DE102006005094A1 - Titanium dioxide and polycarboxylate ether-containing dispersion - Google Patents

Abstract

Dispersion which is free from binders and which contains titanium dioxide and at least one water-soluble polycarboxylate ether, where - the titanium dioxide has a BET surface area of 20 to 400 m <SUP> 2 </SUP> / g, - the water-soluble polycarboxylate ether is a copolymer based at least one oxyalkylene glycol compound and at least one unsaturated monocarboxylic acid derivative or dicarboxylic acid derivative, - the dispersion has a titanium dioxide content of 5 to 50% by weight, based on the total amount of the dispersion.

Description

The The invention relates to a concrete additive based on titanium dioxide and polycarboxylate ethers.

It has long been known, for example US3135617 in that an acceleration of the setting can be achieved by means of finely divided amorphous silicon dioxide. However, this could not prevail because it greatly reduced the processability of the fresh concrete.

WO01 / 90024 discloses a concrete composition containing aggregates, a hydraulic binder, silica sol and a polycarboxylate. The BET surface area of the silica sol is preferably 300 to 900 m ² / g. Silica sols are single particles with a diameter of 3 to 50 nm and only in dispersion resistant. In cement or concrete compositions, they have a high reactivity, but no filler effect. This is probably due to the fact that due to the very small particle diameter of the silica sols dissolve rapidly in an alkaline medium. In order to observe a high early strength when using silica sols, high concentration of silica sols are necessary, resulting in a significant reduction in processability.

WO02 / 070429 discloses a composite material containing inorganic aggregates, ultrafine particles, a cementitious binder and a concrete plasticizer. The composite material allows the production of a highly liquefied concrete in which no bleeding occurs. The ultrafine particles used are mainly "silica fume" particles (silica fume), which are produced in connection with the production of silicon metal or ferrosilicon. "Silica fume" particles are generally in the form of spherical individual particles with a diameter of 150 nm or more in front. They show in cement or concrete compositions a strong filler effect, but are little reactive because of their low specific surface area of about 20 m ² / g. Alumina, fly ash, natural pozzolans, calcium carbonate, alumina, barium sulfate and titanium dioxide can be used as further particles of this size. The stated particles have the disadvantage that they have a small specific surface, which leads to a low nucleation rate of the strength-forming phases and thus to low early strengths. For the purposes of the present text, early strength is understood to mean the strength of a concrete after <48 h of cement hydration.

Of the Proportion of ultrafine particles, based on the total amount of Composite material, amounts 1 to 30 wt .-% or about 10 to 25 wt .-% in the embodiments, based on the sum of cement and ultrafine particles. In order to the required proportion of ultrafine particles is very high.

In US 6752866 discloses a method of improving early strength by adding an aqueous dispersion containing a mineral filler and a specific dispersant to cement. Calcium carbonate, barium carbonate, limestone, dolomite, talc, silica, titanium dioxide, kieselguhr, iron oxide, manganese oxide, lime, kaolin, clay, mica, gypsum, fly ash, slag, calcium sulfate, zeolites, basalt, barium sulfate or aluminum trihydroxide can be used as mineral fillers. Preferably, calcium carbonate is used. The disclosed mean particle diameter of the mineral fillers used are in the range of about 2 to about 10 microns. Essential for the in US 6752866 disclosed invention is a special dispersant. This contains a copolymer obtained by radical copolymerization of an alkoxy polyalkylene glycol urethane with an anionic or nonionic monomer. No specific information is given on the required quantities of mineral filler, dispersant and cement. It can be seen from the exemplary embodiments that the proportion of mineral filler with 10% by weight (silicon dioxide, test number 12) or 30% by weight (silicon dioxide, test number 17) and the proportion of dispersant 0.5 (test number 17) or 0.75 wt .-% (test number 12), based on silica, is. These dispersions show only low stability to sedimentation due to the large particle diameter.

In EP-A-1607378 discloses additives based on pyrogenic metal oxides for cementitious Described systems containing at least one sorbent. The pyrogenic Metal oxides can in the form of watery Dispersions are present. Furthermore, a polycarboxylate-based flow agent be used. However, EP-A-1607378 does not contain any information about the Type of polycarboxylate, still in which quantitative range the polycarboxylate has to be added, nor about the way in which process step the polycarboxylate is added becomes. Furthermore, the technical teaching must be taken that the disclosed metal oxide powders silica, alumina, Titanium dioxide, ceria, zirconia and mixtures thereof in the Essentially similar Show effects.

wagner and Hauck show in Wiss. Z. Hochsch. Archit. Construction. - Weimar 40 (1990), 5.183, that the order of addition of the various Components in the manufacture of a concrete a substantial Influence on the early strength and has the flow requirements, when used early strength-enhancing oxides become. In the investigation, the oxide was separated from the flow agent added. By the combination of flow agent and oxide in one Concrete admixture would the number of possible various sequences of addition reduced and thus also the possibilities of error. Another advantage of the combination in a concrete admixture is that only one metering device is needed, which is for the user represents a cost advantage.

Of the The prior art shows that there is a keen interest in concrete compositions to develop a high early strength have at the same time good processability. The state of the Technology further shows that the currently available superplasticizers and particles in the cement or concrete composition represent a sensitive system. For example, the Order of addition and the concentration of starting materials one decisive influence on processability and early strength of the concrete.

task The invention therefore is to provide a concrete admixture, with which the disadvantages of the prior art can be minimized. Especially The concrete admixture is said to contribute to the early strength of concretes at the same time significantly increase good processability.

• – das Titandioxid eine BET-Oberfläche von 20 bis 400 m²/g aufweist,
• – der wasserlösliche Polycarboxylatether ein Copolymeres auf Basis mindestens einer Oxyalkylenglykolverbindung und mindestens einem ungesättigten Monocarbonsäurederivat oder Dicarbonsäurederivat ist,
• – die Dispersion einen Gehalt an Titandioxid von 5 bis 50 Gew.-%, bezogen auf die Gesamtmenge der Dispersion, aufweist.

The invention relates to a dispersion which is free of binders and which contains titanium dioxide and at least one water-soluble polycarboxylate ether, wherein

• The titanium dioxide has a BET surface area of from 20 to 400 m ² / g,
• The water-soluble polycarboxylate ether is a copolymer based on at least one oxyalkylene glycol compound and at least one unsaturated monocarboxylic acid derivative or dicarboxylic acid derivative,
• - The dispersion has a content of titanium dioxide from 5 to 50 wt .-%, based on the total amount of the dispersion having.

In In the present invention, the terms titanium dioxide and Titanium dioxide particles the same substance.

The Dispersion according to the invention is preferably an aqueous one Dispersion, that is the main component of the liquid Phase is water. The liquid Phase contains about that In addition, the water-soluble Polycarboxylatether.

The Dispersion according to the invention is free of binders. In this case, binders are inorganic Substances, such as cement, or organic matter, which are processable in the plastic state, and in the course of a harden time and thereby connect other substances together.

in the For the purposes of the invention, the term titanium dioxide also includes metal mixed oxides with titanium dioxide as the first component. As a second and further components can especially alumina, potassium oxide, lithium oxide, sodium oxide, Magnesium oxide, calcium oxide, silicon dioxide and / or zirconium dioxide be preferred. It is also possible that a mixture of titanium dioxide with the aforementioned mixed oxides is present.

Farther the type of titanium dioxide is not restricted. This can be the case, for example felled, act by sol-gel or pyrogenic process titania.

A pyrogenic titanium dioxide is preferably a constituent of the dispersion according to the invention. By pyrogen are understood to mean titanium dioxide particles obtained by flame oxidation and / or flame hydrolysis. As starting materials for pyrogenic processes, organic and inorganic substances can be used. Titanium tetrachloride, for example, is particularly suitable. Suitable organic starting compounds may be, for example, Ti (OR) ₄ with R = iso-propyl or butyl. The resulting titanium dioxide particles are largely free from pores and have free hydroxyl groups on the surface. The pyrogenic titanium dioxide particles in the sense of the present invention are present at least partially in the form of aggregated primary particles. As a rule, the fumed titanium dioxide particles are present in a largely aggregated form.

Also The pyrogenic titanium dioxide can be used as pyrogenic mixed oxide with titanium dioxide as the first component. As a second and further components can especially alumina, potassium oxide, lithium oxide, sodium oxide, Magnesium oxide, calcium oxide, silicon dioxide and / or zirconium dioxide be preferred. It is also possible that a mixture of pyrogenic titanium dioxide with the aforementioned Mixed oxides is present

The pyrogenic titanium dioxide according to the invention can also be present in surface-modified form. For example, the surface may be surface-modified with haloorganosilanes, alkoxysilanes, silazanes, siloxanes, polysiloxanes. As silanizing agent, preference may be given to trimethoxyoctylsilane [(CH ₃ O) ₃ -Si-C ₈ H ₁₇ ], octamethylcyclotetrasiloxane or hexamethyldisilazane. Since the stability of the dispersion according to the invention is generally lower for surface-modified titanium dioxide than for non-modified, the latter is given priority.

