DE102006048036A1 - New asymmetrical or asymmetrical borate salts are useful as additives, stabilizers, flame protectors and/or conductivity enhancers in polymers and as electrolytes - Google Patents

Abstract

Symmetrical or asymmetrical borate salts (I), are new. Symmetrical or asymmetrical borate salts of formula (I), are new. Either Z, Za, Zb, Zc : a heteroatom, preferably O or S, or a nitrogen group NR 3>; or Z-Za : Z-X 1>-X 2>-Za; or Zb-Zc : Zb-X 3>-X 4>-Zc; X 1>-X 4>-C(=O)-, -C(R 1>R 2>)-, -C(R 1>R 2>)-C(=O)- or -C(R 1>R 2>)-C(R 1>R 2>)-, which are present in 1,2-aryl substituent of formula (a)-(f) with 0-2 substituents of G 1>, G 2>in the position 3-6, where: X 2>and/or X 4>are present at the first position, or X 1>and X 3>are present at the second position with 0-2 substituent G 1>, G 2>in the position 3-6; G 1>, G 2>H, SR 3>, OR 3>, NR 3>R 4>, or optionally functionalized alkyl-, alkenyl-, alkynyl-, 1-20C cycloalkyl, 1-12C aryl-, silyl-, halogenide- or polymer residue; R 1>, R 2>H, SR 3>, OR 3>, NR 3>R 4>, or optionally functionalized alkyl-, 1-20C cycloalkyl-, 1-12C aryl with 2 substituent G 1>or G 2>, silyl or polymer residue, where one of the alkyl residue is connected with a chelatoborate residue; R 3>-R 6>H or optionally functionalized alkyl-, alkenyl-, alkynyl-, 1-20C cycloalkyl, 1-12C aryl, silyl or polymer residue; My +>a main group metal, alkali metal, alkaline earth metal, rare earth metal, transition metal cation, ammonium ion of formula ((R 3>R 4>R 5>R 6>)N) +>or H +>, preferably lithium, sodium, potassium, cesium, calcium, zinc, neodymium, lanthanum or aluminum cation, tetraalkylammonium cation, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, tetra(n-butyl)ammonium, dialkylanilinium, N,N-dimethylphenylammonium, methylbis(octadecyl)ammonium, dimethyloctadecylammonium, methylbis(tetradecyl)ammonium, N,N-bis(octadecyl)phenylammonium or N,N-bis(octadecyl)(3,5-dimethylphenyl)ammonium cation; and y : an amount of positive charge at the cation My +>(preferably 1-6). Provided that when X 1>-X 3>are -C(=O)-, and Z, Za, Zb, Zc are O, then X 4>is not equal to -C(=O)-. Independent claims are included for: (1) the preparation of (I); and (2) a polymer containing (I) as an additive. [Image] [Image].

Description

object The present invention relates to borate salts, a process for the same Production and use thereof.

Especially The present invention relates to borate salts as additives, Stabilizers, flame retardants, conductivity improvers in polymers as well as electrolytes.

EP-A-0 698 301 discloses lithium complex salts of the type ABL ₂ (wherein A here represents lithium or a quaternary ammonium ion, B boron and L a bidentate ligand bonded to the boron atom via two oxygen atoms) for use in galvanic cells. Such chelate compounds are not commercially available and can only be produced at high costs. Therefore, the proposed products could not prevail on the market.

Very similar Boron compounds are described in EP-A-0 907 217 as constituents in organic Electrolyte cells disclosed. The boron-containing principle is compounds the general formula LiBXX 'used, wherein the ligands X and X 'are the same or may be different and each ligand an electron-withdrawing, oxygen-containing Group which binds to the boron atom contains. The disclosed compounds (Lithium bis (salicylato) borate and a special imide salt) However, also the above-mentioned disadvantages.

The Synthesis and use of various complexes of boron as a basis for the Preparation of conductive salts and various additives in the field of Battery development is disclosed in various patents: DE-C-198 29,030 discloses lithium bis (oxalato) borate (LiBOB), the first for use boron-centered complex salt described as electrolyte, which serves as chelate component a Dicanbonsäune (in this case oxalic acid) used. DE-C-101 08 592 discloses unsymmetrical boron chelate complexes which are well suited as additives in conductive salts.

The in DE-C-198 29 030 and DE-C-101 08 592 disclosed technical teaching is complete Part of the present description.

WO-A-2004/072166 discloses the use of various salts of superacids for Stabilization of halogen-containing polymers, in particular PVC. Among other things, here is the lithium bis (oxalato) borate (LiBOB) as potentially stabilizing component disclosed. As far as below of halogen-containing polymers, for example polyvinyl chloride (PVC), their production, use and processing is mentioned corresponds this is the polymer which is known to the person skilled in the art (M. W. Allsopp, G. Vianello, Ullmann's Encyclopedia of Industrial Chemistry: poly (vinyl chlorides), Wiley-VCH Publisher GmbH & Co. KGaA 2000).

From the described borate salts such as lithium bis (oxalato) borate (LiBOB) is known to be extremely fast hydrolyze on contact with water and thus in aqueous solution the desired one Loss of effect quickly (product brochure LiBOB, Chemetall GmbH Frankfurt / Main 2005).

In The literature is the hygroscopy and susceptibility to hydrolysis the common one Borkomplexes of dicarboxylic acids like oxalic acid and malonic acid in detail Besseler, J. Weidlein, Z. Naturforsch., 1982, 37b, 1020-1025). Among other things, it is described that bis (oxalato) borates hydrolyze very quickly when exposed to moisture.

Especially disadvantageous is this susceptibility the common one Borate salts opposite Water in their processing in the battery industry and manufacturing of battery electrolytes. Hydrolysis produces by-products, which, among other things, the conductivity and storage stability influence and so the desired Impair properties.

Also against the background of the high water content of halogenated polymers, for example, PVC, and the additives added here for processing, a special hydrolysis stability is desired.

Numerous additives for stabilizing halogen-containing polymers against thermal and photochemical degradation are known (R. Wolf, B. Lal Kaul, Ullmann's Encyclopedia of Industrial Chemistry: Plastic Additives, Wiley-VCH Verlag GmbH & Co. KGaA 2000). For example, PVC can be stabilized by a number of additives. Compounds of the heavy metals lead, barium and cadmium are particularly well suited for this, but today are controversial for ecological reasons or because of their heavy metal content ("Kunststoffadditive", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd edition, 1989, p 303-311; "Kunststoff Handbuch PVC", Volume 2/1, W. Becker / D. Braun, Carl Hanser Verlag, 2nd Ed., 1985, pp. 531-538, Kirk-Othmer: "Encyclopedia of Chemical Technology "4 ^th Ed., 1994, Vol. 12, Heat Stabilizers, pp. 1071-1091). EP-A-0 677 550 and WO-A-2003/048232 disclose the use of salts of perchloric acid as a further method of stabilizing halogen-containing polymers. However, these substances are characterized by their persistence in the environment and act there as persistent biocides. Furthermore, it is known that salts of perchloric acid in combination with organic substances can decompose explosively when heated. Also known is the use of mixtures of calcium and zinc stearates for the stabilization of halogen-containing polymers. A disadvantage of this method is that zinc salts formed during stabilization can even accelerate the degradation process during processing ("zinc burning") (R. Wolf, B. Lal Kaul, Ullmann's Encyclopedia of Industrial Chemistry: Plastic Additives, Wiley-VCH Verlag GmbH & Co. KGaA 2000).

