DE102006005093A1 - Silica and polycarboxylate ether-containing dispersion - Google Patents

Abstract

Dispersion which is free of binders and which contains silicon dioxide and at least one water-soluble polycarboxylate ether, the silicon dioxide being a pyrogenic silicon dioxide which is in the form of aggregated primary articles and has a BET surface area of 50 to 250 m <SUP> 2 </SUP> / g is, and. the aggregates in the dispersion have an average diameter of less than 1 μm,. based on the total amount of the dispersion, 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 weight ratio of polycarboxylate ether / silicon dioxide is 0.01 to 100.

Description

The The invention relates to a dispersion based on silica and a polycarboxylate ether, and their use as concrete admixtures.

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.

In WO02 / 070429 discloses a composite material which is inorganic Aggregates, ultrafine particles, a cementitious binder and a concrete liquefier contains. The composite material allows the production of a highly liquefied Concrete where no bleeding occurs. As ultrafine particles are mainly "silica fume "particles used, incurred in connection with the production of silicon metal. "silica fume "particles lie usually as spherical Single particles with a diameter of 150 nm or more before. she show a strong in cement or concrete compositions Filler effect are, however, little because of their low specific surface area reactive. As further particles of this order of magnitude, alumina, Fly ash, pozzolans, calcium carbonate, alumina, barium sulfate and titanium dioxide are used. The specified particles have the disadvantage that they have a small specific surface, resulting in a low nucleation rate of the strength-building Phases and thus too low early strengths leads. Under early strength Within the scope of the present text, the strength of a concrete after <48 h the Cement hydration understood.

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.

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 WO01 / 90024 nothing is disclosed about the influence of the described silica sol on the early strength. However, it is known to the person skilled in the art that in the case of silica sol concentrations in which a significant increase in the early strength is achieved, the processability is also significantly reduced, so that high amounts of flow agent are necessary. It is believed that this is because silica sols dissolve rapidly in the highly alkaline cement or concrete compositions. The silica sols are therefore available only to a small extent as a germ for the formation of the strength-forming calcium silicate hydrate phases available.

WO98 / 12149 discloses a concrete composition containing aggregates, a hydraulic binder and silica sol having a BET surface area of less than 200 m ² / g, the particle size distribution being characterized in that the relative standard deviation of the number distribution of the silica sol is more than 30%, in the exemplary embodiments is about 45% to 70%. The invention aims to increase the early strength without reducing the ultimate strength. In this case, flow agents can be added to the concrete composition. However, the use of the condenser disclosed in WO98 / 12149 results in a drastic reduction in processing time in the presence of the silica sol. In WO98 / 12149 it is stated that preferably 1-8% of particles and particularly advantageously 2% of particles are required, based on the binder be used to achieve an increase in early strength. It is known to the person skilled in the art that with such high silica sol concentrations the processability is markedly reduced and thus high quantities of flow agent are required. This is how Wagner and Hauck show in Wiss. Z. Hochsch. Archit. Construction. - Weimar 40 (1990), p.183 ff., That when using silica sol concentrations of> 1% of the cement content, the flow quantities must be well above 1% of the cement content to obtain a readily processable concrete. High flow rates lead to high costs for the user and can often lead to negative effects such as a greater tendency to bleeding and a lower final strength.

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, with respect to note the additives described in EP-A-1607378 they have a low stability to sedimentation in dispersion form.

wagner and Hauck show in Wiss. Z. Hochsch. Archit. Construction. - Weimar 40 (1990), p.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 at the same time have good processability, without large amounts of fluid must be used. The state of the art further shows that the currently available superplasticizer 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 Siliciumdioxid ein pyrogenes Siliciumdioxid, welches in Form aggregierter Primärpartikel vorliegt, mit einer BET-Oberfläche von 50 bis 250 m²/g ist, wobei – die Aggregate in der Dispersion einen mittleren Durchmesser von weniger als 1 μm aufweisen und – der Anteil an Siliciumdioxid 5 bis 50 Gew.-%, bezogen auf die Gesamtmenge der Dispersion, beträgt,
• – der wasserlösliche Polycarboxylatether ein Copolymeres auf Basis mindestens einer Oxyalkylenglykolverbindung und mindestens einem ungesättigten Monocarbonsäurederivat oder Dicarbonsäurederivat ist,
• – das Gewichtsverhältnis Polycarboxylatether/Siliciumdioxid 0,01 bis 100 beträgt.