The BET surface area of the titanium dioxide present in the dispersion according to the invention is limited to values of 20 to 400 m ² / g. In the case of pyrogenic titanium dioxide, the BET surface area may preferably be 30 to 150 m ² / g, with values of 40 to 60 m ² / g or of 80 to 100 m ² / g being particularly advantageous.

Farther has the dispersion according to the invention an average diameter (number-based) of the titanium dioxide particles in the dispersion of preferably less than <1 μm, more preferably from 50 to 500 nm and most preferably from 70 to 300 nm. Values below 50 nm are technical difficult to implement and have no advantages in the application more on. The mean diameter is nonaggregated when present Particle the mean diameter of the single particles, in aggregated Particles of the diameter of the aggregates.

Of the Proportion of titanium dioxide in the dispersion according to the invention is 5 to 50 wt .-%, based on the total amount of the dispersion. Dispersions according to the invention, which have a titanium dioxide content of 10 to 30 wt .-%, show usually better stability than higher-filled dispersions and be therefore preferred. Dispersions containing less than 5% by weight of titanium dioxide are not economical due to the high water content.

The weight ratio Polycarboxylate ether / titanium dioxide is not limited. Usually are values in the dispersion according to the invention from 0.01 to 100 is advantageous. and values of 0.05-5 are particularly advantageous.

Of the pH value of the dispersion according to the invention can be varied within wide limits. In general, can the pH between 2 and 12 are.

Farther can the dispersion of the invention Bases or acids be added. As bases can for example, ammonia, ammonium hydroxide, tetramethylammonium hydroxide, primary, secondary or tertiary organic amines, caustic soda or potassium hydroxide can be used. As acids can for example phosphoric acid, Sulfuric acid, Hydrochloric acid, nitric acid or carboxylic acids be used.

The Dispersion according to the invention may be a copolymer having the components a), b), c), preferably with the modules a), b), c), and d). Here is the share the assembly a) 51 to 95 mol- &, of the assembly b) 1 to 48.9 mol% of the assembly c) 0.1 to 5 mol% and the assembly d) 0 to 47.9 mol%.

The first assembly a) provides a mono- or dicarboxylic acid derivative with the general Formula Ia, Ib or Ic.

In the monocarboxylic acid derivative Ia R ^{1 is} hydrogen or an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, preferably a methyl group. X in the structures Ia and Ib stands for -OM _a and / or -O - (C _m H _2m O) _n -R ² and -NH- (C _m H _2m O) _n -R ² with the following meaning for M , a, m, n and R ² :
M is hydrogen, a monovalent or divalent metal cation, ammonium, an organic amine radical and a = ½ or 1, depending on whether M is a monovalent or divalent cation. Substituted ammonium groups which are derived from primary, secondary or tertiary C _1-20 -alkylamines, C _1-20 -alkanolamines, C _5-8 -cycloalkylamines and C _8-14 -aryl-amines are preferably used as organic amine radicals. Examples of the corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine, diphenylamine in the protonated (ammonium) form.

R ² is hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an aryl radical having 6 to 14 C atoms, which may optionally be substituted, m = 2 to 4 and n = 0 to 200 can be. The aliphatic hydrocarbons may hereby be linear or branched and saturated or unsaturated. Preferred cycloalkyl radicals are cyclopentyl or cyclohexyl radicals, phenyl or naphthyl radicals which are preferred as aryl radicals, which radicals may in particular be substituted by hydroxyl, carboxyl or sulfonic acid groups.

Instead of or in addition to the dicarboxylic acid derivative according to formula Ib, the assembly a) (mono- or dicarboxylic acid derivative) may also be present in cyclic form according to formula Ic, where Y = O (acid anhydride) or NR ² (acid imide) may represent with the above designated meaning for R ² .

und leitet sich von Oxyalkylenglykol-Alkenylethern ab, in der m, n und R² die oben bezeichnete Bedeutung besitzen. R³ bedeutet wiederum Wasserstoff oder einen aliphatischen Kohlenwasserstoffrest mit 1 bis 5 C-Atomen, der ebenfalls linear oder verzweigt bzw. auch ungesättigt sein kann. p kann Werte zwischen 0 und 3 annehmen.The second module b) corresponds to formula II

and is derived from oxyalkylene glycol alkenyl ethers in which m, n and R ^{2 have} the meaning given above. R ³ is in turn hydrogen or an aliphatic hydrocarbon radical having 1 to 5 C atoms, which may also be linear or branched or unsaturated. p can take values between 0 and 3.

According to the preferred embodiments in the formulas Ia, Ib and II m = 2 and / or 3, so that they are polyalkylene oxide groups derived from polyethylene oxide and / or divert polypropylene oxide. In a further preferred embodiment p in formula II means 0 or 1, d. H. they are vinyl and / or alkyl polyalkoxylates.

The third assembly c) corresponds to the formula IIIa or IIIb

In formula IIIa, R ⁴ can be H or CH ₃ , depending on whether it is acrylic or methacrylic acid derivatives. In this case, S can be -H, -COOM _a or -COOR ⁵ , where a and M have the abovementioned meaning and R ^{5 is} an aliphatic hydrocarbon radical having 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms or Aryl radical having 6 to 14 carbon atoms can be. The aliphatic hydrocarbon radical may also be linear or branched, saturated or unsaturated. The preferred cycloaliphatic hydrocarbon radicals are again cyclopentyl or cyclohexyl radicals and the preferred aryl radicals are phenyl or naphthyl radicals. In the case of T = -COOR ⁵ , S = COOM _a or -COOR ⁵ . In the event that T and S = COOR ⁵ , the corresponding assemblies are derived from the dicarboxylic acid esters.

In addition to these ester structural units, the assemblies c) may have other hydrophobic structural elements. These include the polypropylene oxide or polypropylene oxide-polyethylene oxide derivative with

sein, wobei U² = -NH-CO-, -O-, oder -OCH₂- bedeuten kann und S die oben beschriebene Bedeutung besitzt. Diese Verbindungen stellen Polypropylenoxid(-Polyethylenoxid-)-Derivate von den bifunktionellen Alkenylverbindungen entsprechend Formel IIIa dar.x assumes a value of 1 to 150 and y of 0 to 15. The polypropylene oxide (-polyethylene oxide) derivatives can in this case via a grouping U ¹ with the ethyl radical of the assembly c) according to For mel IIIa, where U ^{1 can be} -CO-NH-, -O- or -CH ₂ -O-. These are the corresponding amide, vinyl or allyl ethers of the assembly according to formula IIIa. R ⁶ can in this case again R ² (meaning of R ² see above) or

wherein U ² = -NH-CO-, -O-, or -OCH ₂ - may mean and S has the meaning described above. These compounds are polypropylene oxide (polyethylene oxide) derivatives of the bifunctional alkenyl compounds according to formula IIIa.

As a further hydrophobic structural element, the compounds corresponding to formula IIIa may contain polydimethylsiloxane groups, which in formula scheme IIIa corresponds to T = -WR ⁷ .

(nachfolgend Polydimethylsiloxan Gruppierung genannt), R⁷ kann = R² sein und r kann hierbei Werte von 2 bis 100 annehmen.W means here

(hereinafter referred to as polydimethylsiloxane grouping), R ⁷ can be = R ² and r can here assume values of 2 to 100.

The polydimethylsiloxane grouping can not only be bonded directly to the ethylene radical according to formula IIIa, but also via the groupings -CO- [NH- (CH ₂ ) ₃ ) _s -WR ⁷ or -CO-O (CH ₂ ) _z -WR ⁷ , where R ^{7 is} preferably = R ² and s = 1 or 2 and z = 0 to 4. R ⁷ can also still

in this connection these are the corresponding difunctional ethylene compounds according to the formula IIIa, which are accessible via the corresponding amide or ester groups are linked together and where only one Ethylene group was copolymerized.

