EP2563846A2

EP2563846A2 - Hydrophilic polyorganosiloxanes

Info

Publication number: EP2563846A2
Application number: EP11716239A
Authority: EP
Inventors: Paul Boehm; Holger Frey; Tammo J. Menke
Original assignee: Momentive Performance Materials GmbH; Momentive Performance Materials Inc
Current assignee: Momentive Performance Materials GmbH; Momentive Performance Materials Inc
Priority date: 2010-04-26
Filing date: 2011-04-20
Publication date: 2013-03-06
Also published as: WO2011134869A3; DE102010028182A1; WO2011134869A2; US20130123530A1

Abstract

The invention relates to glycerol-modified polyorganosiloxane compounds having high hydrophilicity and use thereof.

Description

Hydrophilic polyorganosiloxanes

The invention relates to hydrophilic polyorganosiloxane compounds which are prepared by reacting functionalized polyorganosiloxane compounds with glycidol. The hydrophilic polyorganosiloxane compounds have special properties which make them suitable for particular as additives, the surface treatment, modi ficators and raw materials for elastomers or foams, emulsifiers, wetting agents, lubricants applications as well as foam stabilizers, defoamers or the like.

State of the art

Hydrophilic polyorganosiloxane compounds are used, for example, for the hydrophilization of surfaces such as silicone elastomers, as a reactive component in foams, as defoamers in hydrocarbons or as foam stabilizers in the production of rigid or flexible polyurethane foams. For example, in order to hydrophilize polyorganosiloxane compounds, polar groups such as polyether groups or ionic groups have been introduced into polyorganosiloxane compounds (e.g., DE 19748606 A1, EP 881249 A1). However, these known in the art hydrophilic polyorganosiloxane compounds have in some applications too low hydrophilicity, which is expressed by a too large contact angle at the interface to water or limited solubility in polar solvents such as alcohols.

EP 035080 biomedical moldings based on crosslinkable polyorganosiloxanes are known, for example, have silicon-bonded propoxypropane-l, 2-diol residues by hydrosilylation reaction with protected 3-AUyloxy-propane-1,2-diol and subsequent cleavage the protective group can be obtained. Similar compounds are described in EP-A-0266895 and US 6255429 Bl.

Glycidol functionalized polyorganosiloxanes having more than one glycidol unit per siloxane unit are not described.

It is an object of the present invention to provide novel hydrophilic polyorganosiloxane compounds having increased hydrophilicity or increased solubility in polar media, which serve, inter alia, as emulsifiers. A further object of the present invention is to provide novel hydrophilic polyorganosiloxane To provide compounds with increased durability on hydrophobic surfaces, especially on polyorganosiloxanes.

The inventors of the present patent application succeeded in providing new polyorganosiloxane compounds having increased hydrophilicity or increased solubility in polar media by grafting functionalized polyorganosiloxane starting compounds with glycidol.

The invention therefore provides polyorganosiloxane compounds obtainable by reacting polyorganosiloxane compounds of the formula (I):

[M _a D _b T _c Q _d ] _e (I) where

M = R ₃ Si0 _1/2 , D = R ₂ Si0 _2/2 , T = RSi0 _3/2 , Q = Si0 _4/2 , with a = 1-10 b = 0-1000 c = 0-1 d = 0 - 1 e = 1-10 wherein R = an organic group, with the proviso that R comprises at least one group R ¹ , wherein R ^{1 is} a monovalent straight chain, cyclic or branched, saturated or unsaturated C ₁ to C ₂ o hydrocarbon radical containing one or more groups

selected from -O- and may contain, and which has at least one group selected from -OH, -SH, -NH- and -NH ₂ , with a glycidol compound of the formula (II),

O

^0H (II) wherein R is selected from divalent C] to Cs hydrocarbon radicals, such as in particular methylene (-CH2-) is selected, with the proviso that the polyorganosiloxane compounds obtained at least one

Have radical R having Polyglycidolreste of the formula - (glycidol) _x , wherein x> 1, wherein the Polyglycidolrest is formed by ring-opening polymerization of the epoxy groups of the glycidol of the formula (II). Preferably R is methylene such that the preferred glycidol compound of formula (II) is glycidol of the following formula:

i , Other glycidol compounds include, for example. The introduction of several glycidol groups into the side chains of the polyorganosiloxanes achieves a significant increase in the hydrophilicity by formation of hydroxyl groups and ether groups. The polyglycidol side chains in particular have at least three hydroxyl groups and at least two ether groups (-O-), as can be seen, for example, in the following formula:

The starting compounds of formula (I) are generally prepared by hydrosilylation of SiH-functional polyorganosiloxane compounds with unsaturated functionalized compounds containing at least one group selected from -OH, -SH, -NH- and -NH ₂ or protected derivatives from those in which hydrogen has been replaced in the groups mentioned by protective groups, which can be converted in an additional step again in -OH, -SH, -NH or -NH ₂ groups.

SiH-functional polyorganosiloxane compounds include, for example:

Linear, cyclic or branched polyorganosiloxanes whose siloxy units are suitably selected from

T = RSi0 _3/2 , T ^H = HSi0 _3/2 , Q = Si0 _4/2 , in which these units are preferably selected from MeHSiO- or Me ₂ HSiOo, 5 units in addition to optionally other organosiloxy units, preferably dimethylsiloxy units , The polyorganohydrogen siloxanes can be described, for example, by the general formula (III) in which the symbols M * for M and M, D * for D and D and T * for T and T are shown for the sake of brevity: wherein the indices ae are as defined above. The siloxy units can be present in blocks or randomly linked to one another in the polymer chain. Each siloxane unit of the polyorganosiloxane chain may carry identical or different radicals.

The indices of the formula (IH) describe the average degree of polymerization P _n, measured as number average M _n per GPC, which relate to polyhydrogenmethylsiloxanes. Within the given viscosity limits, other siloxy groups thus give different molecular weights.

The preferred polyorganohydrogensiloxanes are structures selected from the group which can be described by the formulas (I-Ha-I-Hf)

HR ₂ SiO (R ₂ SiO) _z (RHSiO) _p SiR ₂ H (I-Ha)

HMe ₂ SiO (Me ₂ SiO) _z (MeHSiO) _p SiMe ₂ H (I-Hb)

Me ₃ SiO (Me ₂ SiO) _z (MeHSiO) p SiMe ₃ (I-Hc)

Me ₃ SiO (MeHSiO) _p SiMe ₃ (I-Hd)

{[R ₂ R ⁶ SiO _1/2] ₀ - ₃ [R ⁶ SiQ _3/2], [R ⁵ O] _0- i} _i-2 oo (I-He) {[Si0 _4/2}] [R ⁵ 0 _V2 ] OA [R ₂ R ⁶ Si0 _1/2 ] ₀ , oi-io [R ⁶ Si0 _3/2 ] ₀ . ₅ o [RR ⁶ Si0 _2/2 ]} _{1 -10} oo (I-Hf) z - O to 1000,

p = 0 to 100,

z + p = 0 to 1000,

wherein R ⁵ 0i _{/ 2 is} a C ₁ to C ₆ alkoxy radical on the silicon,

R ^e = hydrogen (H) or R, where at least one R ⁶ must be hydrogen. R is defined above, preferably R = methyl.

