DE102008044410A1 - Multifunctional polyorganosiloxanes - Google Patents

Abstract

Polyorganosiloxanes which carry at least two different organic functions per molecule, these being selected from the group carbinol, primary, secondary or tertiary amino group, diamino, triamino, carboxylic acid, aldehyde, keto, beta-ketoamine, carboxylic anhydride , Carbonsäureester-, carboxylic acid amide, vinyl, phosphonic acid, phosphonic ester, carbon-carbon double or triple bond, wherein the olefinic double bond may also be part of a (meth) acrylic function, always always only one type of olefinic double bond or CC triple bond in Combination with another organofunctional group from the specified range is present, wherein the at least two organic functions may be both bonded directly to the silicon, or may be part of silicon-bonded hydrocarbon radicals so that they are not directly bonded to a silicon atom, wherein the silicon-bonded hydrocarbon radicals to which the organic functions may be bonded, also include polymeric hydrocarbon radicals.

Description

The Invention relates to polyorganosiloxanes.

in the The prior art describes numerous patents and publications Preparations, the organically functionalized polyorganosiloxanes and / or Silanes and complementary organically functionalized organic Molecules, be it monomers, oligomers or polymers. As a rule, the respective complementarily functionalized components go after the application, a chemical reaction, so that as a result for the application a chemically reacted, cross-linked Mass present. The respective masses often still contain other ingredients in addition to the polyorganosiloxane, optionally the silane and the organic component. The after curing present masses may also be shaped bodies, like flatly extended structures of variable thickness, which are applied to a carrier that they may Provide protection, decorate it, and the like, such as for example, coatings, paints, printing inks, glazes, etc.

The chemical reactions leading to crosslinking of the preparations, either done without further action only by applying the Preparation or they require complementary measures, such as heating or the use of high-energy radiation. The preparations may optionally be catalysts that accelerate the chemical reaction. Do they react? Preparations without further intervention under ambient conditions, this allows reactions with the surrounding air humidity or reactive components in the air, such as carbon dioxide play a role. In the case of a two-component preparation, at the hardener and resin only a limited time before application the coating or only at the moment of application to a substrate in, for example, a two-component spray device can be united, the two components can also over their respective organic functions react with each other without that reactions with components of the environment in the curing process are involved.

Those Preparations which cease to have further chemical action Networking of the preparation components will usually require during the storage period in at least two preparation proportions kept (2K system), which only a certain time before the application to be united, which is chosen so that the preparation can be applied without previously chemically crosslinked in the container to be. Those preparations used for chemical crosslinking require further measures, such as heating, moisture ingress, which are previously excluded in the container, can already for storage during storage a single preparation (1K system).

US 5,439,977 teaches a formulation containing an epoxy resin and a carboxylic acid anhydride functional component which is storage stable as a 1K system. The chemical crosslinking takes place by heating. In the US 5,439,977 claimed masses are preferably used in the electronics sector. The reaction between an epoxy function and a carboxylic acid function has the advantage that it proceeds with virtually no shrinkage, so that stresses in generated cured mass are minimized. As the catalyst for the reaction, 0.1 to 10% by weight of an amine or a salt thereof is used in the formulations.

US 4,312,974 teaches formulations of a thermosetting epoxy resin and a polycarboxylic acid, which also still contains stoichiometric amounts of piperazine salts and which is curable at temperatures of 50-250 ° C. The preparations are stable in storage, in particular as a 1-component system, and nevertheless cure in the given temperature range during use within advantageous times of 1 minute to 2 hours.

US 4 507 441 teaches formulations of epoxy resins with carboxylic acid functional polyesters containing benzotriazoles as curing catalysts. By the chosen catalysts, the curing time at a given temperature of 150 or 180 ° C is approximately halved.

DE 696 13 285 T3 describes preparations of an organic resin and a functional polyorganosiloxane which may be epoxy, mercapto, acryloyl, methacryloyl, alkenyl and / or haloalkyl functional. The silicone compound is thus either monofunctional based on this organic functionality or it is multifunctional when more of these organic substituents are present in a polyorganosiloxane. The application to which these preparations serve are coatings. The use of silicones as binder component, in contrast to the previously cited documents properties such as weathering resistance, abrasion resistance, sliding properties, etc. improved. If catalysts are required for the respective chemical crosslinking reactions, these are added to the formulations as an ingredient. At least 5% of the Si atoms must carry an organic function, since the silicone compound is otherwise insufficiently anchored in the coating film.

US 2007/0142574 A1 describes epoxy-silicone hybrid resins for semiconductor manufacturing, in DE NEN the epoxy resin and the silicone resin can each react via hydroxy functions with each other. The reaction is accelerated by aluminum catalysts. It is particularly advantageous in this invention that the hybrid mixtures can be produced without additional compatibilizers.

Of the The prior art describes each hardening preparations from complementarily functionalized preparation components. Catalysts or other curing mechanisms (eg Dual Cure) on the chemical implementation of the two complementary functionalized components addition, are only by addition Other components for the preparation and thus an increase in the Complexity of the formulation work possible.

task The invention is to improve the state of the art and in particular To provide polyorganosiloxanes that are reactive towards complementary functionalized molecules and preferably used in applications where curing reactions the components used by chemical reactions a condition for the intended function of the respective Preparation are. In addition, it is the task of the present Invention to provide compounds that allow for several To chemically harden and react mechanisms where appropriate, the implementation of a functional group of Compound of the invention with a complementary catalyze organic function of another preparation ingredient to be able to do this without the addition of additional Catalysts is required, and possibly also with itself even through one of the available reaction mechanisms to harden.

object The invention relates to polyorganosiloxanes according to claim 1.

The The present invention preferably relates to polyorganosiloxanes, the at least two different organic functions per molecule which are selected from the group Carbinol-, primary, secondary or tertiary amino group, Diamino, triamino, carboxylic, aldehyde, keto, β-ketoamine, Carboxylic anhydride, carboxylic acid ester, carboxylic acid amide, Vinyl, phosphonic acid, phosphonic ester function, Carbon-carbon double or triple bond, wherein the olefinic double bond also part of a (meth) acrylic function can always be just one type of olefinic double bond or C-C triple bond in combination with another organofunctional one Group from the specified selection, and one of the at least two different organofunctional groups, preferably one Carboxylic acid function is and the invention organic functions of silicon-bonded hydrogen, alkoxy or aryloxy functions or hydroxy functions, which are additionally present can, are different. The organic functions can both directly bonded to silicon, as well as constituent be of silicon-bonded hydrocarbon radicals, so they do not are bonded directly to a silicon atom.

Prefers is the polyorganosiloxane according to the invention, that one of the at least two different organofunctional groups having a carboxylic acid function.

Prefers is in the Poyorganosiloxan invention, that another of the at least two different organofunctional ones Groups an amino group, a group having an olefinic double bond or a triple bond or a phosphonate functional group is available.