The invention relates to a dispersion containing silicon dioxide and at least one water-soluble polycarboxylate ether, which is characterized in that

• - The silica is a fumed silica, which is in the form of aggregated primary particles, having a BET surface area of 50 to 250 m ² / g, wherein - the aggregates in the dispersion have a mean diameter of less than 1 micron and - the proportion of Silica 5 to 50 wt .-%, based on the total amount of the dispersion is,
• 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 weight ratio of polycarboxylate ether / silicon dioxide is 0.01 to 100.

In In the present invention, the terms silicon dioxide and silica 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.

By pyrogenic silica obtained by flame oxidation and / or flame hydrolysis to understand articles. As starting materials for pyrogenic processes, organic and inorganic substances can be used. Silicon tetrachloride, for example, is particularly suitable. Suitable organic starting compounds may be, for example, Si (OR) ₄ with R = CH ₃ or CH ₂ CH ₃ . The silicon dioxide particles thus obtained are largely free of pores and have free hydroxyl groups on the surface. The silicon 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 silica particles are present in a largely aggregated form.

The Dispersion according to the invention can also pyrogenic mixed oxides with silica as the first component and lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, Containing alumina or zirconia as the second component. It is also possible that a mixture of fumed silica with the aforementioned Mixed oxides is present.

preferred pyrogenic mixed oxides are those in which the mixed oxide component is introduced by means of an aerosol. These are for example Silicon-potassium mixed oxide or silicon-lithium mixed oxide, for example according to DE-A-19650500 or the one yet unpublished European Patent application with the application number 05024753.5 and the filing date November 12, 2005 can be produced. Furthermore, the dispersion of the invention Silicon-aluminum mixed oxide, which according to EP-A-995718 can be produced. The mixed oxides mentioned are characterized by only a slight degree of adhesion of the primary particles out.

Advantageously, the fumed silica can be selected from the group comprising: AEROSIL ^® 90, Aerosil ^® 130, Aerosil ^® 200, Aerosil ^® TT600, Aerosil ^® MOX 80, AEROSIL MOX 170 ^®, all Degussa; CRB-O-SIL ^® LM-150, CAB-O-SIL ^® LM-150D, CAB-O-SIL ^® M-5 CAB-O-SIL ^® M-5P, CAB-O-SIL ^® M-5DP, CAB-O- ^SIL® M-7D, CAB-O- ^SIL® PTG, CAB-O- ^SIL® HP-60, all Cabot Corp .; HDK S13, HDK ^® V15, HDK ^® V15P, HDK ^® N20, HDK ^® N20P all Wacker; REOLOSIL ^® QS-10, QS-20 ^® REOLOSIL REOLOSIL ^® QS-30 REOLOSIL ^® QS-40, REOLOSIL ^® DM-10, all Tokuyama.

The silica according to the invention may also be in surface-modified form. For example, the surface may be surface-modified with haloorganosilanes, alkoxysilanes, silazanes, siloxanes, polysiloxanes. Can preferably be as silanizing agent trimethoxyoctylsilane [(CH ₃ O) ₃ -Si-C ₈ H _17] be, octamethylcyclotetrasiloxane or hexamethyldisilazane. Since the stability of the dispersion according to the invention is generally lower for surface-modified silica than for non-modified, preference is given to the latter.

It is still possible that the dispersion of the invention contains the fumed silica as a single solid. This may be particularly useful if the dispersion as a masterbatch for different Applications should serve.

The BET surface area of the silicon dioxide present in the dispersion according to the invention is limited to values of 50 to 250 m ² / g. Preferably, the silica has a BET surface area of 70 to 170 m ² / g.

Farther has the dispersion according to the invention a mean diameter of the aggregates in the dispersion of preferably 50 to 500 nm, and more preferably one of 70 to 300 nm. Values below 50 nm are pyrogenically generated Silica technically difficult to realize and wise no benefits in the application.

