WO2016116349A1 - Method for producing silicone resins - Google Patents

Abstract

The invention relates to a solvent-free method for producing alkoxy-free and optionally organofunctional silicone resins, and to the organofunctional silicone resins obtainable by said method and the use thereof.

Description

 Process for the preparation of silicone resins

The invention relates to a process for the solvent-free preparation of alkoxy-free and optionally organofunctional silicone resins, as well as the obtainable by the process organofunctional silicone resins and their use.

State of the art:

 There are various processes for the preparation of organofunctional silicone resins.

 In a frequently used process, one starts from silicone resins or these forming silane mixtures and organofunctional silanes, wherein the silane mixtures and the organofunctional silanes contain hydrolyzable alkoxy groups. In principle, all organofunctional alkoxysilanes whose organofunctional groups tolerate hydrolytic conditions can be used for such a procedure.

Reference may be made by way of example to document EP0283009, in particular to example a), where an amino-functional alkoxy-bearing silicone resin is produced.

US5280098 describes the synthesis of epoxy-functional silicone resins using epoxy-functional alkoxy-carrying silanes, resulting in epoxy-functional alkoxy-bearing silicone resins.

When alkoxy-functional starting materials are used, alkoxy-rich end products are always obtained. Organofunctional silanes of technical and economic relevance usually carry 3 alkoxy groups. Since the reactivity of silane-bound alkoxy groups decreases as the number of silane-bound alkoxy groups decreases, only one or at most two alkoxy groups usually react under regular hydrolytic reaction conditions, so that the total number of alkoxy groups attached to the organofunctional silicone resin after the reaction present are at least as high as before, possibly even higher. In order to react the remaining alkoxy groups, either reaction conditions are required which lead to the crosslinking of the organofunctional silicone resins to insoluble products, ie ultimately the conditions that would typically be chosen for curing the materials after application, or very long reaction times, such as So they are given for example during the multi-year service time of the final products.

Alternatively, the procedure is known to proceed from silane mixtures which also contain organofunctional silanes, wherein the silanes each carry a sufficient number of hydrolyzable groups and the oligomeric or polymeric silicone resin structures produced by hydrolysis and condensation to obtain the organic function become. Reference may be made by way of example to the documents DE10151264A1 and DE 10335178 AI, where organic functions are amino groups. Here, oligomeric, ie low molecular weight alkoxy-rich organofunctional resin structures are built up by the hydrolysis and condensation of alkoxysilane mixtures. The organic function is retained, the alkoxy groups are partially hydrolyzed and the resulting silanol groups condense with elimination of water to give silicone resin skeleton structures. Such oligomeric structures contain especially many alkoxy groups. In addition, this procedure is limited to low molecular weight end products.

EP1010714 describes the synthesis of silylhydride-functional silicone resins from alkoxysilicate and alkoxysilane mixtures with Si-H-functional siloxane components, such as, for example, tetramethyldisiloxane, under acidic hydrolytic conditions. The siloxane framework is simultaneously built up for functionalization by hydrolysis and condensation. The catalyst used are sulfonic acids or phosphonitrile compounds. Chlorsila- Neither function as raw materials in this process, since the resulting from hydrolysis hydrochloric acid leads to a partial cleavage of the Si-H bonds. This would make the Si-H content in the resin uncontrollable.

The proposed synthesis is limited to siloxanes with silicate structural elements. Due to the difficult framework conditions, this approach has little scope. Epoxy groups are subsequently incorporated by hydrosilylation. Even if no Si-H groups are lost during the hydrolysis, such reactions on randomly formed polymers still provide only those of them which are sterically accessible, which represents a further imponderability in this approach. EP1398338 teaches the synthesis of vinyl-functional silicone resins having low alkoxy contents, which is a multi-step synthesis employing both acidic and basic conditions. The silicone resins are first acidified from alkoxysilanes and functional disiloxanes, and the remaining alkoxy groups are subsequently hydrolyzed so that they form silanol groups. Under these conditions, the silanol groups are not stable but condense with dehydration and formation of high molecular weight silicone resins. This approach relies on functional groups that survive these reaction conditions unscathed. For example, the process is not tolerant to epoxide groups, carboxy groups, and amino groups as they would undergo transformations through chemical reactions during the process.

