contains copolymer which comprises a main chain and polyether side chains, and iv) 0.01 to 5.0% by weight of the at least one retarder which contains at least one acid,

based on the total weight of the composition.

The filler is particularly preferably aluminum oxide.

According to a further preferred embodiment of the present invention, the composition is free of boron.

The present invention also relates to an article comprising the composition described above.

The said article is preferably a refractory article.

In a further aspect, the present invention relates to the use of a

Composition as flowable refractory compositions comprising

i) calcium aluminate cement,

ii) at least one filler,

iv) at least one retarder which contains at least one acid.

According to a preferred use, the main chain exists

or

According to a further preferred use, the polyether side chains of the at least one copolymer are polyether side chains of the structural unit

(I) -U- (C (0)) _k -X- (AlkO) _z -W (I) where

^* indicates the binding site to the polymer,

X represents oxygen, sulfur or a group NR ¹ ,

k is 0 or 1,

z stands for an integer whose average, based on the polymer in

Ranges from 3 to 300,

Alk represents C2-C4-alkylene, where Alk within the group (Alk-0) _z

can be the same or different,

W represents a hydrogen, a C ₁ -C ₆ -alkyl or an aryl radical or

the group Y-F means where

Y represents a linear or branched alkylene group with 2 to 8 carbon atoms,

that can wear a phenyl ring,

F for a 5- to 10-membered bonded via nitrogen

Nitrogen heterocycle, which as ring members, in addition to the nitrogen atom and carbon atoms, 1, 2 or 3 additional heteroatoms,

selected from oxygen, nitrogen and sulfur, where the nitrogen ring members can have a group R ² , and where 1 or 2 carbon ring members can be present as a carbonyl group,

R ^{1 represents} hydrogen, Ci-C4-alkyl or benzyl, and

R ^{2 represents} hydrogen, Ci-C4-alkyl or benzyl.

According to a further preferred use, the at least one copolymer comprises at least one group from the group consisting of carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and phosphonooxy groups.

According to a further preferred use, the at least one copolymer is a polycondensation product containing

(III) a phosphated one containing an aromatic or heteroaromatic

Structural unit.

According to a particular preferred use, the structural units (II) and (III) are represented by the following general formulas (II)

AU- (C (0)) _k -X- (AlkO) _z -W with

With

D the same or different and represented by a substituted or

unsubstituted aromatic or heteroaromatic compound with 5 to 10 carbon atoms in the aromatic system with

E the same or different and represented by N, NH or O with

m = 2 if E = N and m = 1 if E = NH or O with

R ³ and R ^{4 are} independently the same or different and are represented by a branched or unbranched Cr to C-io-alkyl radical, C5 to Cs-cycloalkyl radical, aryl radical, heteroaryl radical or H with b

the same or different and represented by an integer from 0 to 300.

According to a further preferred use, the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, sulfonic acids, metal salts and mixtures of these.

According to a further preferred use, the metal salts are aluminum salts.

According to a further preferred use, the at least one acid is a sulfonic acid of the formula (VII) R ¹⁷ - (CH ₂ ) _p -S0 ₃ IVf (vii) where

R ^{17 is} a branched or unbranched Ci-C2o-alkyl radical, a C ₆ -Cio-aryl radical which may be unsubstituted or substituted by one or more branched or unbranched Ci-C2o-alkyl radicals, NR ¹⁸ R ¹⁹ or a substituent of the formula ( VII I) stands

R ²⁰ and R ^{21 are} independently hydrogen or a branched or unbranched

Ci-C ₂ o-alkyl radicals,

V stands for -O- or -NH-,

R ^{22 represents} hydrogen or methyl,

p stands for a number between 0 and 10,

M for hydrogen, a metal cation or an ammonium cation, and

a stand for 1 or 1 / valence of the metal cation.

According to a further preferred use, the composition i) comprises 1.0 to 20.0% by weight of calcium aluminate cement,

ii) 60.0 to 98.99% by weight of the at least one filler,

iii) 0.01 to 3.0 wt .-% of the at least one eluent, which is at least one

based on the total weight of the composition.

According to a further preferred use, the filler is aluminum oxide.

According to a further preferred use, the composition is free of boron.