Farther it may be advantageous if the relative standard deviation of Number distribution of the aggregate diameter of the silica smaller than 30%, usually 15% to 25%. The relative standard deviation is a measure of the particle size distribution. For the present invention is that the narrowest possible distribution, ie one possible low standard deviation is beneficial. Through a narrow distribution the aggregate diameter makes it possible to influence the strength development of the concrete in a more targeted manner: The aggregate diameter can influence the time from when the acceleration of hydration by the reactive silicic acids begins.

1 shows the distribution of the aggregate diameter of two silica with 90 and 200 m ² / g BET surface area in a dispersion according to the invention. The determined relative standard deviation of the number distribution of the aggregate diameters is 23% and 25%, respectively. These dispersions can be used with particular preference.

Of the Proportion of silica in the dispersion of the invention is 5 to 50 wt .-%, based on the total amount of the dispersion. Dispersions according to the invention, which have a silicon 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 silica are not economical due to the high water content.

The weight ratio Polycarboxylate ether / silica in the dispersion of the invention is 0.01 to 100. Preferably, this ratio can be 0.05-5.

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, with alkaline pHs of 8 to 12, in particular from 9 to 11.5, in cementitious Systems due to compatibility the components may be preferred.

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.

Furthermore, aluminum salts can be added to the dispersion according to the invention. Suitable aluminum salts may include aluminum chloride, aluminum hydroxychlorides of the general formula Al (OH) _x Cl where x = 2-8, aluminum chlorate, aluminum sulfate, aluminum nitrate, aluminum hydroxynitrates of the general formula Al (OH) _x NO ₃ where x = 2-8, aluminum acetate, alums such as Aluminum potassium sulfate or aluminum ammonium sulfate, aluminum formates, aluminum lactate, aluminum oxide, aluminum hydroxide acetate, aluminum isopropylate, aluminum hydroxide, aluminum silicates and mixtures of the aforementioned compounds. The use of these aluminum compounds in the preparation of silica dispersions has already been described in DE-A-10238463.

Farther it may be advantageous to use the dispersion and / or predispersion a surfactant added, the nonionic, cationic, anionic or amphoteric Art is.

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) from 51 to 95 mol%, of the assembly b) from 1 to 48.9 mol%, the assembly c) 0.1 to 5 mol% and the assembly d) 0 to 47.9 Mol%.

The first component a) represents a mono- or dicarboxylic acid derivative having 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 or -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 cycloali phatic hydrocarbon radical having 5 to 8 carbon atoms, an aryl radical having 6 to 14 carbon atoms, which may optionally be substituted, m = 2 to 4 and n = 0 to 200, The aliphatic hydrocarbons may be linear or branched as well as 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 = 0 (acid anhydride) or NR ² (acid imide) may represent with 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. S can in this case -H, represent -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 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms or a 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.

x nimmt hierbei einen Wert von 1 bis 150 und y von 0 bis 15 an. Die Polypropylenoxid(-Polyethylenoxid-)-Derivate können hierbei über eine Gruppierung U¹ mit dem Ethylrest der Baugruppe c) entsprechend Formel IIIa verknüpft sein, wobei
U¹ = -CO-NH-, -O- oder -CH₂-O- sein kann. Hierbei handelt es sich um die entsprechenden Amid-, Vinyl- oder Allylether der Baugruppe entsprechend Formel IIIa. R⁶ kann hierbei wiederum R² (Bedeutung von R² siehe oben) oder

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.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

x assumes a value of 1 to 150 and y of 0 to 15. The polypropylene oxide (polyethylene oxide -) - 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), wherein
U ¹ = -CO-NH-, -O- or -CH ₂ -O- may be. These are the corresponding amide, vinyl or Allyl ether 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 group d) is derived from an unsaturated dicarboxylic acid derivative of the general formula IVa and / or IVb as defined above for 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 and are used in an amount of preferably 55 to 75 mol%.

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 CH ₂ = CR ³ - (CH ₂ ) _p -O- (C _m H _2m O) _n -R ² 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 particularly advantageous, n preferably having values between 1 and 50.

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 and R ^{5 can be} an aliphatic hydrocarbon radical having 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms and an aryl radical having 6 to 14 C atoms. 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 can be W (ie a polydimethylsiloxane grouping), which corresponds to a dialkenylpolydimethylsiloxane compound such as divinylpolydimethylsiloxane. 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 modules a) to d) relative to other monomers used as described above become.

