WO2013017365A1

WO2013017365A1 - Method for producing polyether siloxanes containing polyethercarbonate unit structures

Info

Publication number: WO2013017365A1
Application number: PCT/EP2012/062976
Authority: WO
Inventors: Matthias Lobert; Sarah Schmitz; Frank Schubert; Frauke Henning; Roland Hubel; Helmut HAHNEL
Original assignee: Evonik Goldschmidt Gmbh
Priority date: 2011-08-03
Filing date: 2012-07-04
Publication date: 2013-02-07
Also published as: DE102011109545A1

Abstract

The present invention relates to carbonate group-containing polyether siloxanes, a method for production thereof, and also use thereof.

Description

For more details, see P o l ye t h e s i l o x n n n s

Polvethercarbonatgrundstrukturen

The present invention relates to polyethersiloxanes containing carbonate groups, to a process for their preparation and to their use. More particularly, the present invention relates to a process for the preparation of polysiloxanes in which unsaturated polyether carbonates are added to SiH-bearing alkyl siloxanes. The unsaturated polyether carbonates are prepared by a technically easy to implement three-step one-pot process, wherein the incorporation of glycerol units, which cause the branching in the polyether carbonate backbone, preferably takes place between two alkoxylation steps.

Polysiloxanes bearing branched polyether groups are known in principle from the scientific literature. They are usually prepared by hydrosilylation of unsaturated branched polyethers onto SiH-bearing alkyl siloxanes.

As early as 1968, US Pat. No. 3,381,019 describes the hydrosilylation of branched, low molecular weight polyhydroxy-functional allyl compounds to Si-H-functional polysiloxanes in toluene as solvent. In 1984, such a process is described in US 4,431,789 for the hydrosilylation reaction of SiH-bearing polysiloxanes with unsaturated polyglycerols. Here, for reasons of compatibility of the reactants, the hydrosilylation is carried out in the presence of a solvent (isopropanol). Furthermore, potassium acetate is used as a buffering agent to avoid unwanted side reactions. Also in the application US 2006/0034875 such unsaturated polyglycerols are hydrosilylated in the presence of isopropanol as a solvent to SiH-bearing polysiloxanes.

This type of implementation requires a further process step after completion of the hydrosilylation in order to remove the auxiliary reagent (s). The hydrosilylated polyglycerols in both cases are base-catalyzed reaction products of allyl alcohol and several moles of glycidol.

A process for producing such polyglycerols is also described in DE 10 2007 043618 (US 2008085980). Here, a base-catalyzed addition of glycidol to allyl alcohol or glycerol monoallyl ether is described. The start connection is through the Addition of NaOH or sodium methylate deprotonated as a catalyst and the resulting by-products water or methanol are removed in vacuo. In addition, the glycidol addition is carried out at temperatures below 100 ° C to avoid unwanted side reactions. As an unwanted side reaction known to those skilled in the art, the rearrangement of allyl groups into corresponding 2-propenyl groups should be mentioned. This grouping is less reactive in subsequent reactions such as hydrosilylations and thus reduces the content of reactive molecules in the polyglycerol composite. The reduced reaction temperature as well as the necessary distillation step prolongs the process time, moreover, provision must be made for a distillation step on an industrial scale, which comes with a significant financial investment.

A completely different process for the synthesis of polysiloxanes which are modified with branched polyglycerols which dispenses with a hydrosilylation reaction is described in EP 1 489 128. According to this patent application, the preparation described above is by means of hydrosilylation of a SiH-functional polysiloxane with an allyl-modified polyglycerol accompanied by undesired side reactions that lead to gelling and to non-reproducible viscosity build-up. Thus, the hydrosilylation of SiH-functional polysiloxanes with z. B. allyl alcohol used as starting compounds. Glycidol is polymerized on these hydroxy-functional polysiloxanes under potassium or potassium methylate catalysis. However, a disadvantage of this process is the occurrence of by-products resulting from equilibration or cleavage reactions.

All previously discussed branched polyglycerol structures are based on pure glycidol homopolymers. Branched copolymers of alkylene oxides such as. Example, ethylene oxide as linear building blocks and glycidol as a branching component are also known.

EP 0 116 978 (US 07 / 356,359) describes the Lewis acid and alkali metal hydroxide catalyzed polymerization of glycidol and ethylene oxide onto polyhydroxy-functional polyethers. However, the use of these compounds to modify polysiloxanes is not described. The branched polyethers described in WO 2007/075927 (US2010234518) are based on the reaction of allyl alcohol with alkylene oxides and glycidol or hydroxy-functional oxetanes as branching component. Also in the application DE 10 2006 031 152 (US 2010240842) describes a corresponding structural motif based on hydroxy-functional oxetanes as branching component. In applications WO 2010/003610 (US 201,1185947) and WO 2010/00361 1 (US Pat. No. 129,933,333) glycidol is also mentioned for the first time as glycerol carbonate as a possible branching component, but only alkoxylation products which are free of carbonate groups are described.

The advantages of using glycerine carbonate instead of glycidol will be explained in detail below. Especially when considering safety-relevant and ecotoxicological aspects, the advantages of the branching component glycerine carbonate become clear.

Glycidol tends to spontaneous polymerizations, which usually take place with decomposition and explosion and thus entails an increased risk potential in itself, which concerns in particular the storage and implementation on an industrial scale. These requirements must be met by large-scale, technical measures and thus also financial investment.

In addition, the industrial production of glycidol is based on methods that are harmful to resources and resources. Thus, glycidol z. B. obtained by dehydrochlorination of 3-chloropropane-1, 2-diol, based on epichlorohydrin as the starting component. For its production, large amounts of toxic halogens such as chlorine are required and in the final dehydrochlorination incurred large amounts of unusable by-products. Thus, only petrochemical raw materials are irrevocably consumed and large quantities of unusable by-products are produced, both of which contribute to an extraordinary burden on our ecosystem.

Furthermore, glycidol also carries a high health-relevant hazard potential in itself, since it is carcinogenic and can also lead to serious eye damage in case of eye contact. Glycerine carbonate, on the other hand, is the much more advantageous compound from an ecotoxicological point of view. It is obtained on an industrial scale from the renewable raw material glycerine. Glycerine is increasingly a by-product of the production of biodiesel from fatty acid esters. The glycerol carbonate can finally be obtained by transesterification with dimethyl carbonate or condensation with urea. The glycerine carbonate is a stable, colorless compound that is toxicologically harmless and not is subject to labeling. In addition, unlike glycidol, glycerol carbonate can be distilled without decomposition, which considerably facilitates any necessary purification.

In the patent applications WO 2010/003610 and WO 2010/00361 1, for the polymerization of glycerol carbonate, reference is made in each case to the scientific publication G. Rokicki et al., Green Chemistry, 2005, 7, 529-539, in which the homopolymerization of glycerol carbonate is described on polyhydroxy-functional starters. Said method is also described in detail in PL 199346. The process described there for the preparation of hyperbranched polyethers describes a very slow and thus time-consuming reaction of glycerol carbonate with polyols, which also takes place in the solvent and thus leads to - on an industrial scale - non-economic processes. The products are all free of carbonate groups. The methods described in the last four mentioned patent applications describe the previously discussed step of distillative separation of the resulting from the reaction of hydroxyl-functional starting compound with the catalyst gap component which is technically disadvantageous. In addition, the hydrosilylation reaction is carried out in the cited documents in the presence of a solvent and / or a buffering agent (vide infra).

The object of the present invention was to provide a process for the preparation of polyethersiloxanes which have one or more branched polyether components, which are preferably highly hydrophilic, and do not have one or more of the disadvantages of the processes of the prior art.