Of the particular advantage in the use of such at least two different ones Organically carrying polyorganosiloxanes is that these multiple functions in the application or during provide a curing process at the same time, for example two different curing mechanisms (dual cure behavior), So for example, a radical crosslinking by an unsaturated C-C bond in addition to the addition of a carboxylic anhydride function to an epoxy function, or a condensation by a carboxylic acid function in addition to the michaelanalogen addition of a likewise present in the polyorganosiloxane according to the invention Acrylate function with an amine, etc. In addition, these offer Polyorganosiloxanes the advantage that optionally catalytically acting organic functions in addition to reactive in the same molecule may be present, for example, a tertiary amine in addition a carboxylic acid, the reaction of the carboxylic acid function accelerate with an epoxy function. A phosphonic acid group, in addition to, for example, a carboxylic acid function can be present in the molecule can lead to an adhesion improvement a polyorganosiloxane according to the invention lead coating to a metallic substrate and increase the corrosion protection while the Carboxylic acid function with, for example, an epoxy function responding.

• 1.) einem oder mehreren Monomeren aus der Gruppe umfassend Vinylester, (Meth)acrylsäureester, Vinylaromaten, Olefine, 1,3-Diene, Vinylether und Vinylhalogenide und gegebenenfalls weiteren damit copolymerisierbaren Monomeren wie Maleinsäure und Maleinsäureanhydrid oder Fumarsäure, und im Falle, dass es sich bei dem Rest B¹ um einen Copolymerrest aus ethylenisch ungesättigten Monomeren und ethylenisch funktionalisierten Partikeln handelt in Gegenwart von
• 2) mindestens einem Partikel P mit einem mittleren Durchmesser von vorzugsweise ≤ 1000 nm, welches mit ethylenisch ungesättigten, radikalisch polymerisierbaren Gruppen funktionalisiert ist, dadurch gekennzeichnet, dass
• 2.1) als Partikel P ein oder mehrere aus der Gruppe der Metalloxide und Halbmetalloxide eingesetzt werden, und/oder
• 2.2) als Partikel P vorzugsweise Siliconharze eingesetzt werden, welche aus Wiederholungseinheiten der allgemeinen Formel [R⁴ _(a+b)SiO_(4-a-b)/2] (II) aufgebaut sind, wobei R⁴ gleich oder verschieden ist, und Wasserstoff-, Hydroxy-, sowie Alkyl-, Cycloalkyl-, Aryl-, Alkoxy- oder Aryloxyreste bedeutet, mit jeweils bis zu 18 C-Atomen, welche gegebenenfalls substituiert sein können, a und b ganze Zahlen im Wert von 0, 1, 2 oder 3 sind, wobei für mindestens 20% der angegebenen Wiederholungseinheiten a + b = 1 oder 0 ist, und für nicht mehr als 60% der Wiederholungseinheiten 0 bedeutet und
• 2.3) vorzugsweise ein Polydiorganosiloxan der allgemeinen Formel [R⁸ _(a+b)SiO_(4-a-b)/2], bedeutet, wobei R⁸ einen Hydroxy-, einen Alkyl-, Cycloalkyl-, Aryl-, Alkoxy- oder Aryloxyrest bedeutet und bis auf das terminale Siliziumatom a + b = 2 ist, für die terminalen Siliziumatome bedeutet a + b = 3, wobei 2.1), 2.2) und 2.3) vorzugsweise jeweils mit einem oder mehreren α-Organosilanen der allgemeinen Formel (R¹O)_3-n(R²)_nSi(CR³ ₂)-X (I) funktionalisiert werden, wobei R¹ für Wasserstoff, einen Alkylrest mit 1 bis 6 Kohlenstoffatomen oder einen Arylrest steht, R² und R³ jeweils unabhängig voneinander für Wasserstoff, einen Alkylrest mit 1 bis 12 Kohlenstoffatomen oder einen Arylrest stehen, n die Werte 0, 1 oder 2 bedeuten kann, und X ein Rest mit 2 bis 20 Kohlenwasserstoffatomen mit einer ethylenisch ungesättigten Gruppe ist, mit der Maßgabe, dass entweder ein Rest B¹ zwei verschiedene organofunktionelle Gruppen aus der oben angegebenen Auswahl enthält oder stets mindestens zwei Reste B¹ pro Molekül voneinander verschiedene organofunktionelle Gruppen bedeuten, oder solche enthalten, was für den Fall, dass eine der mindestens zwei verschiedenen organofunktionellen Gruppen oder die mindestens zwei verschiedenen organofunktionellen Gruppen Bestandteil eines Polymer- oder Copolymerrestes B¹ sind, bedeutet, dass diese eine Art oder mindestens zwei Arten olefinisch ungesättigte Monomere enthalten müssen, die außer der olefinisch ungesättigten Funktion noch eine weitere organische Funktion tragen, die bei dem Polymerisationsvorgang nicht verbraucht werden und in dem Polyorganosiloxan als reaktive Funktion verfügbar sind, wobei für den Fall, dass die mindestens zwei verschiedenen organofunktionellen Gruppen beide in Polymer- oder Copolymerresten enthalten sind, mindestens zwei solcher olefinisch ungesättigter Monomerer mit unterschiedlichen organischen Funktionen vorhanden sein müssen, so dass stets gewährleistet ist, dass in dem erfindungsgemäßen Polyorganosiloxan mindestens zwei unterschiedliche organische Funktionen vorhanden sind, die nicht siliziumgebundener Wasserstoff und/oder eine siliziumgebundene Hydroxy-, Alkoxy- und/oder Aryloxyfunktion sind, wobei die Reste B¹ in dem Falle, dass es sich um zweiwertige Polymer- oder Copolymerreste handelt, zwei Siliziumatome miteinander verbinden, A¹ einen Wasserstoff- oder Kohlenwasserstoffrest, der vorzugsweise bis zu 18 C-Atome enthält und zusätzlich Heteroatome, ausgewählt aus O-, S, Si, Cl, F, Br, P oder N-Atomen, enthalten kann, bedeutet, wobei der Rest A¹ auch über ein Heteroatom an das Siliziumatom gebunden sein kann, und z und p die Werte 0, 1, 2 oder 3, besitzt, wobei für mindestens 20% der Wiederholungseinheiten der allgemeinen Formel (1) z + p = 1 oder 0 ist und z + p für nicht mehr als 60% der Wiederholungseinheiten 0 ist.