Particularly preferred

HMe ₂ SiO (Me ₂ SiO) _z (MeHSiO) _p SiMe ₂ H (I-Hb) where p = 0, ie, α, ω-dimethylhydrogen-terminated polydimethylsiloxanes. The polyorganohydrogensiloxanes are preferably liquid at room temperature, ie they preferably have less than 1000 siloxy units, ie they preferably have viscosities below 40 Pa.s at 25 ° C and D = 1 s ^" '. The unsaturated compounds which are reacted by means of hydrosilylation reaction with the polyorganohydrogensiloxanes and which serve to introduce the functional groups selected from -OH, -SH, -NH- and -NH ₂ are, for example, selected from:

Unsaturated, straight chain, cyclic or branched compounds of 2 to 20

Carbon atoms, which may contain one or more groups selected from -O- and, and having at least one group selected from -OH, -SH, -NH- and - H ₂ or correspondingly protected radicals of these groups.

The unsaturated group is preferably a CH 2 = CH or HC = C group.

Preferred such compounds are, for example:

Allyl alcohol, allylamine,

in which R ^{7 is} a hydroxy-protecting group, such as trimethylsilyl, or two R ⁷ groups represent an alkanediyl radical to form a cyclic dioxolane compound, such as 4-allyloxymethyl-2,2-dimethyl- [1,3-dioxolane: , the deprotected derivative (without protecting group) thereof:

Propargyl alcohol, butmol, cyclohexinol, and OH-protected derivatives thereof. Typical hydrosilylation catalysts include, for example:

Transition metals selected from the group of platinum, rhodium, ruthenium, palladium, nickel, iridium and their compounds. Preference is given to using platinum or compounds of platinum as hydrosilylation catalyst. Preference is given to vinylpolysiloxane-Pt (0) complex compounds, alkenylpolysiloxane-Pt (0) complex compounds, cyclohexene-Pt (0) complex compounds or the like described, for example, in B. Marciniec: Comprehensive Handbook on Hydrosilylation Pergamon Press Ltd. ,

The amount of hydrosilylation catalyst, in particular of the platinum catalyst is 0.1-1000 ppm, calculated as metal, based on the weight of the hydrogen siloxane compound and the unsaturated, functionalized compound. More preferred are 1-50 ppm of metal or metal compounds, especially platinum or platinum compounds, the amount referring to the metal (especially platinum), more preferably 2-24 ppm, even more preferably 3 to 15, most preferably 4 to 9, 5 ppm.

In the group of Pt, Rh, Ir, Pd, Ni and Ru compounds, ie their salts, complexes or metals, the hydrosilylation catalyst is selected, for example from the Pt catalysts, in particular Pt ° complex compounds Olefms, particularly preferably with vinylsiloxanes, such as, for example, 1: 1 complexes with 1,3-divinyltetra methyldisiloxane and / or tetravinyltetramethyltetracyclosiloxane, amine, azo or phosphite complex compounds. These Pt catalysts are exemplified in US 3,715,334 or US 3,419,593. The preferred Pt ⁰ -Olefmkomplexe one prepares in the presence of 1,3-di-vinyl-tetramethyldisiloxane (M ^Vl ₂ ) by reduction of hexachloroplatinic acid or other platinum chlorides. Likewise, of course, other platinum compounds, as far as they allow rapid crosslinking can be used, such as the photoactivatable Pt catalysts of EP 122008, EP 146307 or US 2003-0199603. For economic reasons, amounts between 10 and 300 ppm of metal are preferred, amounts below 10 ppm ensure only a low conversion rate or can be inhibited by impurities. As carriers for the catalysts, all solids can be selected as long as they do not undesirably inhibit hydrosilylation. The carriers can be selected from the group of powdered silicas or gels or organic resins or polymers. They are suitably selected so that a good separation of the solid can be carried out after hydrosilylation.

The polyorganosiloxane compounds of the formula (I) derived from the reaction of the polyorganohydrogensiloxane compounds with unsaturated functionalized compounds preferably comprise siloxy units selected from the following formulas:

wherein

R, when more of said siloxy units are present, may be the same or different and is selected from C ₁ to C ₂₂ alkyl, which may be optionally substituted by one or more fluorine atoms, C ₂ to C ₂₂ alkenyl, and C _{6 to} Cio aryl,

R ^{1 is} as defined above, and

f is from 0-600.

Therein the Q to C ^'but inserted ₂₂ alkenyl expedient to Flydrosilylierung before the reaction with glycidol by an equilibration or condensation reaction.

The D units further comprise siloxygrapps of the following formula wherein R in a single siloxy unit may be the same or different, or, when plural siloxy units are present, may be the same or different in different ones of the siloxy units and is selected from C) to C ₂₂ alkyl which may optionally be substituted by one or more fluorine atoms, C ₂ to C ₂₂ alkenyl and C ₁₀ -C 10 aryl, and

g is from 0-700,

wherein R, when more of said siloxy units are present, may be the same or different and is selected from C 1 to C ₂₂ alkyl, which may optionally be substituted by one or more fluorine atoms, C ₂ to C ₂₂ alkenyl and C _{6 to} C ₁₀ -Aryl, and h is 0-10,

wherein R ^{1 is} as defined above, and

i is from 0 - 10, wherein R, when more of said siloxy units are present, may be the same or different and is selected from C 1 to C ₂₂ alkyl, which may optionally be substituted by one or more fluorine atoms, C ₂ to C ₂₂ alkenyl and C _{6 to} C ₁₀ -Aryl, R ^{1 is} as defined above, and

wherein R, when more of said siloxy units are present, may be the same or different and is selected from C 1 to C ₂₂ alkyl, which may be optionally substituted by one or more fluorine atoms, C ₂ to C ₂₂ alkenyl and C 6, to Cio-aryl , and k is from 0-30,

wherein 1 = 0-10, f + g + h + i + j + k + 1 = 12 to 1000.

In the siloxy units with the indices f to 1, the C ₂ to C ₂₂ alkenyl groups are useful after hydro silylation but before the reaction with glycidol by a Aquilibrierungs- or condensation reaction inserted because they should not participate in this hydrosilylation reaction.

In a preferred embodiment of the present invention, the polyorganosiloxane compounds have two or more, preferably from 2 to 1000, radicals R ¹ .

In a further preferred embodiment of the present invention, the starting compounds of the formula (I) fulfill one or more of the following merlanals: R is selected from: C 1 to C ₁₀ -alkyl which may optionally be substituted by 1 to 13 fluorine atoms, preferably methyl , C2 to Cs alkenyl, and phenyl,

R ¹ is selected from: monovalent, straight-chain, cyclic or branched, saturated or unsaturated C] to Cio hydrocarbon radicals having one or more groups

selected from -O- and may contain, and having at least one group selected from -OH, -NH- and -NH ₂ , f = 1 to 200, preferably 1 to 100, preferably 1 to 50, preferably 1 to 30, preferably 3 to 30, preferably 5 to 30, g = 10 to 700, preferably 10 to 200, preferably 10 to 150, preferably 20 to 150, preferably 30 to 150, preferably 30 to 100, h = 0 to 5 and preferably 0, i = 0 to 5 and preferably 0,

1 = 0 to 5 and preferably 0, f + g + h + i + j + k + 1 = 10 to 500, preferably 10 to 200, preferably 10 to 150, preferably 20 to 150, preferably 30 to 150, preferably 30 to 100th In a further preferred embodiment of the present invention, the compounds of the formula (I) fulfill one or more of the following features:

R is selected from: C 1 - to C 6 -alkyl which may optionally be substituted by 1 to 13 fluorine atoms, preference is given to methyl, C 2 to C 5 -alkenyl, preferably vinyl, and phenyl,

R ¹ is selected from: monovalent, straight-chain, cyclic or branched, saturated or unsaturated C ₂ to C 10 hydrocarbon radicals which have one or more

Groups selected from -O- and may contain, and the at least one

Group -NH ₂ have.