Likewise prevents the water content or water addition during processing of polymers such as polyurethanes, the use of known borate salts. As far as subsequently of polyurethanes, their production, processing and use is mentioned, this corresponds to the polymer that known to the person skilled in the art (N. Adam, G. Avar, H. Blankenheim, W. Friederichs, M. Giersig, E. Weigand, Michael Halfmann, F.-W. Wittbecker, D.-R. Larimer, U. Maier, S. Meyer-Ahrens, K.-L. Noble, H.-G. Wussow, Ullmann's Encyclopedia of Industrial Chemistry: Polyurethanes, Wiley-VCH Verlag GmbH & Co. KGaA 2005).

The Hygroscopy and the susceptibility to hydrolysis the common one Borkomplexes of dicarboxylic acids like oxalic acid and malonic acid has hitherto also prevented their use as flame retardants and conductivity improvers in polymers, in particular halogen-containing polymers such as PVC or in polyurethanes, although boron complexes are the conventional additives in many Superior properties are.

The usual in polymers as flame retardants and conductivity improvers for prevention namely, additives used in electrostatic charging have a Series of disadvantages. The properties of flame retardants are familiar to the expert (R. Wolf, B. Lal Kaul, Ullmann's Encyclopedia of Industrial Chemistry: Plastic Additives, Wiley-VCH Publisher GmbH & Co. KGaA 2000).

When Flame retardants are, for example, inorganic substances such as aluminum hydroxide, Magnesium hydroxide but also antimony trioxide and antimony pentoxide or Barium borates common. Of the barium and antimony compounds it is known that these are toxic. Likewise used as a flame retardant red phosphorus, this too is toxic.

Further are used as flame retardants halogenated hydrocarbons, notably chlorine- and bromine-substituted aromatics and aliphatics used. These compounds are for a very expensive, they also complicate the thermal disposal of plastics, as the combustion at high temperatures must become. Also need The exhaust gases are specially treated for the escape of environmental toxins prevent. It is known that when burning halogenated Hydrocarbons poisons such as 2,3,7,8-tetrachlorodioxin can arise.

One Another disadvantage of plastics is that they are easy electrostatically charge and thereby electrostatic discharges can cause. Electrostatic discharges can damage or destroy sensitive electronic components, magnetic Change disk or Clear or cause explosions and fire in a flammable environment. each Year alone in the electrical industry estimated 40 Billion euros damage only by electrostatic discharges. To reduce the electrostatic charge of plastics or even avoid it, the conductivity of plastics is increased, thus no high charges occur and charges are dissipated, before they become dangerous Build up sizes. This usually happens by different amounts and types of additives such as powdered carbon black, carbon fibers, Metal fibers, metal coated carbon fibers and metal powders. However, these additives have the disadvantage that they are the mechanical Properties of plastics partly deteriorate significantly.

In summary The flame retardants are toxic and environmentally harmful, while the conductivity often degrade the mechanical properties of the polymers. This is not boron complexes or not in the conventional one Dimensions too expect.

task The object of the present invention is to overcome the disadvantages of the prior art Technology to overcome.

Especially The object of the present invention is to provide substances on the basis to provide boron as additives, stabilizers, flame retardants, conductivity are suitable in polymers and / or as an electrolyte.

Further The additives are based on substances from renewable raw materials such as tartaric acid, other natural acids or amino acids be.

According to the invention Task surprisingly solved by the features of the main claim. Preferably embodiments can be found in the subclaims.

wobei gilt:
Z, Z', Z'', Z''' = unabhängig voneinander ein Heteroatom, beispielsweise Sauerstoff O oder Schwefel S, oder eine Stickstoffgruppe NR³
und:

(in der linearisierten Schreibweise: Z-Z' = ZX¹-X²Z' und Z''-Z''' = Z''X³-X⁴Z''')
und:
X¹, X², X³, X⁴ = unabhängig voneinander -C(=O)- oder -C(R¹R²)- oder -C(R¹R²)-C(=O)- oder -C(R¹R²)-C(R¹R²)-, wobei gilt: wenn X¹ = X² = X³ = -C(=O)- und gleichzeitig Z, Z', Z'', Z''' = O, dann X⁴ ≠ -C(=O)-,
und/oder:
X¹, X², X³, X⁴ = unabhängig voneinander -C(=O)- oder -C(R¹R²)- oder -C(R¹R²)-C(=O)- oder -C(R¹R²)-C(R¹R²)- als Substituent an einem 1,2-Aryl, mit bis zu 2 weiteren Substituenten G¹, G² in den Positionen 3 bis 6 oder X² bzw. X⁴ entsprechen den Kohlenstoffatomen an der 1 Position und mit X¹ und X³ unabhängig voneinander -C(=O)- oder -C(R¹R²)- oder -C(R¹R²)-C(=O)- oder -C(R¹R²)-C(R¹R²)- an der 2 Position eines 1,2-Aryl, mit bis zu 2 Substituenten G¹, G² in den Positionen 3 bis 6 oder X¹, X² bzw. X³, X⁴ entsprechen den Kohlenstoffatomen an der 1 bzw. 2 Position eines 1,2-Aryl, mit bis zu 2 Substituenten G¹, G² in den Positionen 3 bis 6,

wobei G¹, G² = unabhängig voneinander H oder SR³ oder OR³ oder NR³R⁴, oder eine funktionalisierte oder eine unfunktionalisierte verzweigte oder eine unverzweigte Alkyl-, Akenyl-, Alkinyl-, Cycloalkylgruppe mit 1 bis 20 C-Atomen oder eine Arylgruppen mit 1 bis 12 C-Atomen oder Silyl oder Halogenid oder ein Polymerrest ist,
und:
R¹, R² = unabhängig voneinander H, SR³ oder OR³ oder NR³R⁴, oder eine funktionalisierte oder eine unfunktionalisierte verzweigte oder unverzweigte Alkyl-, Cycloalkylgruppe mit 1 bis 20 C-Atomen oder eine Arylgruppe mit 1 bis 12 C-Atomen mit bis zu 2 Substituenten G¹, G², oder Silyl oder ein Polymerrest ist und/oder einer der Alkylreste R¹ oder R² mit einem weiteren Chelatoboratrest verbunden sein kann,
und:
R³, R⁴, R⁵, R⁶ = unabhängig voneinander H oder eine funktionalisierte oder eine unfunktionalisierte verzweigte oder unverzweigte Alkyl-, Akenyl-, Alkinyl-, Cycloalkylgruppe mit 1 bis 20 C-Atomen oder eine Arylgruppen mit 1 bis 12 C-Atomen oder Silyl, oder ein Polymerrest ist,
und:
y = die Anzahl der positiven Ladungen am Kation M^y+ angibt, mit y = 1, 2, 3, 4, 5 oder 6,
und:
M^y+ = ein Hauptgruppenmetall-, Alkalimetall-, Erdalkalimetall-, Seltenerdmetall- oder Übergangsmetallkation oder [(R³R⁴R⁵R⁶)N]⁺ oder H⁺.In particular, the object is achieved by symmetrical or unsymmetrical borate salts of general formula I shown below: embedded image

where:
Z, Z ', Z'',Z''' = independently of one another a heteroatom, for example oxygen O or sulfur S, or a nitrogen group NR ³
and:

(in linearized notation: ZZ '= ZX ¹ -X ² Z' and Z '' - Z '''=Z''X ³ -X ⁴ Z''')
and:
X ¹ , X ² , X ³ , X ⁴ = independently -C (= O) - or -C (R ¹ R ² ) - or -C (R ¹ R ² ) -C (= O) - or -C (R ¹ R ² ) -C (R ¹ R ² ) -, where: if X ¹ = X ² = X ³ = -C (= O) - and at the same time Z, Z ', Z ", Z"'= O, then X ⁴ ≠ -C (= O) -,
and or:
X ¹ , X ² , X ³ , X ⁴ = independently -C (= O) - or -C (R ¹ R ² ) - or -C (R ¹ R ² ) -C (= O) - or -C (R ¹ R ² ) -C (R ¹ R ² ) - as a substituent on a 1,2-aryl, with up to 2 further substituents G ¹ , G ² in the positions 3 to 6 or X ² or X ⁴ correspond the carbon atoms at the 1 position and with X ¹ and X ³ independently of one another -C (= O) - or -C (R ¹ R ² ) - or -C (R ¹ R ² ) -C (= O) - or - C (R ¹ R ² ) -C (R ¹ R ² ) - at the 2 position of a 1,2-aryl, with up to 2 substituents G ¹ , G ² in the positions 3 to 6 or X ¹ , X ² or X ³ , X ⁴ correspond to the carbon atoms at the 1 or 2 position of a 1,2-aryl, with up to 2 substituents G ¹ , G ² in the positions 3 to 6,

where G ¹ , G ² = independently of one another H or SR ³ or OR ³ or NR ³ R ⁴ , or a functionalized or an unfunctionalized branched or unbranched alkyl, alkenyl, alkynyl, cycloalkyl group having 1 to 20 C atoms or is an aryl group having 1 to 12 C atoms or silyl or halide or a polymer radical,
and:
R ¹ , R ² = independently of one another H, SR ³ or OR ³ or NR ³ R ⁴ , or a functionalized or an unfunctionalized branched or unbranched alkyl, cycloalkyl group having 1 to 20 C atoms or an aryl group having 1 to 12 C atoms Atoms with up to 2 substituents G ¹ , G ² , or silyl or a polymer radical and / or one of the alkyl radicals R ¹ or R ^{2 may be} connected to a further chelatoborate radical,
and:
R ³ , R ⁴ , R ⁵ , R ⁶ = independently of one another H or a functionalized or an unfunctionalized branched or unbranched alkyl, alkenyl, alkynyl, cycloalkyl group having 1 to 20 C atoms or an aryl group having 1 to 12 C atoms Atoms or silyl, or is a polymer radical,
and:
y = the number of positive charges at the cation M ^{y +} indicates, with y = 1, 2, 3, 4, 5 or 6,
and:
M ^{y +} = a main group metal, alkali metal, alkaline earth metal, rare earth metal or transition metal cation or [(R ³ R ⁴ R ⁵ R ⁶ ) N] ⁺ or H ⁺ .

According to the invention, M ^{y +} is preferably a lithium, sodium, potassium, cesium, calcium, zinc, neodymium, lanthanum or aluminum cation, or a triple hydrocarbon-substituted ammonium cation, a tetrabutyl-substituted ammonium cation or a dialkylanilinium cation.

Ammonium cations preferred according to the invention are trimethylammonium, triethylammonium, tripropylammonium, triisopropylammonium, tri (n-butyl) ammonium, N, N-dimethylphenylammonium, N, N-dimethylbenzylammonium, N, N-diethylphenylammonium, N, N-diethylbenzylammonium, N, N-dimethyl ( 2,4,6-trime ethylphenyl) ammonium, N, N-dimethyl (2,4,6-triethylphenyl) ammonium, N, N-dimethyl (2,4,6-trimethylbenzyl) ammonium, N, N-dimethyl (2,4,6-triethylbenzyl) ammonium, N, N-di (tetradecyl) phenylammonium, N, N-di (tetradecyl) (2,4,6-trimethylphenyl) ammonium, N, N-di (octadecyl) phenylammonium, N, N-di (octadecyl) ( 2,4,6-trimethylphenyl) ammonium, methyldicyclohexylammonium, N, N-dimethylphenylammonium, triphenylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, tetra (n-butyl) ammonium.

Particularly preferred according to the invention are tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, tetra (n-butyl) ammonium, N, N-dimethylphenylammonium, methylbis (octadecyl) ammonium, dimethyloctadecylammonium, methylbis (tetradecyl) ammonium, N, N-bis (octadecyl) phenylammonium and N, N-bis (octadecyl) (3,5-dimethylphenyl) ammonium. Furthermore, mixtures of different substituted ammonium cation are preferred. Examples of these are the ammonium cations of commercially available amines which contain mixtures of two C ₁₄ , C ₁₆ or C ₁₈ alkyl groups and one methyl group. Such amines are available from Chemtura under the trade name Kemamine ^™ T9701 and from Akzo-Nobel under the trade name Armeen ^™ M2HT.

Examples of R ¹ and R ² are: H, F, Cl, Br, I, OH, methyl, chloromethyl, bromoethyl, hydroxymethyl, methoxymethyl, ethoxymethyl, mercaptomethyl, (methylmercapto) methyl, (ethylmercapto) methyl, aminomethyl, carboxymethyl, carboxyhydroxymethyl , (Methylcarboxy) methyl, hydroxy (methylcarboxy) methyl, (ethylcarboxy) methyl, hydroxy (ethylcarboxy) methyl, ethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 2-bromoethyl, 2 -Methoxyethyl, 2-ethoxyethyl, 2-mercaptoethyl, 2- (methylmercapto) ethyl, 2- (ethylmercapto) ethyl, 2-aminoethyl, carboxyethyl, carboxy-2-hydroxyethyl, carboxy-1-hydroxyethyl, (methylcarboxy) ethyl, (ethylcarboxy ) ethyl, (methylcarboxy) -2-hydroxyethyl, (methylcarboxy) -1-hydroxyethyl, (ethylcarboxy) -2-hydroxyethyl, (ethylcarboxy) -1-hydroxyethyl, ethenyl, ethynyl, n -propyl, iso -propyl, propene-3 -yl, propyn-3-yl, 1-hydroxypropyl, 2-hydroxypropyl, 1-mercaptopropyl, 2-mercaptopropyl, 2-aminopropyl, 3-hydroxypropyl, 3-mercaptopropyl, 3-aminopropyl, 1-chlorobutyl, 2 Chlorobutyl, 3-chlorobutyl, 4-chlorobutyl, 1-bromobutyl, 2-bromobutyl, 3-bromobutyl, 4-bromobutyl, n-butyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 1-bromopropyl, 2-bromopropyl , 3-bromopropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 1-mercaptobutyl, 2-mercaptobutyl, 3-mercaptobutyl, 4-mercaptobutyl, 1-aminobutyl, 2-aminobutyl, 3-aminobutyl, 4 -Aminobutyl, carboxybutyl, (methylcarboxy) butyl), (ethylcarboxy) butyl, 1-buten-4-yl, 1-butyn-4-yl, 2-buten-4-yl, 2-butyn-4-yl, 2 Butyl, iso-butyl, tert-butyl, 2-hydroxybutyl, 2-mercaptobutyl, 2-aminobutyl, 3-hydroxybutyl, 3-mercaptobutyl, 3-aminobutyl, 4-hydroxybutyl, 4-mercaptobutyl, 4-aminobutyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, n-heptyl, iso-heptyl, n -octyl, isooctyl, 2-ethyl-1-hexyl, 2,2,4-trimethylpentyl, nonyl, decyl, Dodecyl, n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, vinyl, 1-propenyl, 2-propenyl, naphthyl, anthranyl, phenanthryl, o-tolyl, p-tolyl, m-tolyl, xylyl, ethylphenyl , Mesityl, phenyl, pentafluorophenyl, benzyl, mesistyl, neophyl, thexyl, trimethylsilyl, triisopropylsilyl, tri (tert-butyl) silyl), dimethylthexylsilyl, trimethylsilylethynyl, dimethyltertbutylsilylethynyl, dimethylthexylsilylethynyl, triisopropylsilylethynyl, tri-tert-butylsilylethynyl where: amino is NR ³ R ⁴ .