According to a further preference, the composition is a refractory

Composition. It is preferably a free-flowing, refractory

Composition. Accordingly, the essential constituents are preferably calcium aluminate cement and aluminum oxide, which are preferably present in a total amount of at least 60% by weight, preferably at least 70% by weight and more preferably at least 80% by weight. According to a further preference, the composition contains less than 3.0% by weight of Portland cement, more preferably less than 2.0% by weight, particularly preferably less than 1.0% by weight, based on the total weight of the composition ,

According to a further preference, the composition contains less than 3.0% by weight, more preferably less than 2.0% by weight, particularly preferably less than 1.0% by weight, of a sulfate source selected from the group anhydrite (CaS0 ₄ ), calcium sulfate hemihydrate (CaS0 ₄ x 0.5 H ₂ 0) and / or gypsum (CaS0 ₄ x 2 H ₂ 0), based on the total weight of the

Composition.

The present invention is described in more detail below.

As discussed above, the present invention relates to a composition for flowable refractory compositions comprising

i) calcium aluminate cement,

ii) at least one filler,

iv) at least one retarder which contains at least one acid.

In the context of the present invention, the term “refractory mass” refers to a composition from which refractory articles are obtained by tempering in the presence of water.

One of the main components of the composition according to the invention is calcium aluminate cement.

In the context of the present invention, the term “cement” refers to a

organic, finely ground hydraulic binder. The different types of cement are classified according to DIN EN 197-1 (1 1/2011) in the categories CEM l-V. The term "cement" also includes cements according to EN 14216, calcium aluminate cements, calcium sulfo aluminate cements (CSA cements) and mixtures thereof.

Calcium aluminate cements include minerals of the formula CaO x Al ₂ 0 ₃ . They can be obtained, for example, by melting calcium oxide (CaO) or limestone (CaCOs) with bauxite or aluminate. Calcium aluminate cements comprise about 20 to 40% by weight of CaO, up to 5% by weight of SiO ₂ , about 40 to 80% by weight of Al ₂ 0 ₃ and up to about 20% by weight of Fe ₂ 0 _3rd Calcium aluminate cements are defined in the standard DIN EN 14647 (01/2006).

Calcium sulfo aluminate cements can be made from tricalcium aluminate (3 CaO x AI ₂ Os), anhydrite (CaS0 ₄ ), calcium sulfate hemihydrate (CaS0 ₄ x 0.5 H ₂ 0) and / or gypsum (CaS0 ₄ x 2 H ₂ 0) getting produced. The composition according to the invention preferably contains 1.0 to 20.0% by weight, more preferably 2.0 to 15.0% by weight, even more preferably 3.0 to 10.0% by weight, particularly preferably 4.0 to 6.0% by weight. % Calcium aluminate cement based on the total weight of the composition.

Another component of the composition according to the invention is a filler.

In the context of the present invention, the term “filler” refers to materials that can be added to increase the volume without impairing the properties of the composition.

In the field of refractory materials, the use of aluminum oxide as a filler has proven to be particularly advantageous. Accordingly, the filler used according to the invention is preferably aluminum oxide.

The filler preferably contains calcined aluminum oxide, more preferably the filler consists of calcined aluminum oxide. In particular, it is calcined aluminum oxide with an average grain size of 0.001 to 8 mm. According to a preferred embodiment of the present invention, the filler contains at least one calcined aluminum oxide of the grain size mentioned. In particular, the filler can be two or more calcined

Contain aluminum oxides of different grain sizes.

Processes for the production of calcined aluminum oxide are known to the person skilled in the art.

For example, calcined aluminum oxide can be obtained from commercially available aluminum hydroxide by thermal treatment and subsequent grinding. The calcining can be carried out at temperatures of 1200 to 1800 ° C in an aluminum oxide crucible or a gas-heated rotary kiln, the subsequent grinding can be carried out in industrial mills in a wet or dry process with suitable grinding media.

The composition according to the invention preferably contains 60.0 to 98.99% by weight, more preferably 70.0 to 92.0% by weight, even more preferably 80.0 to 90.0% by weight, particularly preferably 83, 0 to 88.0% by weight of the at least one filler, based on the

Total weight of the composition.

As explained above, the at least one filler is preferably

Aluminum oxide, particularly preferably around calcined aluminum oxide.

Accordingly, the composition according to the invention preferably contains 60.0 to 98.99% by weight, more preferably 70.0 to 92.0% by weight, even more preferably 80.0 to 90.0% by weight, particularly preferably 83 , 0 to 88.0 wt .-% aluminum oxide, more preferably calcined aluminum oxide, based on the total weight of the composition. The composition according to the invention further contains at least one flow agent which contains at least one copolymer which comprises a main chain polyether side chains.