In a further preferred embodiment of the present invention, the polyorganosiloxane compounds according to the invention have radicals R ² which have arisen from the reaction of radicals R ¹ with several glycidol molecules in each case by ring-opening of the epoxide, as shown below, for example:

+ Glycidol

Compound of the formula (I)

+ Glycidol

The reaction scheme is to be understood schematically. The addition of the glycidol molecules can also be carried out to other hydroxy groups, for example to form branched, dendrimeric hydrophilic side chains, such as, for example: polysiloxane

or in particular when using α, ω-functional polysiloxane compounds difunctional polysiloxane compounds such:

wherein in each case to the starting compound of the formula (I) per side chain R in the present case five glycidol molecules have added and where f is the index of a corresponding

Represents D unit.

The reaction of the starting compounds of the formula (I) with glycidol is preferably carried out in polar organic solvents, such as tetrahydrofuran, dioxane, DMF etc., at temperatures of 20 to 100 ° C and subsequent removal of excess glycidol and solvents. Glycidol is naturally used in a molar excess based on the molar amount of the radicals R, so that on average at least about two, preferably at least three, more preferably at least four glycidol molecules have added to a NHR, NH ₂ , SH or OH-modified siloxy unit (- (Gly)> 2). The reaction is preferably carried out in the presence of basic catalysts which do not react with glycidol, and which do not depolymerize the polysiloxane chain, such as, for example, alkali metal alkoxides, such as tert-butylpotassium. In case of use amino-functional starting compounds of the formula (I), the presence of a basic catalyst is surprisingly not required in many cases.

In this way, highly hydroxy-containing, polydiorganosiloxanes having a completely new property profile and the like can be obtained. be prepared with the highest hydrophilicity, whereby new applications are accessible.

The polyorganosiloxane compounds according to the invention thus expediently have polyglycidol radicals of the formula

(Glycidol) _x , wherein x is from 2 to 20, preferably 4 to 18, and the polyglydol residue is formed by ring-opening polymerization of the epoxy groups of the glycidol, as explained above.

The radicals R ¹ in the compounds of the formula (I) are suitably selected from radicals of the formula:

^■ RY wherein R is selected from monovalent, linear, branched or cyclic alkyl radicals having up to 20 carbon atoms which may have one or more ether groups -O-, where appropriate, and which may be substituted with one or more hydroxyl groups, optionally, and wherein Y is at least one group selected from -OH, -SH, -NH ₂ or -NHR ⁴ , wherein R is selected from straight, branched or cyclic alkyl radicals having up to 10 carbon atoms. The glycidol compounds of the formula (II) add to these compounds:

(II) wherein R is as defined above, in particular glycidol: to the radicals Y with ring opening of the epoxide ring and continuation of the oligomerization or polymerization of further Glycidolmoleküle to the continuously formed free hydroxy groups.

In a particularly preferred embodiment, the polyorganosiloxane compounds are prepared from compounds of formula (I) wherein R ^{1 is} selected from radicals of the formula:

(CH ₂ ) ₃ - O - X - Y wherein X is selected from the group consisting of:

and ^z and Y are as defined above, preferably hydroxy or amino, (CH ₂ ) -Y wherein n is 1 to 8 and Y is as defined above, preferably hydroxy or amino, and P-γ 3

wherein R is an alkyl group having 8 to 20 carbon atoms which contains a cycloalkyl group and Y is as defined above, preferably hydroxy or amino. In a further preferred embodiment, the starting compounds of the formula (I) have, based on the total amount of the siloxy units, at least 25 mol% siloxy units which have radicals R ¹ which have functional groups which are reacted with the glycidol compounds of the formula (II ) are capable of reaction.

In a further preferred embodiment of the inventive polyorganosiloxane compounds, the molar ratio of the radicals R ¹ to the glycidol compound units relative to the glycidol compounds of the formula (II) in the polyorganosiloxane compounds obtained is at least 1: 4, preferably at least 1 : 5.

In a further preferred embodiment of the polyorganosiloxane compounds according to the invention, these have at least 8 mmol hydroxyl groups per gram of the polysiloxane compound according to the invention.

The polyglycidol side chains have, in particular, at least three (3), preferably at least 4, more preferably at least 5 hydroxyl groups per side chain R, as can be seen, for example, in the following formula:

A particularly preferred embodiment of the polyorganosiloxane compounds according to the invention is shown in the following general formula:

or

wherein

f = 1 to 200, preferably 1 to 100, preferably 1 to 50, preferably 1 to 30, preferably 3 to 30, preferably 5 to 30,

g = 10 to 700, preferably 10 to 200, preferably 10 to 150, preferably 20 to

150, preferably 30 to 150, preferably 30 to 100,

R is as previously defined,

m = 0 to 20,

n = 0 to 20 and

m and / or n> 2, and

Glycidol means a glycidol moiety resulting from the epoxide ring opening reaction of glydol compounds of formula (II).

The present invention furthermore relates to a process for the preparation of the polyorganosiloxane compounds according to the invention, which comprises reacting compounds of the formula (I) with glycidol compounds of the formula (II), preferably with glycidol itself. Regarding the reaction conditions, reference may be made to the above descriptions as well as to the examples. In the process according to the invention for preparing the polyorganosiloxane compounds, preference is given to starting compounds of the formula (I) with more than 1 mol, preferably more than 2 mol, more preferably more than 3 mol, even more preferably more than 4 mol, of the glycidol compounds of the formula (II) each remainder R reacted. The higher the excess of the glycidol compounds used, the higher the number of glycidol units in the radicals R and the higher the hydrophilicity of the resulting polysiloxane compounds.

The present invention further relates to the use of the polyorganosiloxane compounds according to the invention as

emulsifier, defoamers,

Coagulant (coagulant) for Kauts chuklati ces

Phase separation agent in crude oil production

Hydrophilierungsadditiv,

- Wetting agent and adjuvant in crop protection emulsions

antistatic agent,

Anti-fogging coating

hydrogen generating additive in Si-H group-containing compositions,

- fiber treatment agents,

Foam stabilizer, in particular for polyurethane hard and soft foams, crosslinking component in the production of elastomers or elastomeric foams. The present invention furthermore relates to the use of the polyorganosiloxane compounds according to the invention for the preparation of cosmetic formulations.

The polyorganosiloxane compounds according to the invention are preferred as emulsifiers, in dishwasher, in detergent compositions, hydrophilizing additive, wetting agent or adjuvant for the efficient application of pesticides, as additives for oil-water phase separation in crude oil production, as plasticizers for natural and artificial Fibers and pulps including paper, as a defoamer for diesel fuel, as an antistatic agent, as a hydrogen generating additive in Si-H group-containing compositions and / or foam stabilizer, in particular used in the production of polyurethane foams.