Examples of R ³ , R ⁴ , R ⁵ , and R ⁶ are: H, methyl, hydroxymethyl, mercaptomethyl, aminomethyl, (formamide) yl, (dimethylformamide) yl, (formamidine) yl, (N, N-dimethylformamidine) yl, Ethyl, 2-hydroxyethyl, 2-mercaptoethyl, 2-aminoethyl, ethenyl, ethynyl, n-propyl, isopropyl, cyclopropyl, propen-3-yl, propyn-3-yl, 2-hydroxypropyl, 2-mercaptopropyl, 2-aminopropyl, 3-hydroxypropyl, 3-mercaptopropyl, 3-aminopropyl, n-butyl, 1-buten-4-yl, 1-butyne-4-yl, 2-buten-4-yl, 2-butyne-4 yl, 2-butyl, iso-butyl, tert-butyl, 2-hydroxybutyl, 2-mercaptobutyl, 2-aminobutyl, 3-hydroxybutyl, 3-mercaptobutyl, 3-aminobutyl, 4-hydroxybutyl, 4-mercaptobutyl, 4-aminobutyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, n-heptyl, iso-heptyl, n -octyl, isooctyl, 2-ethyl-1-hexyl, 2,2,4-trimethylpentyl, Nonyl, decyl, dodecyl, n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, vinyl, 1-propenyl, 2-propenyl, naphthyl, anthranyl, phenanthryl, o-tolyl, p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, Phenyl, benzyl, derivatives of substituted and unsubstituted aromatics such as benzene, fluorene, indene, indane, trimethylsilyl, triisopropylsilyl, tri (tert-butyl) silyl), dimethylthexylsilyl, trimethylsilylethynyl, dimethyltertbutylsilylethynyl, dimethylthexylsilylethynyl, triisopropylsilylethynyl, tri-tert-butylsilylethynyl, where: amino is NR ³ R ⁴ ,

Examples of G ¹ and G ² are: H, OH, SH, NH ₂ , N (methyl) ₂ , O-methyl, S-methyl, methyl, hydroxymethyl, mercaptomethyl, aminomethyl, ethyl, 2-hydroxyethyl, 2-mercaptoethyl, 2-aminoethyl, ethenyl, ethynyl, n -propyl, iso -propyl, propen-3-yl, propyn-3-yl, 2-hydroxypropyl, 2-mercaptopropyl, 2-aminopropyl, 3-hydroxypropyl, 3-mercaptopropyl, 3 Aminopropyl, n-butyl, 1-buten-4-yl, 1-butyne-4-yl, 2-buten-4-yl, 2-butyne-4-yl, 2-butyl, iso-butyl, tert-butyl, 2-hydroxybutyl, 2-mercaptobutyl, 2-aminobutyl, 3-hydroxybutyl, 3-mercaptobutyl, 3-aminobutyl, 4-hydroxybutyl, 4-mercaptobutyl, 4-aminobutyl, n-pentyl, isopentyl, neo-pentyl, tert-butyl Pentyl, hexyl, n-heptyl, iso-heptyl, n-octyl, isooctyl, 2-ethyl-1-hexyl, 2,2,4-trimethylpentyl, nonyl, decyl, dodecyl, n-dode cyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, vinyl, 1-propenyl, 2-propenyl, naphthyl, anthranyl, phenanthryl, o-tolyl, p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl, 4-hydroxyphenyl, Styryl, pentafluorophenyl, benzyl, trimethylsilyl, triisopropylsilyl, tri (tert-butyl) silyl), dimethylthexylsilyl, trimethylsilylethynyl, dimethyltertbutylsilylethynyl, dimethylthexylsilylethynyl, triisopropylsilylethynyl, tri-tert-butylsilylethynyl, fluorine, chlorine, bromine, iodine, where: amino is NR ³ R ⁴ .

Examples of ZZ 'or Z "-Z'" are:

The following compounds are preferred according to the invention: hydrogen (malonato, oxalato) borate (HMOB), hydrogen bis (malonato) borate (HBMB), hydrogen (glycolato, oxalato) borate (HGOB), hydrogen bis (glycola to) borate (HBGB), hydrogen (lactato, oxalato) borate (HLOB), hydrogen bis (lactato) borate (HBLB), hydrogen (oxalato, salicylato) borate (HOSB), hydrogen bis (salicylato) borate (HBSB) , Hydrogen (oxalato, tartrato) borate (HOTB), hydrogen (polytartrato) borate (HPTB), hydrogen (oxalato, catecholato) borate] (HOCB), hydrogen bis (catecholato) borate (HBCB) and the ammonium, alkali metal, alkaline earth metal , Rare earth metal and Hauptguppenmetall- and transition group metal salts of said acids. Particular preference is given to the lithium, sodium, potassium, cesium, calcium, zinc, neodymium, lanthanum, aluminum, tetraalkylammonium salts, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, tetra (n-butyl ) ammonium, and dialkylanilinium salts N, N-dimethylphenylammonium, methylbis (octadecyl) ammonium, dimethyloctadecylammonium, methylbis (tetradecyl) ammonium, N, N-bis (octadecyl) phenylammonium and N, N-bis (octadecyl) ( 3,5-dimethylphenyl) ammonium salts of said acids. Furthermore, mixtures of variously substituted ammonium cations are preferred as cations. Examples of these are the ammonium cations of commercially available amines which contain mixtures of two C ₁₄ , C ₁₆ or C ₁₈ alkyl groups and one methyl group. Such amines are available, for example, from Chemtura under the trade name Kemamine ^™ T9701 and from Akzo-Nobel under the trade name Armeen ^™ M2HT.