In principle, all processes have in common that they are carried out either using organic solvents or that organic solvents are formed during the reactions, for example in the form of the alcohols obtainable from the silicon-bonded alkoxy groups. In the present text, substances are characterized by specification of data obtained by instrumental analysis. The underlying measurements are either carried out according to publicly available standards or determined according to specially developed procedures. To ensure the clarity of the teaching taught, the methods used are given here:

Viscosity:

Unless stated otherwise, the viscosities are determined by rotational viscometric measurement in accordance with DIN EN ISO 3219. Unless otherwise stated, all viscosity data apply at 25 ° C and atmospheric pressure of 1013 mbar. Refractive index:

 The refractive indices are determined in the wavelength range of visible light, unless otherwise stated at 589 nm at 25 ° C and normal pressure of 1013 mbar according to the DIN standard

51,423th

Transmission:

 The transmission is determined by UV VIS spectroscopy. A suitable device is, for example, the Analytik Jena Specord 200.

The measurement parameters used are range: 190-1100 nm

Increment: 0.2 nm, integration time: 0.04 s, measurement mode:

Step operation. The first step is the reference measurement (background). A quartz plate attached to a sample holder (dimension of the quartz plates: HxB about 6 7 cm, thickness about 2.3 mm) is placed in the sample beam path and measured against air. Thereafter, the sample measurement takes place. A quartz plate attached to the sample holder with a sample applied - layer thickness applied to the sample approx. 1 mm - is placed in the sample beam path and measured against air. Internal offsetting against background spectrum is provided by the transmission spectrum of the sample. Molecule compositions:

Molecular compositions are determined by nuclear magnetic resonance spectroscopy (for concepts, see ASTM E 386: High Resolution Magnetic Resonance Imaging (NMR): Terms and Symbols), which measures the ¹ H nucleus and the ⁹ Si nucleus.

Description 1H-MR measurement

Solvent: CDC13, 99.8% d

 Sample concentration: approx. 50 mg / 1 ml CDC13 in 5 mm NMR

tube

Measurement without addition of TMS, spectral referencing of residual CHC13 in CDC13 to 7.24 ppm

Spectrometer: Bruker Avance I 500 or Bruker Avance HD 500 Probe Head: 5 mm BBO Probe Head or SMART Probe Head (Fa.

 Bruker)

Measuring parameters:

Pulprog = zg30

TD = 64k

 NS = 64 or 128 (depending on the sensitivity of the sample head)

 S = 20.6 ppm

AQ = 3.17 s

Dl = 5 s

 SF01 = 500.13 MHz

Oil = 6, 175 ppm

Processing parameters:

SI = 32k

 D = EM

LB = 0.3 Hz Depending on the spectrometer type used, individual adjustments of the measuring parameters may be necessary.

Description 29Si-NMR measurement

Solvent: C6D6 99.8% d / CC14 1: 1 v / v with 1 wt% Cr (acac) 3

 as relaxation reagent

Sample concentration: approx. 2 g / 1.5 ml solvent in 10 mm

 NMR tubes

Spectrometer: Bruker Avance 300

Probe head: 10 mm lH / 13C / 15N / 29Si glass-free QNP probe head

 (Bruker)

 Measurement parameters:

Pulprog = zgig60

TD = 64k

NS = 1024 (depending on the sensitivity of the probe head) SW = 200 ppm

AQ = 2, 75 s

Dl = 4 s

 SFOl = 300.13 MHz

Oil = -50 ppm

Processing parameters:

SI = 64k

WDW = EM

LB = 0.3 Hz

Depending on the spectrometer type used, individual adjustments of the measuring parameters may be necessary. Molecular weight distributions:

Molecular weight distributions are determined as weight average Mw and as number average Mn, using the method of gel permeation chromatography (GPC or Size Exclusion Chromatography (SEC)) with polystyrene standard and refractive index detector (RI detector). Where not stated otherwise THF used as eluent and DIN 55672-1 applied. The polydispersity is the quotient Mw / Mn.

Glass transition temperatures:

The glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, perforated Tigel, heating rate 10 K / min.