The at least one copolymer is preferably a comb polymer consisting of a linear main chain which, at regular intervals, contains longer side chains which are almost the same length as one another.

The copolymer is preferably in the main chain

or

The structural unit is preferably composed of a carbon chain with at least 16 carbon atoms with at least one group from the group consisting of alkyl, carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and

Phosphonooxy group substituted. The said group is particularly preferably a carboxy group.

Accordingly, the structural unit comprising a carbon chain with at least 16 carbon atoms is preferably a polycarboxylate.

In the structural unit consisting of a (CC-0) _n chain, n is preferably a number of at least 5, more preferably a number of 5 to 70, even more preferably a number of 7 to 50.

The structural unit comprising an aromatic or a heteroaromatic is preferably a polycondensation product.

The side chains of the copolymer are preferably polyether side chains.

According to a preferred embodiment of the present invention, said polyether side chains are polyether side chains of structural unit (I)

^* -U- (C (0)) _k -X- (AlkO) _z -W (I) where

^* indicates the binding site to the polymer, U stands for a chemical bond or an alkylene group with 1 to 8 C atoms, which is unsubstituted or with at least one group from the series carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy , Sulfinoalkyloxy and phosphonooxy is substituted,

X represents oxygen, sulfur or a group NR ¹ ,

k is 0 or 1,

z stands for an integer whose average, based on the polymer in

Ranges from 3 to 300,

Alk represents C2-C4-alkylene, where Alk within the group (Alk-0) _z

can be the same or different,

W represents a hydrogen, a C ₁ -C ₆ -alkyl or an aryl radical or

the group Y-F means where

Y represents a linear or branched alkylene group with 2 to 8 carbon atoms,

that can wear a phenyl ring,

F for a 5- to 10-membered bonded via nitrogen

R ^{1 represents} hydrogen, Ci-C4-alkyl or benzyl, and

R ^{2 represents} hydrogen, Ci-C4-alkyl or benzyl.

The at least one branched copolymer preferably contains at least one group from the series carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfo alkyloxy, sulfinoalkyloxy and phosphonooxy group. The said group is particularly preferably a carboxy group.

According to a preferred embodiment of the present invention, said polyether side chains are therefore polyether side chains of structural unit (I)

^* -U- (C (0)) _k -X- (AlkO) _z -W (I) where

^* indicates the binding site to the polymer,

U stands for a chemical bond or an alkylene group with 1 to 8 C atoms, which is unsubstituted or substituted with at least one carboxy group, and the other radicals have the meanings given above.

In a preferred embodiment, the branched copolymer is a polycondensation product containing (II) a structural unit containing an aromatic or heteroaromatic and the polyether group, and / or

(III) a phosphated structural unit containing an aromatic or heteroaromatic.

The structural units (II) and (III) are preferably represented by the following general formulas

(II) AU- (C (0)) _k -X- (AlkO) _z -W with

(III) With

D the same or different and represented by a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 carbon atoms in the aromatic system.

Furthermore, E is the same or different and is represented by N, NH or O, m = 2 if E = N and m = 1 if E = NH or O.

R ³ and R ⁴ are, independently of one another, the same or different, and are particularly preferably represented by a branched or unbranched C 1 to C 10 alkyl radical, C 5 to Ce cycloalkyl radical, aryl radical, heteroaryl radical or H, preferably by H, methyl, ethyl or phenyl by H or methyl and particularly preferably by H. Furthermore, b is the same or different and is represented by an integer from 0 to 300. If b = 0, E = O. D = phenyl, E = O, R ³ and R ⁴ = H and b = 1.

The polycondensation product preferably contains a further structural unit (IV), which is represented by the following formula With Y independently of one another, the same or different, and represented by (II), (III) or other constituents of the polycondensation product.

R ⁵ and R ⁶ are preferably identical or different and represented by H, CH3, COOH or a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 carbon atoms. Here, R ⁵ and R ⁶ in structural unit (IV) are preferably independently represented by H, COOH and / or methyl.

In a particularly preferred embodiment, R ⁵ and R ⁶ are represented by H.

The molar ratio of the structural units (II), (III) and (IV) of the phosphated polycondensation product according to the invention can be varied within a wide range. It has proven to be expedient that the molar ratio of the structural units [(II) + (III)]: (IV) is 1: 0.8 to 3, preferably 1: 0.9 to 2 and particularly preferably 1: 0.95 to 1, 2 is.