Particularly according to the invention preferred are borate salts, both derivatives of boric acid as also of tartaric acid are.

The borate salts according to the invention are by reacting boric acid and / or one or more boric acid esters with 0.5 to 3 equivalents, preferably 1 to 2.5 equivalents of the protonated compounds HZ-Z'H or HZ '' - Z '''H and a carbonate [(M ^{y +} ) ₂ (CO ₃ ) _y ] of the chosen cation M ^{y +} or a hydroxide [(M ^{y +} ) (OH) _y ] of the chosen cation M ^{y +} or an oxide ((M ^{y +} ) ₂ (O) _y ] of the chosen cation M ^{y +} or an alkoxide [(M ^{y +} ) (OR ³ ) _y ] of the chosen cation M ^{y +} or an alkyl [(M ^{y +} ) (R ³ ) _y ] of the chosen cation M ^{y +} and / or a compound NR ³ R ⁴ R ⁵ and / or a compound [(NR ³ R ⁴ R ⁵ R ⁶ ) ⁺ Q ^- ] or a mixture of at least two of the carbonates and / or hydroxides and / or oxides and / or alcoholates and / or alkyls of selected cation M ^{y +} and / or a compound NR ³ R ⁴ R ⁵ or a compound [(NR ³ R ⁴ R ⁵ R ⁶ ) ⁺ Q ^- ] in a suitable solvent, wherein Q ^{- is} a suitable anion, for example e in halide, sulfate, hydrogen sulfate, especially chloride. The ratio of the equivalent of boric acid or boric acid ester to the equivalent of the chosen cation M ^{y +} is (y ± 1) to 1, preferably (y ± 0.1) to 1. Water can be added to the reaction mixture. The resulting reaction water or the reaction alcohol is removed, later the solvent is completely removed. Suitable solvents are, for example, benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene, cumene, other derivatized benzenes, hexane, heptane, cyclohexane, methylcyclohexane, hydrocarbon mixtures such as halpasol, Shellsol example Shellsol D80 or D100, chloroform, carbon tetrachloride , But also ethyl acetate, acetone, ethylene carbonate, acetonitrile, wherein the latter, the water or alcohol is removed by distillation.

The borate salts according to the invention are characterized by a high hydrolytic stability and low hygroscopy, this means their stability across from Water is very high and they hydrolyze very slowly. This especially in comparison with the salts of bis (oxalato) borate (BOB), again in particular in comparison with lithium bis (oxalato) borate (LiBOB).

The borate salts according to the invention are only slightly toxic and burn to ecologically harmless substances. In a preferred embodiment according to the invention Do not contain heavy metals, especially lead and no Cadmium.

The borate salts according to the invention are suitable as additives in polymers and / or mixtures of polymers, in particular as stabilizers, again in particular against the thermal and / or photochemical degradation, flame retardant, the is called as a flame-retardant additive and / or conductivity improvers, in particular to prevent or reduce electrostatic charges. They are degraded to flame-retardant compounds, without the disadvantages the conventional one Own flame retardant. They also increase the conductivity of polymers without deteriorating their mechanical properties.

Examples of polymers are polylactate, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthenate (PEN), polyamides, for example nylon, Nomex, Keflar, halogen-containing polymers, for example PVC, polytetrafluoroethene (PTFE, ^Teflon® ), polyolefins, for example polyethylene (PE), polypropylene (PP), as well as polystyrenes, polyacrylates and polyurethanes.

In addition, the borate salts of the invention are additives in thermoplastic elastomers such as butadiene rubber (BR), polyisoprene, butadiene-styrene polymers (SBR, SBS rubbers) or nature rubbers, natural latex and synthetic latex and mixtures of at least two of these elastomers.

The borate salts according to the invention offer in particular as a component of halogen-containing polymers both an excellent initial color and color stability.

The Polymers can be prepared from uniform monomers or mixtures consist of different monomers. It may also contain recyclate and / or be made of polymer recyclates.

By suitable choice of the substituents X ¹ , X ² , X ³ , X ⁴ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , G ¹ and G ² , an adaptation of the compatibility of the borate salts of the invention the polymer can be achieved. It can be adjusted according to the requirements, whether for reasons of occupational hygiene, licensing restrictions or processing safety, a very low migration and Plate Out free behavior.

The suitable choice of the substituents X ¹ , X ² , X ³ , X ⁴ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , G ¹ and G ^{2 also} offers the possibility of the borate salts according to the invention directly in to embed the polymers.

The borate salts according to the invention can be added directly during the preparation, the polymerization of the polymers, as a co-monomer and thus directly by suitable choice of the substituents X ¹ , X ² , X ³ , X ⁴ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , G ¹ and G ^{2 are incorporated} into the polymer matrix. However, the borate salts according to the invention can also be added to the polymer matrix at any time before and / or during and / or after the preparation and / or during the compounding of the polymers.

Also can the borate salts according to the invention the polymers later added become.

The Embedding of borate salts according to the invention in the polymer matrix can be based on physical forces.

The embedding of the hydrolysis-borate salts of the invention in the polymer matrix can be by chemical bonding of suitable substituents X ^1, X ^2, X ^3, X ^4, R ^1, R ^2, R ^3, R ^4, R ^5, R ^6, G ¹ and G ² with constituents of monomers for polymer production and / or oligomers and / or a polymer.

The borate salts according to the invention are the polymers, preferably halogen-containing polymers, especially preferably PVC or PTFE, or polyurethanes, in proportions of 0.0001 to 10% (w / w) by weight. Preferred is a Addition of 0.01 to 3 wt .-%.

Around the entry in the monomer and / or oligomer and / or polymer can simplify the borate salts according to the invention a suitable solvent or suspending agents are added.

The borate salts according to the invention can but also without prior addition of a suitable solvent or suspending agent or other liquid components in the polymers be introduced. Therefor become the Boratsalze invention preferably used as a powder in a fine form. In this case it is particularly preferred that the borate salts according to the invention by a produce appropriate synthesis process as a finely divided powder or the particle size after to reduce the synthesis by a suitable milling process.

Around to be better processed, the powder can be used in conjunction with a suitable auxiliary, for example, with waxes, paraffins and / or oils, pelleted or granulated or treated dust-free.

Furthermore can the borate salts according to the invention with other additives necessary for processing the polymers are mixed.

The borate salts according to the invention can with the usual in the processing of halogen-containing polymers mixed-metal stabilizers such as barium-cadmium, barium-zinc, and / or calcium-zinc compounds, preferably the carboxylates such as stearates, laureates, oleates, Alkyl benzoates, Napthenaten or phenolates, are applied.

Possibly can the polymer mixture for coloring further additives and / or organic and / or inorganic dyes and / or organic and / or inorganic Pigments, in usual Amounts of 0.0001 to 5 wt .-% are added.

The the borate salts according to the invention Polymers containing additives may be used in all of them Possible polymers Use, for example as bottles, films, Films, fibrous materials, shaped articles, Shoe soles, foams, vitreous materials, Car tires, rubbers, paints, powder coatings, pipelines, drinking water pipes, Sewage pipes, profiles, window profiles, food packaging, Computer keyboards, computer cases, Screen housing Electrical components, blister packaging and engineering plastics.