In the field of cosmetics there is a need to replace W / O or O / W emulsifiers based on polyethylene oxide by emulsifiers, which have the lowest possible effect for triggering allergies. The assignment to the group of W / O or O / W emulsifiers can be made on the basis of the so-called HLB values (hydrophilic-lipohilic balance). W / O emulsifiers preferably have a value of <8. The hydrophilicity of the polyorganosiloxane compounds according to the invention can be controlled in particular by two parameters:

2

the molar amount of glycidol units per radical R, and

2 1 the molar ratio of hydrophilic siloxy units with R, which arise from R.

The molar ratio of the hydrophilic siloxy radicals with the indices f, i and / or j to the lipophilic, ie "unmodified", only R-containing siloxy units having the indices g, h and / or k is preferably in the polysiloxane compounds according to the invention from 5: 1 to 1:10, more preferably from 2: 1 to 1: 7, even more preferably from 1: 1 to 1: 5.

The polysiloxane compounds in which the ratio of the hydrophilic groups with the indices (f + i + j) to the hydrophobic groups (g + h + k) is <1 (ie less hydrophilic compounds) are preferably used for their use as W / O emulsifiers, as a foam stabilizer for polyurethane hard and soft foams, especially rigid foams, or as defoamers as in defoamer formulations in hydrocarbons such as for diesel fuels or as a defoamer. Preferably, this group of compounds has an HLB value of <8.

Another preferred embodiment of the invention is the use of the less highly hydrophilically modified polyorganosiloxanes as emulsifier or adjuvant in compositions for forestry and agriculture and horticulture.

The preferred polysiloxane compounds herein in which the ratio (f + i + j) to (g + h + k) <1 (less hydrophilic compounds) are preferably linear polyorganosiloxanes having an average chain length of 1 for this use. 100 D units according to the indices g + f. These compounds improve the dispersibility of the active materials and stabilize the emulsions as they are diluted with additional water.

Many pesticides require a dosage form with an additional adjuvant for application to the plant to spray the crop protection composition, wet the leaf, and distribute and hold the active ingredients on the leaf. Often, the adjuvant is a wetting agent that performs many other functions. It can, inter alia also help to transport the bioactive agents through the cell wall. The adjuvants can be admixed both directly to the crop protection compositions and as an additional component from a separate auxiliary tank. Typical compositions are mentioned, for example, in WO 2008/116863 pages 16-18, which are to be included here for a detailed explanation of the description by citing:

In a typical pesticidal composition, the polysiloxanes of the present invention are present in an amount of from 0.005% to 2% by weight. This concerns the undiluted as well as the diluted crop protection composition.

Optionally, the crop protection compositions may contain adjuvants, cosurfactants, solvents, antifoaming agents, addition aids, drift retardants, fertilizers and the like.

Solvents include; Solvents which are liquid at 25 ° C, for example water, alcohols, aromatic solvents, oils (ie mineral oils, vegetable oils, silicone oils, etc.), Q-Cs-alkyl esters of vegetable oils, fatty acids, glycols, as well as 2,4-trimethyl, 1, 3-pentanediol, N-methylpyrrolidone and other solvents mentioned in US 5674832 for reference.

Another preferred embodiment of the invention is the use of more or less strongly hydrophilically modified polyorganosiloxanes in coating compositions. Exemplary coating compositions may contain the compounds of the present invention as a wetting agent or as a surfactant compound for emulsification, compatibilizing the coating components, leveling agents, flow improvers, deaerators for reducing surface disruption. In addition, the compounds of the invention can improve the properties of the dried, cured paint film, such as improved scratch resistance, anti-blocking properties, hydrophilic or hydrophobic properties. The coating compositions may be present as both solvent and water based coating or powder compositions.

The coating compositions cover architectural coatings, original part coatings such as automotive coatings and coil coatings, special applications such as coatings for industrial maintenance and shipbuilding and other marine applications, ie in particular seawater contact. Typical binders include polyester, alkyd, acrylic, epoxy and polyurethane resins or polymers.

In a further preferred use, the less hydrophilically modified polysiloxanes in which the indices of the siloxy units have a ratio of (f + i + j) to (g + h + k) <1 are used for defoaming diesel oils or diesel fuels, wherein the concentration of silicon in the diesel oil is below 5 ppm, more preferably below 2 ppm. Another preferred use is the use of less hydrophilic modified polysiloxanes with (f + i + j) to (g + h + k) <1 as a foam stabilizer in cold or thermosetting polyurethane hard or soft foams, preferably in amounts of 0 , 5 to 5 wt.%, More preferably 1 to 3 wt.% Per used polyol component with additional blowing agents whose boiling points is between -60 to 50 ° C, in particular cyclopentane, iso-pentane and / or iso-butane. The ratio of (f + i + j) to (g + h + k) is preferably 1: 1 to 15, more preferably 1: 2 to 9. The sum of the siloxy units (f + i + j + g + h + k) is 15 to 200, more preferably 30 to 150, measured as the average degree of polymerization Pn based on the average number average Mn from a gel chromatographic molecular weight determination (GPC). Preference is given to using linear polyorganosiloxanes with the siloxy units having the indices f and g. By changing the ratio of the hydropilic indices f, h and / or j to the lipophilic indices g, i and / or k, the solubility properties can be significantly changed.

If the ratio of hydrophilic indices to the lipophilic indices is equal to or greater than 1, in particular effects such as reduced sliding friction and antistatic properties on hydrophobized surfaces can be achieved. If the ratio (f + i + j) to (g + h + k) is 1 or greater than 1 (more hydrophilic compounds) is a use as a wetting agent, compatibilizer against lipophilic phases, eg emulsifier in O / W emulsions. The HLB values for these more hydrophilic polysiloxanes are preferably> 8. Preference is given here to use as heat-sensitisable coagulants (heat-sensitized phase release agents, coagulants) in rubber latex compositions for the production of rubber articles from latexes of various emulsion polymers, such as SBR or NBR and natural rubber latex. The latices serve to produce gums gloves, condoms or other balloons. The use of the hydrophilic polysiloxanes according to the invention prevents premature heat-activated coagulation of the latices at room temperature. The coagulation point is shifted to> 35 ° C. The polyorganosiloxanes of this group can also be used as phase breakers for breaking emulsions in the oil and gas industry for more efficient separation of crude oil and water.

Furthermore, use as a plastic and as a thermoplastic or elastomer additive for hydrophilization and improved wettability of thermoplastic or elastomeric surfaces, as explained below, possible and as a wetting agent for foam stabilization in liquid all-purpose cleaners, hydrous soaps or liquid dishwashing detergents, if the HLB value is greater than 8 is.

Furthermore, the hydrophilically modified polysiloxanes can be used as anti-blocking additives, as lubricants or lubricant additives, as softeners for cotton or paper towels, as plasticizers or in softening compositions for self-emulsifying alkylene oxide-free or shear-stable emulsifiers in textile treatment compositions become.

The use as a defoamer such. As in diesel fuel, adjuvant for the application of pesticides is less preferred for this group of siloxanes.