Surprisingly, it has been found that polyethersiloxanes having branched polyether components can be prepared in a simple manner by a process comprising the steps of (a) providing branched polyethercarbonates having at least one olefinically unsaturated group, (b) providing SiH-functional siloxanes, and (c) reacting the SiH-functional siloxanes from (b) with the branched polyethercarbonates having at least one olefinically unsaturated group from step (a) to form SiC linkages. It was also completely surprising that the carbonate-containing polyether carbonates are stable. In the IR spectra before and after three weeks storage at 60 ° C, no differences were seen. The present invention therefore provides a process for the preparation of polyether carbonate-containing polysiloxanes containing branched structures, which is characterized in that it comprises the steps of (a) providing branched polyether carbonates having at least one olefinically unsaturated group and at least one structural unit -O-C (0) -0-, (b) providing SiH-functional siloxanes, and (c) reacting the SiH-functional siloxanes of (b) with the branched polyethercarbonates having at least one olefinically unsaturated group from step (a) to form SiC linkages.

Likewise provided by the present invention are polysiloxane compounds of the formulas (IV) and (V) described below, their use in particular as an additive in coating compositions, polymeric molding compounds or thermoplastics and compositions containing the polysiloxane compounds of the formulas (IV) and (V) according to the invention in a proportion of 0.1 to 10 wt .-% based on the composition.

The polysiloxane compounds according to the invention of the formulas (IV) and (V) described below and the compositions according to the invention can be used for a wide variety of applications. In particular, the use is to be mentioned as surface-active substances, such as. As nonionic surfactants, emulsifiers or wetting agents. Due to the high density of functional groups in the hydrophilic polyethercarbonate segment, they can be used for all applications in which associative interactions are important. An example is the possible H-bonding of the terminal OH groups (if present) of the branched structures. The compounds of the invention or the compositions of the invention may, for. Example, as an additive for ceramic formulations, as an additive in coating compositions, polymeric molding materials or thermoplastics, as crosslinking agents and as an additive for polyurethane compounds, in the manufacture of paints, varnishes, adhesives, as a support of catalysts or in biomedical technology are commonly used. A Use as an additive for cosmetic formulations and detergents is also possible.

The process according to the invention has the advantage that compounds are obtained in which the carbonate structures are at least partially retained. By the carbonate functions and / or the branching polyether (carbonate) can be obtained, which are liquid despite the incorporation of larger amounts of ethylene oxide under normal conditions. The use of glycerol carbonate as a starting material also has the advantage that it is non-toxic compared to glycidol and does not tend to autopolymerize.

The process according to the invention also has the advantage that the hydrosilylation process step can also be carried out in the absence of solvents and / or acid-buffering agents without any loss of product quality having to be accepted. Also, the undesirable side reactions reported in EP 1 489 128 A1 could not be observed with the method according to the invention. A further advantage of the present invention is that it is possible to dispense with the removal of the alcohols produced in the preparation of the polyether carbonates without having to accept any loss of quality of the end product.

The objects according to the invention are described below by way of example, without the invention being restricted to these exemplary embodiments. Given below, ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their content, in particular with regard to the facts in connection with which the document was cited, should be included in full in the disclosure of the present invention. When chemical (sum) formulas are used in the present invention, the indicated indices may represent both absolute numbers and averages. For polymeric compounds, the indices are preferably averages Percentages are by weight unless otherwise specified. If measurements are given below, these measurements have been carried out under normal conditions (25 ° C and 1013 mbar) unless otherwise specified. If mean values are given below, the weight average is, unless stated otherwise.

The process according to the invention for the preparation of polyether carbonate-containing polysiloxanes containing branched structures is characterized in that it comprises the following steps:

(a) providing branched polyether carbonates which have at least one olefinically unsaturated group and at least one structural unit -O-C (O) -O-,

(b) providing SiH-functional siloxanes, and

(c) Substituting the S i H-functional siloxanes from (b) with the branched polyethercarbonates having at least one olefinically unsaturated group from step (a) to form SiC linkages.

Step (a):

The term "branched polyether carbonate" here stands for a polyether carbonate in which both the main chain and at least one side chain contain polyether and / or polyether carbonate structures.

Branched polyether carbonates which have at least one olefinically unsaturated group and at least one structural unit -O-C (O) -O- are preferably of the formula (I)

Z (-X-M1 M2 _ir _i M3i3-M4-M7 _w -M5i ₅ -M6i6 _i7 -M8i8-M9i9-Jiio) i provided / used, wherein (-XJ) k (I)

i = 1 to 10, preferably 1 to 5, preferably 2 to 3,

k = 0 to 9, preferably 0 to 5, preferably 1 to 3,

i + k = 1 to 10, preferably 1 to 5, particularly preferably 1 to 3,

i1 to i10 = each independently 0 to 500, preferably 0 to 100 and particularly preferably 0.1 to 30,

Z = any organic, terminally unsaturated, radical, preferably terminally unsaturated, linear, cyclic or branched, aliphatic or aromatic hydrocarbon radical which may also contain heteroatoms, as well as further substituted, functional, organic, saturated or unsaturated radicals,

X is O, NH, N-alkyl, N-aryl or S, preferably O or NH, particularly preferably O, J = independently of one another hydrogen, a linear, cydic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 30 C atoms, a carboxylic acid radical having 1 to 30 carbon atoms or a heteroatom-substituted, functional, organic, saturated or unsaturated Radical, preferably hydrogen, a linear or branched, saturated hydrocarbon radical having 1 to 18 carbon atoms or a carboxylic acid radical having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl or acetyl radical,

where X ¹ to X ⁴ independently of one another are hydrogen or linear, cyclic or branched, aliphatic or heteroaromatic, saturated or unsaturated hydrocarbon radicals having 1 to 50 carbon atoms, preferably with 2 to 50 carbon atoms, which may optionally contain halogen atoms, with the proviso that X ¹ to X ^{4 are} not selected such that M ^{3 is} equal to M1 or M2,

wherein Y independently of one another is a linear, cydic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 2 to 30 C atoms, which may also contain heteroatoms,

wherein the monomers M1 to M9 may be arranged in any ratios, both blockwise, alternately or randomly, and may have a distribution gradient, and in particular the monomers M1 to M4 are freely permutable, with the provisos that i9> 0, preferably from 0 , 1 and 100, preferably 0.5 to 50 and particularly preferably 1 to 10, that preferably at least one unit M5 or M6 is contained, in which no radical J joins directly at any end, and that two monomer units of the type M9 not follow one another. Preferably, the radical J in formula (I) is a hydrogen atom, a methyl or acetyl radical. The sum Σ i5 to i9 is preferably> i + 1, preferably> i + 2. The index i 10 is dependent on the number of units with the index i5 and i6 and preferably satisfies the condition i 10 = 1 + (i5 + i6 ). The branched polyethercarbonate of the formula (I) preferably has at least one structural unit resulting from the fact that the monomer unit M9 is linked directly to an M5, M6, M7 or M8 unit.

The number of radicals J in the polyethercarbonate of the formula (I) depends on the number of branches, ie the number of units M5 and M6 and the indices i and k.

As substituents, the hydrocarbon radicals Z may preferably have halogens. As heteroatoms, the hydrocarbon radicals Z may in particular have nitrogen and / or oxygen, preferably oxygen. Particularly preferred hydrocarbon radicals Z have no substituents and no heteroatoms and very particularly preferably have from 2 to 20 carbon atoms. The monomer unit M1, M2, M7 or M8, preferably M1 or M2, preferably forms the last member of a monomer chain.

It may be particularly advantageous if i1 is greater than 0 and i2, i3 and i4 are equal to zero.

The branched polyethercarbonate to be hydrosilylated is preferably made up of a suitable initiator and various monomer units M.

The branched polyether carbonates, in particular the branched polyether carbonates of the formula (I), are preferably prepared by reacting starters of the general formula (II)

Z (XH) _j (II)

With

X is O, NH, N-alkyl, N-aryl or S, preferably O or NH, particularly preferably O, j = 1-10, preferably 1 to 5, particularly preferably 1 to 3,

and Z as defined above,

alkoxylated (polymerized), being used as (alkoxylation) reagent at least one glycene carbonate and preferably a different of glycene carbonate reagent, in particular alkylene oxide.