The situation is similar with the compounds according to formula IIIa where T = (CH ₂ ) _z -V- (CH ₂ ) _z -CH = CH-R ² , where z = 0 to 4, V is either a polydimethylsiloxane radical W or may be a -O-CO-C ₆ H ₄ -CO-O radical and R ^{2 has} the meaning given above. These compounds are derived from the corresponding dialkenyl-phenyl-dicarboxylic acid esters or dialkenyl-polydimethylsiloxane derivatives.

wobei R², V und z die bereits beschriebene Bedeutung besitzen.It is also possible in the context of the present invention that not only one, but both ethylene groups of the difunctional ethylene compounds have been copolymerized. This essentially corresponds to the assemblies according to formula IIIb

wherein R ² , V and z have the meaning already described.

The fourth assembly d) is derived from an unsaturated Dicarboxylic acid derivative the general formula IVa and / or IVb with the above Meaning of a, M, X and Y.

Preferably the copolymers contain 55 to 75 mol% of the formula Ia and / or Ib, 19.5 to 39.5 mol% of groups of the formula II, 0.5 to 2 mol% of the groups of the formula IIIa and / or IIIb and 5 to 20 mol% Assemblies of the formula IVa and / or IVb.

According to one preferred embodiment contain the copolymers of the invention in addition up to 50 mol%, in particular up to 20 mol% based on the sum of the assemblies a to d, structures based on monomers based on vinyl or (Meth) acrylic acid derivatives such as styrene, methylstyrene, vinyl acetate, vinyl propionate, ethylene, Propylene, isobutene, hydroxyalkyl (meth) acrylates, acrylamide, methacrylamide, N-vinylpyrrolidone, allylsulfonic acid, methallyl, vinylsulfonic vinylphosphonic AMPS, methyl methacrylate, methyl acrylate, butyl acrylate, allyl hexyl acrylate et al based.

The Number of repeating structural units in the copolymers is not limited. However, it has proven to be particularly advantageous to use medium To set molecular weights of 1 000 to 100 000 g / mol.

The Preparation of the copolymers can be done in various ways. It is essential that 51 to 95 mol% of an unsaturated Mono or dicarboxylic acid derivative, 1 to 48.9 mol% of an oxyalkylene alkenyl ether, 0.1 to 5 mol% a vinylic polyalkylene glycol, polysiloxane or ester compound and 0 to 55 mol% of a dicarboxylic acid derivative polymerized with the help of a radical initiator.

When unsaturated Mono- or dicarboxylic acid derivatives, which form the structural groups of the formula Ia, Ib or Ic are preferably used: acrylic acid, methacrylic acid, itaconic, anhydride, itaconic and itaconic acid monoamide.

Instead of of acrylic acid, methacrylic acid, itaconic and itaconic acid monoamide can also their monovalent or divalent metal salts, preferably sodium, Potassium, calcium or ammonium salts are used.

As acrylic, methacrylic or itaconic acid esters especially derivatives are used, the alcoholic component of a polyalkylene glycol of the general formula HO- (C _m H _2m O) _n -R ² with R ² = H, aliphatic hydrocarbon radical having 1 to 20 carbon atoms , cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, optionally substituted aryl radical having 6 to 14 carbon atoms and m = 2 to 4 and n = 0 to 200.

The preferred substituents on the aryl radical are -OH, -COO or -SO ₃ groups.

The unsaturated Monocarboxylic acid derivatives can only exist as a monoester while in the case of dicarboxylic acid itaconic Diester derivatives also possible are.

The Derivatives of the formula Ia, Ib and Ic can also be used as a mixture of esterified and free acids present and are used in an amount of preferably 55 to 75 mol%.

bedeuten R³ = H oder ein aliphatischer Kohlenwasserstoffrest mit 1 bis 5 C-Atomen und p = 0 bis 3. R², m und n besitzen die bereits oben genannte Bedeutung. Als besonders vorteilhaft hat sich hierbei die Verwendung von Polyethylenglykolmonovinylether (p = 0 und m = 2) erwiesen, wobei n vorzugsweise Werte zwischen 1 und 50 besitzt.The second component for the preparation of the copolymers of the invention is an oxyalkylene glycol alkenyl ether, which is preferably used in an amount of 19.5 to 39.5 mol%. In the preferred oxyalkylene glycol alkenyl ethers corresponding to the formula V

R ³ = H or an aliphatic hydrocarbon radical having 1 to 5 C atoms and p = 0 to 3. R ² , m and n have the meaning already mentioned above. In this case, the use of polyethylene glycol monovinyl ether (p = 0 and m = 2) has proved to be particularly advantageous, where n preferably has values between 1 and 1 50 owns.

wobei S vorzugsweise -H, oder COOM_a und U¹ = -CO-NH-, -O- oder -CH₂O- sein können, d. h. es handelt sich um die Säureamid-, Vinyl- oder Allylether der entsprechenden Polypropylenglykol- bzw. Polypropylenglykol-Polyethylenglykol-Derivate. Die Werte für x sind 1 bis 150 und für y = 0 bis 15. R⁶ kann entweder wiederum R¹ sein oder

bedeuten, wobei U² = -NH-CO-, -O- sowie -OCH₂- und S = -COOM_a und vorzugsweise -H ist.As a third component for introducing the assembly c) is preferably 0.5 to 2 mol% of a vinylic polyalkylene glycol, polysiloxane or ester compound used. As preferred vinylic polyalkylene glycol compound, derivatives corresponding to formula VI are used,

wherein S may preferably be -H, or COOM _a and U ¹ = -CO-NH-, -O- or -CH ₂ O-, ie it is the acid amide, vinyl or allyl ethers of the corresponding polypropylene glycol or polypropylene glycol-polyethylene glycol derivatives. The values for x are 1 to 150 and for y = 0 to 15. R ⁶ can either be R ¹ again or

where U ² = -NH-CO-, -O- and -OCH ₂ - and S = -COOM _a and preferably -H.

In the case of R ⁶ = R ² and R ^2, preferably H is the polypropylene glycol (polyethylene glycol) -monamides or ethers of the corresponding acrylic (S = H, R ⁴ = H), methacrylic (S = H, R ⁴ = CH ₃ ) or maleic acid (S = COOM _a , R ⁴ = H) derivatives. Examples of such monomers are maleic acid N- (methylpolypropylene glycol) monoamide, maleic acid N- (methoxy-polypropylene glycol-polyethylene glycol) monoamide, polypropylene glycol vinyl ether and polypropylene glycol allyl ether.

In the case of R ⁶ ≠ R ² are bifunctional vinyl compounds whose polypropylene glycol (polyethylene glycol) derivatives via amide or ether groups (-O- or -OCH ₂ -) are interconnected. Examples of such compounds are polypropylene glycol-bis-maleamic acid, polypropylene glycol diacrylamide, polypropylene glycol dimethacrylamide, polypropylene glycol divinyl ether, polypropylene glycol diallyl ether.

wobei R⁴ = -H und CH₃,

und r = 2 bis 100 und R⁷ bevorzugt = R¹ ist. Beispiele für solche Monomere sind Monovinylpolydimethylsiloxane.The preferred vinylic polysiloxane compound used are derivatives corresponding to formula VII,

where R ⁴ = -H and CH ₃ ,

and r = 2 to 100 and R ^{7 is} preferably = R ¹ . Examples of such monomers are monovinylpolydimethylsiloxanes.

wobei s = 1 oder 2 sein kann, R⁴ und W die oben genannte Bedeutung besitzen und R⁷ entweder = R² oder aber

sein kann und S vorzugsweise Wasserstoff darstellt.As further vinylic polysiloxane compound derivatives according to the formula VIII in question,

where s = 1 or 2, R ⁴ and W have the abovementioned meaning and R ^{7 is} either = R ² or

may be and S is preferably hydrogen.

Examples of such monomers having a vinyl function (R ⁷ = R ² ) are polydimethylsiloxanepropylmaleamic acid or polydimethylsiloxanedipropyleneaminomaleamic acid. In the case of R ⁷ ≠ R ² are Divinylverbindungen such. B. polydimethylsiloxane bis (propylmaleinamidsäure) or polydimethylsiloxane bis (dipropylenaminomaleinamidsäure).

wobei z 0 bis 4 sein kann und R⁴ bzw. W die oben genannte Bedeutung besitzen. R⁷ kann entweder R² oder aber

sein, wobei S bevorzugt Wasserstoff bedeutet. Beispiele für solche monovinylischen Verbindungen (R⁷ = R¹) sind Polydimethylsiloxan-(1-propyl-3-acrylat) oder Polydimethylsiloxan-(1-propyl-3-methacrylat).As a further vinylic polysiloxane compound is a preferred derivative according to the formula:

where z can be 0 to 4 and R ⁴ or W have the abovementioned meaning. R ⁷ can either be R ² or else

be, where S is preferably hydrogen. Examples of such monovinylic compounds (R ⁷ = R ¹ ) are polydimethylsiloxane (1-propyl-3-acrylate) or polydimethylsiloxane (1-propyl-3-methacrylate).