These more hydrophilic compounds have improved solubility in polar solvents such as alcohols, other oxygen, sulfur and nitrogen containing hydrocarbons compared to pure polydimethylsiloxanes.

In a further preferred embodiment of the invention, this relates to the use of the hydrophilic lipophilic modified polysiloxane compounds according to the invention for the preparation of viscosity regulators, antistatic agents, mixture components for silicone rubbers which can be crosslinked peroxide or by hydrosilylation (platinum catalysis) to form elastomers, and there for the modification of surface properties, to modify the diffusion of gases, liquids, etc., or modify the swelling behavior of the silicone elastomers, for example, to water. In particular, the use as an additive for hydrophilizing surfaces of polydimethylsiloxane elastomers in general or as a viscosity modifier (eg, thickener) in non-crosslinked siliceous silicone rubbers is preferred. Silicone rubbers here are in particular low-viscosity casting or sealing compounds known as room-temperature-crosslinking (RTV) -l or 2-component rubbers. For these RTV-IK or 2-K rubbers, the setting of high or low flow limits is desired depending on the application. The polysiloxanes according to the invention are used in amounts of from 0.5 to 55% by weight, based on the silicone rubbers, in the preparation of the rubber mixture or on the surface of the respective elastomers.

A preferred use is in dental impression compositions whose surface is rendered hydrophilic. , Hydrophilic surfaces here means that according to the invention hydrophilic organo-modified polydimethylsiloxanes in pure form has a contact angle to water of clearly showing at 90 ° preferably less than 75 ^0, measured as indicated below, after the dynamic determination method. The statically determined contact angle is less than 50 °. On the other hand, a dynamic contact angle of more than 120 ^{° is} measured on non-hydrophilically modified polydimethylsiloxanes.

They can also be applied as a lubricant by dipping, pouring or brushing on the surface and be removed after proper use or assembly in part again by rubbing or rinsing.

Another preferred application of the hydroxyl group-containing siloxanes is the use in hydrogen-foamed siloxane foams, especially when the compounds according to the invention additionally contain alkenyl groups, such as vinyl groups. The compounds according to the invention in these mixtures with the SiH crosslinkers in the presence of hydrosilylation catalysts during the crosslinking reaction on the one hand generate hydrogen for the cell structure and, on the other hand, participate in the network structure of the elastomer matrix. As a result, crosslinked hydrophilic polyorganosiloxane foams are obtained. These are preferably used, for example, where Siloxane foams are intended for skin contact, such as decubitus pads, wound dressings or wound plasters, if necessary, with antimicrobial agents etc.

In a further preferred embodiment of the invention, this relates to the use of the hydrophilic / lipophilic functionalized polysiloxane compounds according to the invention for the preparation of modifiers for thermoplastic materials, such as polyolefins, polyamides, polyurethanes, poly (meth) acrylates, polycarbonates. These include, for example, the use as or production of low-temperature impact modifiers.

For this purpose, the polyorganosiloxane compounds according to the invention can themselves be used directly as modifiers or else be provided in advance in a suitable form by coating, mixing, compounding or masterbatching.

Another use of the copolymers of the invention are coatings such as anti-fouling, non-stick coatings, body-tissue compatible coatings, and materials.

Other uses include anti-fogging coatings or precursors for making them for fog-free headlamp lenses (inside), anti-fog windows for residential buildings, for vehicles or medical devices, and additives for cleaning, cleaning or care products, as an additive for personal care products. as a mold release agent, as a biocompatible material in medical applications such as contact lenses, as a coating material for as a coating material for wood, paper, cardboard, natural and synthetic fibers and pulps, textile fibers or textile fabrics, as a coating material for natural products such as Leather and furs. The hydroxyl-modified polyorganosiloxanes according to the invention can thereby replace conventional hydroxyl-containing siloxanes or other siloxanes with organofunctional groups in compositions in processes for leather production or preparation, fat-liquoring, retanning.

These uses include the preparation of fabric softeners for treating textile fibers before, during and after washing, agents for modifying natural and synthetic fibers such as hair, cotton fibers and synthetic fibers such as polyester fibers and polyamide fibers, and the like Blended fabrics, textile finishing agents, and detergent-containing formulations, such as detergents or cleaners.

The preferred amounts here are 0.1 to 5 wt.% 0.3 to 3 wt.% Based on the pulp.

In these preferred fields of application of the polyorganosiloxanes according to the invention, the use of hydrophilically modified polyorganosiloxanes having predominantly hydrophilic properties as an additive for hydrophilization, improved wettability and antistatic finish of thermoplastic and elastomeric surfaces. The preferred amounts are from 0.2 to 15 wt.% 0.5 to 10 wt.% Based on the thermoplastic or elastomer composition.

Since an identifiable tendency for micelle formation is observed in the hydrophilic modified polyorganosiloxanes according to the invention, they provide a suitable basis for the coating of active ingredients, in particular in aggregated form, and allow the rheological properties of cosmetic creams in particular to be influenced.

In the case of the embodiment in which the polyorganosiloxanes modified according to the invention are adjusted to be less hydrophilic, they can replace conventional W / O emulsifiers in known standard formulations for cosmetic preparations.

The hydrophilic / lipophilic modified polyorganosiloxanes can thus serve as cosmetics, personal care products, paint additives, additives in detergents, defoamer formulations and textile processing.

An exemplary use of the compound according to the invention as W / O emulsifier is shown in the following general composition.

0.1-20% by weight of W / O polyorganosiloxane according to the invention

10 - 60 wt.% Oil phase

0-10% by weight of additives

20-89.9% by weight of water phase A typical exemplary composition of a W / O cream according to the invention, which is not intended to limit the scope of the invention, contains the following components.

0.2-10% by weight of polysiloxane compound according to the invention

0 - 5 wt.% Co-emulsifier

5 - 55 wt.% Oil or a combination of oils

0-10% by weight stabilizers

0 - 10 wt.% Viscosity and consistency regulator

0 - 20% by weight of active ingredients for skin treatment

0-10% by weight of further fillers

0-10% by weight adjuvant

up to 100% by weight filled up with water.

Analytical characterizations:

Gel permeation chromatography (GPC)

The GPC measurements in chloroform were performed in an apparatus consisting of a Waters 717 Plus Autosampler, a TSP P 100 pump, and a set of three PSS SDV columns (104/500/50 Ä). The signal was determined by means of a Wyatt Optilab DSP RI detector.

For measurements in DMF with the addition of 1 g / 1 lithium bromide, an Agilent 1100 Series with poly-HEMA column, RI and UV (254nm) detector was used as the measuring device. The measurements were carried out at 35 ° C and a flow rate of 1.0 ml / min. Calibration was performed using linear polystyrene standards from Polymer Standards Service. Signaling was performed with a Wyatt Optilab DSP RI detector.

NMR spectroscopy

Nuclear magnetic resonance spectra were recorded at room temperature with the following equipment

added:

- Ή spectra: Bruker AC 300 for 300 MHz

- ²⁹ Si spectra: Bruker AMX 400 for 79.49 MHz

The chemical shifts are reported in ppm and refer to the proton signal of the deuterated solvent. Contact angle measurement

The measurements of contact angles with water were made on a Dataphysics Contact Angle System OCA 20 and were evaluated using the SCA 20 software. The contact angles given are in each case average values from 5 measurements of a dynamic determination according to Halliwell, C.M .; Cass, A.E.G .; Analytical Chemistry 2001, 73, 2476-83.