If only glycene carbonate is used as the reagent, then the starter Z (XH) _{j is} preferably a polyether alcohol.

The initiator (II) is preferably an alkyl, aryl or aralkyl compound of j = 1 to 3 which is hydroxy-functional and ω-unsaturated. The initiators (II) are preferably alkyl, aryl or aralkyl compounds where j = 1 to 5, preferably] = 1 to 3, which are o (XH) -functional, preferably α-hydroxy-functional and ω are unsaturated. Such initiators are preferably (meth) allylic compounds. When the term "(meth) allylic" is used, it includes "allylic" and "methallylic" respectively. When allylic starters are used in the context of this invention, this term always also encompasses the methallylic analogs, with the allylic compounds being preferred as starters in each case.

If starters (II) are used with j = 1, they preferably have a structure of the general formula (II) where X = O. Starters of the general formula (II) where Z is CH ₂ = CH-CH ₂ -XH, C 1 -C 4 -CHRO-CHrCHz-XH, CH ₂ CHCH-XH, CH ₂ CHCH- (CH ₂ ) ₄ -XH are preferably used or CH ₂ = CH- (CH ₂ ) 9 -XH wherein X is preferably each O, or Z = polyether, such as. B. polymers of ethylene oxide and / or propylene oxide and / or other alkylene oxides and / or glycidyl ethers.

Particular preference is given to using, as mono-hydroxy-functional allylic starters of the formula (II), allyl alcohol or 2-allyloxyethanol, very particularly preferably allyl alcohol. But can also be used, the corresponding methallyl compounds such. As methallyl alcohol or Methallylpolyalkylenoxide.

Examples of mono-hydroxy-functional starters of the formula (II) which have an aromatic radical Z are, for example, B. allyl or methallyl-substituted phenol derivatives.

Examples of preferably used α-hydroxy-co-alkenyl-substituted starters are in particular 5-hexen-1-ol and 10-undecene-1-ol, with 5-hexen-1-ol being particularly preferred.

Examples of suitable cyclic unsaturated, hydroxy-functional compounds are e.g. 2-cyclohexen-1-ol, 1-methyl-4-isopropenyl-6-cyclohexene-2-ol and 5-norbornene-2-methanol.

As can be seen from the formula (II), it is also possible to use starters, in particular allylic starters according to formula (II) with j> 1, such as, for example, B. dihydroxy-functional (j = 2), trihydroxy-functional (j = 3) or polyhydroxy-functional (j> 3) starter use. These have increased polydispersities with increasing hydroxy functionality, which may also advantageously influence the physical properties of the end products. So z. B. a higher proportion of branches to a lower viscosity of the products obtained.

Such polyhydroxy-functional starters are preferably monoallylically etherified di-, tri- or polyols, such as, for example, monoallyl ethers of glycerol, trimethylolethane and trimethylolpropane, monoallyl or mono (methallyl) ethers of di (trimethylol) ethane, di (trimethylol) propane and pentaerythritol. The starter according to formula (II) with j> 1 is particularly preferably derived from a compound from the group comprising 5,5-dihydroxymethyl-1,3-dioxane, 2-methyl-1,3-propanediol, 2-methyl-2- ethyl-1, 3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, dimethylpropane, glycerol, trimethylolethane, trimethylolpropane, diglycerol, di (trimethylolethane), di (trimethylolpropane), pentaerythritol, Di (pentaerythritol), anhydroenneaheptitol, sorbitol and mannitol. Very particular preference is given to using di- or poly-hydroxy-functional allylic starting compounds, trimethylolpropane monoallyl ether or glycerol monoallyl ether. As a multi-hydroxy-functional starter d the formula (II) Kings also cyclic, polyhydroxy-functional starting compounds such. B. 5-norbornene-2-dimethanol and 5-norbornene-2,3-dimethanol.

The preparation of the branched polyether carbonates is preferably carried out such that the initiator is reacted with one or more alkylene oxide (s), with glycerol carbonate and optionally with one or more glycidyl ethers. This reaction can be carried out using the respective pure substances or using mixtures of one or more of the educts. The order of the reaction steps can be arbitrary, so that both statistical structures or arbitrary structures of the polyether skeleton as well as gradient-like or block-like structures can be obtained.

The branched polyethercarbonate provided with a hydrosilylatable group can be prepared by a three-stage, ring-opening polymerization process in the one-pot procedure. The branched polyether carbonates are preferably prepared by first reacting the initiator with one or more alkylene oxides other than glycerol carbonate, reacting with glycerol carbonate, and then preferably further reacting with alkylene oxides other than glycerol carbonate. and / or glycidyl ethers. Of course, the process can also be interrupted after each of the three process steps. The respective intermediately obtained product can be bottled and stored until further reaction, but also reacted further in the same or another suitable reaction vessel. The process steps do not have to be carried out immediately after each other, however, too long a storage time of the intermediates may adversely affect the quality of the final product.

If an allyl polyether is used as initiator, it may be possible to dispense with the first alkoxylation step. To ensure the preservation of well-defined structures, the reaction is carried out as an anionic ring-opening polymerization under controlled monomer addition.

The simultaneous addition of alkylene oxides and / or glycidyl ethers with glycerol carbonate is also feasible, but less preferred due to the pressure build-up due to CO 2 release during the glycerol carbonate reaction. Preferably, therefore, no simultaneous addition of glycerol carbonate and alkylene oxides and / or glycidyl ethers. As alkylene oxides it is generally possible to use all alkylene oxides known to the person skilled in the art, pure or in any desired mixtures, which lead to the monomer units M1, M2 or M3 defined in formula (I). Preference is given to ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, octene-1-oxide, decene-1-oxide, dodecene-1-oxide, tetradecene-1-oxide, hexadecene-1-oxide, Octadecene 1-oxide, C20 / 28 epoxide, a-pinene epoxide, cyclohexene oxide, 3-perfluoroalkyl-1, 2-epoxypropane and styrene oxide used. Particular preference is given to using ethylene oxide, propylene oxide, dodecene-1-oxide and styrene oxide. Very particular preference is given to using ethylene oxide and propylene oxide which correspond to the monomer units M1 or M2 defined in formula (I). Any glycidyl ethers used may result in the monomer units M4 mentioned in formula (I) which may be substituted by alkyl, aryl, alkaryl or alkoxy. The term "alkyl" as used herein preferably linear or branched C1-C30, such as C1-C12 or C _r C ₈ -, - alkyls or alkenyls. The term "alkyl" particularly preferably represents methyl, ethyl, propyl, butyl, tert-butyl, 2-ethylhexyl, allyl and C12-C14. The term "aryl" is preferably phenylglycidyl ether and the term "alkaryl" is preferably o-cresylglycidyl ether, p-tert-butylphenylglycidyl ether or benzylglycidyl ether. The term "alkoxy" preferably represents methoxy, ethoxy, propoxy, butoxy, phenylethoxy and comprises between 1 and up to 30 alkoxy units or a combination of two or more alkoxy units. 1, 4-butanediol diglycidyl ether, 1, 6- hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycerol-3-glycidyl ethers, Glycerintriglycidether, trimethylolpropane or Pentraerythrittetraglycidylether be used for the production of branched polyether carbonates. the use of such tri- or tetra-functional monomers leads also for building branched structural elements. As branching agent, glycene carbonate is used in the process according to the invention. In the context of the present invention, a branching agent is understood as meaning a molecule which, after reaction into the polyether skeleton, provides two reactive groups on which a further chain structure can take place. The glycene carbonate introduces into the polyether carbonate R _v the monomer units M5 to M8 and M9 defined in the formula (I).