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 assembly a) (dicarboxylic acid derivative) may also be present in cyclic form corresponding to the formula IVb, where Y = 0 (= 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 = H or CH ₃ can be, depending on whether 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 carbon may be hydrogen radical having 5 to 8 carbon atoms or an aryl radical having 6 to 14 carbon atoms. 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.

x nimmt hierbei einen Wert von 1 bis 150 und y von 0 bis 15 an. Die Polypropylenoxid(-Polyethylenoxid-)-Derivate können hierbei über eine Gruppierung U¹ mit dem Ethylrest der Baugruppe c) entsprechend Formel IIIa verknüpft sein, wobei U¹ = -CO-NH-, -O- oder -CH₂-O- sein kann. Hierbei handelt es sich um die entsprechenden Amid-, Vinyl- oder Allylether der Baugruppen entsprechend Formel IIIa. R⁶ kann hierbei wiederum R¹ (Bedeutung von R¹ siehe oben) oder

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.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

x assumes a value of 1 to 150 and y of 0 to 15. The polypropylene oxide (polyethylene oxide) derivatives may hereby be linked via a grouping U ¹ to the ethyl radical of the group c) corresponding to formula IIIa, where U ^{1 is} -CO-NH-, -O- or -CH ₂ -O- can. 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 a polydimethylsiloxane group), R ⁷ may be R = ¹ and r can in this case assume values from 2 to 100th

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 ) ₂ -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.

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 CH ₂ = CR ³ - (CH ₂ ) _p -O- (C _m H _2m O) _n -R ¹ 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 is.

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,
W=

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 ,
W =

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 polydimethylsiloxanepropylmalein amic acid or polydimethylsiloxanedipropyleneaminomaleamic acid. In the case of R ⁷ ≠ R ¹ are divinyl compounds such as 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 Divinylverbindungen, such as 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 and R ^{5 can be} an aliphatic hydrocarbon radical having 3 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms and an aryl radical having 6 to 14 C atoms. 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 according to the invention can furthermore contain a copolymer whose base is an oxyalkenyl glycol (meth) acrylate 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,
Ethoxypolyethylene glycol polypropylene glycol mono (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 aliphatic alcohols having 1 to 20 carbon atoms with (meth) acrylic acid; unsaturated dicarboxylic acids like maleic acid, fumaric acid, citraconic, 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 with aliphatic alcohols of 1 to 20 C atoms, with glycols having 2 to 4 C atoms, with (alkoxy) polyalkylene glycols of 2 to 100 of the above-mentioned glycols; unsaturated Amides such as (meth) acrylamide and (meth) acrylalkylamide; Vinyl esters like 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, styrene, mono- and divalent metal salts, ammonium salts and / or organic Amine salts thereof.

• a) unter Rühren zu einer wässerigen Startdispersion von Siliciumdioxid, in der die Aggregate einen mittleren Durchmesser von weniger als 1 μm aufweisen, einen Polycarboxylatether in Form eines Pulvers oder als wässerige Lösung des Polycarboxylatethers gibt und gegebenenfalls mit Wasser weiter verdünnt oder
• b) ein Siliciumdioxidpulver in einer wässerigen Lösung eines Polycarboxylatethers mittels eines geeigneten Dispergieraggregates dispergiert und nachfolgend gegebenenfalls mit Wasser weiter verdünnt oder
• c) das Siliciumdioxidpulver 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
you

• a) with stirring to an aqueous starting dispersion of silica in which the aggregates have an average diameter of less than 1 micron, a polycarboxylate in the form of a powder or as an aqueous solution of the Polycarboxylatethers and optionally further diluted with water or
• b) dispersing a silica 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 silica 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.

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

The Dispersion of the silica powder may be at low fill levels be carried out in apparatuses which introduce a comparatively low shear energy into the system (e.g., 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.

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 silica in the cementitious preparation is 0.01 up to <2% by weight, based on the cement.