The molar ratio of the structural units (II): (III) is normally 1:10 to 10: 1, preferably 1: 7 to 5: 1 and particularly preferably 1: 5 to 3: 1.

The groups A and D in the structural units (II) and (III) of the polycondensation product are mostly substituted by phenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, naphthyl, 2- Hydroxynaphthyl, 4-hydroxynaphthyl, 2-methoxynaphthyl, 4-methoxynaphthyl preferably represents phenyl, where A and D can be chosen independently of one another and can also each consist of a mixture of the compounds mentioned. The groups X and E are preferably independently represented by O.

Z in structural unit (I) is preferably represented by an integer from 5 to 280, in particular 10 to 160 and particularly preferably 12 to 120 and b in structural unit (III) by an integer from 0 to 10, preferably 1 to 7 and particularly preferably 1 to 5. The respective radicals, the length of which is defined by z or b, can consist of uniform assemblies, but it can also be expedient that it is a mixture of different assemblies. Furthermore, the residues of the structural units (II) and (III) can each independently have the same chain length, z or b being represented by a number. However, it will generally be expedient for the mixtures in question to have mixtures with different chain lengths, so that the residues of the structural units in the polycondensation product have different numerical values for z and independently for b.

In a particular embodiment, the present invention further provides that it is a sodium, potassium, ammonium and / or calcium salt and preferably a sodium and / or potassium salt of the phosphated polycondensation product. The phosphated polycondensation product according to the invention frequently has a weight-average molecular weight of 5000 g / mol to 150,000 g / mol, preferably 10,000 to 100,000 g / mol and particularly preferably 20,000 to 75,000 g / mol.

The phosphated to be used preferably according to the present invention

Polycondensation products can be prepared according to processes known to those skilled in the art. Suitable methods are described, for example, in WO 2006/042709 and WO 2010/040612.

In a further preferred embodiment, the flow agent is at least one copolymer which can be obtained by polymerizing a mixture of monomers comprising

(V) at least one ethylenically unsaturated monomer, which at least

a residue from the series carboxylic acid, carboxylic acid salt,

Carboxylic acid esters, carboxylic acid amide, carboxylic acid anhydride and

Carboximide includes

and

(VI) at least one ethylenically unsaturated monomer comprising the

Polyether group, the polyether group being preferred by

the structural unit (I) is represented.

The copolymers according to the present invention contain at least two monomer units. However, it can also be advantageous to use copolymers with three or more monomer units.

In a preferred embodiment, the ethylenically unsaturated monomer (V) is represented by at least one of the following general formulas from the group (Va), (Vb) and (Vc):

In the mono- or dicarboxylic acid derivative (Va) and the monomer (Vb) present in cyclic form, where Z = O (acid anhydride) or NR ¹⁶ (acid imide), R ⁷ and R ⁸ independently of one another represent hydrogen or an aliphatic Hydrocarbon radical with 1 to 20 carbon atoms, preferably a methyl group. B means H, -COOM _a , -CO-0 (C _q H _2q O) _r - R ⁹ , -CO-NH- (C _q H _2q O) _r -R ⁹ .

M denotes hydrogen, a mono-, di- or trivalent metal cation, preferably sodium, potassium, calcium or magnesium ion, furthermore ammonium or an organic amine residue and a = 1/3, 1/2 or 1, depending on whether M is a mono-, di- or trivalent cation. Preferred organic amine residues are preferably substituted ammonium Groups used which are derived from primary, secondary or tertiary Ci _-2 o-alkylamines, Ci- ₂ o-alkanolamines, Cs-s-cycloalkylamines and C6-14 arylamines. Examples of the corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine,

Diethanolamine, triethanolamine, methyldiethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine, diphenylamine in the protonated (ammonium) form.

R ⁹ denotes hydrogen, an aliphatic hydrocarbon radical with 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical with 5 to 8 C atoms, an aryl radical with 6 to 14 C atoms, which can optionally be substituted, q = 2, 3 or 4 and r = 0 to 200, preferably 1 to 150. The aliphatic hydrocarbons can be linear or branched and saturated or unsaturated. The preferred cycloalkyl radicals are cyclopentyl or

Cyclohexyl radicals, phenyl or naphthyl radicals to be regarded as preferred aryl radicals, which in particular may also be substituted by hydroxyl, carboxyl or sulfonic acid groups.