In order to prepare branched polyether carbonates claimed in this disclosure of the invention, a branching is introduced into the polyether skeleton with the aid of the branching agent glycerol carbonate. Theoretically, 1 mol of branching agent per mole of XH group, in particular hydroxyl groups of the initiator, is sufficient. However, since the alkaline-catalyzed reaction of glycerol carbonate is not exclusively under nucleophilic attack on the CH ^ group of the carbonate ring, but the nucleophilic attack also takes place at the carbon of the carbonate group, and carbonate esters are formed. In order to ensure a sufficient degree of branching and content of carbonate ester groups, it is therefore preferred to use at least 2 mol of branching agent with respect to 1 mol of the XH group, preferably hydroxyl groups, of the initiator (II) used.

In order to keep the degree of branching manageable bar, it may be advantageous to limit the content of branching upwards. The ideal parameter here is the percentage molar content of branching agent, based on the molar content of the sum of all monomers from which the polyethercarbonate skeleton is made, ignoring the mole of starting alcohol. This molar content should preferably be at most 80 mol%, more preferably at most 50 mol%, and most preferably at most 35 mol%.

To prepare the branched polyether carbonates, the XH groups, preferably hydroxy groups of the preferably allyl-functional starters, are preferably at least partially deprotonated by alkali metal hydroxide or alkoxide, preferably sodium methoxide, potassium methoxide or potassium hydroxide, more preferably sodium methoxide. The amount of alkali metal hydroxide or alkoxide used is preferably from 5 to 25 mol%, preferably from 10 to 20 mol%, based on the number of XH groups, preferably OH groups of the initiators used.

The mixture of alcohols and alcoholates thus obtained is in the first process step with alkylene oxides preferably at a temperature between 80 ° C and 200 ° C, preferably from 90 ° C to 170 ° C and more preferably reacted from 100 to 125 ° C. The reaction preferably takes place at pressures in the range from 0.001 to 100 bar, preferably in the range between 0.005 and 10 bar and very particularly preferably between 0.01 and 5 bar (in each case absolute pressures).

After the quantitative reaction of the alkylene oxide, a deodorization step may optionally follow to remove traces of unreacted alkylene oxides. In such a deodorization step, the reactor is preferably at the temperature resulting from the alkoxylation, preferably up to a vacuum of less than or equal to 100 mbar, more preferably up to a vacuum of less than or equal to 60 mbar and more preferably to a vacuum of less than or equal to 30 mbar evacuated. In this evacuated reactor is now in the second process step, the glycerol carbonate, preferably at a temperature between 120 ° C and 220 ° C, more preferably between 140 ° C and 200 ° C and most preferably at a temperature between 160 ° C and 180 ° C. supplied to the reaction mixture.

As the rate of addition of the glycerin carbonate increases, and the chosen reaction temperature, the ratio of glycerol carbonate-based branching units M5-M8 to carbonate ester segments M9 can be controlled. The faster the rate of addition of the splitter and / or the lower the temperature, the higher the content of M9 units. Preferably, the addition of the branching agent takes place at a rate of 0.1 to 10, preferably 0.5 to 5 and particularly preferably 1 to 2.5 mol / h based on the number of (XH) groups of the starter used. The reaction of the glycerol carbonate can be partly due to the release of C0 ₂ and consequently by a pressure build-up in the reactor noticeable. This pressure build-up can be counteracted by continuous or periodic release. The rate of addition of the glycerol carbonate is preferably chosen so that the pressure in the reactor at no time exceeds a value of 2 bar (bar overpressure). Higher pressures in the reactor should be avoided, since at high temperatures and pressures, the rearrangement of allyl groups in no longer hydrosilylatable propenyl groups takes place increasingly and this would constitute an intolerable quality defect.

The reaction in the second process closes, preferably after an after-reaction (same conditions without further addition of branching agent) for a period of 1 minute to 20 hours, preferably 0.1 h to 1 0 h and particularly preferably from 1 h to 5 h from the last branching addition, preferably as a third process step, a further reaction with alkylene oxides. The conditions here correspond to those of the alkylene oxide addition of the first process step.

The (living) anionic ring-opening polymerization is controlled in all three process steps by the rapid exchange of protons between the alcohol and alcoholate groups of the growing chains. Since an additional hydroxyl group is generated with each mole of branching agent reacted, the effective concentration of alkoxide ions decreases as a result of the process. As a result, the reaction speed of the third process step may be slower than that of the first process step. To take this effect into account, it may be advantageous to carry out a renewed catalyst dosing after the second reaction step. Of course, in order to achieve a faster conversion of the glycerol carbonate, renewed catalyst dosing may also take place after the first reaction step, but this is less preferred.

The low molecular weight alcohol formed from the reaction of the catalyst with the molecule to be deprotonated can be distilled off both during the first process step and during the third process step in vacuo. However, it is clearly preferable to distill the, caused by the catalysis alcohol at any time, since this step would cause additional equipment and thus financial investment. Moreover, since the quality of the end product is in no way adversely affected by the presence of this secondary component (s), this process step is preferably dispensed with.

After completion of the third process step, a neutralization step may follow, in which the alkali z. B. is neutralized by the addition of appropriate amounts of inorganic acids such as phosphoric acid or organic acids such as lactic acid. Treatment with an acidic ion exchanger is also possible, but less preferred.

The branched polyethercarbonates have at least one branching generation, preferably at least two branching generations. The term "generation" is, as in WO 2002/40572 (US2004059086), in the present case also used to designate pseudo-generations. The C NMR shifts of the branched polyether carbonates were evaluated analogously to H. Frey et al., Macromolecules 1999, 32, 4240-1260.

The carbonate segments can be detected analytically by C-NMR and IR spectroscopy. Signals in the range of 155-165 ppm for the carbonyl carbon of the carbonate ester unit (s) can be seen in 13 C NMR. The IR shows the C = 0 absorptions of the carbonate ester oscillation in the range of 1740-1750 and optionally 1800-1810 wavenumbers.

The polydispersity (MJM _n ) of the branched polyethercarbonates of the formula (I), determined by means of GPC, is preferably <3.5, preferably <2.5 and particularly preferably from> 1.05 to <1.8. A particular embodiment of the synthesis of a branched polyether carbonate according to the claimed in the present application process, in which 4 moles of ethylene oxide, then 3 moles of glycerol carbonate and finally 4 moles of ethylene oxide and propylene oxide are randomly attached to the starter allyl alcohol, z. B. lead to a molecular structure of the branched polyether carbonate shown in formula (III). It can be seen from the structure of formula (III) that only one third of the theoretically possible amount of units M9 provided by the glycerol carbonate was incorporated. The other two-thirds escaped as C0 ₂ in the reaction.

The terminal hydroxy groups of the branched polyether carbonates may remain free or may be partially or completely modified to allow for optimum compatibility in the application matrix. As modification are esterifications or Etherifications as well conceivable as further condensation or addition reactions with z. B. isocyanates. As mono-isocyanates compounds such. As n-butyl isocyanate, cyclohexyl isocyanate, toluene isocyanate, or monoadducts of IPDI or MDI are used, preferably n-butyl isocyanate, toluene isocyanate, particularly preferably n-butyl isocyanate. It is also possible to use difunctional isocyanates such as MDI, IPDI or TDI, but this is less preferred. The terminal hydroxy groups preferably remain free, are acetylated, methylated or endcapped with carbonates.

All other known modification possibilities of hydroxy groups can also be used. The mentioned chemical reactions do not have to be quantitative. Thus, the free hydroxy groups may only partially, i. in particular at least one hydroxyl group to be chemically modified. The chemical modifications of the free hydroxy groups of the branched polyethercarbonates can be chemically modified both before and after the hydrosilylation reaction with the Si-H-functional polysiloxane

Step (b):

The SiH-functional siloxanes are preferably prepared in process step (b) by carrying out the equilibration process known from the prior art. The equilibration of the branched or linear, optionally hydrosilylated, poly (organo) siloxanes having terminal and / or pendant SiH functions is in the prior art, for. In documents EP 1 439 200 A1 (US 2004147703), DE 10 2007 055 485 A1 (US 2010249339) and DE 10 2008 041 601 (US2010056649). These references are hereby incorporated by reference and with respect to process step (b) are considered part of the disclosure of the present invention.