In a preferred embodiment can the borate salts according to the invention be used as a stabilizer in halogen-containing polymers, For example, for the production of bottles, films, films, Fibers, Moldings, Lacquers, pipelines, drinking water pipes, sewage pipes, profiles, Window profiles, food packaging, computer keyboards, Computer case, Screen housing Electrical components, blister packaging and engineering plastics can serve.

Also suitable for The above applications are mixtures of at least two borate salts according to the invention according to formula I.

object In addition, the present invention is the above Polymers containing as additive one borate salt or more borate salts according to formula I included.

The The following examples are intended to illustrate the invention without restricting it to the following:

Example 1: General Synthesis of hydrolysis-resistant borate salts

In a suitable solvent, 1 equivalent of boric acid or 1 equivalent of boric acid ester, for example trimethylborate or triisopropylborate with the 0.5 to 3 equivalents, preferably 1 to 2.5 equivalent of the protonated compounds HZ-Z'H or HZ '' - Z ''' H and 1 / y equivalents of a carbonate [(M ^{y +} ) ₂ (CO ₃ ) _y ] of the chosen cation M ^{y +} or 1 / y equivalents of a hydroxide [(M ^{y +} ) (OH) _y ] of the selected cation M ^{y +} or 1 / y equivalents of an oxide [(M ^{y +} ) ₂ (O) _y ] of the chosen cation M ^{y +} or 1 / y equivalent of an alkoxide [(M ^{y +} ) (OR ³ ) _y ] of the chosen cation M ^{y +} , wherein OR ^{3 is} preferably an alcoholate such as -methoxide, -ethoxide, propoxide, isopropoxide, 2-ethylhexoxide, tert-butoxide, tertamoxide, amoxide, or 1 / y equivalent of an alkyl [(M ^{y +} ) (R ³ ) _y ] of the chosen cation M ^{y +} or 1 equivalent of a compound NR ³ R ⁴ R ⁵ or 1 equivalent of a compound [(NR ³ R ⁴ R ⁵ R ^{6) +} Q ^-] with Q ^- or 1 / y equivalents of a mixture of at least at least two of the carbonates and / or hydroxides and / or oxides of the chosen cation M ^{y +} and / or a compound NR ³ R ⁴ R ⁵ and / or a compound NR ³ R ⁴ R ⁵ R ⁶⁺ are reacted, wherein Q ^{- is} a suitable anion is, for example, a halide, sulfate, hydrogen sulfate, especially chloride. Water can be added to the reaction mixture. The resulting reaction water or the reaction alcohol is initially removed by azeotropic distillation, the solvent is completely removed in vacuo. Suitable solvents are, for example, benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene, cumene, other derivatized benzenes, hexane, heptane, cyclohexane, methylcyclohexane, hydrocarbon mixtures such as Shellsol, Shellsol D80, Shellsol D100, Halpasol, chloroform, Carbon tetrachloride, but also ethyl acetate, acetone, ethylene carbonate, acetonitrile, wherein the latter, the water or alcohol is removed by distillation.

Example 2: Preparation of calcium bis (dimalonatoborate) Ca (BMB) ₂

Boric acid (43 g, 0.7 mol), calcium oxide (21 g, 0.35 mol) and malonic acid (155 g, 1.4 mol) are suspended in 375 g of toluene. After the addition of 10 ml of water is heated to boiling. The water is made azeotropic Distillation removed.

To After completion of the reaction, the toluene is removed on a high vacuum. The remaining one Solid is crushed by means of a ball mill.

Example 3: Determination the susceptibility to hydrolysis of borate salts

Approximately 5% solutions of LiBMB, LiMOB and LiBOB (Comparative System) are prepared in water and stirred for 2 hours at room temperature: The degree of hydrolysis of the compounds is shown in Table 1: TABLE 1

Example 4 Determination of the Hydrolysis Susceptibility of Borate Salts in D ₂ O

The susceptibility to hydrolysis of borate salts in D ₂ O is determined by integration of the signals of the ¹¹ B NMR measurements. All investigated borates - apart from LiBOB and the other salts of the BOB anion - show a medium to good stability in water. Table 2 shows the degree of hydrolysis of the various borate salts after four hours in D ₂ O.

Table 2:

Example 5: Determination the hygroscopicity of borate salts.

Various Metal borate will be 7 weeks of rel. Humidity of 30 % exposed. The borates according to the invention show less or no hygroscopicity compared to LiBOB and other salts of BOB anion. In Table 3 is the weight gain [%] of the borates are shown as a measure of hygroscopy.

Table 3:

Claims (25)

Symmetrical or unsymmetrical borate salts, characterized by the general formula I:

where Z, Z ', Z ", Z''' = independently of one another a heteroatom, preferably oxygen or sulfur, or a stick substance group NR ³ and:

and: X ¹ , X ² , X ³ , X ⁴ = independently -C (= O) - or -C (R ¹ R ² ) - or -C (R ¹ R ² ) -C (= O) - or -C (R ¹ R ² ) -C (R ¹ R ² ) -, where: when X ¹ = X ² = X ³ = -C (= O) - and simultaneously Z, Z ', Z ", Z '''= O, then X ⁴ ≠ -C (= O) -, and / or: X ¹ , X ² , X ³ , X ⁴ = independently of one another -C (= O) - or -C (R ¹ R ² ) - or -C (R ¹ R ² ) -C (= O) - or -C (R ¹ R ² ) -C (R ¹ R ² ) - as a substituent on a 1,2-aryl, with up to Two further substituents G ¹ , G ² in the positions 3 to 6 or X ² or X ⁴ correspond to the carbon atoms at the 1 position and with X ¹ and X ³ independently of one another -C (= O) - or -C (R ¹ R ² ) - or -C (R ¹ R ² ) -C (= O) - or -C (R ¹ R ² ) -C (R ¹ R ² ) - at the 2-position of a 1,2-aryl, with up to 2 substituents G ¹ , G ² in positions 3 to 6 or X ¹ , X ² and X ³ , X ⁴ correspond to the carbon atoms at the 1 or 2 position of a 1,2-aryl, with up to 2 substituents G ¹ , G ² in positions 3 to 6,