In the case of R ⁷ ≠ R ² are Divinylverbindungen such. Polydimethylsiloxane bis (1-propyl-3-acrylate) or polydimethylsiloxane bis (1-propyl-3-methacrylate).

wobei S = COOM_a oder -COOR⁵ bedeuten und R⁵ ein aliphatischer Kohlenwasserstoffrest mit 3 bis 20 C-Atomen, ein cycloaliphatischer Kohlenwasserstoffrest mit 5 bis 8 C-Atomen sowie ein Arylrest mit 6 bis 14 C-Atomen sein kann. a und M besitzen die oben genannte Bedeutung. Beispiele für solche Esterverbindungen sind Di-n-butylmaleinat bzw. -fumarat oder Mono-n-butylmaleinat- bzw. -fumarat.As vinylic ester compound in the context of the present invention it is preferred to use derivatives corresponding to the formula X,

where S = COOM _a or -COOR ⁵ is an aliphatic hydrocarbon radical having 3 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, and an aryl group having 6 to 14 carbon atoms can ⁵ and R be. a and M are as defined above. Examples of such ester compounds are di-n-butylmaleinate or fumarate or mono-n-butylmaleinate or fumarate.

wobei z wiederum 0 bis 4 sein kann und R² die bereits bekannte Bedeutung besitzt. V kann hierbei W (also eine Polydimethylsiloxan-Gruppierung) sein, was einer Dialkenylpolydimethylsiloxan-Verbindung wie z. B. Divinylpolydimethylsiloxan entspricht. Alternativ hierzu kann V auch -O-CO-C₆H₄-CO-O- sein. Diese Verbindungen stellen Dialkenylphthalsäure-Derivate dar. Ein typisches Beispiel für solche Phthalsäure-Derivate ist Diallylphthalat.Furthermore, it is also possible to use compounds corresponding to the formula XI

where z can in turn be 0 to 4 and R ^{2 has} the already known meaning. V here W (ie a polydimethylsiloxane moiety), giving a dialkenylpolydimethylsiloxane compound such as e.g. B. Divinylpolydimethylsiloxane corresponds. Alternatively, V can also be -O-CO-C ₆ H ₄ -CO-O-. These compounds are dialkenylphthalic acid derivatives. A typical example of such phthalic acid derivatives is diallyl phthalate.

The Molecular weights of the compounds which form the assembly c), can be varied within wide limits and are preferably between 150 and 10 000.

As the fourth component for the preparation of the copolymers, it is preferable to use 5 to 20 mol% of an unsaturated dicarboxylic acid derivative (XII): M _a OOC-CH = CH-COX XII with the already given meaning for a, M and X.

For the case X = OM _a , the unsaturated dicarboxylic acid derivative is derived from maleic acid, fumaric acid, mono- or divalent metal salts of these dicarboxylic acids, such as the sodium, potassium, calcium or ammonium salt or salts with an organic amine radical. Additionally used monomers which form the unit Ia are polyalkylene glycol monoesters of the abovementioned acids having the general formula XIII: M _a OOC-CH = CH-COO- (C _m H _2m O) _n R ² have, with the already given meaning for a, m, n and R ² .

mit der oben angegebenen Bedeutung für Y.The fourth component can also be derived from the unsaturated dicarboxylic anhydrides and imides of the general formula XIV (5 to 20 mol%)

with the meaning given above for Y.

According to the invention can after a preferred embodiment even up to 50, preferably up to 20 mol% of the sum of the components a) to d) other monomers are used as described above.

The Dispersion according to the invention may further contain a copolymer whose base is an oxyalkenyl glycol alkenyl ether and the copolymer contains the components a), b) and c). there is the proportion of the assembly a) 10 to 90 mol% of the assembly b) 1 to 89 mol% of the assembly c) 0.1 to 5 mol% and the assembly d) 0.1 to 10 mol%.

The first assembly a) provides an unsaturated dicarboxylic acid derivative according to the formula IVa or IVb.

For the dicarboxylic acid derivative corresponding to formula Id, M = hydrogen, a mono- or divalent metal cation, ammonium ion, an organic amine radical, and a = 1, or in the case where M is a divalent cation, 1/2. Then, together with a grouping likewise containing M _a with a = 1/2, a bridging over M occurs, which exists only theoretically as M _a with a = 1/2.

The monovalent or divalent metal cation is preferably sodium, potassium, calcium or magnesium ions. Substituted ammonium groups which are derived from primary, secondary or tertiary C ₁ - to C ₂₀ -alkylamines, C ₁ - to C ₂₀ -alkanolamines, C ₅ - to C ₈ -cycloalkylamines and C ₆ - to C are preferably used as organic amine radicals ₁₄ -aryl amines. Examples of corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine, diphenylamine in the protonated (ammonium) form. In addition, X also denotes -OM _a or -O- (C _m H _2m O) _n -R ¹ where R ¹ = H, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an aryl radical having 6 to 14 carbon atoms, which may optionally be substituted, m = 2 to 4 and n = 0 to 200 may be. The aliphatic hydrocarbon radicals may hereby be linear or branched and also saturated or unsaturated.

Preferred cycloalkyl radicals are cyclopentyl or cyclohexyl radicals, phenyl or naphthyl radicals which are preferred as aryl radicals, which radicals may in particular be substituted by hydroxyl, carboxyl or sulfonic acid groups. Alternatively, X may be -NHR ² and / or -NR ² ₂ , which corresponds to the mono- or disubstituted monoamides of the corresponding unsaturated dicarboxylic acid, where R ^{2 may} in turn be identical to R ¹ or instead may be -CO-NH ₂ .

Instead of the dicarboxylic acid derivative corresponding to formula IVa, the subunit a) (dicarboxylic acid derivative) can also be in cyclic form corresponding to the formula IVb, where Y = O (= acid anhydride) or NR ² (acid imide) and R ^{2 is} the one described above Has meaning.

die sich von den Oxyalkylenglykol-Alkenylethern ableitet, bedeuten R³ wiederum Wasserstoff oder ein aliphatischer Kohlenwasserstoffrest mit 1 bis 5 C-Atomen (der ebenfalls linear oder verzweigt bzw. auch ungesättigt sein kann). p kann Werte zwischen 0 und 3 annehmen und R², m und n besitzen die oben genannte Bedeutung. Gemäß einer bevorzugten Ausführungsform bedeuten in Formel II p = 0 und m = 2 oder 3, so dass es sich um Baugruppen handelt, die sich vom Polyethylenoxid- oder Polypropylenoxid-Vinylether ableiten.In the second assembly according to formula II,

which is derived from the oxyalkylene glycol alkenyl ethers, R ^{3 is} in turn hydrogen or an aliphatic hydrocarbon radical having 1 to 5 C atoms (which may also be linear or branched or unsaturated). p can assume values between 0 and 3 and R ² , m and n have the abovementioned meaning. According to a preferred embodiment, in formula II p = 0 and m = 2 or 3, so that they are assemblies derived from the polyethylene oxide or polypropylene oxide vinyl ether.

The third assembly c) corresponds to the formula IIIa or IIIb

In formula IIIa, R ⁴ can be H or CH ₃ , depending on whether it is acrylic or methacrylic acid derivatives. In this case, S can be -H, COOM _a or -COOR ⁵ , where a and M have the abovementioned meaning and R ^{5 is} an aliphatic hydrocarbon radical having 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms or an aryl radical with 6 to 14 carbon atoms can be. The aliphatic hydrocarbon radical may also be linear or branched, saturated or unsaturated. The preferred cycloaliphatic hydrocarbon radicals are again cyclopentyl or cyclohexyl radicals and the preferred aryl radicals are phenyl or naphthyl radicals. In the case of T = -COOR ⁵ , S = COOM _a or -COOR ⁵ . In the event that T and S = COOR ⁵ , the corresponding assemblies are derived from the dicarboxylic acid esters.

In addition to these ester structural units, the assemblies c) may have other hydrophobic structural elements. These include the polypropylene oxide or Polvpropylenoxid polyethylene oxide derivatives with

sein, wobei U² = -NH-CO-, -O- oder -OCH₂- bedeuten kann und S die oben beschriebene Bedeutung besitzt. Diese Verbindungen stellen Polypropylenoxid(-Polyethylenoxid-)-Derivate von den bifunktionellen Alkenylverbindungen entsprechend Formel IIIa dar.x assumes a value of 1 to 150 and y of 0 to 15. The polypropylene oxide (Polyethyleneo xid -) - derivatives of formula IIIa may be linked in accordance with this via a group U ¹ with the ethyl radical of the structural group c), where U ¹ = -CO-NH-, -O- or -CH ₂ -O- may be. These are the corresponding amide, vinyl or allyl ethers of the assemblies according to formula IIIa. R ⁶ here again can be R ¹ (meaning of R ¹ see above) or

wherein U ² = -NH-CO-, -O- or -OCH ₂ - may mean and S has the meaning described above. These compounds are polypropylene oxide (polyethylene oxide) derivatives of the bifunctional alkenyl compounds according to formula IIIa.