Step (c):

The step (c) is preferably carried out as hydrosilylation. In this case, the olefinically unsaturated polyether carbonates from step (a) are SiC-linked with the SiH-functional siloxanes from step (b) by means of noble metal catalysis.

The preparation of the silicone polyether block copolymers used can be carried out by a process known from the prior art in which branched or linear polyorganosiloxanes having terminal and / or pendant SiH functions, with an unsaturated polyether or a polyether mixture of at least two unsaturated Polyethers are implemented. The reaction is preferably carried out as a noble metal-catalyzed hydrosilylation, such as. As described in EP 1 520 870 (US2005075468). The document EP 1 520 870 is hereby incorporated by reference and is regarded as part of the disclosure content relating to process step (c) of the present invention. The noble metal catalyst used is preferably a platinum-containing catalyst.

The reactions may be carried out in accordance with procedure (c) in the presence or absence of saturated polyethers. Preferably, process step (c) is carried out in the presence of saturated polyethers. It is possible to carry out process step c) in the presence of other solvents other than saturated polyethers. Preferably, no solvents other than saturated polyethers are used. Process step c) can also be carried out in the presence of acid-buffering agents. Preferably, however, it is carried out in the absence of acid-buffering agents. Preferably, the process step is carried out in the absence of acid-buffering agents and solvents other than saturated polyethers.

In step (c), in addition to the branched polyether carbonates of (a), it is possible to use further linear and / or branched, unsaturated polyether compounds which are different from these. This is particularly advantageous if it is to be possible to adapt it to the compatibility with the application matrix of the polyether carbonate-containing polysiloxanes.

By different proportions of M1 and M2 in the unbranched allyl polyether, the properties of the inventive polysiloxane can be influenced. Thus, especially due to the greater hydrophobicity of the M2 units compared to the M1 units by the choice of suitable M1: M2 ratios, the hydrophobicity or respectively the hydrophilicity of the inventive polysiloxane can be controlled. It is possible to use more than one unbranched allyl polyether. To better control the compatibility, it is also possible to use mixtures of different unbranched allyl polyethers.

These polyethers can be prepared by any of the methods known in the art. The alkoxylation of unsaturated starting compounds can be both under base, acid or double metal cyanide (DMC) catalysis. The preparation and use of DMC alkoxylation catalysts has been known since the 1960's and is illustrated, for example, in US 3,427,256, US 3,427,334, US 3,427,335, US 3,278,457, US 3,278,458 or US 3,278,459. Even more effective DMC catalysts, in particular zinc-cobalt hexacyanocomplexes, have been developed in the subsequent period, for example in US Pat. Nos. 5,470,813 and 5,482,908.

It is possible to use exclusively unsaturated polyether carbonates or else any desired mixtures of these polyether carbonates with unsaturated polyethers which have no unit M9. The molar proportion of the unsaturated polyether carbonates used to the carbonate-free polyethers (polyether without M9 unit) is preferably from 0.001 to 100 mol%, preferably from 0.5 to 70 mol% and particularly preferably 1 to 50 mol% based on the Sum of unsaturated polyether carbonates and carbonate-free unsaturated polyethers.

By means of the method according to the invention z. For example, the polysiloxane compounds described below can be prepared.

The polysiloxane compounds of the formula (IV) according to the invention

RRRR ² R ^J R

R 1 a. -Si- O- -Si- O- ^■ Si- O- ^■ Si- O- ^■ Si- O- -Si R 1 b l_ RJ a L Rp Jbl L Rv Jb2l_ R ² J e l_ R ² J d ^R

R ² =

are characterized by the fact that

a is independently 0 to 2000, preferably 0 to 1000, in particular 1 to 500,

b1 independently of one another is 0 to 60, preferably 0 to 15, in particular 0 or 1 to 5,

b2 is independently 0 to 60, preferably 0 to 15, in particular 0 or 1 to 8, c is independently 0 to 10, preferably 0 to 6, preferably 0 or 1 to 3, d is independently 0 to 10, preferably 0 to 5, preferably 0 or 1 to 3, R is at least one radical from the group of linear, cyclic or branched, saturated or unsaturated hydrocarbon radical having 1 to 20 C atoms or aromatic hydrocarbon radical having 6 to 20 C atoms, preferably a methyl radical,

R ^{1 is} independently R or -OR ⁴ ,

R ^{1a is} independently R, R _v , R is _P or -OR ⁴ ,

R is independently R, R _v, R _P or-OR ⁴ ^1b

R ³ independently of one another R or an optionally substituted with hetero atoms, saturated or unsaturated, organic radical, preferably selected from the group of

Alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloyloxyalkyl, methacryloxyalkyl, methacryloxypropyl or vinyl radicals, particularly preferably a methyl, chloropropyl, vinyl or methacryloxypropyl radical is

R ⁴ independently of one another are alkyl radicals having 1 to 10 carbon atoms, preferably methyl, ethyl or isopropyl radical,

R _P independently of each other -OR ⁴ , hydrogen or bonded via a Si-C bond unbranched polyether radicals of alkylene oxide units having 1-30 carbon atoms, from arylene oxide units and / or from glycidyl ether units having a weight-average molecular weight between 200 and 30,000 g / mol and / or an aliphatic, cycloaliphatic and / or aromatic polyester or polyetherester radical having a weight-average molecular weight between 200 and 30,000 g / mol linked via a Si-C bond,

Rv are identical or different branched polyether carbonate radicals which, in addition to alkylene oxides and / or lactones, and / or anhydrides, and / or glycidyl ethers, contain at least one branching unit based on glycerol carbonate, preferably R _{v is} a radical of the formula linked via an Si-C bond (la) is

-Z '(- X-M1 _ir M2 _i M3i3-M4 _w -M5i ₅ -M6i6-M7 _i7 -M8i8-M9i9-Jio) i (-XJ) k (la)

With

i = 1 to 10, preferably 1 to 5, preferably 2 to 3

k = 0 to 9, preferably 0 to 5, preferably 1 to 3

i + k = 1 to 10, preferably 1 to 5, particularly preferably 1 to 3

i1 to i10 = each independently 0 to 500, preferably 0 to 100 and particularly preferably 0.1 to 30

Z = any organic, radical, preferably linear, cyclic or branched, aliphatic or aromatic hydrocarbon radical which also contains heteroatoms, and may contain further substituted, functional, organic, saturated or unsaturated radicals,

X is O, NH, N-alkyl, N-aryl or S, preferably O or NH, preferably O,

J = independently of one another hydrogen, a linear, cydic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 30 C atoms, a carboxylic acid radical having 1 to 30 carbon atoms or a heteroatom-substituted, functional, organic, saturated or unsaturated radical, preferably hydrogen, linear or branched, saturated hydrocarbon radical having 1 to 18 carbon atoms or a carboxylic acid radical having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl or acetyl radical,

where X ¹ to X ⁴ independently of one another are hydrogen or linear, cyclic or branched, aliphatic or heteroaromatic, saturated or unsaturated hydrocarbon radicals having 1 to 50 C atoms, preferably 2 to 50 carbon atoms, which may optionally contain halogen atoms, with the proviso that X ¹ to X ^{4 are} not selected such that M3 is equal to M1 or M2,

M5

wherein the monomers M1 to M9 may be arranged in any ratios, both blockwise, alternately or randomly, and may have a distribution gradient, and in particular the monomers M1 to M4 are freely permutable, with the provisos that i9> 0, preferably from 0 , 1 and 100, preferably 0.5 to 50 and particularly preferably 1 to 10, that preferably at least one unit M5 or M6 is contained, in which no radical J joins directly at any end, and that two monomer units of the type M9 not successive, wherein on average at least one radical R _v per molecule of the formula (IV) is present,

provided that the sum of b1 and b2 = b is that, per molecule of formula (IV), the average number £ a of D units per molecule is not greater than 2000, preferably not greater than 1000 and preferably not greater than 500 and the average number £ b of R _P and R _v bearing units per molecule is no greater than 100, preferably not larger than 60, the mean number £ c is not greater than 20, preferably not greater than 10 and preferably no + d per molecule is greater than 5, and

averaged over all the compounds of the formula (IV) obtained at most 20 mol%, preferably less than 10 mol%, particularly preferably 0 mol% of the radicals R _P , R ¹ , R ^1a or

R ^{1b are of} the type -OR ⁴ .