A preferred subject of the invention are polyorganosiloxanes or mixtures thereof, composed of repeating units of the general formula (1): [A 1 z B 1 p SiO (4-pz) / 2 ] (1), in which
the radicals B ¹ (organic copolymer) independently of one another hydrogen, hydroxyl, alkoxy or aryloxy radical having up to 18 carbon atoms,
or a C1 to C12 hydrocarbon radical or a polymeric hydrocarbon radical, which preferably has an organofunctional radical from the group consisting of carbinol radical, carboxylic acid radical, carboxylic acid amide radical, carboxylic anhydride radical, primary, secondary or tertiary amino, diamino or triamino radicals, phosphonic acid radical, phosphonic acid ester radical, carboxylic acid ester radical, a Aldehyde, a keto, a β-ketoamine, or an olefinically or acetylenically unsaturated C2-C18 radical, wherein the olefinically or acetylenically unsaturated radical may have one or more olefinically or acetylenically unsaturated groups, which are not cumulated, ie z. B. no ketene and wherein the olefinic double bond may also be part of a (meth) acrylic function, always always only one type of olefinic double bond or C-C triple bond in combination with another organofunctional group from the group named here in a polyorganosiloxane of repeating units of the general Formula (1) is present
wherein said organofunctional radicals may also be bonded directly to a silicon atom,
and it is also possible for a residue B ^{1 to} contain two such organofunctional groups,
wherein polymeric hydrocarbon radicals B ^{1 are} mono- or divalent polymer radicals of ethylenically unsaturated monomers or
a copolymer radical B ¹ of ethylenically unsaturated monomers and of ethylenically functionalized nanoparticles, obtainable by means of free-radically initiated polymerization of

• 1.) one or more monomers from the group consisting of vinyl esters, (meth) acrylic esters, vinyl aromatics, olefins, 1,3-dienes, vinyl ethers and vinyl halides and optionally other monomers copolymerizable therewith such as maleic acid and maleic anhydride or fumaric acid, and in the case that the radical B ¹ is a copolymer radical of ethylenically unsaturated monomers and ethylenically functionalized particles in the presence of
• 2) at least one particle P having an average diameter of preferably ≦ 1000 nm, which is functionalized with ethylenically unsaturated, radically polymerizable groups, characterized in that
• 2.1) as particles P one or more of the group of metal oxides and semi-metal oxides are used, and / or
• 2.2) as particles P preferably silicone resins are used, which are composed of recurring units of the general formula [R ⁴ _{(a + b)} SiO _{(4-ab) / 2} ] (II), wherein R ^{4 is the} same or different, and hydrogen , Hydroxy, as well as alkyl, cycloalkyl, aryl, alkoxy or aryloxy radicals, each having up to 18 carbon atoms, which may be optionally substituted, a and b are integers in the value of 0, 1, 2 or 3 wherein, for at least 20% of the specified repeat units, a + b = 1 or 0, and for no more than 60% of the repeat units, 0 and
• 2.3), preferably a polydiorganosiloxane of the general formula [R ⁸ _{(a + b)} SiO _{(4-ab) / 2} ], where R ^{8 is} a hydroxy, an alkyl, cycloalkyl, aryl, alkoxy or aryloxy radical and for the terminal silicon atom a + b = 2, for the terminal silicon atoms a + b = 3, where 2.1), 2.2) and 2.3) preferably in each case with one or more α-organosilanes of the general formula (R ¹ O) _3-n (R ² ) _n Si (CR ³ ₂ ) -X (I), wherein R ^{1 is} hydrogen, an alkyl radical having 1 to 6 carbon atoms or an aryl radical, R ² and R ^{3 are} each independently hydrogen , an alkyl radical having 1 to 12 carbon atoms or an aryl radical, n can denote the values 0, 1 or 2, and X is a radical having 2 to 20 hydrocarbon atoms with an ethylenically unsaturated group, with the proviso that either a radical B ¹ contains two different organofunctional groups from the above selection or always mean at least two radicals B ¹ per molecule different from each other or contain organofunctional groups, which in the event that one of the at least two different organofunctional groups or the at least two different organofunctional groups are part of a polymer or copolymer radical B ¹ means that these must contain one or at least two types of olefinically unsaturated monomers which carry, in addition to the olefinically unsaturated function, another organic function which is not consumed in the polymerization process and in which polyorganosiloxane is available as a reactive function, in which case at least two different organofunctional groups are both contained in polymer or copolymer residues, at least two such olefinically unsaturated monomers having different organic functions must be present, so that it is always ensured that in the invention at least two different organic functions are present, which are not silicon-bonded hydrogen and / or a silicon-bonded hydroxy, alkoxy and / or aryloxy function, wherein the radicals B ¹ in the event that they are divalent polymer or copolymer residues, connect two silicon atoms to one another, A ^{1 contains} a hydrogen or hydrocarbon radical which preferably contains up to 18 C atoms and additionally heteroatoms selected from O--, S, Si, Cl, F, Br, P or N atoms, may mean that the radical A ^{1 may} also be bonded to the silicon atom via a heteroatom, and z and p are 0, 1, 2 or 3 , wherein for at least 20% of the repeat units of the general formula (1) z + p = 1 or 0 and z + p is not more than 60% of the repeat units is 0.

Examples of preferred radicals A ¹ are preferably linear and branched alkyl and alkoxy radicals having up to 8 carbon atoms, with methyl, ethyl, iso and n-propyl and iso and n-octyl being particularly preferred as alkyl radicals. As alkoxy, methoxy, ethoxy and iso and n-propoxy are particularly preferred.

The polyorganosiloxanes of the invention are preferred both about their organic functions and about the optionally present hydrogen, hydroxy, aryl and / or Alkyloxy functions reactive towards complementary functionalized molecules and are preferably used for Use in applications where hardening reactions of the used Components by chemical reactions a condition for the intended function of the respective Preparation is.

Examples of alkoxy and aryloxy radicals B ¹ are preferably methoxy, ethoxy, n-propyloxy, isopropoxy, n-butyloxy, isobutoxy, isomeric pentyl, hexyl, heptyl and octyloxy radicals. Preference is given to methoxy, ethoxy and isomeric octyloxy radicals.

Examples of carboxylic acid radicals are those of the general formula (2) Y ¹ -COOH (2), wherein Y ¹ preferably represents a chemical bond or a divalent linear or branched hydrocarbon radical having up to 18 carbon atoms, wherein Y ^{1 may} also contain heteroatoms and the radical Y ¹ directly bonded to the silicon atom may be a carbon or an oxygen atom. Heteroatoms can in particular be introduced into the radical Y ¹ in that the reaction which leads to the attachment of the carboxylic acid function to the polyorganosiloxane takes place between complementary organofunctional groups on the polyorganosiloxane and the organic carrier of the carboxylic acid function. Heteroatom-containing preferably fragments which may typically be contained in the radical Y ¹ are -N (R) -C (= O) -, -COC-, -N (R) -, -C (= O) -, - OC (= O) -, -S-, -OC (= O) -O-, -N (R) -C (= O) -N (R) -, where unsymmetrical radicals in both possible directions in the radical Y. ¹ can be installed.

Examples of carboxylic acid ester radicals are preferably those of the general formula (2) Y ² -COO-Y ¹ (2), wherein Y ^{2 represents} a linear or branched hydrocarbon radical having up to 18 carbon atoms, wherein Y ^{2 may} also contain heteroatoms. The radical Y ² may in particular contain further organic functions such as double bonds, acid or amine radicals. If Y ² z. For example, by ring opening and condensation of a maleic anhydride to a silanol function, Y ² would be a radical of the formula (cis) -C = C-COOH and Y ^{1 is} a chemical bond or a divalent linear or branched hydrocarbon radical of up to 18 Carbon atoms, wherein Y ^{1 may} also contain heteroatoms and the radical Y ¹ directly bonded to the silicon atom may be a carbon or an oxygen atom. Heteroatoms can in particular be introduced into the radical Y ¹ in that the reaction which leads to the attachment of the carboxylic acid function to the polyorganosiloxane takes place between complementary organofunctional groups on the polyorganosiloxane and the organic carrier of the carboxylic acid function. Heteroatom-containing fragments which may typically be included in the radical Y ¹ are -N (R) -C (= O) -, -COC-, -N (R) -, -C (= O) -, -OC (= O) -, -S-, -OC (= O) -O-, -N (R) -C (= O) -N (R) -, where unsymmetrical radicals in both possible directions in the radical Y ¹ can be installed.