where G ¹ , G ² = independently of one another H or SR ³ or OR ³ or NR ³ R ⁴ , or a functionalized or an unfunctionalized branched or unbranched alkyl, alkenyl, alkynyl, cycloalkyl group having 1 to 20 C atoms or R ¹ , R ² = independently of one another H, SR ³ or OR ³ or NR ³ R ⁴ , or a functionalized or an unfunctional unalloyed branched or unbranched alkyl, cycloalkyl group having 1 to 20 C atoms or an aryl group having 1 to 12 C atoms with up to 2 substituents G ¹ , G ² , or silyl or a polymer radical and / or one of the alkyl radicals R ¹ or R ^{2 may be} joined to another chelatoborate residue, and: R ³ , R ⁴ , R ⁵ , R ⁶ = independently H or a functionalized or an unfunctionalized branched or unbranched alkyl, alkenyl, alkynyl, cycloalkyl group of 1 to 20 is C atoms or an aryl group having 1 to 12 C atoms or silyl, or a polymer radical, and: y = the number of positive charges on the cation M ^{y +} indicates, with y = 1, 2, 3, 4, 5 or 6, and: M ^{y +} = a main group metal, alkali metal, alkaline earth metal, rare earth metal or transition metal cation or [(R ³ R ⁴ R ⁵ R ⁶ ) N] ⁺ or H ⁺ , preferably a lithium, sodium, potassium, Cesium, calcium, zinc, neodymium, lanthanum or aluminum cation, a tetraalkylammonium cation, tetramethylamine onium, tetraethylammonium, tetrapropylammonium, tetraisopropylammonium, tetra (n-butyl) ammonium, and dialkylanilinium-N, N-dimethylphenylammonium, methylbis (octadecyl) ammonium, dimethyloctadecylammonium, methylbis (tetradecyl) ammonium, N, N-bis (octadecyl) phenylam monium or N, N-bis (octadecyl) (3,5-dimethylphenyl) ammonium cation. Borate salts according to claim 1, characterized in that R ¹ and R ^{2 are} independently selected from: H, F, Cl, Br, I, OH, methyl, chloromethyl, bromoethyl, hydroxymethyl, methoxymethyl, ethoxymethyl, mercaptomethyl, (methylmercapto) methyl , (Ethylmercapto) methyl, aminomethyl, carboxymethyl, carboxyhydroxymethyl, (methylcarboxy) methyl, hydroxy (methylcarboxy) methyl, (ethylcarboxy) methyl, hydroxy (ethylcarboxy) methyl, ethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-chloroethyl, 2- Chloroethyl, 1-bromoethyl, 2-bromoethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-mercaptoethyl, 2- (methylmercapto) ethyl, 2- (ethylmercapto) ethyl, 2-aminoethyl, carboxyethyl, carboxy-2-hydroxyethyl, carboxy 1-hydroxyethyl, (methylcarboxy) ethyl, (ethylcarboxy) ethyl, (methylcarboxy) -2-hydroxyethyl, (methylcarboxy) -1-hydroxyethyl, (ethylcarboxy) -2-hydroxyethyl, (ethylcarboxy) -1-hydroxyethyl ethenyl, ethynyl, n Propyl, iso-propyl, propen-3-yl, propyn-3-yl, 1-hydroxypropyl, 2-hydroxypropyl, 1-mercaptopropyl, 2-mercaptopropyl, 2 -Aminopropyl, 3-hydroxypropyl, 3-mercaptopropyl, 3-aminopropyl, 1-chlorobutyl, 2-chlorobutyl, 3-chlorobutyl, 4-chlorobutyl, 1-bromobutyl, 2-bromobutyl, 3-bromobutyl, 4-bromobutyl, n-butyl , 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 1-bromopropyl, 2-bromopropyl, 3-bromopropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 1-mercaptobutyl, 2-mercaptobutyl, 3 -Mercaptobutyl, 4-mercaptobutyl, 1-aminobutyl, 2-aminobutyl, 3-aminobutyl, 4-aminobutyl, carboxybutyl, (methylcarboxy) butyl), (ethylcarboxy) butyl, 1-buten-4-yl, 1-butyne-4 yl, 2-buten-4-yl, 2-butyne-4-yl, 2-butyl, iso-butyl, tert-butyl, 2-hydroxybutyl, 2-mercaptobutyl, 2-aminobutyl, 3-hydroxybutyl, 3-mercaptobutyl, 3-aminobutyl, 4-hydroxybutyl, 4-mercaptobutyl, 4-aminobutyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, 2-ethyl-1-hexyl, 2,2,4-trimethylpentyl, nonyl, decyl, dodecyl, n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, vinyl, 1-propenyl, 2-propenyl, N aphthyl, anthranyl, phenanthryl, o-tolyl, p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl, pentafluorophenyl, benzyl, mesistyl, neophyl, thexyl, trimethylsilyl, triisopropylsilyl, tri (tert-butyl) silyl), dimethylthexylsilyl, trimethylsilylethynyl , Dimethyltertbutylsilylethinyl, Dimethylthexylsilylethinyl, Triisopropylsilylethinyl, Tritertbutylsilylethinyl where amino NR ³ R ⁴ means. Borate salts according to claim 1 or 2, characterized in that R ³ , R ⁴ , R ⁵ and R ^{6 are} independently selected from: H, methyl, hydroxymethyl, mercaptomethyl, aminomethyl, (formamide) yl, (dimethylformamide) yl, (formamidine yl, (N, N-dimethylformamidine) yl, ethyl, 2-hydroxyethyl, 2-mercaptoethyl, 2-aminoethyl, ethenyl, ethynyl, n -propyl, iso -propyl, propen-3-yl, propyn-3-yl, 2-hydroxypropyl, 2-mercaptopropyl, 2-aminopropyl, 3-hydroxypropyl, 3-mercaptopropyl, 3-aminopropyl, n-butyl, 1-buten-4-yl, 1-butyn-4-yl, 2-butene-4 yl, 2-butyn-4-yl, 2-butyl, iso-butyl, tert-butyl, 2-hydroxybutyl, 2-mercaptobutyl, 2-aminobutyl, 3-hydroxybutyl, 3-mercaptobutyl, 3-aminobutyl, 4-hydroxybutyl, 4-mercaptobutyl, 4-aminobutyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, hexyl, n-heptyl, iso-heptyl, n-octyl, isooctyl, 2-ethyl-1-hexyl, 2,2,4-trimethylpentyl, nonyl, decyl, dodecyl, n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, vinyl, 1-propenyl, 2-propenyl, naphthyl, anthra nyl, phenanthryl, o -tolyl, p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl, benzyl, trimethylsilyl, triisopropylsilyl, tri (tert-butyl) silyl), dimethylthexylsilyl, trimethylsilylethynyl, dimethyltertbutylsilylethynyl, dimethylthexylsilylethynyl, triisopropylsilylethynyl, tri-tert-butylsilylethynyl, wherein Amino NR ³ R ⁴ means. Borate salts according to at least one of claims 1 to 3, characterized in that G ¹ and G ^{2 are} independently selected from: H, OH, SH, NH ₂ , N (methyl) ₂ , O-methyl, S-methyl, methyl, Hydroxymethyl, mercaptomethyl, aminomethyl, ethyl, 2-hydroxyethyl, 2-mercaptoethyl, 2-aminoethyl, ethenyl, ethynyl, n -propyl, iso -propyl, propen-3-yl, propyn-3-yl, 2-hydroxypropyl, 2- Mercaptopropyl, 2-aminopropyl, 3-hy hydroxypropyl, 3-mercaptopropyl, 3-aminopropyl, n-butyl, 1-buten-4-yl, 1-butyne-4-yl, 2-buten-4-yl, 2-butyne-4-yl, 2-butyl, isobutyl, tert-butyl, 2-hydroxybutyl, 2-mercaptobutyl, 2-aminobutyl, 3-hydroxybutyl, 3-mercaptobutyl, 3-aminobutyl, 4-hydroxybutyl, 4-mercaptobutyl, 4-aminobutyl, n-pentyl, isobutyl Pentyl, neo-pentyl, tert-pentyl, hexyl, n-heptyl, iso-heptyl, n-octyl, isooctyl, 2-ethyl-1-hexyl, 2,2,4-trimethylpentyl, nonyl, decyl, dodecyl, n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, vinyl, 1-propenyl, 2-propenyl, naphthyl, anthranyl, phenanthryl, o-tolyl, p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl, 4- Hydroxyphenyl, styryl, pentafluorophenyl, benzyl, trimethylsilyl, triisopropylsilyl, tri (tert-butyl) silyl), dimethylthexylsilyl, trimethylsilylethynyl, dimethyltertbutylsilylethynyl, dimethylthexylsilylethynyl, triisopropylsilylethynyl, tri-tert-butylsilylethynyl, fluoro, chloro, bromo, iodo wherein amino means NR ³ R ⁴ . Borate salts according to at least one of claims 1 to 4, characterized in that ZZ 'and Z''-Z''' are independently selected from:

Borate salts according to at least one of claims 1 to 5, characterized in that they are the following compounds is: hydrogen (malonato, oxalato) borate (HMOB), hydrogen bis (malonato) borate (HBMB), hydrogen (glykolato, oxalato) borate (HGOB), hydrogen bis (glycolato) borate (HBGB), hydrogen (lactato, oxalato) borate (HLOB), hydrogen bis (lactato) borate (HBLB), hydrogen (oxalato, salicylato) borate (HOSB), hydrogen bis (salicylato) borate (HBSB), hydrogen (oxalato, tartrato) borate (HOTB), hydrogen (polytartrato) borate (HPTB), Hydrogen (oxalato, catecholato) borate] (HOCB), hydrogen bis (catecholato) borate (HBCB) and their ammonium, alkali metal, alkaline earth metal, main group metal, Rare earth and transition metal salts. Borate salts according to at least one of claims 1 to 6, characterized in that it derivatives of both the boric acid and as well as tartaric acid are. Borate salts according to at least one of claims 1 to 7, characterized in that they are the following compounds Lithium poly (tartrato) borate, sodium poly (tartrato) borate, Potassium poly (tartrato) borate, aluminum poly (tartrato) borate, calcium poly (tartrato) borate. Borate salts according to at least one of claims 1 to 6, characterized in that they are the following compounds Lithium dimalonatoborate, calcium bis (dimalonatoborate), aluminum tris (dimalonatoborate), Kalziumbis (disalicylatoborat). Borate salts according to at least one of claims 1 to 9, characterized in that M ^{y + is} a lithium, sodium, potassium, cesium, calcium, zinc, neodymium, lanthanum, aluminum, tetraalkylammonium, tetramethylammonium, Tetraethylammonium, tetrapropylammonium, tetrabutylammonium, dimethylanilinium ion or a mixture of trialkylammonium ions of amines containing mixtures of two C ₁₄ , C ₁₆ or C ₁₈ alkyl groups and a methyl group. A process for preparing borate salts according to at least one of claims 1 to 10 by reacting boric acid and / or one or more boric acid esters with protonated compounds HZ-Z'H or HZ '' - Z '''H and a carbonate [(M ^{y +} ) ₂ (CO ₃ ) _y ] of the cation M ^{y +} or a hydroxide [(M ^{y +} ) (OH) _y ] of the cation M ^{y +} or an oxide [(M ^{y +} ) ₂ (O) _y ] of the cation M ^{y +} or an alkoxide [(M ^{y +} ) (OR ³ ) _y ] of the cation M ^{y +} or an alkyl [(M ^{y +} ) (R ³ ) _y ] of the cation M ^{y +} or a compound NR ³ R ⁴ R ⁵ or a compound [(NR ³ R ⁴ R ⁵ R ⁶ ) ⁺ Q ^- ] or a mixture of at least two of the carbonates and / or hydroxides and / or oxides and / or alkoxides and / or alkyls and / or a compound [(NR ³ R ⁴ R ⁵ R ⁶ ) ⁺ Q ^- ] and / or a compound NR ³ R ⁴ R ⁵ in a suitable solvent, wherein Q ^{- is} an anion, preferably a halide, more preferably chloride, sulfate or hydrogen sulfate. Method according to claim 11, characterized in that that the reaction mixture is added to water. A method according to claim 11 or 12, characterized in that the resulting reaction Was or the resulting reaction alcohol is removed, preferably by azeotropic distillation. Method according to claim at least one of claims 11 to 13, characterized in that after the reaction, the solvent completely in vacuum Will get removed. Method according to claim at least one of claims 11 to 14, characterized in that the solvent is selected from: benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene, cumene, other derivatized benzenes, hexane, heptane, cyclohexane, methylcyclohexane, other hydrocarbon mixtures such as Shellsol or Halpasol, chloroform, Carbon tetrachloride, ethyl acetate, acetone, ethylene carbonate, acetonitrile or Mixtures of at least two of these solvents. A method according to any one of claims 11 to 15, characterized in that the ratio of the equivalent of boric acid or boric acid ester to the equivalent of the protonated compounds HZ-Z'H or HZ '' - Z '''H 1 to 0.5 to 3, more preferably 1 to 1 to 2.5 and the ratio of the equivalent of boric acid or boric acid ester to the equivalent of the cation M ^{y +} (y ± 1) to 1, more preferably (y ± 0.1) to 1. Use of borate salts after at least one the claims 1 to 10 as an additive in polymers. Use according to claim 17, characterized that the borate salts in polymers as a stabilizer, preferably against the thermal and / or photochemical degradation serve. Use according to claim 17 or 18, characterized that the borate salts in polymers as flame retardants and / or conductivity serve. Use according to at least one of claims 17 to 19, characterized in that the polymers are selected from: polylactate, polyesters, preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthenate (PEN), polyamides, preferably nylon, Nomex, Keflar, halogen-containing Polymers, preferably PVC, polytetrafluoroethene (PTFE, ^Teflon® ), polyolefins, preferably polyethylene (PE), polypropylene (PP), polystyrenes, polyacrylates and polyurethanes. Use according to at least one of claims 17 to 20, characterized in that the polymers are selected of thermoplastic elastomers, preferably of butadiene rubber (BR), polyisoprene, butadiene-styrene polymers or natural rubbers or natural latex or synthetic latex or Mixtures of at least two of these elastomers. Use according to at least one of claims 17 to 21, characterized in that the borate salts are preferred to the polymer a halogen-containing polymer, particularly preferably PVC or PTFE, or a polyurethane in amounts of 0.0001 to 10, preferably 0.01 to 3 wt .-% are added. Use according to at least one of claims 17 to 22, characterized in that containing the borate salts Polymers, preferably containing the borate salts containing halogen Polymers, for the production of bottles, films, films, fibrous materials, Moldings, Soles, foams, vitreous materials, Car tires, rubbers, paints, powder coatings, pipelines, drinking water pipes, Sewage pipes, profiles, window profiles, food packaging, computer keyboards, computer cases, display cases, electrical components, Blister packaging and engineering plastics are used. Use of borate salts or a mixture of at least two borate salts according to at least one of claims 1 to 10 as an electrolyte, especially for batteries. Polymers containing as additive a borate salt after at least one of the claims 1 to 10 or more borate salts according to at least one of claims 1 to 10 included.