The compounds of the formula (IV) can be expressed for the purposes of the invention by the following formula (V). The polysiloxane compounds of the formula (V) according to the invention

[M ¹ ] _m1 [M ^a ] _ma [M [Dt [D ^R ] i [D ^v ] _b2 n _d [Q] c are characterized by the fact that

M ^a = [R ^1a ]

M ¹ = [R ¹ ]

D ^v = [SiRR ^v 02e]

D ^R = [SiRR ^p 02e]

T = [SiR'C

m1 = 2c + d

ma = mb = 1

a = 0 to 2000, preferably 0 to 1000, in particular 1 to 500,

b1 = 0 to 60, preferably 0 to 15, in particular 0 or 1 to 5,

b2 = 0 to 60, preferably 0 to 15, in particular 0 or 1 to 8,

b1 + b2 = b; Sum £ b not greater than 100, preferably not greater than 60,

d = 0 to 10, preferably 0 to 5, preferably 0 or 1 to 3,

c = 0 to 10, preferably 0 to 6, preferably 0 or 1 to 3,

Is not greater than 20, preferably not greater than 10, and preferably not greater than 5,

wherein the indications for the indices m1, m2, a, b1, b2, b, £ b, d, c, £ c + d represent average data per molecule of the formula (V),

R at least one radical from the group of linear, cyclic or branched, saturated or unsaturated hydrocarbon radical having 1 to 20 carbon atoms or aromatic

Hydrocarbon radical having 6 to 20 C atoms, preferably a methyl radical, R ^{1 is} independently R or -OR ⁴ ,

R ^{1a is} independently R, R _v , R is _P or -OR ⁴ ,

R is independently R, R _v, R _P or-OR ⁴ ^1b R ³ independently of one another R or a heteroatom-substituted, saturated or unsaturated, organic radical, preferably selected from the group of the alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloxyalkyl, Methacryloxyalkyl, methacryloxypropyl or vinyl radicals, particularly preferably a methyl, chloropropyl, vinyl or methacryloxypropyl radical,

R _{v is the} same or different branched polyether carbonate radicals which, in addition to alkylene oxides and / or lactones, and / or anhydrides, and / or glycidyl ethers, contain at least one branching unit based on glycerol carbonate, preferably R _{v is} a residue attached via an Si-C bond Formula (Ia) is -Z '(- X-M1 _ir M2 _i M3i3-M4 _w -M5i ₅ -M6i6-M7 _i7 -M8i8-M9i9-Jio) i (-XJ) k (la)

i = 1 to 10, preferably 1 to 5, preferably 2 to 3

k = 0 to 9, preferably 0 to 5, preferably 1 to 3

i + k = 1 to 10, preferably 1 to 5, particularly preferably 1 to 3

71 = any organic, radical, preferably linear, cyclic or branched, aliphatic or aromatic hydrocarbon radical which may also contain heteroatoms, as well as further substituted, functional, organic, saturated or unsaturated radicals,

X is O, NH, N-alkyl, N-aryl or S, preferably O or NH, preferably O,

J = independently hydrogen, a linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, a carboxylic acid radical having 1 to 30 carbon atoms or a heteroatom-substituted, functional, organic, saturated or unsaturated radical, preferably hydrogen, linear or branched, saturated hydrocarbon radical having 1 to 18 carbon atoms or a carboxylic acid radical having 1 to 10 carbon atoms, preferably rstoffatom, a methyl or acetyl radical,

where X ¹ to X ⁴ independently of one another are hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 to 50 C atoms, preferably 2 to 50 C atoms, which may optionally contain halogen atoms, with the proviso that X ¹ to X ^{4 are} not chosen such that M3 is equal to M1 or M2,

wherein the monomers M1 to M9 may be arranged in any ratios, both blockwise, alternately or randomly, and may have a distribution gradient, and in particular the monomers M1 to M4 are freely permutable, with the provisos that i9> 0, preferably from 0 , 1 and 100, preferably 0.5 to 50 and particularly preferably 1 to 10, that preferably at least one unit M5 or M6 is contained, in which no radical J joins directly at any end, and that two monomer units of the type M9 not successive, wherein on average at least one radical R _v per molecule of the formula (V) is present, averaged over all compounds of formula (V) at most 20 mol%, preferably less than 10 mol%, particularly preferably 0 mol% of the radicals Radicals R _P , R ¹ , R ^1a or R ^1b , of the type -OR ⁴ are. Preferred polysiloxanes according to the invention are those which have radicals R _v which are based on the abovementioned branched polyethers of the formula (I).

The radical R _v preferably has at least one structural unit resulting from the fact that the monomer unit M9 is linked directly to a unit M5, M6, M7 or M8.

The number of residues J in R _v depends on the number of branches, ie the number of units M5 and M6 and the indices i and k. The index i 10 is dependent on the number of units with the index i5 and i6 and preferably satisfies the condition i 10 = 1 + (i5 + i6).

By varying proportions of M1 and M2 in the radical R _v , the properties of the polysiloxane according to the invention can be influenced. Thus, especially due to the greater hydrophobicity of the M2 units compared to the M1 units by choosing appropriate M1: M2 ratios the hydrophobicity or respectively the hydrophilicity of the polysiloxane according to the invention are controlled.

As substituents, the hydrocarbon radicals Z may preferably have halogens. As heteroatoms, the hydrocarbons Z may in particular have nitrogen and / or oxygen, preferably oxygen. Particularly preferred hydrocarbon radicals Z have no substituents and no heteroatoms and very particularly preferably have from 2 to 20 carbon atoms. Compounds of the general formulas (IV) and (V) in which b1 is at least 1 are advantageously used in those systems which require compatibility adaptation; however, if b1 is zero then a necessary adaptation of the compatibility can also be achieved by the intrinsic structure of the branched polyether carbonate be achieved. The polysiloxane compounds according to the invention are preferably obtainable by the process according to the invention described above.

The polysiloxane compounds according to the invention preferably have a structure of the formulas (IV) and (V) in which Σ i5 + i6> i + 1.

Preferred polysiloxane compounds according to the invention are those in which the radical R _{v has} at least one structural unit resulting from the fact that the monomer unit M9 is linked directly to a unit selected from M5, M6, M7 or M8. The polysiloxane compounds according to the invention can, for. B. be used as Add itiv in coating compositions, polymeric molding compounds or thermoplastics.

Preferred compositions according to the invention, in particular coating compositions, polymeric molding compounds or thermoplastics, are those which contain from 0.1 to 10% by weight of polysiloxane compounds according to the invention.

Preferred novel coating compositions or polymeric molding compositions preferably comprise from 0.5 to 7.5% by weight, particularly preferably from 1 to 5% by weight, of at least one polysiloxane compound of the formulas (IV) and (V) according to the invention. Preferred thermoplastics according to the invention preferably contain from 0.1 to 5% by weight, preferably from 0.2 to 2% by weight, particularly preferably from 0.5 to 1% by weight, of at least one polysiloxane compound of the formulas (IV) and (V). The polysiloxane compounds of the formulas (IV) and (V) according to the invention and the compositions according to the invention can be used for a wide variety of applications. In particular, the use is to be mentioned as surface-active substances, such as. As nonionic surfactants, emulsifiers or wetting agents. Due to the high density of functional groups in the hydrophilic polyethercarbonate segment, they can be used for all applications in which associative interactions are important. An example is the possible H-bonding of the terminal OH groups (if present) of the branched structures.