Z furthermore represents O or NR ^1S , where R ^{16 is} independently the same or different and is represented by a branched or unbranched Cr to Cio-alkyl radical, Cs to Ce cycloalkyl radical, aryl radical, heteroaryl radical or H.

The following formula represents the monomer (Vc):

Here, R ¹⁰ and R ¹¹ independently of one another represent hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an optionally substituted aryl radical having 6 to 14 C atoms.

Furthermore R ^{12 is the} same or different and is replaced by (C _n H _2n ) -S03H with n = 0, 1, 2, 3 or 4,

(C _n H _2n ) -OH with n = 0, 1, 2, 3 or 4; (C _n H _2n ) -P03H ₂ with n = 0, 1, 2, 3 or 4, (C _n H _2n ) -0P03H ₂ with n = 0, 1, 2, 3 or 4, (C ₆ H ₄ ) -S0 ₃ H, (C ₆ H ₄ ) -P0 ₃ H ₂ , (C ₆ H ₄ ) -0P0 ₃ H ₂ and (C _n H _2n ) -NR ¹⁴ _b with n = 0,

1, 2, 3 or 4 and b represented by 2 or 3.

R ¹³ means H, -COOM _a , -C0-0 (C _q H _2q 0) rR ⁹ , -CO-NH- (C _q H _2q O) rR ⁹ , where M _a , R ⁹ , q and r are the same as above have the meanings mentioned.

R ¹⁴ stands for hydrogen, an aliphatic hydrocarbon radical with 1 to 10 C atoms, a cycloaliphatic hydrocarbon radical with 5 to 8 C atoms, an optionally substituted aryl radical with 6 to 14 C atoms. Furthermore, Q is identical or different and is represented by NH, NR ¹⁵ or O, where R ^{15 is} an aliphatic hydrocarbon radical having 1 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms or an optionally substituted aryl radical having 6 to 14 carbon atoms.

In a particularly preferred embodiment, the ethylenically unsaturated monomer (VI) is represented by the following general formulas

(Vi) wherein all radicals have the meanings given above.

In particular, the copolymer has an average molecular weight (Mw) between 5000 and 150,000 g / mol, particularly preferably 10,000 to 80,000 g / mol and very particularly preferably 15,000 to 60,000 g / mol, which is determined by gel permeation chromatography. The polymers are analyzed by means of size exclusion chromatography for average molecular weight and conversion (column combinations: Shodex OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Showa Denko, Japan; eluent: 80% by volume aqueous solution of HCO2NH4 (0.05 mol / L) and 20 vol .-% MeOH; injection volume 100 pL; flow rate 0.5 ml_ / min)).

The copolymer according to the invention preferably meets the requirements of the industrial standard EN 934-2 (February 2002).

The composition according to the invention preferably contains 0.01 to 3.0% by weight, more preferably 0.025 to 2.0% by weight, even more preferably 0.05 to 1.0% by weight, particularly preferably 0.08 to 0.15% by weight .-% of the at least one flow agent, which contains at least one copolymer, based on the total weight of the composition.

The at least one superplasticizer particularly preferably consists of the at least one copolymer as defined above. According to a particularly preferred embodiment of the present invention, the composition contains, in addition to the at least one

Superplasticizer, which contains at least one copolymer, no other superplasticizer.

Furthermore, the composition according to the invention contains at least one retarder which contains at least one acid.

In the context of the present invention, the terms “retarder” and “solidification retarder” refer to an additive which slows down the hardening of a binder composition. According to a preferred embodiment of the present invention, the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, sulfonic acids, metal salts and mixtures thereof.

The at least one acid is particularly preferably selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, sulfonic acids, metal salts and mixtures of these.

With regard to the metal salts, those metal salts are suitable in the context of the present invention which react acidic in aqueous solution. Salts of magnesium, calcium, iron, zinc, aluminum and mixtures of these are particularly preferred.

The metal salt is particularly preferably at least one aluminum salt. Aluminum chloride is particularly preferred.