As a further hydrophobic structural element, the compounds corresponding to formula IIIa may contain polydimethylsiloxane groups, which in formula scheme IIIa corresponds to T = -WR ⁷ .

(nachfolgend Polydimethylsiloxan-Gruppierung genannt), R⁷ kann = R¹ sein und r kann hierbei Werte von 2 bis 100 annehmen.W means here

(hereinafter referred to as polydimethylsiloxane grouping), R ⁷ can be = R ¹ and r can here assume values of 2 to 100.

The polydimethylsiloxane group W can not only be bonded directly to the ethylene radical according to formula IIIa, but also via the groupings -CO- [NH- (CH ₂ ) ₃ ] _s -WR ⁷ or -CO-O (CH ₂ ) _z -WR ⁷ , where R ^{7 is} preferably = R ¹ and s = 1 or 2 and z = 0 to 4.

sein. Hierbei handelt es sich um die entsprechenden difunktionellen Ethylenverbindungen entsprechend der Formel IIIa, die über die entsprechenden Amid- oder Estergruppierungen miteinander verknüpft sind und wobei nur eine Ethylengruppe copolymerisiert wurde.R ⁷ can also still

be. These are the corresponding difunctional ethylene compounds corresponding to the formula IIIa, which are linked together via the corresponding amide or ester groups and wherein only one ethylene group has been copolymerized.

The situation is similar with the compounds according to formula IIIa where T = - (CH ₂ ) _z -V- (CH ₂ ) _z -CH = CH-R ¹ , where z = 0 to 4, V is either a polydimethylsiloxane radical W or a -O-CO-C can be ₆ H ₄ -CO-O radical and R ^{1 has} the meaning given above. These compounds are derived from the corresponding dialkenyl-phenyl-dicarboxylic acid esters or dialkenyl-polydimethylsiloxane derivatives.

wobei R¹, V und z die bereits beschriebene Bedeutung besitzen.It is also possible in the context of the present invention that not only one, but both ethylene groups of the difunctional ethylene compounds have been copolymerized. This essentially corresponds to the assemblies according to formula IIIb

wherein R ¹ , V and z have the meaning already described.

Preferably These copolymers consist of 40 to 55 mol% of the formula IVa and / or IVb, 40 to 55 mol% of groups of the formula II and 1 to 5 mol% of the formula IIIa or IIIb. According to one preferred embodiment contain the copolymers in addition even up to 50 mol%, in particular up to 20 mol%, based on the sum of the assemblies a), b) and c), assemblies whose monomer a vinyl, acrylic acid or methacrylic acid derivative represents.

The monomeric vinyl derivatives can preferably prefers a compound that is selected from the group styrene, ethylene, propylene, isobutene or vinyl acetate. As a preferred monomeric acrylic acid derivative derive the additional Assemblies in particular of acrylic acid or methyl acrylate. As a preferred monomeric methacrylic acid derivative is methacrylic acid, methyl methacrylate and hydroxyethyl methacrylate.

The Number of repeating structural elements of the copolymers is not limited, but It has proved to be particularly advantageous, the number of structural elements to adjust so that the copolymers have an average molecular weight from 1000 to 200,000.

bedeuten R³ = H oder ein aliphatischer Kohlenwasserstoffrest mit 1 bis 5 C-Atomen und p = 0 bis 3. R¹, m und n besitzen die bereits oben genannte Bedeutung. Als besonders vorteilhaft hat sich hierbei die Verwendung von Polyethylenglykolmonovinylether (p = 0 und m = 2) erwiesen, wobei n vorzugsweise Werte zwischen 2 und 15 besitzt.The second component of the copolymers is an oxyalkylene glycol alkenyl ether, which is preferably used in an amount of 40 to 55 mol%. In the preferred oxyalkylene glycol alkenyl ethers corresponding to the formula V

R ³ = H or an aliphatic hydrocarbon radical having 1 to 5 C atoms and p = 0 to 3. R ¹ , m and n have the meaning already mentioned above. In this case, the use of polyethylene glycol monovinyl ether (p = 0 and m = 2) has proven particularly advantageous, n preferably having values between 2 and 15.

wobei S vorzugsweise -H oder COOM_a und U¹ = -CO-NH-, -O- oder -CH₂O- sein können, d. h. es handelt sich um die Säureamid-, Vinyl- oder Allylether der entsprechenden Polypropylenglykol- bzw. Polypropylenglykol-Polyethylenglykol-Derivate.The third component essential to the invention for introducing the components c) is preferably 1 to 5 mol% of a vinylic polyalkylene glycol, polysiloxane or ester compound. As preferred vinylic polyalkylene glycol compound, derivatives corresponding to formula VI are used,

where S may preferably be -H or COOM _a and U ¹ = -CO-NH-, -O- or -CH ₂ O-, ie it is the acid amide, vinyl or allyl ethers of the corresponding polypropylene glycol or polypropylene glycol -polyethylene glycol derivatives.

bedeuten, wobei
U² = -NH-CO-, -O- sowie -OCH₂- und S = -COOM_a und vorzugsweise -H ist.The values for x are 1 to 150 and for y = 0 to 15. R ⁶ can either be R ¹ again or

mean, where
U ² = -NH-CO-, -O- and -OCH ₂ - and S = -COOM _a and preferably -H.

In the case of R ⁶ = R ¹ and R ¹ is preferably H, there are the polypropylene glycol (-polyethylene glycol) monoamides or ethers of the corresponding acrylic (S = H, R ⁴ = H), methacrylic (S = H, R ⁴ = CH ₃ ) or maleic acid (S = COOM _a , R ⁴ = H) derivatives. Examples of such monomers are maleic acid N- (methylpolypropylene glycol) monoamide, maleic acid N- (methoxy-polypropylene glycol-polyethylene glycol) monoamide, polypropylene glycol vinyl ether and polypropylene glycol allyl ether.

In the case of R ⁶ ≠ R ¹ are bifunctional vinyl compounds whose Polvpropylenglykol- (polyethylene glycol) - derivatives via amide or ether groups (-O- or -OCH ₂ -) are interconnected. Examples of such compounds are polypropylene glycol-bis-maleamic acid, polypropylene glycol diacrylamide, polypropylene glycol dimethacrylamide, polypropylene glycol divinyl ether, polypropylene glycol diallyl ether.

wobei R⁴ = -H und CH₃,

und r = 2 bis 100 und R⁷ bevorzugt = R¹ ist. Beispiele für solche Monomere sind Monovinylpolydimethylsiloxane.The preferred vinylic polysiloxane compound used are derivatives corresponding to formula VII,

where R ⁴ = -H and CH ₃ ,

and r = 2 to 100 and R ^{7 is} preferably = R ¹ . Examples of such monomers are monovinylpolydimethylsiloxanes.

wobei s = 1 oder 2 sein kann, R⁴ und W die oben genannte Bedeutung besitzen und R⁷ entweder = R¹ oder aber sein kann und S vorzugsweise Wasserstoff darstellt.As further vinylic polysiloxane compound derivatives according to the formula VIII in question,

where s = 1 or 2, R ⁴ and W have the abovementioned meaning and R ⁷ can be either = R ¹ or else and S is preferably hydrogen.

Examples of such monomers having a vinyl function (R ⁷ = R 1) are polydimethylsiloxanepropylmaleamic acid or polydimethylsiloxanedipropyleneaminomaleamic acid. In the case of R ⁷ ≠ R ¹ are Divinylverbindungen such. B. polydimethylsiloxane bis (propylmaleinamidsäure) or polydimethylsiloxane bis (dipropylenaminomaleinamidsäure).

wobei z 0 bis 4 sein kann und R⁴ bzw. W die oben genannte Bedeutung besitzen. R⁷ kann entweder R¹ oder aber

sein, wobei S bevorzugt Wasserstoff bedeutet. Beispiele für solche monovinylischen Verbindungen (R⁷ = R¹) sind Polydimethylsiloxan-(1-propyl-3-acrylat) oder Polydimethylsiloxan-(1-propyl-3-methacrylat).As a further vinylic polysiloxane compound is a preferred derivative corresponding to the formula IX in question,

where z can be 0 to 4 and R ⁴ or W have the abovementioned meaning. R ⁷ can either be R ¹ or else

be, where S is preferably hydrogen. Examples of such monovinylic compounds (R ⁷ = R ¹ ) are polydimethylsiloxane (1-propyl-3-acrylate) or polydimethylsiloxane (1-propyl-3-methacrylate).