In general, when measuring the contact angle α with water for the surface properties of a material:

α <90 °: hydrophilic surface

α ~ 90 °: hydrophobic surface

a> 90 °: superhydrophobic surface

Examples

The l -0-isopropylidene-3-alyloxy-1,2-propanediol ("Solketal") used for the subsequent hydrosilylations in Examples 1 to 4 was previously generated by a Williamson coupling of allyl bromide and the ketal of glycerol according to the following scheme

Synthesis of 1,2,0-isopropyl-3-allyloxy-1,2-propanediol (II)

In a 1 1 round bottom flask, 28 g (0.5 mol) of finely ground potassium hydroxide were added to a solution of 28.8 ml (0.2 mol) of Solketal in 400 ml of a 20:80 mixture of DMSO: toluene with stirring and dissolved , To the solution, 20.8 ml (0.24 mol) of allyl bromide was added and the resulting mixture was stirred for 12 hours at 25 ° C room temperature. For work-up, the mixture was filtered and washed with saturated ammonium chloride solution until neutralization. The aqueous phase was then extracted three times with about 100 ml of toluene. The toluene phases were combined, dried with sodium sulfate and the solvent was evaporated on a rotary evaporator. There were obtained 29.26 g (85% of theory) of the product (II). Example 1 (starting material)

la)

Hydrosilylation of 1,2,4-isopropylidene-3-allyloxy-1,2-propanediol

In a 100 ml Schlenk flask 6.00 g of a polydimethylmethylhydrogen siloxane of the empirical formula MDi ₂ 6D ^H nM together 2.00 g, 2-0-isopropylidene-3-allyloxy-l, 2-propanediol (II) were dissolved in 30 ml of dioxane and the solution with stirring to 70 ° C erwännt. The air was removed from the flask by the introduction of argon and 30 .mu.l of a solution of a platinum catalyst (1,3-divinyl-1,3-tetramethyldisiloxane Pt complex 2% Pt. ('Karstedt catalyst')) in an argon atmosphere. Countercurrent added. After adding the Catalyst, the flask was sealed with a septum which was then punctured by a cannula attached to an argon-filled balloon. After about 12 hours of stirring, the mixture was allowed to cool and the solvent was evaporated on a rotary evaporator. For further purification, the reaction product was stirred for 12 h at 70 ° C at 1 mbar. This gave 6.63 g (90% of theory) of a product having structural units of the formula (III), ie the units with the index f and g can be present randomly distributed ('random'distribution).

1 H NMR (300 MHz, CDCl ₃ ) d [ppm] = -0.06-0.15 (s, Si-CH ₃ ), 0.42-0.55 (br, Si-CH ₂ ), 1.36 (s, R ₂ C (CH ₃ ) ₂ ), 1 -42 (s, R ₂ C (CH ₃ ) 2), 1.55-1.67 (br, Si-CH ₂ -CH ₂ ), 3.37-3.45 (br,

CH ₂ -CH ₂ -O), 3.48-3.56 (m, RO-CH ₂ -CHR-OR), 3.70-3.77 (m, 0-CH ₂ -CHOR-CH ₂ -OR), 4.02-4.10 (m, 0-CH ₂ -CHOR-CH ₂ OR), 4.22-4.30 (m, R ₂ CH-OR)

lb) 2nd stage:

Deprotection of polyorganosiloxanes grafted with 1,2,0-isopropylidene-3-allyloxy-1,2-propanediol

To remove the protective groups, 6.60 g of the polymer of example 1a were stirred with 1 g of an acidic ion exchange resin Dowex 50 at 25 ° C. for 60 minutes in 40 ml of a 1: 1 mixture of methanol and pentane. The mixture was then freed by filtration from the ion exchanger, the phases were separated and the pentane phase extracted twice more with methanol. The methanolic phase was finally freed from the solvent for 12 h at 1 mbar. 6.15 g (97% of theory) of a product having structural units of the general empirical formula (IV) were obtained. The molecular weight had increased to the value mentioned in Tab.

H-NMR (300 MHz, DMSO-d6) d [ppm] = -0.29-0.18 (s, S1-CH3), 0.34-0.53 (br, Si) C7 / 2). 1.39-1.57 (br, Si-CH2-CH2), 3.1-3.44 (br, CH20R, CH20H), 3.48-3.59 (br, C / JOH), 4.25-4.55 (br, R-OH).

Alternatively, compounds of the formula IV according to the invention can also be prepared by reacting hydrogenpolysiloxanes with allyl alcohol or protected allyl alcohol and subsequent reaction of the resulting hydroxypropyl polysiloxane compounds with glycidol, in accordance with the reaction route described in claim 1.

Example 2 (starting material)

2a)

Hydrosilylation of 1,2,4-isopropylidene-3-allyloxy-1,2-propanediol

In a 100 ml Schlenk flask 6.00 g of a Polydimethylmethylhydrogen- siloxane of the empirical formula MD ₃ 9D ^H i6M together 6,10 gl, 2-0-Isopropyliden-3-allyloxy-l, 2-propanediol dissolved in 30 ml of dioxane and the solution heated to 70 ° C with stirring. The air was removed from the flask by the introduction of argon and 30 .mu.l of a solution of a platinum catalyst (1,3-divinyl-1,3-tetramethyldisiloxane Pt complex 2% Pt. ('Karstedt catalyst')) in an argon atmosphere. Countercurrent added. After addition of the catalyst, the flask was sealed with a septum. After about 12 hours of stirring, the mixture was allowed to cool and the solvent was evaporated on a rotary evaporator.

For further purification, the reaction product was stirred for 12 h at 70 ° C at 1 mbar. This gave 9.32 g (92% of theory) of a product having structural units of the general empirical formula (III). The 'H-NMR confirmed an OH content of about 2 mmol / g. and 10 mol% modified siloxy units.

2 B

Deprotection of polysiloxanes grafted with 1,2,0-isopropylidene-3-allyloxy-1,2-propanediol

For this purpose, as in 1b), 9.30 g of polymer 2a) were stirred with 1 g of acidic ion exchange resin Dowex 50 at room temperature for 60 minutes in 40 ml of a 1: 1 mixture of methanol and pentane. This gave 8.41 g (95% of theory) of a product having structural units of the general empirical formula (IV). The molecular weight had increased to the Tab.1 value.

The Ή-NMR confirmed an OH content of about 5.2 mmol / g and 27.8 mol.% Modified siloxy units.

Example 3 (starting material)

3a

Hydrosilylation of 1,2,4-isopropylidene-3-alyloxy-1,2-propanediol

Example 1 was repeated in which, instead of the polydimethylmethylhydrogensiloxane mentioned there, 6.00 g of a polydimethylmethylhydrogensiloxane having the empirical formula MDiD.sub.M together with 16.40 g, 2-0-isopropylidene-3-allyloxy-1,2-propanediol in 30 ml of dioxane dissolved used.

This gave 14.91 g (88% of theory) of a product having structural units of the general empirical formula (III).