The carboxylic acid ester radical may also preferably be present in reverse bound, that is to say a remainder of the form Y ^{1 is} -COOY ³ , wherein Y ^{1 represents} a chemical bond or a divalent linear or branched hydrocarbon radical having up to 18 carbon atoms, wherein Y ^{1 may} also contain heteroatoms and the radical Y ¹ directly bonded to the silicon atom may be a carbon or an oxygen atom. Heteroatoms can in particular be introduced into the radical Y ¹ in that the reaction which leads to the attachment of the carboxylic acid function to the polyorganosiloxane takes place between complementary organofunctional groups on the polyorganosiloxane and the organic carrier of the carboxylic acid function. Heteroatom-containing fragments which may typically be present in the radical Y ¹ are preferably: -N (R) -C (= O) -, -COC-, -N (R) -, -C (= O) -, -OC (= O) -, -S-, -OC (= O) -O-, -N (R) -C (= O) -N (R) -, where unsymmetrical radicals in both possible directions in the rest Y ¹ can be installed.

Y ³ is preferably a linear one or branched hydrocarbon radical having up to 18 carbon atoms, wherein Y ^{3 may} also contain heteroatoms.

Examples of carboxylic acid amide radicals are those of the formula (10) Y ¹ -C (= O) NR ³ ₂ (10) where the radicals R ³ independently of one another preferably denote a hydrogen atom or an optionally fluorine-, chlorine- or bromine-substituted C ₁ - to C ₁₈ -hydrocarbon radical, preferably a C ₁ -, C ₂ -, C ₃ -, C ₄ -, C ₅ or C ₆ hydrocarbon radical and
Y ^{1 has} the same meaning as stated above.

Y¹-R⁵C-C(=O)-O-C(=O)R⁶ (3b),wobei Y¹ die oben angegebene Bedeutung hat und R5 und R6 unabhängig voneinander vorzugsweise jeweils einen C1-C8 Kohlenwasserstoffrest bedeuten, der gegebenenfalls Heteroatome enthalten kann.Examples of carboxylic acid anhydride radicals are preferably those of the general formulas (3a) or (3b)

Y ¹ -R ⁵ CC (= O) -OC (= O) R ⁶ (3b), where Y ^{1 has} the abovementioned meaning and R 5 and R 6 independently of one another preferably each represent a C ¹ -C 8 hydrocarbon radical which may optionally contain heteroatoms.

Preferred examples of amino groups containing radicals B ¹ are those of the general formula (6) -R ⁷ - [NR ⁸ (CH ₂ ) _c ] _d NR ⁹ ₂ (6), in the
R ^{7 has} the meaning of Y ¹ and preferably denotes a divalent C ₁ , C ₂ , C ₃ , C ₄ , C ₅ or C ₆ hydrocarbon radical,
R ⁸ and R ^{9 is} a hydrogen atom or an optionally fluorine-, chlorine- or bromine-substituted C ₁ - to C ₁₈ -hydrocarbon radical, preferably C ₁ -, C ₂ -, C ₃ -, C ₄ -, C ₅ - or C _6- hydrocarbon radical,
c is an integer with a value ≥ 1, and
d represent the values 0, 1, 2, 3 or 4.

Examples of preferred amino groups containing radicals B ¹ are preferably the radicals aminoethyl-aminopropyl, aminoethyl-aminoethyl-aminopropyl, N-methylaminopropyl, N- (n-butyl) aminopropyl, N- (n-hexyl) aminopropyl, N-cyclohexylaminopropyl, N- Phenylaminopropyl, aminopropyl, N-phenylaminomethyl, N-cyclohexylaminomethyl, N- (n-butyl) aminomethyl, N- (n-hexyl) aminomethyl, N-methylaminomethyl, these examples being by no means restrictive. Preference is given to aminoethylaminopropyl, aminoethylaminoethylaminopropyl, N-methylaminopropyl, N- (n-butyl) aminopropyl, N- (n-hexyl) aminopropyl, N-cyclohexylaminopropyl, N-phenylaminopropyl, aminopropyl, N-phenylaminomethyl, N- Cyclohexylaminomethyl, particularly preferred are aminoethyl-aminopropyl, aminoethyl-aminoethyl-aminopropyl.

Examples of phosphonic acid residues and phosphonic acid ester residues are preferably those of the general formula (7) Y ¹ -P (= O) (OR ¹ ) ₂ (7) where the radicals R ¹ preferably independently of one another are hydrogen or hydrocarbon radicals having up to 18 carbon atoms. Preferred phosphonic acid radicals are those in which R ^{1 is} hydrogen. Preferred phosphonic acid ester radicals are those in which R ^{1 is} methyl or ethyl.

Vinyl esters suitable for the preparation of polymeric or copolymeric radicals B ¹ are preferably those of carboxylic acids having 1 to 15 C atoms. Preference is given to vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of α-branched monocarboxylic acids having 9 to 11 C atoms, for example VeoVa9 ^R or VeoVa10 ^R (trade name of the company Resolution). Particularly preferred is vinyl acetate.

For the preparation of polymeric or copolymeric radicals B ¹ suitable monomers from the group of acrylic acid esters or methacrylic esters are preferably esters of unbranched or branched alcohols having 1 to 15 carbon atoms. Preferred methacrylic esters or acrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate.

When Vinylaromatics preferred are styrene, alpha-methylstyrene, the isomers Vinyltoluenes and vinylxylenes and divinylbenzenes. Particularly preferred Styrene.

Among the vinyl halide compounds, vinyl chloride, vinylidene chloride, tetrafluoroethylene, difluoroethylene, hexylperfluoroethylene, 3,3,3-trifluoropropene, perfluoropropyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene and vinyl fluoride are also preferable. Particularly preferred is vinyl chloride. A preferred vinyl ether is, for example, methyl vinyl ether.

The preferred olefins are ethene, propene, 1-alkylethene and multiply unsaturated alkenes, and the preferred dienes are 1,3-butadiene and isoprene. Particularly preferred are ethene and 1,3-butadiene.