In the case of R ⁷ ≠ R ¹ are divinyl compounds, such. Polydimethylsiloxane bis (1-propyl-3-acrylate) or polydimethylsiloxane bis (1-propyl-3-methacrylate).

wobei S = COOM_a oder -COOR⁵ bedeuten und R⁵ ein aliphatischer Kohlenwasserstoffrest mit 3 bis 20 C-Atomen, ein cycloaliphatischer Kohlenwasserstoffrest mit 5 bis 8 C-Atomen sowie ein Arylrest mit 6 bis 14 C-Atomen sein kann. a und M besitzen die oben genannte Bedeutung. Beispiele für solche Esterverbindungen sind Di-n-butylmaleinat bzw. -fumarat oder Mono-n-butyl-maleinat- bzw. -fumarat.As vinylic ester compound in the context of the present invention it is preferred to use derivatives corresponding to the formula X,

where S = COOM _a or -COOR ⁵ is an aliphatic hydrocarbon radical having 3 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, and an aryl group having 6 to 14 carbon atoms can ⁵ and R be. a and M are as defined above. Examples of such ester compounds are di-n-butylmaleinate or fumarate or mono-n-butyl maleinate or fumarate.

wobei z wiederum 0 bis 4 sein kann und R¹ die bereits bekannte Bedeutung besitzt. V kann hierbei W (also eine Polydimethylsiloxan-Gruppierung) sein, was einer Dialkenylpolydimethylsiloxan-Verbindung, wie z. B. Divinylpolydimethylsiloxan, entspricht. Alternativ hierzu kann V auch -O-CO-C₆H₄-CO-O- sein. Diese Verbindungen stellen Dialkenylphthalsäure-Derivate dar. Ein typisches Beispiel für solche Phthalsäure-Derivate ist Diallylphthalat.Furthermore, it is also possible to use compounds corresponding to formula XI,

where z can in turn be 0 to 4 and R ^{1 has} the already known meaning. Here, V can be W (ie a polydimethylsiloxane grouping), which is a dialkenylpolydimethylsiloxane compound, such as. B. Divinylpolydimethylsiloxane corresponds. Alternatively, V can also be -O-CO-C ₆ H ₄ -CO-O-. These compounds are dialkenylphthalic acid derivatives. A typical example of such phthalic acid derivatives is diallyl phthalate.

The Molecular weights of the compounds which form the assembly c), can be varied within wide limits and are preferably between 150 and 10,000.

Farther can even up to 50 mol%, in particular up to 20 mol%, based on the monomers having the components according to the formulas II, III and IV of a vinyl, acrylic acid or methacrylic acid derivative copolymerized become. As monomeric vinyl derivative is preferably styrene, ethylene, Propylene, isobutene or vinyl acetate use, as a monomeric acrylic acid derivative is preferred acrylic acid or methyl acrylate used while as monomeric methacrylic acid derivatives after all preferably methacrylic acid methyl methacrylate and hydroxyethyl methacrylate.

The The aforementioned copolymers are disclosed in EP-A-736553.

worin
R¹ für ein Wasserstoffatom oder die Methylgruppe steht,
R²O für eine Gattung oder ein Gemisch von zwei oder mehr Gattungen einer Oxyalkylengruppe mit 2-4 Kohlenstoffatomen steht, mit der Maßgabe, dass zwei oder mehrere Gattungen des Gemischs entweder in Form eines Blocks oder in zufälliger Form zugegeben werden können,
R³ für ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen steht, und
m ein Wert ist, welcher die durchschnittliche Anzahl der Zugabemole von Oxyalkylengruppen ist, wobei m eine ganze Zahl im Bereich von 1 bis 200 ist.The dispersion of the invention may further comprise a copolymer whose base is an oxyalkenylglycol (meth) acrylic ester and the copolymer contains the following components:
5-98 wt .-% of a monomer of the type (a) (alkoxy) polyalkylene glycol mono (meth) acrylic ester of the general formula XV

wherein
R ^{1 represents} a hydrogen atom or the methyl group,
R ² O represents a genus or a mixture of two or more genera of an oxyalkylene group having 2-4 carbon atoms, with the proviso that two or more genera of the mixture may be added either in the form of a block or in random form,
R ^{3 is} a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and
m is a value which is the average number of moles of oxyalkylene groups, m being an integer in the range of 1 to 200.

worin
R⁴ für ein Wasserstoffatom oder die Methylgruppe steht, und M¹ für ein Wasserstoffatom, ein einwertiges Metallatom, ein zweiwertiges Metallatom, eine Amoniumgruppe oder eine organische Amingruppe,

• – und 0 bis 50 Gew.-% eines anderen Monomeren (c), das mit diesen Monomeren copolymerisierbar ist, mit der Maßgabe, dass die Gesamtmenge von (a), (b) und (c) 100 Gew.-% ist.

95 to 2 wt .-% of a monomer of the (meth) acrylic acid type (b) of the general formula XVI

wherein
R ^{4 represents} a hydrogen atom or the methyl group, and M ^{1 represents} a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group or an organic amine group,

• And 0 to 50% by weight of another monomer (c) copolymerizable with these monomers, with the proviso that the total amount of (a), (b) and (c) is 100% by weight.

Typical monomers (a) are:
Hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate,
Polyethylene glycol mono (meth) acrylate,
Polypropylene glycol mono (meth) acrylate,
Polybutylenglykolmono (meth) acrylate,
Polyethylene glycol polypropylene glycol mono (meth) acrylate,
Polyethylenglykolpolybutylenglykolmono (meth) acrylate,
Polypropylenglykolpolybutylenglykolmono (meth) acrylate,
Polyethylenglykolpolypropylenglykolpolybutylenglykolmono (meth) acrylate,
Methoxypolyethylene glycol (meth) acrylate,
Methoxypolypropylene glycol (meth) acrylate,
Methoxypolybutylenglykolmono (meth) acrylate,
Methoxypolyethylenglykolpolypropylenglykolmono (meth) acrylate,
Methoxypolyethylenglykolpolybutylenglykolmono (meth) acrylate,
Methoxypolypropylenglykolpolybutylenglykolmono (meth) acrylate,
Methoxypolyethylenglykolpolypropylenglykolpolybutylenglykolmono (meth) acrylate,
Ethoxypolyethylene (meth) acrylate,
Ethoxypolypropylenglykolmono (meth) acrylate,
Ethoxypolybutylenglykolmono (meth) acrylate,
Ethoxypolyethylenglykolpolypropylenglykolmono (meth) acrylate,
Ethoxypolyethylenglykolpolybutylenglykolmono (meth) acrylate,
Ethoxypolypropylenglykolpolybutylenglykolmono (meth) acrylate
and or
Ethoxypolyethylenglykolpolypropylenglykolpolybutylenglykolmono (meth) acrylate.

typical Monomers (b) are: acrylic acid and methacrylic acid, mono- and divalent metal salts, ammonium salts and / or organic Amine salts thereof.

Typical monomers (c) are: esters of aliphatic alcohols having 1 to 20 carbon atoms with (meth) acrylic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mono- and divalent metal salts, ammonium salts and / or organic amine salts thereof; Mono- or diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid with aliphatic alcohols of 1 to 20 carbon atoms, with Gly kolen having 2 to 4 carbon atoms, with (alkoxy) polyalkylene glycols of 2 to 100 Zugabemolen the aforementioned glycols; unsaturated amides such as (meth) acrylamide and (meth) acrylalkylamide; Vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene; unsaturated sulfonic acids such as (meth) allylsulfonic acid, sulfoethyl (meth) acrylate, 2-methylpropanesulfonic acid (meth) acrylamide, styrenesulfonic acid, mono- and divalent metal salts, ammonium salts and / or organic amine salts thereof.

• a) unter Rühren zu einer wässerigen Startdispersion von Titandioxid einen Polycarboxylatether in Form eines Pulvers oder als wässerige Lösung des Polycarboxylatethers gibt und gegebenenfalls mit Wasser weiter verdünnt oder
• b) ein Titandioxidpulver in einer wässerigen Lösung eines Polycarboxylatethers mittels eines geeigneten Dispergieraggregates dispergiert und nachfolgend gegebenenfalls mit Wasser weiter verdünnt oder
• c) das Titandioxidpulver in einer wässerigen Phase, vorzugsweise in Wasser, dispergiert und anschließend die entstandene Dispersion zu einer wässerigen Lösung des Polycarboxylatethers gibt. Das Einmischen der Dispersion kann in diesem Fall unter sehr niedriger Scherenergie erfolgen, beispielsweise mittels eines Propellerrührers.