The compounds of the invention or the compositions of the invention may, for. Example, as an additive for ceramic formulations, as an additive in coating compositions, polymeric molding materials or thermoplastics, as crosslinking agents and as an additive for polyurethane compounds, in the manufacture of paints, varnishes, adhesives, as a support of catalysts or in biomedical technology are commonly used. Use as an additive for cosmetic formulations and cleansers is also possible.

Characters:

With reference to FIG. 1, the present invention is explained in detail without the invention being restricted to the embodiment shown there.

FIG. 1 shows the IR spectrum of the branched polyether carbonate prepared according to Example 1. The bands at wavenumbers of about 1745 and 1805 are assigned to the CO units M9. Measurement Methods:

To determine parameters or measured values, the methods described below are preferably used. In particular, these methods were used in the examples of the present patent. The levels of branching can be detected for example by NMR analysis or MALDI Tof analyzes.

The NMR spectra were measured with a Bruker 400 MHz spectrometer using a 5 mm QMP head. Quantitative NMR spectra were measured in the presence of a suitable accelerating agent. The sample to be examined was dissolved in a suitable deuterated solvent (methanol, chloroform) and transferred into 5 mm or optionally 10 mm NMR tubes. MALDI-Tof analyzes were performed on a Shimadzu Biotech Axima (CFR 2.8.420081127) Reflectron device, with pulse extraction optimized to a molecular weight of 1000 g / mol. The sample was dissolved in chloroform (4-5 g / L) and 2 μί of this solution was applied to graphite as a matrix. The carbonate segments (M9) can be detected by C-NMR analyzes or preferably by IR spectroscopy. In I R spectroscopy, the M9 units can be detected by bands at wavenumbers of about 1745 and possibly about 1805.

The I R analyzes were measured on a diamond using the Tensor 27 I R spectrometer from Bruker Optics using the abandoned total reflection method. The resolution was 4 cm ^-1 and 32 sample scans were performed.

In the context of this invention, weight-average and number-average molecular weights are calibrated for the prepared polyether carbonates against a polypropylene glycol standard (76-6000 g / mol) and the end products calibrated against a polystyrene standard are determined by gel permeation chromatography (GPC). The GPC was run on an Agilent 1 1 00 equipped with a RI detector and an SDV 1000/10000 A column combination consisting of a 0.8 cm x 5 cm guard column and two 0.8 cm x 30 cm main columns at a temperature of 30 ° C and a flow rate of 1 mL / min (mobile phase: THF). The sample concentration was 10 g / L and the injection volume 20 μί.

The wet-chemical analysis was carried out in accordance with standard international methods: iodine number (IZ; DGF CV 1 1 a (53), acid number (SZ, DGF CV 2), OH number (ASTM D 4274 C). In the examples given below, the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.

Examples:

Example 1: Preparation of a Branched, Pure EO-containing Polvethercarbonats

In a 5 liter autoclave 138 g of allyl alcohol and 12.9 g Natnummethylat were under

Nitrogen and it was evacuated to an internal pressure of 30 mbar. While stirring, the reaction mixture was heated to 115 ° C and at this temperature 691 g of ethylene oxide were added. After quantitative conversion of the EO, the reactor contents were deodorized by evacuation to 30 mbar to remove any traces of unreacted EO. Subsequently, the temperature was increased to 170 ° C and over a period of 2 h 622 g of glycerol carbonate were added continuously. After an approximately two-hour post-reaction, the reaction mixture was cooled to 115 ° C and it was annealed another 1009 g of EO. After a one-hour post-reaction, the mixture was deodorized and neutralized with 25% by weight phosphoric acid. The branched polyether obtained had an OH number of 183.1 mg KOH / g and an IV of 24.2 mg I _2/100 g. According to GPC, Mp = 444, Mw = 776, Mn = 507 and Mw / Mn = 1.5. By way of example, the IR spectrum is shown in the appendix, in which the carbonate ester vibrations at 1805 and 1746 cm ^{-1 are} recognizable.

Example 2: Preparation of a more branched, reindeer E O-containing polycarbonate carbonate

In a 5 liter autoclave 119.6 g of allyl alcohol and 11, 1 g Natnummethylat submitted under nitrogen and evacuated to an internal pressure of 30 mbar. With stirring, the reaction mixture was heated to 1 15 ° C and at this temperature, 599.5 g of ethylene oxide were added. After quantitative conversion of the EO, the reactor contents were deodorized by evacuation to 30 mbar to remove any traces of unreacted EO. Subsequently, the temperature was increased to 170 ° C and over a period of 2 h 1071 g of glycerol carbonate were added continuously. After a post-reaction of about 3 hours, the reaction mixture was cooled to 115 ° C. and a further 1434 g of EO were added. After a one-hour post-reaction, the mixture was deodorized and neutralized with 25% phosphoric acid. The obtained branched Polyether had an OH number of 205.3 mg KOH / g and an IV of 16.8 mg I _2/100 g. According to GPC, Mp = 456, Mw = 885, Mn = 545 and Mw / Mn = 1.62.

Example 3 Preparation of a branched, EO- and PO-containing polycarbonate carbonate In a 5 liter autoclave, 116.9 g of allyl alcohol and 10.9 g of sodium methoxide were placed under nitrogen and evacuated to an internal pressure of 30 mbar. With stirring, the reaction mixture was heated to 1 15 ° C and at this temperature, 585.9 g of ethylene oxide were added. After quantitative conversion of the EO, the reactor contents were deodorized by evacuation to 30 mbar to remove any traces of unreacted EO. Subsequently, the temperature was increased to 170 ° C and over a period of 2 h 526.8 g of glycerol carbonate were added continuously. After about two and a half hours of post reaction, the reaction mixture was cooled to 115 ° C and 1157.3 g of PO were added. After a one-hour post-reaction, the mixture was deodorized and neutralized with 25% phosphoric acid. The branched polyether obtained had an OH number of 175.7 mg KOH / g and an IV of 21, 5 mg I _2/100 g. According to GPC, Mp = 517 Mw = 875, Mn = 579 and Mw / Mn = 1.5.

B e i s p e l 4: A cetylierung a low-branched, pure EO-containing Polvethercarbonats

Under protective gas was in a 2 liter three-necked flask equipped with dropping funnel and reflux condenser, the branched polyethercarbonate of Example 1 together with catalytic amounts of conc. Submitted hydrochloric acid and heated. Then, acetic anhydride was added slowly. After complete addition, the mixture was stirred for a further 4 h. Then optionally present acid residues were distilled off to obtain a terminally acetylated, branched polyether having an iodine value IV of 22.7 mg I _2/100 g.

Example 5 Production of Hydrogen Siloxanes According to EP 1 439 200 A1

In accordance with the desired stoichiometry, the SiH-functional and non-functional siloxanes used as raw materials in Example 1 of EP 1439200 A1 were mixed and mixed with 6% by weight of predried Lewatit® K-2621 ion exchange resin. The mixture was stirred for 6 hours at 70 ° C and filtered after cooling. In this way, liquid, clear hydrogen siloxanes were obtained whose structure according to formulas (IV) and (V) are listed in Table 1. Table 1: Structure of gem. Example 5 produced hydrogen siloxane

Example 6: Preparation of a polyether carbonate-modified siloxane

In a 500 ml four-necked flask with attached KPG stirrer, reflux condenser and internal thermometer, 61.7 g of the hydrogen siloxane from Example 5 and 136.2 g of the polyether carbonate from Example 1 were heated to 70 ° C. with stirring. 5 ppm of platinum in the form of a platinum O catalyst modified according to EP 1520870 were added by syringe. The gas volumetric determined conversion was quantitative after 3 hours. A yellow cloudy product was obtained which forms a clear solution with water.

Example 7: Preparation of a polyether carbonate-modified siloxane

In a 500 ml four-necked flask with attached KPG stirrer, reflux condenser and internal thermometer, 49.4 g of the hydrogen siloxane from Example 5 and 157.0 g of the polyether carbonate from Example 2 were heated to 70 ° C. with stirring. 5 ppm of platinum in the form of a platinum O catalyst modified according to EP 1520870 were added by syringe. The gas volumetric determined conversion was quantitative after 2 hours. A yellow cloudy product was obtained which forms a clear solution with water.