Examples for other monomers that can be used are preferably ethylenically unsaturated mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid amides and -nitriles, preferably acrylamide and acrylonitrile; Mono- and Diesters of fumaric acid and maleic acid such as Diethyl and diisopropyl esters and maleic anhydride, ethylenically unsaturated sulfonic acids or their Salts, preferably vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, ethylenically unsaturated phosphonic acids or their Salts and esters. Further examples are precrosslinking comonomers such as polyunsaturated ethylenic comonomers, for example Divinyl adipate, diallyl maleate, allyl methacrylate or triallyl cyanurate, or post-crosslinking comonomers, for example acrylamidoglycolic acid (AGA), Methylacrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl carbamate, alkyl ethers such as the isobutoxy ether or ester of N-methylolacrylamide, the N-Methylolmethacrylamids and N-Methylolallylcarbamats. Suitable are also epoxy-functional comonomers such as glycidyl methacrylate and glycidyl acrylate. Mention may also be made of monomers with hydroxy or CO groups, for example methacrylic acid and acrylic acid hydroxyalkyl esters such as hydroxyethyl, hydroxypropyl or hydroxybutyl or methacrylate and compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate.

Suitable particles P for the preparation of copolymeric radicals B ¹ are preferably also those of the group silicon oxides and metal oxides. In the case of metal oxides, the oxides of the metals aluminum, titanium, zirconium, tantalum, tungsten, hafnium, zinc and tin are preferred. For the silicon oxides, colloidal silica, fumed silica, precipitated silica, silica sols and silicone resins are particularly preferred. In the metal oxides, aluminum oxides such as corundum, mixed aluminum oxides with other metals and / or silicon, titanium oxides, zirconium oxides, iron oxides are particularly preferred.

From the field of silicone resins, those are suitable which consist of any combination of M units (R ₃ SiO-), D units (-OSiR ₂ O-), T units (RSiO ₃ ^3- ) and Q units ( SiO ₄ ^4- ), with the proviso that always T and / or Q units are contained and their share of the units that make up the silicone resin, in total at least 20 mol% and upon presentation in each case only one of these Units each share is at least 20 mol%.

At the Most preferred silicone resins are those that are substantially only from M and Q units or only from D and T units or only build up from T units.

The Particles P preferably have an average diameter of 1 nm to 100 μm, more preferably 1 nm to 10 μm, the particle size being determined by transmission electron microscopy the dispersions obtained or those obtainable from the dispersions Movies is determined.

In addition, silanes of the general formula (R ⁵ ) _4-m- Si (OR ⁶ ) _m (8) may also be incorporated or copolymerized into the copolymeric radicals B1, where m is preferably a number in the value of 1, 2, 3 or 4, R ^{5 is} preferably an organofunctional radical selected from the group consisting of alkoxy radical and aryloxy radical having in each case 1 to 12 C atoms, phosphonic acid monoester radical, phosphonic diester radical, phosphonic acid radical, methacryloyloxy radical, acryloyloxy radical, vinyl radical, mercapto radical, isocyanate radical, the isocyanate radical being optionally protective may be reactive, hydroxy, hydroxyalkyl, vinyl, epoxy, Glycidyloxyrest, morpholino, piperazino, a primary, secondary or tertiary amino radical having one or more nitrogen atoms, wherein the nitrogen atoms may be substituted by hydrogen or monovalent aromatic, aliphatic or cycloaliphatic hydrocarbon radicals , Carbonsäureanhydridrest, aldehyde radical, urethane radical, urea radical, wherein the radical R ⁵ may be bonded directly to the silicon atom or may be separated by a carbon chain of 1 to 6 carbon atoms thereof and R ^{6 is} a monovalent linear or branched aliphatic or cycloaliphatic hydrocarbon radical or a monovalent aromatic hydrocarbon radical having in each case 1 to 12 C atoms, or a radical -C (= O) -R ⁷ , where R ^{7 is} a monovalent linear or branched aliphatic or a cycloaliphatic hydrocarbon radical having in each case 1 to 12 C atoms or a means monovalent aromatic hydrocarbon radical. The selected silane or optionally the selected silanes may be present in unhydrolyzed form, in hydrolyzed form or in hydrolyzed and partially condensed or hydrolyzed and condensed form, or in a mixture of these forms.

The organofunctional radicals B ¹ can preferably be introduced into the polyorganosiloxane, for example, by adding a suitable Precursor of the polyorganosiloxane with organofunctional silanes. Thus, for example, alkoxy-functional or silanol-functional polyorganosiloxanes can be reacted with alkoxy- or hydroxy-functional silanes or alkoxy- and / or hydroxy-functional hydrolysis products thereof in the manner of a condensation reaction, so that the organofunctional silanes or their hydrolysis products are bonded to the alkoxy and Si-O-Si bonds / or hydroxy-functional polyorganosiloxane bound present. It is also conceivable to react an organic molecule with a polyorganosiloxane. In this case, the organic molecule carrying the organofunctional group to be introduced into the polyorganosiloxane must have another functional group with which it can react with the polyorganosiloxane. The polyorganosiloxane on its side must itself have a functional group with which it can react with the organic molecule. Thus, for example, it is conceivable that a dicarboxylic acid functional organic molecule is reacted with a carbinol- or silanol-functional polyorganosiloxane, consuming one of the two carboxylic acid groups of the organic molecule while leaving the other unused. The same would be conceivable with a carboxylic acid anhydride, for example with a succinic anhydride or maleic anhydride, wherein after formation of a half ester also remains an unused carboxylic acid group. The organic molecule would in both cases be linked via an ester bond to the polyorganosiloxane. Reactions between complementary organic groups are adequately described in the literature, which is why reference is made here to published knowledge and its application with regard to the introduction of functional groups in this way.

The second way in which functional groups can be introduced into the polyorganosiloxanes of the invention is to introduce them as part of a polymeric or copolymeric radical B ¹ . For this one must select suitable monomers, which have on the one hand an olefinically unsaturated group and on the other hand an organic function, which is not consumed during the radical polymerization. Such a monomer may be, for example, acrylic acid or glycidyl methacrylate. Further details are given above.

The polyorganosiloxanes which have a polymeric or copolymeric radical B ¹ can also be referred to as organosilicon hybrids.

The Polyorganosiloxanes according to the invention are preferably for the production of coatings, as a constituent of preparations and used for the preparation of coatings.

Except for coatings and for the production of preparations for coatings are the inventive Polyorganosiloxanes also for a variety of other uses.

The Polyorganosiloxanes according to the invention are suitable especially good for use in anti-corrosive preparations. In particular, they are suitable for use as binders for high-temperature resistant corrosion protection and so-called Protective Coatings, ie coatings applied to metal in particular, which cure at ambient conditions without application of elevated temperature and the task have the metal substrate against weathering and To protect against corrosion and at the same time to be decorative.