Another object of the invention is a process for the preparation of the dispersion according to the invention, in which

• a) with stirring to an aqueous starting dispersion of titanium dioxide, a polycarboxylate in the form of a powder or as an aqueous solution of the polycarboxylate ether and optionally further diluted with water or
• b) dispersing a titanium dioxide powder in an aqueous solution of a polycarboxylate ether by means of a suitable dispersing unit and subsequently optionally further diluted with water or
• c) dispersing the titanium dioxide powder in an aqueous phase, preferably in water, and then adding the resulting dispersion to an aqueous solution of the polycarboxylate ether. The mixing in of the dispersion can in this case take place under very low shear energy, for example by means of a propeller stirrer.

The Dispersion of the titania powder may be at low levels of filling carried out in apparatuses which are a comparatively low shear energy in the system (eg dissolvers, rotor-stator systems).

In order to achieve high fill levels, shear energies of> 1000 kJ / m ^{3 must be} applied in order to obtain a stable dispersion with low viscosity. High shear energies can be achieved, for example, with stirred ball mills, high-pressure homogenizers or planetary kneaders. Optionally, with dispersion units which provide a lower energy input, for example a dissolver, first a predispersion can be produced.

Under suitable dispersing aggregates are to be understood as those whose Energy input is sufficient to disperse the titanium dioxide powder so that the aggregates have an average diameter of less than 1 to have.

The Dispersion of the titania powder may be at low levels of filling carried out in apparatuses which are a comparatively low shear energy in the system (eg dissolvers, rotor-stator systems).

In order to achieve high fill levels, shear energies of> 1000 kJ / m ^{3 must be} applied in order to obtain a stable dispersion with low viscosity. High shear energies can be achieved, for example, with stirred ball mills, high-pressure homogenizers or planetary kneaders.

Especially For example, the process disclosed in DE-A-10317066 can be used.

Furthermore, a method disclosed in WO2005 / 063369 can advantageously be used, in which at least two streams of predispersion are pumped by pumps, preferably high-pressure pumps, through a respective nozzle into a grinding chamber enclosed by a reactor housing to a collision point, the grinding chamber being flooded with the predispersion is and is removed by overpressure of nachströmenden in the grinding chamber predispersion from the grinding chamber. Similarly, a method is performed which is described in the German patent specification DE 10204470 is disclosed. In this case, at least two streams of a predispersion via pumps, preferably high-pressure pumps, injected through a nozzle in a reactor chamber enclosed by a reactor chamber reactor space to a collision point and introduced into the reactor space via an opening so steam that prevails in the reactor chamber, a steam atmosphere, mainly from water vapor consists, and the finely divided dispersion and steam and / or partially condensed steam, which consists predominantly of water, are removed by overpressure of the incoming water vapor on the gas inlet side of the reactor space.

Possibly can with dispersing aggregates give a lower energy input provide, for example, a dissolver, first produces a predispersion become.

An advantageously usable starting dispersion is obtained by adding an aggregated Ti in water tandioxidpulver having a specific surface area of 20 to 150 m ² / g, at least one aminoalcohol having 1 to 6 carbon atoms and at least one carboxylic acid from the group comprising dibasic carboxylic acids and / or hydroxycarboxylic acids having 2 to 6 carbon atoms, from which a predispersion by energy input of produced less than 200 kJ / m ³ and then produced by milling the predispersion by means of a high energy mill at a pressure of at least 500 bar, a dispersion in which the aggregated titanium dioxide powder has a mean volume-related aggregate diameter of less than 150 nm.

Of the Content of titanium dioxide is at least 20% by weight. The used titanium dioxide may preferably be pyrogenated titanium dioxide.

The aminoalcohol is preferably present at 2.5 to 7.0 μmol / m ² specific surface TiO ₂ and the carboxylic acid at 1.0 to 3.5 μmol / m ² specific surface TiO ₂ in the dispersion. Values for the amino alcohol of 3.3 to 5.0 μmol / m ² specific surface area TiO ₂ and 1.5 to 2.5 μmol / m ² specific surface TiO ₂ for the carboxylic acid are particularly preferred.

suitable Amino alcohols are: monethanolamine, diethanolamine, triethanolamine, Monoisopropanolamine, diisopropanolamine, triisopropanolamine, N, N-dimethylisopropanolamine, 3-amino-1-propanol, 1-amino-2-propanol and / or 2-amino-2-methyl-1-propanol.

suitable carboxylic acids are: oxalic acid, malonic, Succinic acid, glutaric, Adipic acid, maleic acid, fumaric acid, lactic acid, malic acid, tartaric acid and / or Citric acid.

These Starting dispersion is characterized by the small aggregate size of the titanium dioxide particles by their stability and low viscosity out. Further dispersions are in the still unpublished German patent application with the application number 102004037118.0 of 30 July 2004 included.

One Another object of the invention is the use of the dispersion of the invention as concrete admixture.

One Another object of the invention is a cementitious preparation, which is the dispersion of the invention contains.

Preferably is the proportion of titanium dioxide in the cementitious preparation is 0.01 to <2 wt .-%, based on cement.

Examples

analytics: The particle diameter in the dispersion is determined by means of dynamic Light scattering, measuring device: Horiba LB-500, certainly. The relatively coarse P5 and P6 powders are laser diffracted according to ISO 13320-1 measured.

The BET surface area is determined according to DIN 66131.

The Production of standard mortar was carried out in accordance with DIN EN 196. The exam the strength was in accordance with DIN 1164 on prisms of size 4 × 4 × 16 cm.

used materials

• P1: Aeroxide ^© P25 TiO ₂ : BET surface area 50 m ² / g, content of titanium dioxide> 99.50% by weight.
• P2: titanium dioxide powder according to WO2005 / 054136, Example A7: BET surface area 91 m ² / g.
• P3: Titanium-silicon mixed oxide powder according to DE-A-102004001520, Example 12: BET surface 43 m ² / g, content titanium dioxide 49 wt.%, Content of silicon dioxide 51 wt.
• P4: Aerosil ^© 200: BET surface area 200 ± 25 m ² / g, content of silica> 99.8% by weight
• P5: TiPure R ^© 706, Dupont: BET surface area <10 m ² / g, content of titanium dioxide 93 wt .-%.
• P6: ^© Tioxide TR 92, Huntsman: BET surface area <10 m ² / g, content of titanium dioxide 94 wt .-%.

polycarboxylatether (PCE) is prepared according to EP-A-1189955, example 2, with the amounts changed so will be that a 45 percent solution is obtained.

dispersions

D1a: To 1 kg of a solution of PCE1 in water (concentration 102 g / l water) are 299 g P1 and dispersed using a ball mill.

D1b, D1c, D1d, D2, D3, D4, D5 and D6 are used analogously to D1a produced by P1, P2, P3, P4, P5 and P6, but with different Amounts of PCE1 solution and different powders. D7 contains no titanium dioxide, but only PCE and does not constitute a dispersion. The composition The dispersions are shown in Table 1.

Table 1: Dispersions

• a) for D3: sum of TiO ₂ and SiO ₂ for D4: only SiO ₂

Production of standard mortars

Cement: CEM I 52.5 Mergelstetten, temperature 20 ° C. The mortar mixtures are the dispersions added according to Table 1. The oxide content and the PCE1 content in wt .-%, based on the cement weight, are listed in Table 2. From The various dispersions were always dosed so much that the initial flow was 24 +/- 1 cm. The one for this required Quantities are also listed in Table 2. The water / cement ratio was in all experiments 0.4.

The Results of the strengths measured after 8 h are in the table 2 summarized.

outgoing of the dispersions of the invention D1a-d, D2 and D3 are significant increases in early strength across from the pure solvent D7 observed.

A comparison of D1a and D2 with D5 and D6 clearly shows that a high specific surface area is advantageous if high early strengths are to be achieved. Surprisingly, however, that the dispersions with titanium dioxide D1a and titanium-silicon mixed oxide D3 at the same concentration of the solid based on the binder comparable good or even a much higher early strength compared to D4 (Aerosil ^© 200) have, although the specific surface of the Titanium dioxide-containing particles is significantly lower. It has previously been thought that reactive oxides with the larger specific surface area must give the higher early strength. It can be concluded that, in addition to a high specific surface, the titanium dioxide content makes a significant contribution to increasing the early strength.