Examples

analytics: Number distribution of aggregate size distribution determined by means of dynamic light scattering, measuring device: Horiba LB-500, measuring range 0.003 μm up to 6 μm, Number of iterations: 800. The relative coarse powder P2 is by laser diffraction according to ISO 13320-1 measure

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.

raw materials

Silica dispersions Start (SD):

• SD1: 32.5 kg demineralized water are placed in a 60 l stainless steel batch tank. Subsequently, 17.5 kg of AEROSIL 90 are drawn under shear conditions with the help of the suction pipe of the Ystral Conti-TDS 3 (stator slots: 4 mm ring and 1 mm ring, rotor / stator distance approx. 1 mm). Thereafter, it is post-sheared at 3000 rpm for 10 minutes. After the milling is adjusted to pH 10 with sodium hydroxide solution. The silica particles have a d ₅₀ value of 154 nm. The viscosity of the dispersion is 6 mPas at a shear rate of 10 s ^-1 and at 23 ° C.
• SD2: 32.5 kg demineralized water are placed in a 60 l stainless steel preparation vessel. Subsequently, with the help of the suction pipe of the Ystral Conti-TDS 3 (stator slots: 4 mm ring and 1 mm ring, rotor / stator distance approx. 1 mm) 17.5 kg AEROSIL 200 are drawn under shear conditions. Thereafter, at 3000 rev / min for 10, min nachgeschert. After grinding, it is diluted with demineralized water to a concentration which is slightly above 20 wt .-%, diluted. With sodium hydroxide solution, a pH of 10 is set. Thereafter, the remaining water required is metered in to achieve a final silica concentration of 20% by weight. The silica particles have a d ₅₀ value of 81 nm. The viscosity of the dispersion is 40 mPas at a shear rate of 10 s ^-1 and at 23 ° C.
• SD3: In a 60 l stainless steel batch tank 36 kg of demineralized water and 104 g of 30% KOH solution are presented. Using a dispersing and suction mixer from Ystrahl (at 4500 rpm) 16.5 kg with 0.44 wt .-% potassium-doped silica, prepared according to DE 196 50 500 , sucked in and coarsely predispersed. This predispersion is supported by a rotor / stator continuous homogenizer type Z 66 from Ystral with four machining rings, a stator slot width of 1 mm and a speed of 3000 rpm. After the powder introduction, the dispersion is completed with the rotor / stator continuous homogenizer type Z 66 from Ystral at a speed of 11 500 rpm. During this 15 minute dispersion at 11,500 rpm, the pH is adjusted and maintained at a pH of 10.5 by addition of further KOH solution. In this case, a further 779 g of KOH solution were used and adjusted by the addition of 1.5 kg of water, a solids concentration of 30 wt .-%. The resulting dispersion is milled with a Wet-Jet-Mill, Ultimaizer System from Sugino Machine Ltd. Model HJP-25050, at a pressure of 250 MPa and a diamond nozzle diameter of 0.3 mm and two grinding passes. The dispersion has a content of doped silicon dioxide of 30% by weight The silica particles have a d ₅₀ value of 71 nm The viscosity of the dispersion is 7.5 mPas at a shear rate of 500 s ^-1 and at 23 ° C.

Silica powder (P):

• P4: Pyrogenic SiO ₂ doped with 0.1% by weight of Li ₂ O; with 90 m ² / g of specific surface
• P5: Precipitated silica with 1 65 m ² / g specific surface area, aver. Aggregate diameter D ₅₀ (number-based): 5 .mu.m
• P6: silica fume with 20 m ² / g specific surface area. Particle diameter D ₅₀ (number-based): 0.13 μm

Polycarboxylate ethers (PCE)

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 (D):

• D1 (according to the invention): to 1000 g SD1 are stirred 250 g of an aqueous solution of PCE (PCE content: 45% by weight) given.
• D2 (according to the invention): to 1000 g SD2 are stirred 183 g of an aqueous solution of PCE (PCE content: 45% by weight) given.
• D3 (according to the invention): to 1000 g SD3 are stirred 250 g of an aqueous solution of PCE (PCE content: 45% by weight).
• D4 (according to the invention): to 1000 g of an aqueous solution of PCE (PCE content: 45% by weight) is first added 3.2 kg of water. Thereafter, 1400 g of P1 are dispersed in the diluted PCE solution using a ball mill.
• D5 (comparative example): To 1000 g of an aqueous solution of PCE (content PCE: 45 Wt .-%) is initially 4.4 kg of water. Thereafter, using a ball mill 1100 g P5 in the diluted PCE solution dispersed.
• D6 (comparative example): To 1000 g of an aqueous solution of PCE (content PCE: 45 Wt .-%) is initially 2.9 kg of water. Thereafter, using a ball mill 1750th g P6 in the diluted PCE solution dispersed.