• – Steuerung des elektrischen Leitfähigkeit und des elektrischen Widerstandes
• – Steuerung der Verlaufseigenschaften einer Zubereitung
• – Steuerung des Glanzes eines feuchten oder gehärteten Filmes oder eines Objektes
• – Erhöhung der Bewitterungsbeständigkeit
• – Erhöhung der Chemikalienresistenz
• – Erhöhung der Farbtonstabilität
• – Reduzierung der Kreidungsneigung
• – Reduzierung oder Erhöhung der Haft- und Gleitreibung auf Festkörpern oder Filmen erhalten aus Zubereitungen, die erfindungsgemäßen Polyorganosiloxane enthalten
• – Stabilisierung oder Destabilisierung von Schaum in der Zubereitung, die die erfindungsgemäßen Polyorganosiloxane enthält
• – Verbesserung der Haftung der Zubereitung, die erfindungsgemäße Polyorganosiloxane enthält, zu Substraten auf die die Zubereitung aufgetragen wird,
• – Steuerung des Füllstoff- und Pigmentnetz- und -dispergierverhaltens,
• – Steuerung der rheologischen Eigenschaften der Zubereitung, die die erfindungsgemäßen Polyorganosiloxane enthält,
• – Steuerung der mechanischen Eigenschaften, wie z. B. Flexibilität, Kratzfestigkeit, Elastizität, Dehnbarkeit, Biegefähigkeit, Reißverhalten, Rückprallverhalten, Härte, Dichte, Weiterreißfestigkeit, Druckverformungsrest, Verhalten bei verschiedenen Temperaturen, Ausdehnungskoeffizient, Abriebfestigkeit sowie weiterer Eigenschaften wie der Wärmeleitfähigkeit, Brennbarkeit, Gasdurchlässigkeit, Beständigkeit gegen Wasserdampf, Heißluft, Chemikalien, Bewitterung und Strahlung, der Sterilisierbarkeit, von Festkörpern oder Filmen erhältlich aus der Zubereitung die die erfindungsgemäßen Polyorganosiloxane enthält
• – Steuerung der elektrischen Eigenschaften, wie z. B. dielektrischer Verlustfaktor, Durchschlagfestigkeit, Dielektrizitätskonstante, Kriechstromfestigkeit, Lichtbogenbeständigkeit, Oberflächenwiderstand, spezifischer Durchschlagswiderstand,
• – Flexibilität, Kratzfestigkeit, Elastizität, Dehnbarkeit, Biegefähigkeit, Reißverhalten, Rückprallverhalten, Härte, Dichte, Weiterreißfestigkeit, Druckverformungsrest, Verhalten bei verschiedenen Temperaturen von Festkörpern oder Filmen erhältlich aus der Zubereitung die die erfindungsgemäßen Polyorganosiloxane enthält.

In addition to the purpose of coating metals, the polyorganosiloxanes of the invention may also be used to manipulate further properties of preparations containing the polyorganosiloxanes of the invention or of solids or films obtained from formulations containing the polyorganosiloxanes of the invention, such as e.g. B .:

• - Control of electrical conductivity and electrical resistance
• - Control of the flow properties of a preparation
• Control the gloss of a wet or cured film or object
• - Increasing the weathering resistance
• - increase of chemical resistance
• - Increase of color stability
• - Reduction of the tendency to chalk
• - Reduction or increase of static friction and sliding friction on solids or films obtained from preparations containing polyorganosiloxanes according to the invention
• Stabilization or destabilization of foam in the preparation containing the polyorganosiloxanes of the invention
• Improving the adhesion of the preparation containing polyorganosiloxanes according to the invention to substrates to which the preparation is applied,
• Control of filler and pigment wetting and dispersing behavior,
• Control of the rheological properties of the preparation containing the polyorganosiloxanes of the invention,
• - Control of mechanical properties, such. B. Flexibility, scratch resistance, elasticity, ductility, bending ability, tear behavior, rebound behavior, hardness, density, tear propagation resistance, compression set, behavior at different temperatures, Auszehnungskoeffizi Ent, abrasion resistance and other properties such as thermal conductivity, flammability, gas permeability, resistance to water vapor, hot air, chemicals, weathering and radiation, the sterilizability of solids or films available from the preparation containing the polyorganosiloxanes according to the invention
• - Control of electrical properties, such. Dielectric breakdown factor, dielectric strength, dielectric constant, tracking resistance, arc resistance, surface resistance, resistivity,
• Flexibility, scratch resistance, elasticity, extensibility, bendability, tear behavior, rebound behavior, hardness, density, tear propagation resistance, compression set behavior at different temperatures of solids or films obtainable from the preparation containing the polyorganosiloxanes according to the invention.

Examples for applications in which the invention Polyorganosiloxanes can be used to the top to manipulate designated properties are the manufacture of coating materials and impregnations and thereof coatings and coatings to be obtained on substrates, like metal, glass, wood, mineral substrate, artificial and natural fibers for the manufacture of textiles, carpets, floor coverings, or other fiber-produced goods, leather, Plastics such as films, molded parts. The invention Polyorganosiloxanes can be used in preparations with appropriate Selection of the preparation components also as an additive for the purpose of defoaming, flow promotion, Hydrophobing, hydrophilization, filler and pigment dispersion, filler and pigment wetting, substrate wetting, promotion of Surface smoothness, reduction of adhesion and sliding resistance on the surface of the additive from the preparation available hardened mass. The polyorganosiloxanes according to the invention can in liquid or in hardened solid form be incorporated in elastomer compositions. This can be for the purpose strengthening or improving other functional properties like the control of transparency, heat resistance, the yellowing tendency, weathering resistance used become.

Special Significance possess the polyorganosiloxanes of the invention in coatings for metal substrates. Silicone resins in the areas of protective coatings and OEM (original equipment manufacture) metal coatings such as metal tape coatings (Coil Coatings) have long been used to increase the longevity of the Improve coating under Beitterungsbedingungen. in principle There are two ways in the corresponding silicone resins Coating preparations are introduced. For one thing the organic resins overcooked with the silicone resins, that is made a silicone organic resin, which is then hardened and other formulation ingredients are mixed and applied. The second way is to use the organofunctional silicone resins with a complementary functionalized organic resin to mix and let the two react with each other. there No cooking is needed before. This second variant is mainly used in the field of protective coatings, where the Curing at ambient temperature takes place while former method in the field of metal tape coatings usual is where at significantly elevated temperature within very cured for a short time. Carboxylic acid functions react with a number of different, different organic functions, where the reactions are either catalyzed at ambient temperature take place or at elevated temperature. Carboxylic acid functions Thus, the option to operate both methods offer a silicone functionalization to ensure an organic binder.

in the Generally there are 30% silicone content in the organic binder sufficient and the usual amount. With less the achieved improvement of the long-term stability under Weathering conditions generally insufficient, with more Silicon is usually a deterioration mechanical or other properties observed. For wood coatings is in contrast, already with the addition of 10 or 20 wt.%, Depending on Use case, already a very good improvement in long-term stability observed, which often meets the requirements.

By blending organofunctional silicone resins with organofunctional organic resins to produce a silicone organic polymer by the reaction between them, one can proceed by using the silicone as a hardener or as a resin and mixing it stoichiometrically, or under or over stoichiometrically , depending on the desired effect that you want to achieve, if necessary. It is conceivable and usually actually the case that one uses a significantly larger amount of silicone than 30 wt.%. This is caused by the fact that the functional density of the silicone building block can not be set so high that a smaller amount is sufficient for approximately stoichiometric use. In order to reduce the silicone content to 30% by weight, which is generally sufficient for metal coatings, the use of mixtures of the silicone building block with identically functionalized organic constituents is conceivable here, which must be very well matched with regard to their reactivity. That is, for example, an amino-functional silicone resin having an amino-functional organi rule hardener, which must have a comparable reactivity for a good performance of the coating usually. This brings in several ways cost savings. On the one hand due to the lower silicone content, since silicone is generally more expensive than an organic component and, secondly, in the synthesis of the silicone, it is no longer necessary to produce the highest possible functional density, which makes the production of the silicone building block more expensive.