A comparison of D3 and D4 in Table 2 also shows a further positive effect of the titanium dioxide content of the particles: at an equally high concentration of the reactive solid of 0.5% of the binder, although approximately the same high early strengths are achieved, however, the flow agent requirement at D4 is approx. 30% h ago. This means that the processability of the fresh concrete by reactive particles containing titanium dioxide is influenced much less than by reactive silicas of the same specific surface. For the user, this means a cost saving because he has to use less superplasticizer.

1 shows the heat development in the cement paste specimen in mW / g of cement over a period of 0.5-24 h after adding the mixing water to the cement. The cement used was CEM I 42.5 Bernburg. D1a is metered in such a way that the amount of titanium dioxide is 0.5% by weight, based on the cement used (curve 1). The water / cement ratio was constant at 0.5. The comparison is made against a sample containing no titanium dioxide (curve 2). The heat development is due to the exothermic reaction of the silicate phases in the cement with water. The maximum of the curve obtained by calorimetry can with the strength development in the cement. correlated, ie a maximum occurring at an earlier point in time means an early onset of early strength development in the component.

Out The results can be clearly concluded that the use D1a causes a significant acceleration of cement hydration. The beginning of silicate hydration, as well as the maximum of heat development are much earlier as in the case of the blank value.

Claims (14)

Dispersion which is free of binders and which contains titanium dioxide and at least one water-soluble polycarboxylate ether, characterized in that - the titanium dioxide has a BET surface area of from 20 to 400 m ² / g, The water-soluble polycarboxylate ether is a copolymer based on at least one oxyalkylene glycol compound and at least one unsaturated monocarboxylic acid derivative or dicarboxylic acid derivative, the dispersion has a titanium dioxide content of from 5 to 50% by weight, based on the total amount of the dispersion. Dispersion according to claim 1, characterized in that that the titanium dioxide is a mixed oxide with titanium dioxide as the first component and alumina, potassium oxide, lithium oxide, sodium oxide, magnesium oxide, Calcium oxide, silicon dioxide and / or zirconium dioxide as the second component is. Dispersion according to claims 1 or 2, characterized that the titanium dioxide is a pyrogenic titanium dioxide. A dispersion according to claim 3, characterized in that the pyrogenic titanium dioxide has a BET surface area of 30 to 150 m ² / g. Dispersion according to Claims 1 to 4, characterized that the titanium dioxide particles in the dispersion have a middle, have number-related diameter of less than 1 micron. Dispersion according to Claims 1 to 5, characterized that the proportion of titanium dioxide in the dispersion in total 5-50 wt .-%, based on the total amount of the dispersion. Dispersion according to Claims 1 to 6, characterized that the weight ratio Polycarboxylate ether / titanium dioxide 0.01 to 100. Dispersion according to Claims 1 to 7, characterized in that the base of the copolymer is an oxyalkenylglycol-alkenyl ether and the copolymer contains the following constituents: a) 51 to 95 mol% of the structural groups of the formula Ia and / or Ib and / or Ic

where R ¹ = hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms X = -OM _a , -O- (C _m H _2m O) _n -R ² , -NH- (C _m H _2m O) _n -R ² M = hydrogen, a mono- or divalent metal cation, ammonium ion, an organic amine radical, a = ½ or 1 R ² = hydrogen, 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 Y = O, NR ² m = 2 to 4 and n = 0 to 200, b) 1 to 48.9 mol% of the general formula II

where R ^{3 is} hydrogen or an aliphatic hydrocarbon radical having 1 to 5 C atoms p is 0 to 3 and R ² , m and n have the abovementioned meaning, c) 0.1 to 5 mol% of the formula IIIa or IIIb

where S = -H, -COOM _a , -COOR ⁵ T = -U ¹ - (CH (CH ₃ ) -CH ₂ -O) _x - (CH ₂ -CH ₂ -O) _y -R ⁶ -WR ⁷ - CO- [NH- (CH ₂ ) ₃ ] _s -WR ⁷ -CO-O- (CH ₂ ) _z -WR ⁷ - (CH ₂ ) _z -V- (CH ₂ ) _z -CH = CH-R ² - COOR ⁵ in the case of S = -COOR ⁵ or COOM _a U ¹ = -CO-NH-, -O-, -CH ₂ O- U ² = -NH-CO-, -O-, -OCH ₂ - V = -O-CO-C ₆ H ₄ -CO-O- or -W-

R ⁴ = H, CH ₃ R ⁵ = aliphatic hydrocarbon radical having 3 to 20 carbon atoms, cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, aryl radical having 6 to 14 carbon atoms

r = 2 to 100 s = 1, 2 z = 0 to 4 x = 1 to 150 y = 0 to 15 and d) 0 to 47.9 mol of structural groups of the general formula IVa and / or IVb

with the meaning given above for a, M, X and Y. Dispersion according to Claims 1 to 7, characterized in that the base of the copolymer is an oxyalkenylglycol-alkenyl ether and the copolymer contains the following constituents: a) 10 to 90 mol% of the groups of the formula IVa and / or IVb

where M = hydrogen, mono- or divalent metal cation, ammonium ion, organic amine radical, a = 1, or in the case where M is a divalent metal cation, is 1/2, X = also -OM _a or -O- (C _m H _2m O) _n -R ¹ where R ¹ = H, aliphatic hydrocarbon radical having 1 to 20 C atoms, cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, optionally substituted aryl radical having 6 to 14 C atoms, m = 2 to 4, n = 0 to 200, -NHR ² and / or -NR ² ₂ with R ² = R ¹ or -CO-NH ₂ and Y = O, NR ^{2 are} b) 1 to 89 mol% of the formula II

wherein R ³ = H, aliphatic hydrocarbon radical having 1 to 5 C atoms p = 0 to 3 and R ¹ , m, n have the abovementioned meaning and c) 0.1 to 10 mol% of the formula IIIa or IIIb

where S = -H, -COOM _a , -COOR ⁵

-WR ⁷ -CO- [NH- (CH ₂ ) ₃ ] _s -WR ⁷ -CO-O- (CH ₂ ) _z -WR ⁷ - (CH ₂ ) _z -V- (CH ₂ ) _z -CH = CH -R ¹ -COOR ⁵ in the case of S = -COOR ⁵ or COOM _a U ¹ = -CO-NH-, -O-, -CH ₂ O- U ² = -NH-CO-, -O-, -OCH ₂ V = -O-CO-C ₆ H ₄ -CO-O- or -W- W =

R ⁴ = H, CH ₃ R ⁵ = aliphatic hydrocarbon radical having 3 to 20 C atoms, cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, aryl radical having 6 to 14 C atoms

r = 2 to 100; s = 1, 2; z = 0 to 4 x = 1 to 150; y = 0 to 15. Dispersion according to Claims 1 to 7, characterized in that the base of the copolymer is an oxyalkenylglycol (meth) acrylic ester and the copolymer contains the following components: 5-98% by weight of a monomer of the type (a) (alkoxy) polyalkylene glycol mono ( meth) acrylic esters of the general formula XV

wherein R ^{1 represents} a hydrogen atom or the methyl group, R ² O represents a genus or a mixture of two or more genera of an oxyalkylene group having 2-4 carbon atoms, with the proviso that two or more genera of the mixture are in the form of one block or may be added in a random form, R ^{3 is} a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m is a value which is the average number of addition moles of oxyalkylene groups, m being an integer in the range of 1 to 200 is. 95 to 2 wt .-% of a monomer of the (meth) acrylic acid type (b) of the general formula XVI

wherein R ^{4 is} a hydrogen atom or the methyl group, and M ^{1 is} a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group or an organic amine group, and 0 to 50 wt .-% of another monomer (c), with copolymerizable with these monomers, provided that the total amount of (a), (b) and (c) is 100% by weight. Process for the preparation of the dispersion according to Claims 1 to 10, characterized in that one a) with stirring a watery one Starting dispersion of titanium dioxide a polycarboxylate in the form of a powder or as an aqueous solution of the polycarboxylate ether and optionally further with water dilute or b) a titanium dioxide powder in an aqueous solution a polycarboxylate ether by means of a suitable dispersing aggregate dispersed and subsequently optionally further diluted with water or c) the titanium dioxide powder in an aqueous Phase, preferably in water, and then dispersing the resulting Dispersion to an aqueous solution of the polycarboxylate ether. Use of the dispersion according to claims 1 to 10 as concrete admixture. Cementitious preparation containing the dispersion according to claims 1 to 10th Cement-containing preparation according to claim 13, characterized characterized in that it is 0.01 to <2 Wt .-% titanium dioxide, based on cement contains.