3b

Removal of the protective group of polyorganosiloxanes grafted with 1,2-O-isopropylidene-3-allyloxy-1,2-propanediol The deprotection was carried out using 14.90 g of the polymer of Example 3a as in 1b or 2b

There were obtained 12.04 g (95% of theory) of a product having structural units of the general empirical formula (IV). The molecular weight had increased to the Tab.l value. The ¹ H-NMR confirmed an OH content of about 8 mmol / g and 66.7 mol.% Modified siloxy units.

Example 4 (starting material)

Following the procedure of Example 1, a polymethylhydrogensiloxane having the empirical formula MD ^H ₂₆ M was reacted with 1, 2-0-isopropylidene-3-allyloxy-l, 2-propanediol and the protective group was removed.

The Ή-NMR confirmed an OH content of about 9.5 mmol / g and 93 mol.% Modified siloxy units.

Example 5

5a) Hydrosilylation of allylamine (starting material)

In a 100 ml Schlenk flask, 6 g of a polydimethyl-co-methylhydrogenated siloxane of the empirical formula MD 9D ^H i6M were dissolved together with 2.10 g of allylamine in 30 ml of dioxane and the solution was heated to 50 ° C. with stirring. The air was removed by flowing argon from the flask and 30 .mu.l of a solution of a platinum catalyst (l, 3-divinyl-l, 3-tetramethyldisiloxane Pt complex 2% Pt ('Karstedt catalyst')) in argon Countercurrent added. After addition of the catalyst, the flask was sealed with a septum. After about 12 hours of stirring, the mixture was allowed to cool and the solvent was evaporated on a rotary evaporator.

For further purification and removal of solvents and glycidol, the reaction product was stirred for 12 h at 70 ° C at 1 mbar. This gave 6.33 g (86% of theory) of a product having structural units of the general empirical formula (V) in addition to small amounts of isomeric forms, ie. Addition of allylamine obtained in the 2-position.

(V) 5b) (product according to the invention)

Grafting of aminoalkyl-functionalized polydimethylsiloxanes

with glycidol and further oligomerization

A 100 ml round bottom flask was charged with 1.00 g of the amino-functionalized polydimethylsiloxane and placed under argon atmosphere. The polymer of Example 5a was dissolved by the addition of 30 ml of dry THF and the resulting solution was added with vigorous stirring with 3.62 g of glycidol. The resulting mixture was stirred for 12 h at 25 ° C room temperature. For working up, the solvent was evaporated in a rotary evaporator and then the unreacted glycidol by stirring at 80 ° C and 1 mbar.

3.25 g (89% of theory) of a product having structural units of the schematic empirical formula (VI) were obtained. The molecular weight had increased to the Tab.l value. The increase in the molecular weight corresponds to about 11 oligomerized glycidol units on average at each nitrogen. The 1H-NMR confirmed an OH content of about 1 1.6 mmol / g and 28.1 mol.% Modified siloxy units.

H-NMR (300 MHz, DMSO-d6) d [ppm] 3.19-3.79 (br, CH2-OR,

C / J 2 -OH, CH-OR, CH-OH), 4.47-4.88 (br, R-OH)

(VI)

is to be understood schematically. The exact structure of the glycidol addition products can not be determined exactly from the spectroscopic data. In addition, mixtures of glycidol addition products may be present. Can be determined exactly the Mass increase by glycidol addition by determination of the molecular weight of the final product.

Example 6

6a) hydrosilylation of allylamine

The hydrosilylation was carried out as in Example 5a) but with 6 g of a polydimethylmethylhydrogensiloxane of the empirical formula which was dissolved together with 5.40 g of allylamine in 30 ml of dioxane.

This gave 7.89 g (82% of theory) of a product having structural units of the general empirical formula (V).

6b)

Grafting of aminoalkyl-functionalized polydimethylsiloxanes

with glycidol and further oligomerization

A 100 ml round bottom flask was charged with 1.00 g of the amine-functionalized polysiloxane 6a) and placed under argon atmosphere. The polymer was dissolved by adding 30 ml of dry THF, and 7.33 g of glycidol were added to the resulting solution with vigorous stirring. The resulting mixture was stirred at room temperature overnight. For workup, the solvent was removed on a rotary evaporator and then the unreacted glycidol by stirring at 80 ° C under high vacuum. 5.61 g (88% of theory) of product of the formula (VI) were obtained.

The increase in the molecular weight corresponds to about 1 1 oligomerized glycidol units on average at each nitrogen. The 1H NMR confirmed an OH content of about 13.4 mmol / g and 76 mol.% Modified siloxy units.

Example 7

Moreover, the following dimethylhydrogensiloxy schedule Erten polydimethyl siloxanes were a) of the formula M ^H ^H Ü8M hydrosilylated with allylamine and then reacted b) with glycidol.

The increase in the molecular weight corresponds to about 1 1 oligomerized glycidol units on average at each nitrogen. The H-NMR confirmed an OH content of about 10.7 mmol / g and 20 mol% modified siloxy units. A product of the general formula (VII) is obtained.

H H

(VII)

Indices m + n = l l

Example 8

Analogously to Example 7, a polyorganosiloxane of the invention is prepared from MH ⁿ D ₂ voM H ⁿ with allylamine and subsequent reaction with glycidol.

The increase in the molecular weight corresponds to about 11 oligomerized glycidol units on average at each nitrogen. The 'H-NMR confirmed an OH content of about 1.3 mmol / g and 0.7 mol.% Modified siloxy units. A product of the general formula (VII) with g = 270 is obtained.

With the glycidol-modified polyorganosiloxanes according to the invention, solubility tests are carried out in various solvents.

While the modified polyorganosiloxane of Example 8 still performs well in non-polar organic solvents such as pentane to chloroform, i.e., due to its comparatively long PDMS chain. DK (Relative Dielectric Constant) of 1.8 to 4.8 dissolves, do not behave or dissolve less well in the polar solvents with a DK of 18.6 to 80.4, observed in the compounds of Examples 5 to 7, the reverse Behavior. These compounds are essentially soluble only in methanol and water (soluble here means 10 g of modified polyorganosiloxanes per 100 ml of solvent at 25 ° C). This demonstrates that the compounds according to the invention can be varied within wide limits with regard to their hydrophilic properties.

Table 1 summarizes the preparation examples. Table 1 - Examples 1 to 8:

* Starting material.

Claims

claims

1. Polyorganosiloxane compounds obtainable by reaction of

Polyorganosiloxane compounds of the formula (I):

[M _a D _b T _c Q _d ] e (I) where

M = R ₃ Si0 _1/2, D = R ₂ Si0 _2/2, T = RSi0 _3/2,

Q = Si0 _4/2 , where a = 1-10 b = 0-1000 c = 0-1 d = 0-1 e = 1-10 where

R = an organic group, with the proviso that R comprises at least one group R ¹ , wherein R ^{1 is} a monovalent straight-chain, cyclic or branched, saturated or unsaturated C ₂ to C ₂₀ hydrocarbon radical containing one or more N

Groups selected from -O- and may contain, and which has at least one group selected from -OH, -SH, -NH- and -NH ₂ , with a glycidol compound of the formula (II),

(Π) wherein R is selected from divalent Ci to Cs hydrocarbon radicals, such as in particular methylene (-CH2-) is selected, with the proviso that the polyorganosiloxane compounds obtained have at least one radical R, the one or more Polyglycidolreste the

formula

- (Glycidol) _x , wherein x> 1, wherein the Polyglycidolrest is formed by ring-opening polymerization of the epoxy groups of the glycidol of the formula (II).