Examples:

Preparation of the invention resins

Example 1 (carboxylate / phosphonate functional; Reaction in ethyl acetate):

150 g of a silicone resin consisting of 59% _Ph-SiO3 / 2 units and from 41 mol% Me ₂ SiO _2/2 units is constructed, wherein 25 mol% of the bound on the silicon oxygen atoms carrying methyl substituents, together with 10 g Vinyltrimethoxysilane and 14 g of acrylic acid dissolved in 350 g of ethyl acetate presented and stirred at 50 ° C for 1 h. Subsequently, 14 g of vinylphosphonic acid are added to the homogeneous solution and heated to reflux conditions. 10 g of a 70% solution of tert-butyl perpivalate in water are metered in over 2 hours. The mixture is then stirred for 3 h at 70 ° C. A suspension of the organically modified resin in ethyl acetate is obtained. Analysis by 1H-NMR and 29Si-NMR indicates the complete polymerization of the monomers and the condensation of the silane.

Example 2 (carboxylate / amine functional; Reaction in ethyl acetate):

150 g of a silicone resin consisting of 59% _Ph-SiO3 / 2 units and from 41 mol% Me ₂ SiO _2/2 units is constructed, wherein 25 mol% of the bound on the silicon oxygen atoms carrying methyl substituents, together with 10 g Vinyltrimethoxysilane and 14 g of acrylic acid dissolved in 350 g of ethyl acetate presented and stirred at 50 ° C for 1 h. Subsequently, 14 g of dimethylaminoethyl methacrylate (DMAEMA) are added to the homogeneous solution and heated to reflux conditions. 10 g of a 70% solution of tert-butyl perpivalate in water are metered in over 2 hours. The mixture is then stirred for 3 h at 70 ° C.

you receives a suspension of the organically modified resin in ethyl acetate. Analysis by 1H-NMR and 29Si-NMR shows the complete polymerization the monomers and the condensation of the silane.

Example 3 (carboxylate / amine functional; Reaction in toluene:

150 g of a silicone resin consisting of 59% _Ph-SiO3 / 2 units and from 41 mol% Me ₂ SiO _2/2 units is constructed, wherein 25 mol% of the bound on the silicon oxygen atoms carrying methyl substituents, together with 10 g Vinyltrimethoxysilane and 14 g of acrylic acid dissolved in 350 g of toluene presented and stirred at 50 ° C for 1 h. Subsequently, 14 g of dimethylaminoethyl methacrylate (DMAEMA) are added to the homogeneous solution and heated to 80.degree. 10 g of a 70% solution of tert-butyl perpivalate in water are metered in over 2 hours. The mixture is then stirred for 3 h at 70 ° C.

you receives a suspension of the organically modified resin in toluene. Examination by 1H-NMR and 29Si-NMR shows the complete Polymerization of the monomers and the condensation of the silane.

Example 4 (carboxylate / phosphonate functional; Reaction in toluene):

150 g of a silicone resin consisting of 59% _Ph-SiO3 / 2 units and from 41 mol% Me ₂ SiO _2/2 units is constructed, wherein 25 mol% of the bound on the silicon oxygen atoms carrying methyl substituents, together with 10 g vinyltrimethoxysilane and 14 g of maleic anhydride dissolved in 350 g of toluene presented and stirred at 50 ° C for 1 h. Subsequently, 14 g of vinylphosphonic acid are added to the homogeneous solution and heated to 80.degree. 10 g of a 70% solution of tert-butyl perpivalate in water are metered in over 2 hours. The mixture is then stirred for 3 h at 70 ° C.

you receives a suspension of the organically modified resin in toluene. Examination by 1H-NMR and 29Si-NMR shows the complete Polymerization of the monomers and the condensation of the silane.

Example 5 (carboxylate / phosphonate functional; Reaction in toluene):

150 g of a silicone resin, the SiO1 / 2 units consists of equal parts of _SiO4 / 2 and Me _3, wherein 3 mol% of oxygen atoms, which are present bonded to the silicon substituted with ethoxy, said ethoxy groups to the SiO ₄ / 2 units and less than 1 mol% of the silicon-bonded oxygen atoms carry hydrogen substituents are presented together with 10 g of vinyltrimethoxysilane and 14 g of acrylic acid dissolved in 350 g of toluene and stirred at 50 ° C for 1 h. Subsequently, 14 g of vinylphosphonic acid are added to the homogeneous solution and heated to reflux conditions. It is metered over 2 hours 10 g of a 70% Lö tert-butyl perpivalate in water. The mixture is then stirred for 3 h at 70 ° C.

you receives a suspension of the organically modified resin in toluene. Examination by 1H-NMR and 29Si-NMR shows the complete Polymerization of the monomers and the condensation of the silane.

Example 6 (amine / phosphonate functional; Reaction in methoxypropylacetate):

150 g of a silicone resin consisting of 59% _Ph-SiO3 / 2 units and from 41 mol% Me ₂ SiO _2/2 units is constructed, wherein 25 mol% of the bound on the silicon oxygen atoms carrying methyl substituents, together with 10 g Vinyltrimethoxysilane and 14 g of vinyl phosphonic dissolved in 350 g of methoxypropyl acetate presented and stirred at 50 ° C for 1 h. Subsequently, 14 g of dimethylaminoethyl methacrylate are added to the homogeneous solution and heated to 80 ° C. 10 g of a 70% solution of tert-butyl perpivalate in water are metered in over 2 hours. The mixture is then stirred for 3 h at 70 ° C.

you receives a suspension of the organically modified resin in methoxypropyl acetate. Examination by 1H-NMR and 29Si-NMR shows the complete polymerization of the monomers and the condensation of the silane.

Example 7: Carboxylic ester, carboxylic acid, vinyl-functional silicone resin

200 g of a 75% xylene solution of a Methylphenylsiliconharzes constructed to 53 mol% of PhSiO _3/2 units and 47 mol% of _{Me2 SiO2} / 2 units, and 12.5 mole % silicon-bonded OH groups and 1.1 mol% of silicon-bonded ethoxy groups and having an average molecular weight of Mw = 1900 g / mol are mixed with 28 g of 2,2-dimethyl-2-sila-1,4-dioxane and 0.4 g of a 10% lithium methylate solution was added. The mixture is heated to 60 ° C and stirred for 90 min at this temperature. The methanol is removed from the mixture at 200 mbar and 60 ° C and allowed to cool, with 200 ml of toluene are added. In the cooled to room temperature mixture 21 g of maleic anhydride are added, these are dissolved with stirring at room temperature and then heated to 90 ° C. The mixture is stirred for 5 h at 90 ° C. The solvent is removed at 80 ° C and 80 mbar. The resulting reaction product is clear, yellowish and liquid. For characterization, a 1H-NMR and a 29Si-NMR spectrum are recorded, and the molecular weight and the acid number (in mg KOH / g of substance) are determined. The acid number is 40. The double bond from the maleic anhydride is retained, the maleic acid is present as a half ester bonded to the silicone backbone.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - US 5439977 [0005, 0005]
• US 4312974 [0006]
• US 4507441 [0007]
• - DE 69613285 T3 [0008]
• US 2007/0142574 A1 [0009]