Claims

claims:

Process for the preparation of polyether carbonate-containing polysiloxanes containing branched structures, characterized in that it comprises the following steps:

(a) providing branched polyethercarbonates which have at least one olefinically unsaturated group and at least one structural unit -O-C (O) -O-,

(b) providing SiH-functional siloxanes, and

(c) reacting the SiH-functional siloxanes of (b) with the branched polyethercarbonates having at least one olefinically unsaturated group from step (a) to form SiC linkages.

A method according to claim 1, characterized in that in step (c) in addition to the branched polyether from (a) further of these different linear and / or branched, unsaturated polyether compounds are used.

Process according to Claim 1 or 2, characterized in that the reactions according to process step (c) are carried out in the presence of saturated polyethers.

Process according to at least one of Claims 1 to 3, characterized in that branched polyether carbonates having at least one olefinically unsaturated group are compounds of the formula (I)

Z (-X-M1 M2 _ir _i M3i3-M4-M7 _w -M5i ₅ -M6i6 _i7 -M8i8-M9i9-Jiio) i (-XJ) k (I) are used, wherein

i = I to 10,

k = 0 to 9,

i + k = I to 10,

i1 to i10 = each independently 0 to 500,

X = independently of one another O, NH, N-alkyl, N-aryl or S,

Z = any organic, terminal olefinically unsaturated radical,

J is independently hydrogen, a linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, a carboxylic acid radical having 1 to 30 carbon atoms or a heteroatom-substituted, functional, organic, saturated or unsaturated Rest,

wherein Y independently of one another is a linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 2 to 30 C atoms, which may also contain heteroatoms,

wherein the monomers M1 to M9 may be arranged in any ratios, both blockwise, alternately or randomly, and may have a distribution gradient, and in particular the monomers M1 to M4 are freely permutable, with the provisos that i9> 0, that is preferably at least one unit M5 or M6 is included, with no residue directly connected to a residue J, and that two monomer units of type M9 do not follow each other,

5. The method according to claim 4, characterized in that the radical J in formula (I) is a hydrogen atom, a methyl or acetyl radical.

6. The method according to claim 4 or 5, characterized in that the sum Σ i5 to i9> i + 1.

7. The method of claim 4 to 6, characterized in that i1 is greater than 0 and i2, i3 and i4 are equal to 0.

Method according to one of claims 1 to 7, characterized in that the branched polyether having at least one olefinically unsaturated group, are provided by starter of the general formula (II)

Z (XH) _j (II)

With

X = independently of one another O, NH, N-alkyl, N-aryl or S,

j = 1-10,

and Z as defined in claim 4,

alkoxylated or polymerized being used as (alkoxylation) reagent at least one glycerol carbonate and a different of glycerol carbonate alkylene oxide.

9. The method according to claim 8, characterized in that the initiator (II) is an alkyl, aryl or aralkyl compound with j = 1 to 3, which is α-hydroxy-functional and ω- unsaturated.

10. Polysiloxane compounds of the formula (IV)

RRRR ^ R ³ R

R 1 a _ ^■ Si- O- Si- O- Si- O- ^■ ^■ ^■ Si- O- Si- O- -Si- -R 1 b

LRJ a L Rp Jbl L Rv Jb2L R ² J e LR ² J d ^R

RRR ^ R ^J R

R ² = ^■ O-Si-O-Si-O-Si- ^■ O-Si-O-Si-R

RpJbiL ^R vJb2L R ^ J c L ^R Jd LRJ a

(IV) independently from 0 to 2000,

b1 independently 0 to 60,

b2 independently 0 to 60,

c are independently 0 to 10,

d are independently 0 to 10,

R is at least one radical from the group of linear, cyclic or branched, saturated or unsaturated hydrocarbon radical having 1 to 20 C atoms or aromatic hydrocarbon radical having 6 to 20 C atoms,

R ^{1 is} independently R or -OR ⁴ ,

1a

independently R, R _v , R is _P or OR,

1b

independently R, R _v , R is _P or OR,

R ³ independently of one another R or a heteroatom-substituted, saturated or unsaturated, organic radical, preferably selected from the group of the alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloxyalkyl, Methacryloxyalkyl, methacryloxypropyl or vinyl radicals,

R ⁴ independently of one another are alkyl radicals having 1 to 10 carbon atoms, preferably methyl, ethyl or isopropyl radical, R _P independently of one another -OR, hydrogen or unbranched polyether radicals bonded via Si-C bonds and comprising alkylene oxide units having 1-30 carbon atoms, arylene oxide units and / or glycidyl ether units having a weight-average molecular weight between 200 and 30,000 g / mol and / or aliphatic and / or cycloaliphatic and / or aromatic polyester or polyetherester residue bonded via Si-C bonds and having a weight-average molecular weight of between 200 and 30,000 g / mol,

Rv is a residue of the formula (Ia) attached via an Si-C bond

-Z '(- X-M1 M2 _ir _i M3i3-M4-M7 _w -M5i ₅ -M6i6 _i7 -M8i8-M9i9-Jiio) i (-XJ) ki = 1 to 10, preferably 1 to 5, preferably 2 to 3

k = 0 to 9, preferably 0 to 5, preferably 1 to 3

i + k = 1 to 10, preferably 1 to 5, particularly preferably 1 to 3

X = identical or different O, NH, N-alkyl, N-aryl or S,

Z = any organic radical,

J is independently hydrogen, a linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, a carboxylic acid radical having 1 to 30 carbon atoms or a heteroatom-substituted, functional, organic, saturated or unsaturated radical .

where X ¹ to X ⁴ independently of one another are hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 to 50 carbon atoms, preferably 2 to 50 carbon atoms Atoms, which may optionally contain halogen atoms, with the proviso that X ¹ to X ^{4 are} not selected such that M3 is equal to M1 or M2,

wherein the monomers M1 to M9 may be arranged in any ratios, both blockwise, alternately or randomly, and may have a distribution gradient, and in particular the monomers M1 to

M4 are freely permutable, with the provisos that at least one radical Rv is present, i9> 0, that preferably at least one unit M5 or M6 is contained, in which no radical J joins directly at any end, and that two monomer units of Type M9 do not follow each other,

wherein on average at least one radical R _v per molecule of the formula (IV) is present, with the proviso that the sum of b1 and b2 = b is that, per molecule of formula (IV), the average number £ a of D units per molecule is not greater than 2000, and the average number £ b of R _P and R _v carrying units per molecule is not greater than 100, the mean number £ c + d per molecule is not greater than 20, and

averaged over all the compounds of the formula (IV) obtained, not more than 20 mol%, of

Radicals R _P , R ¹ , R ^1a or R ^1b , of the type -OR ⁴ are.

11. Polysiloxane compounds according to claim 10, obtainable according to at least one of the processes of claims 1 to 9.

12. Polysiloxanverbindungen according to claim 10 or 11, characterized in that Σ i5 + i6> i + 1.

13. Polysiloxanverbindungen according to at least one of claims 10 to 12, characterized in that the radical R _{v has} at least one structural unit, which results from the fact that the monomer unit M9 is directly linked to a unit selected from M5, M6, M7 or M8.

Use of polysiloxane compounds according to at least one of claims 10 to 13 as a surface-active substance, as an additive for ceramic formulations, as an additive in coating compositions, polymeric molding compounds or thermoplastics, as a crosslinker and as an additive for polyurethane compounds, in the manufacture of paints, lacquers, adhesives, as Carriers of catalysts or in the biomedical technology in general or as an additive for cosmetic formulations and cleaning agents.

15. Compositions, in particular coating compositions, polymeric molding compounds or thermoplastics, containing 0.1 to 10 wt .-% of polysiloxane compounds according to any one of claims 10 to 13.