R ¹⁷ - (CH ₂ ) p-S0 ₃ Ma (VII) where

R17 is a branched or unbranched Ci-C2o-alkyl radical, a C ₆ -Cio-aryl radical which may be unsubstituted or substituted by one or more branched or unbranched Ci-C2o-alkyl radicals, NR ¹⁸ R ¹⁹ or a substituent of the formula (VIII ) stands,

R ²⁰ and R ^{21 are} independently hydrogen or a branched or unbranched

Ci-C2o-alkyl radical,

V stands for -O- or -NH-,

R ^{22 represents} hydrogen or methyl,

p stands for a number between 0 and 10,

M for hydrogen, a metal cation or an ammonium cation, and

a stand for 1 or 1 / valence of the metal cation.

The at least one acid is more preferably a sulfonic acid of the formula (VII), where R ^{17 represents} an unbranched C ₁ -C ₆ -alkyl radical or NR ¹⁸ R ¹⁹ ,

R ²⁰ and R ²¹ independently of one another represent an unbranched C ₁ -C ₆ -alkyl radical,

W stands for -NH-,

R ^{22 represents} hydrogen,

p stands for a number between 0 and 5,

M for hydrogen, a metal cation or an ammonium cation, and

a stand for 1 or 1 / valence of the metal cation.

The at least one acid is particularly preferably a sulfonic acid of the formula (VII), where

R ^{17 represents} an unbranched Ci-C2-alkyl radical or NR ¹⁸ R ¹⁹ ,

R ¹⁸ and R ^{19 represent} hydrogen,

R ²⁰ and R ^{21 represent} methyl,

W stands for -NH-,

R ^{22 represents} hydrogen,

p represents a number between 0 and 2, and

M stands for hydrogen.

According to a particularly preferred embodiment of the present invention, the at least one acid is amidosulfonic acid, methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid or mixtures thereof.

The composition according to the invention preferably contains 0.01 to 5.0% by weight, more preferably 0.012 to 3.0% by weight, particularly preferably 0.0125 to 0.12% by weight of the at least one retarder which comprises at least one Acid contains, based on the total weight of the composition.

Accordingly, the composition according to the invention preferably contains 1.0 to 20.0% by weight, more preferably 2.0 to 15.0% by weight, even more preferably 3.0 to 10.0% by weight, particularly preferably 4.0 to 6.0% by weight. % Calcium aluminate cement, 60.0 to 98.99% by weight, more preferably 70.0 to 92.0% by weight, even more preferably 80.0 to 90.0% by weight, particularly preferably 83.0 to 88.0% by weight of the at least one filler, 0.01 to 3.0% by weight, more preferably 0.025 to 2.0% by weight, even more preferably 0.05 to 1, 0% by weight, particularly preferably 0.08 to 0.15% by weight of the at least one superplasticizer which contains at least one copolymer and 0.01 to 5.0% by weight, more preferably 0.012 to 3.0% by weight , particularly preferably 0.0125 to 0.12% by weight of the at least one retarder which contains at least one acid, based on the total weight of the composition.

The composition according to the invention more preferably consists of 1.0 to 20.0% by weight, more preferably 2.0 to 15.0% by weight, even more preferably 3.0 to 10.0% by weight, particularly preferably 4.0 to 6.0% by weight % Calcium aluminate cement, 60.0 to 98.99% by weight, more preferably 70.0 to 92.0% by weight, even more preferably 80.0 to 90.0% by weight, particularly preferably 83.0 to 88.0% by weight of the at least one filler, 0.01 to 3.0% by weight, more preferably 0.025 to 2.0% by weight, even more preferably 0.05 to 1.0% by weight, particularly preferably 0.08 to 0.15% by weight of the at least one superplasticizer which contains at least one copolymer, and 0.01 to 5.0 wt .-%, more preferably 0.012 to 3.0 wt .-%, particularly preferably 0.0125 to 0.12 wt .-% of the at least one retarder, which at least contains an acid based on the total weight of the composition.

According to a preferred embodiment of the present invention, the composition according to the invention is free of boron.

In the context of the present invention, the terms “free of boron” or “free of boron” mean that the composition according to the invention does not contain any boron and boron-containing compounds. The composition according to the invention preferably contains less than 1.0% by weight, more preferably less than 0.1% by weight, particularly preferably less than 0.01% by weight of boron, based on the total weight of the composition. The proportion of boron and boron-containing compounds is particularly preferably below the detection limit of common analysis methods.

According to another preferred embodiment of the present invention, boron and boron are not used in the preparation of the composition according to the invention

Connections used.

The present invention further relates to an article comprising the composition described above.

The said article is preferably a refractory article.