Claims (7)

Polyorganosiloxanes which are at least two different carry organic functions per molecule, with these being selected are from the group carbinol, primary, secondary or tertiary amino group, diamino, triamino, carboxylic acid, Aldehyde, keto, β-ketoamine, carboxylic acid anhydride, carboxylic ester, Carboxylic acid amide, vinyl, phosphonic acid, phosphonic ester function, Carbon-carbon double or triple bond, wherein the olefinic double bond also part of a (meth) acrylic function can always be just one type of olefinic double bond or C-C triple bond in combination with another organofunctional one Group from the specified selection exists, the at least two organic functions are both bound directly to the silicon can, as well as part of silicon-bonded hydrocarbon radicals They can not be directly attached to a silicon atom are bonded, wherein the silicon-bonded hydrocarbon radicals, to which the organic functions can be bound, also include polymeric hydrocarbon radicals. Polyorganosiloxanes or mixtures thereof according to Claim 1, constructed from repeating units of the general formula (1): [A ¹ _z B ¹ _p SiO _{(4-pz) / 2} ] (1) where the radicals B ¹ (organic copolymer) independently of one another denote a hydrogen, hydroxyl, alkoxy or aryloxy radical having up to 18 C atoms, or a C 1 to C 12 hydrocarbon radical or a polymeric hydrocarbon radical which is an organofunctional radical the group carbinol radical, carboxylic acid radical, carboxylic acid amide radical, carboxylic anhydride radical, primary, secondary or tertiary amino, diamino or triamino radicals, phosphonic acid radical, phosphonic ester radical, carboxylic acid ester radical, an aldehyde, a keto, a β-ketoamine, or an olefinically or acetylenically unsaturated C2 -C18 radical, wherein the olefinically or acetylenically unsaturated radical may have one or more olefinically or acetylenically unsaturated groups, which are not gekummuliert, and wherein the olefinic double bond may also be part of a (meth) acrylic function, always always only one kind olefinic double bond or CC triple in combination with another organofunctional group from the group named herein in a polyorganosiloxane of repeating units of the general formula (1), wherein said organofunctional radicals may also be bonded directly to a silicon atom, and it is also possible that in a radical B ^{1 contains} two such organofunctional groups, wherein polymeric hydrocarbon radicals B ^{1 are} mono- or divalent polymer radicals of ethylenically unsaturated monomers or a copolymer radical B ¹ of ethylenically unsaturated monomers and of ethylenically functionalized nanoparticles, obtainable by free-radically initiated polymerization of 1.) one or a plurality of monomers from the group comprising vinyl esters, (meth) acrylic esters, vinyl aromatics, olefins, 1,3-dienes, vinyl ethers and vinyl halides and optionally other monomers copolymerizable therewith, such as maleic acid and maleic anhydride or fumaric acid, and the like d in the case that the radical B ¹ is a copolymer radical of ethylenically unsaturated monomers and ethylenically functionalized particles in the presence of 2) at least one particle P having an average diameter of preferably less than 1000 nm, which with ethylenically unsaturated, radically polymerizable Groups being functionalized, 2.1) as particles P one or more from the group of metal oxides and semi-metal oxides are used, and / or 2.2) as particles P silicone resins are used which consist of repeating units of the general formula [R ⁴ _{(a + b)} SiO _{(4-ab) / 2} ] (II) wherein R ^{4 is the} same or different, and is hydrogen, hydroxy, and alkyl, cycloalkyl, aryl, alkoxy or aryloxy, each having up to 18 C atoms, which may optionally be substituted, a and b are integers in the value of 0, 1, 2 or 3, wherein for at least 20% of the specified repeat units a + b = 1 od it is 0, and for no more than 60% of the repeating units is 0, and 2.3) P can be a polydiorganosiloxane of the general formula [R ⁸ _{(a + b)} SiO _{(4-ab) / 2} ], where R ^{8 is} a hydroxy - denotes an alkyl, cycloalkyl, aryl, alkoxy or aryloxy radical and, except for the terminal silicon atom, a + b = 2, for the terminal silicon atoms, a + b = 3, where 2.1), 2.2) and 2.3) each with one or more α-organosilanes of the general formula (R ¹ O) _3-n (R ² ) _n Si (CR ³ ₂ ) -X (I) may be functionalized, wherein R ^{1 is} hydrogen, an alkyl group with 1 R ² and R ^{3 are} each independently hydrogen, an alkyl radical having 1 to 12 carbon atoms or an aryl radical, n are 0, 1 or 2, and X is a radical having 2 to 20 carbon atoms with an ethylenically unsaturated group, with the proviso that either a radical B ^{1 is} two different organofunctional e contains groups from the above-mentioned selection or always ver at least two radicals B ¹ per molecule ver mean, or contain, organofunctional groups which, in the event that one of the at least two different organofunctional groups or the at least two different organofunctional groups is part of a polymer or copolymer radical B ¹ , means that they are one species or at least two species olefinic contain unsaturated monomers which carry, in addition to the olefinically unsaturated function, another organic function which is not consumed in the polymerization process and in which polyorganosiloxane is available as a reactive function, in which case the at least two different organofunctional groups both in polymer contain at least two such olefinically unsaturated monomers having different organic functions, so that it is always ensured that in the polyorganosiloxane at least two different organic F are non-silicon-bonded hydrogen and / or a silicon-bonded hydroxy, alkoxy and / or aryloxy function, wherein the radicals B ¹ in the event that they are divalent polymer or copolymer radicals, two silicon atoms connect, A ^{1 is} a hydrogen or hydrocarbon radical, which contains up to 18 carbon atoms and may additionally contain heteroatoms selected from O, S, Si, Cl, F, Br, P or N atoms, where the radical A ¹ can also be bonded to the silicon atom via a heteroatom, and z and p have the values 0, 1, 2 or 3, wherein for at least 20% of the repeat units of the general formula (1) z + p = 1 or 0 and z + p is not more than 60% of the repeating units 0. Polyorganosiloxane according to Claim 1 or 2, characterized characterized in that the at least two organic functions only bonded to the silicon. Polyorganosiloxane according to Claim 1 or 2, characterized characterized in that the at least two organic functions only bonded to silicon-bonded hydrocarbon radicals. Polyorganosiloxane according to Claim 1 or 2, characterized characterized in that the at least two organic functions both bonded to the silicon are also part of silicon-bonded Hydrocarbon radicals are. Polyorganosiloxane according to one or more of the claims 1 to 5, characterized in that one of the at least two different organofunctional groups has a carboxylic acid function. Polyorganosiloxane according to Claim 6, characterized that is another of the at least two different organofunctional ones Groups an amino group, a group having an olefinic double bond or a triple bond or a phosphonate functional group having.