2. Polyorganosiloxane compounds according to claim 1, wherein the compounds of formula (I) comprise siloxy units selected from the following formulas:

wherein R, when more of said siloxy units are present, is the same or

may be different and is selected from C 1 to C ₂₂ alkyl, which may optionally be substituted by one or more fluorine atoms, C ₂ to C ₂₂ alkenyl, and C ₆ -C ₁₀ aryl,

R ^{1 is} as defined above, and

f is from 0-600,

R may be the same or different in a single siloxy unit or, if more than one siloxy unit, may be the same or different in different ones of the siloxy units and selected from C ₁ to C ₂ 2 alkyl which may be optionally substituted by one or more fluorine atoms, C C ₂ to C ₂₂ alkenyl, and C _{6 to} C ₁₀ aryl, and

g is from 0-700,

R, when more of said siloxy units are present, may be the same or different and is selected from Ci to C ₂₂ alkyl, which may optionally be substituted by one or more fluorine atoms, C? to C ₂₂ alkenyl and C ₆ -C 10 aryl, and

h is 0-10, wherein R ^{1 is} as defined above, and

i is from 0 - 10,

wherein

R, when more than one of said siloxy units are present, may be identical or different and is selected from C 1 to C ₂₂ -alkyl, which may optionally be substituted by one or more fluorine atoms, C ₂ to C ₂₂ -alkenyl and C ₆ -C ₁₀ - aryl,

R ^{1 is} as defined above, and

R, when more of said siloxy units are present, may be the same or different and is selected from Ci to C ₂₂ alkyl, which may optionally be substituted by one or more fluorine atoms, C ₂ to C ₂₂ alkenyl and Q, -Cio-aryl , and

k is 0-30, wherein 1 = 0-10, f + g + h + i + j + k + 1 = 12 to 1000.

3. polyorganosiloxane compounds according to claim 1 or 2, wherein

Compounds of formula (I) have two or more radicals R ¹ .

4. polyorganosiloxane compounds according to any one of claims 1 to 3, wherein in the compounds of formula (I) one or more of the following features are fulfilled:

R is selected from C _\ to Cio-alkyl that may be substituted with 1 to 13 fluorine atoms optionally substituted C2 to Cs alkenyl, and phenyl,

R ¹ is selected from: monovalent, straight-chain, cyclic or branched, saturated or unsaturated C 1 to C 10 hydrocarbon radicals which have one or more groups selected from -O- and

and at least one group selected from

Include -OH, -NH-, and -NH _2, f = 1 to 200, preferably 1 to 100, preferably 1 to 50, preferably 1 to 30, preferably 3 to 30, preferably 5 to 30, g = 10 to 700, preferably 10 to 200, preferably 10 to 150, preferably 20 to 150, preferably 30 to 150, preferably 30 to 100, h = 0 to 5 and preferably 0, i = 0 to 5 and preferably 0,

1 = 0 to 5 and preferably 0, f + g + h + i + j + k + 1 = 10 to 500, preferably 10 to 200, preferably 10 to 150, preferably 20 to 150, preferably 30 to 150, preferably 30 to 100th

5. polyorganosiloxane compounds according to any one of claims 1 to 4, wherein in the compounds of formula (I) one or more of the following features are fulfilled:

R is selected from: C] to C ₆ -alkyl, which may optionally be substituted by 1 to 13 fluorine atoms, vinyl and phenyl,

R ¹ is selected from: monohydric, straight-chain, cyclic or branched, saturated or unsaturated C ₂ to C 10 -hydrocarbon radicals residues containing one or more groups selected from -O- and

and having at least one group -NH ₂ .

6. polyorganosiloxane compounds according to any one of claims 1 to 5, wherein Polyglycidolreste have the formula - (glycidol) _x ,

which result from the ring-opening polymerization or oligomerization of glycidol compounds of the formula (II), and in which x is from 2 to 20, preferably 4 to 18.

7. polyorganosiloxane compounds according to any one of claims 1 to 6, wherein in the compounds of formula (1) R ^{1 is} selected from radicals of

Formula:

-R-Y

R is selected from divalent, straight-chain, branched or cyclic alkyl radicals having up to 20 carbon atoms, which may optionally have one or more ether groups -O- and which may optionally be substituted by one or more hydroxyl groups, and Y is at least one group selected from OH, -SH, -NH ₂ or -NHR ⁴ , wherein R is selected from straight, branched or cyclic alkyl radicals of up to 10 carbon atoms.

8. polyorganosiloxane compounds according to claim 7, wherein R ^{1 is} selected from radicals of the formula:

(CH ' _? 2) 3 ^ - O - X - Y wherein X is selected from the group consisting of H ^0H

^~ S ^~ ? ^~ S ^"0H - ccc-

IH _{2 and} H ₂ HH ₂ and Y is as defined above

^" (CH ₂ ) -Y wherein n is 1 to 8 and Y is as defined above, and

- R-Y

wherein R ^{3 is} an alkyl group having 8 to 20 carbon atoms which contains a cycloalkyl group, and Y is as defined above.

9. polyorganosiloxane compounds according to any one of claims 1 to 8, wherein the compounds of formula (I) based on the total amount of the siloxy units at least 25 mol% siloxy units having radicals R ¹ .

10. polyorganosiloxane compounds according to any one of claims 1 to 9, wherein the molar ratio of the radicals R ¹ to the glycidol units in the polyorganosiloxane compounds obtained is at least 1: 5.

11. Polyorganosiloxane compounds according to any one of claims 1 to 10, which have at least 8 mmol hydroxyl groups per gram of the polysiloxane compound.

12. polyorganosiloxane compounds according to any one of claims 1 to 11,

or

wherein

g = 10 to 700, preferably 10 to 200, preferably 10 to 150,

preferably 20 to 150, preferably 30 to 150, preferably 30 to

100

R is as previously defined,

m = 0 to 20,

n = 0 to 20 and

m and / or n> 2, and

Glycidol means a glycidol unit, which results from the epoxide ring opening reaction of glydol compounds of formula (II).

13. A process for the preparation of the polyorganosiloxane compounds according to claims 1 to 12, characterized in that compounds of the formula (I) are reacted with glycidol compounds of the formula (II).

14. A process for the preparation of the polyorganosiloxane compounds according to claims 1 to 12, characterized in that compounds of the formula (I) are reacted with more than 1 mol of glycidol compounds of the formula (II) per radical R.

15. Use of the polyorganosiloxane compounds obtained according to one of claims 1 to 12 as

- emulsifier,

defoamers,

oagulant for autoshuklatices,

Phase separation agent in crude oil production,

Hydrophilierungsadditiv,

Wetting agents and adjuvants in crop protection emulsions,

antistatic agent,

Anti-fogging coating,

hydrogen generating additive in Si-H group-containing compositions, Fiber treatment agent,

Foam stabilizer, in particular for hard and soft polyurethane foams,

crosslinking component in the production of elastomers or elastomeric foams.