Examples

used material

Tabular Alumina T 60 is the commercial calcined aluminum oxide of the grain sizes from Almatis GmbH given in Table 1.

Reactive Alumina CL 370 is commercially available from Almatis GmbH.

Ca-aluminate cement CA 270 is commercially available from Almatis GmbH.

Superplasticizer 1 is the commercial superplasticizer Castament FS 10 from BASF Construction Solutions GmbH, which is a powdery polymerization product based

Is polyethylene glycol.

Superplasticizer 2 is the commercial superplasticizer Castament FW 10 from BASF Construction Solutions GmbH, which is a powdery polymerization product based

Is polyethylene glycol and, unlike the Castament FS 10, contains additional lithium ions and therefore leads to accelerated hydration.

Superplasticizer 3 is the commercial superplasticizer naphthalene sulfonate polymer Flube OS 39 from Bozetto S.p.a.

Boric acid, amidosulfonic acid, phosphoric acid, acetic acid, aluminum chloride, 2-acrylamido-2-methylpropanesulfonic acid, hydrochloric acid, methanesulfonic acid, the acidic ion exchanger Dowex 50 WX 2 and aluminum dihydrogen phosphate are commercially available compounds from Sigma Aldrich.

Manufacture of binder mixtures

The production takes place in a Hobart A 200 plate mixer. All dry

Components of a total amount of 5000 g are premixed for 60 seconds at a stirring speed of 107 revolutions per minute before the total amount of mixing water required is added in one step. After the water has been added, the mixture is stirred for a further 4 minutes.

The composition of the dry binder mixtures is summarized in Table 1, the amounts of flow agent, mixing water and retarder added in Table 2. Table 1: Dry components of the binder mixtures

Table 2: Additions of superplasticizers, mixing water and retarders

1) Based on the total amount of dry components according to Table 1

2) The exact retarder dosages are shown in Table 3

3) In Comparative Example 5 instead, a total of 0.1% by weight was used instead.

Superplasticizer 3 and, in comparison example 6, a total of only 0.5% by weight

Superplasticizer 3 used.

slump-flow

Four discharge cones according to EN 1402-4: 2003 are filled with the freshly prepared binder mixture. The flow rate is determined after 10, 30, 60 and 120 minutes after filling by lifting the outlet cone and removing material which adheres to the wall of the outlet cone and carefully adding it to the flowing mass. When the material comes to a standstill (two minutes after the discharge cone has been raised), the diameter of the flow cake is determined in two directions perpendicular to each other. The values in [cm] given in the table correspond to the arithmetic mean of both directions.

Since the inner diameter of the outlet cone is 10 cm, the material did not move at a flow of 10 cm after lifting the outlet cone.

To determine the fresh concrete density, the freshly prepared material was slowly poured into a 250 mL plastic beaker and the ratio between its own weight and volume was determined. strength values

Flexural strength and compressive strength according to DIN EN 196-1 were determined 24 hours after mixing, using test specimens with the dimensions 40x40x160 mm ³ , which were stored at 20 ° C. and 65% atmospheric humidity. The values given in Table 3 correspond to arithmetic mean from three measured test specimens.

The flow rates and strength values summarized in Table 3 show that the flow rates and strengths of refractory masses with boron-free retarders using branched polyalkylene oxide side chains as flow agents are comparable with the properties of compositions containing boric acid. According to Table 2, a relatively small amount of mixing water is required for this.

The strengths are similar or better than in the case of the boric acid-containing system. Compared to the reference without a delay, the processing time is at least 60 minutes, while the reference system without a delay can only be processed for 10 minutes.

Table 3: Flow and strength values

1) 0.1% by weight of superplasticizer 3

2) 0.5% by weight of superplasticizer 3

5 3) cannot be processed

Claims

Expectations

1. A composition for flowable refractory compositions comprising

i) calcium aluminate cement,

ii) at least one filler,

iv) at least one retarder which contains at least one acid.

2. The composition of claim 1, wherein the main chain

i) consists of at least one structural unit which consists of a carbon chain with at least 16 carbon atoms,

or

ii) consists of at least one structural unit which consists of a (CCO) _n chain, where n is a number of at least 5,

or

iii) consists of at least one structural unit which comprises an aromatic or a heteroaromatic.