The relationship from PCE to silica is adjusted so that at a dosage the dispersion to a cement-containing preparation, the silica content 0.5 wt .-%, based on the cement content corresponds. The initial flow rate of the mortar is always in the range 24 cm +/- 1 cm.

The Composition of the dispersions is shown in Table 1. Contains D7 no silica, but only PCE and does not provide dispersion dar. D7 is the clarity because of listed in Table 1 nevertheless.

The dispersions according to the invention show no noticeable change within a period of 6 months in terms of sedimentation and viscosity.

manufacturing of standard mortar

Cement: CEM I 52.5 Mergelstetten, temperature 20 ° C. The mortar mixtures are the dispersions corresponding to a silicon dioxide content of 0.5 wt .-%, based added to the cement weight. The water / cement ratio was always 0.4. The results are summarized in Table 1. The results obtained show a significant increase in the early strength when using the dispersions of the invention.

Farther Tests are carried out in the calorimeter. As cement, CEM I 42.5 Bernburg used. The dispersions of the invention are used D1, D2, and D3. The dispersions are metered so that the proportion on silica 0.5 wt .-% based on the cement used is. The Water / cement ratio is constant at 0.5. The comparison is made against the dispersion D6, which contains "silica fume" and D7, which contains no silica but PCE. In all experiments was the initial flow rate 24 +/- 1 cm.

The curves obtained ( 2 ) show the released energy in J / g CEM versus time in hours in the cement paste specimen. The heat development is due to the exothermic reaction of the silicate phases in the cement with water. This process is called cement hydration. In general, the greater the evolution of heat up to a certain point in the hydration reaction, the greater is the strength of a component at that time

The illustration clearly shows the higher reactivity of the mortar to which the dispersions according to the invention were added.

Claims (14)

Dispersion which is free of binders and which is silica and at least one water-soluble containing polycarboxylate ethers, characterized in that - the silica is a fumed silica, which is present in the form of aggregated primary particles, with a BET surface area of 50 to 250 m ² / g, wherein - the aggregates in the dispersion has a mean diameter of less than 1 μm and the proportion of silicon dioxide is 5 to 50% by weight, based on the total amount of the dispersion, of 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 weight ratio of polycarboxylate ether / Silica is 0.01 to 100. Dispersion according to claim 1, characterized in that that the fumed silica mixed oxides with silica as first component and lithium oxide, sodium oxide, potassium oxide, magnesium oxide, Calcium oxide, alumina or zirconia as the second component includes. Dispersion according to claims 1 or 2, characterized that the aggregates in the dispersion have a mean diameter from 50 to 500 nm. Dispersion according to Claims 1 to 3, characterized that the relative standard deviation of the number distribution of the aggregate diameter of the silica is less than 30%. Dispersion according to Claims 1 to 4, characterized the proportion of silicon dioxide in the dispersion is in total 10-30% by weight, based on the total amount of the dispersion. Dispersion according to Claims 1 to 5, characterized that the weight ratio Polycarboxylatether / silica is 0.05-5. Dispersion according to Claims 1 to 6, characterized the pH of the dispersion is 8 to 12. 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 monovalent 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 groups 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 structural 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 = 0, NR ² 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 Me metal atom, an ammonium group or an organic amine group, and 0 to 50% by weight of another monomer (c) copolymerizable with these monomers, provided that the total amount of (a), (b) and (c) 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 silica in which the aggregates have an average diameter less than 1 μm a polycarboxylate ether in the form of a powder or as watery solution of a polycarboxylate ether, and optionally with water dilute or b) a silica powder in an aqueous solution of a polycarboxylate ether dispersed by means of a suitable dispersing unit and subsequently optionally further diluted with water or c) the silica powder in a watery Phase, preferably dispersed in water, and then the resulting dispersion to an aqueous solution of the polycarboxylate gives. 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 the concrete mixture contains 0.01 to <2% by weight of silica, based on cement, contains.