3. The composition according to claim 1 or 2, wherein the polyether side chains of the at least one copolymer are polyether side chains of the structural unit (I),

'-U- (C (0)) _k -X- (AlkO) zW (I) where

^* indicates the binding site to the polymer,

X represents oxygen, sulfur or a group NR ¹ ,

k is 0 or 1,

z stands for an integer whose average, based on the polymer in

Ranges from 3 to 300,

Alk represents C2-C4-alkylene, where Alk within the group (Alk-0) _z

can be the same or different,

W represents a hydrogen, a Ci-C _ö alkyl or an aryl radical or

the group Y-F means where

Y represents a linear or branched alkylene group with 2 to 8 carbon atoms,

that can wear a phenyl ring, F for a 5- to 10-membered bonded via nitrogen

selected from oxygen, nitrogen and sulfur,

R ^{1 represents} hydrogen, CrC4-alkyl or benzyl, and

R ^{2 represents} hydrogen, Ci-C4-alkyl or benzyl.

4. Composition according to one of the preceding claims, wherein the at least one copolymer at least one group from the series carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and

Phosphonooxy group includes.

5. The composition according to any one of the preceding claims, wherein the at least one copolymer is a polycondensation product containing

(III) a phosphated one containing an aromatic or heteroaromatic

Structural unit.

6. The composition according to claim 5, wherein the structural units (II) and (III) by

following general formulas are represented

(II)

AU- (C (0)) _k -X- (AlkO) _z -W with

With D identical or different and represented by a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 carbon atoms in the aromatic system

E the same or different and represented by N, NH or O with

m = 2 if E = N and m = 1 if E = NH or O with

R ³ and R ^4, independently of one another, are the same or different and are represented by a branched or unbranched C 1 -C 10 -alkyl radical, C 1 -C 5 -cycloalkyl radical, aryl radical, heteroaryl radical or H with b

the same or different and represented by an integer from 0 to 300.

7. Composition according to one of the preceding claims, wherein the at least one acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, sulfonic acids, metal salts and mixtures of these.

8. The composition according to any one of the preceding claims, wherein the metal salts are aluminum salts.

9. The composition according to claim 7, wherein the at least one acid is a sulfonic acid of the formula (VII),

R ¹⁷ - (CH ₂ ) _p -S0 ₃ M (VII) where

R ¹⁷ for a branched or unbranched Ci-C2o-alkyl radical, a C6-C10-

Aryl radical which may be unsubstituted or substituted by one or more branched or unbranched C 1 -C 20 -alkyl radicals, NR ¹⁸ R ¹⁹ or a substituent of the formula (VIII),

R ¹⁸ and R ¹⁹ can be the same or different independently of one another and for

Are hydrogen or branched or unbranched Ci-C2o-alkyl radicals, R ²⁰ and R ²¹ independently of one another represent hydrogen or a branched or unbranched Ci-C2o-alkyl radical,

V stands for -O- or -NH-,

R ^{22 represents} hydrogen or methyl,

p stands for a number between 0 and 10,

M for hydrogen, a metal cation or an ammonium cation, and

a stand for 1 or 1 / valence of the metal cation.

10. The composition of claim 9, wherein the at least one acid is a sulfonic acid of formula (VII), wherein

R ^{17 represents} an unbranched Ci-C2-alkyl radical or NR ¹⁸ R ¹⁹ ,

R ¹⁸ and R ^{19 represent} hydrogen,

R ²⁰ and R ^{21 represent} methyl,

W stands for -NH-,

R ^{22 represents} hydrogen,

p represents a number between 0 and 2, and

M stands for hydrogen.

11. A composition according to any one of the preceding claims comprising

i) 1.0 to 20.0% by weight of calcium aluminate cement,

ii) 60.0 to 98.99% by weight of the at least one filler,

iii) 0.01 to 3.0% by weight of the one superplasticizer which contains at least one copolymer which comprises a main chain and polyether side chains, and iv) 0.01 to 5.0% by weight of the at least one retarder which contains at least one acid,

based on the total weight of the composition.

12. The composition according to any one of the preceding claims, wherein the filler is aluminum oxide.

13. The composition according to any one of the preceding claims, wherein the composition is free of boron.

14. The composition according to any one of the preceding claims, wherein the composition Portland cement in an amount of less than 3.0 wt .-% based on the

Contains total weight of the composition.

15. An article comprising a composition according to any one of claims 1 to 14, which is preferably a refractory article

16. Use of a composition according to any one of claims 1 to 14 in flowable refractory compositions.