Task:

The object was therefore to provide a process which makes it possible to produce alkoxy-free and, if desired, organofunctionalized silicone resins, in which process no organic solvents are to be used and no organic solvents are to be formed during the process. This object is achieved by the present invention.

The object of the present invention is a process for the preparation of silicone resins (i) from units of the formulas (Ia), (Ib), (VII) and (Id)

[R¹⁷ ₂Si0_2/2] [R ¹⁷ Si0 _3/2 ] [Si0 _4/2 ]

[R ¹⁷ ₂ Si0 _2/2 ]

(Ia) (Ib) (VII) (Id) wherein

R ^{1 is the} same or independently different monovalent hydrocarbon radicals,

R ^{17 is the} same or independently of one another the meaning of R ¹ or -OH,

R ^{2 are} identical or independently different monovalent organofunctional hydrocarbon radicals, olefinically unsaturated hydrocarbon radicals or a hydrogen

Substance residue, where the radical R ² has a carbon atom atom is attached to the silicon atom, or the hydrogen radical is bonded directly to the silicon atom, c = 0 or 1

 mean,

 with the stipulations that

 at least 5 mol% of the formula (VII) are contained,

at least 20 mol% of the formula (Ia) are contained,

wobei R¹ die oben angegebenen Bedeutungen hat, at most 20 mol% of the formula (Ib) are present, by reacting at least one silane (ii) of the formula (II)

where R ^{1 has} the meanings given above,

 and a the values 2, 3 or 4,

wobei R¹ und R² die oben angegebenen Bedeutungen hat, und b die Werte 0 oder 1 haben kann, oder mit mindestens einem Disiloxan (iv) der Formel (IV) mean with at least one silane (iii) of the formula (III)

where R ¹ and R ^{2 have} the meanings given above, and b may have the values 0 or 1, or with at least one disiloxane (iv) of the formula (IV)

[R ¹ ₍₃ - _b ) R ² _b Si] ₂ O (IV), where R ¹ and R ² and b have the meanings given above,

and the disiloxanes (iv) have a symmetrical structure, so that the radicals R ¹ and R ² have the same meaning on both silicon atoms, or with a mixture of at least one silane (iii) and at least one disilioxane (iv) in a water blanket with the provisos that

 always at least 5 mol% of a silane (ii) with a = 3 are used, based on the total reactants used, no organic solvents are used, the reaction taking place via the following process steps:

 1) Preparation of a starting material template by

 Case a) if only silanes (ii) or mixtures of silanes (ii) and disiloxanes (iv) are used: the silanes (ii) are mixed with all or part of the silanes (iii) or mixtures of silanes (iii) and Disilioxanes (iv) or

 Case b) if only disiloxanes (iv) are used: presentation of only the silanes (ii) or mixing of the silanes (ii) with the total amount of disiloxanes (iv)

 2) Preparation of a water mask of PH-neutral water or PH acidic water by additional

 Case a): mixing in of the residual amount of disiloxane (iv), if in step 1) only partial quantities were used,

 Case b): mixing the total amount of disiloxanes (iv) if not done in step 1)

 3) Addition of the educt template from step 1) into the water template from step 2) or vice versa

 4) Hydrolysis and condensation and

Case a): addition of the residual amount of silane (iii), if in step 1) only partial quantities were used, 5) Purification of the resulting silicone resin (i) from the forming silicone phase.

Preference is given to using a silane (ii) with a = 3 in an amount of at least 10 mol%, particularly preferably in an amount of at least 15 mol%, in particular of at least 30 mol%.

The process has some special peculiarities that distinguish it and distinguish it from the state of the art.

It is incessant that the silanes (ii) for the respective synthesis are mixed at least with a subset of the otherwise used silanes (iii) in step 1). If the disiloxanes (iv) are also used at the same time, they may also be mixed in part or completely in this step 1), but do not have to be mixed. However, if only silanes (ii) and disiloxanes (iv) and no silanes (iii) are used for the synthesis, the silanes (ii) are either completely mixed in step 1) with the disiloxanes (iv) or the disiloxanes (iv) are dissolved in Step 2) completely into the water mask.

In addition, further reactive siloxanes or silanes may be added which do not correspond to (ii), (iii) or (iv). This takes place as silanes or siloxanes and, in particular in the case of the silanes, also in the form of hydrolyzates and / or condensates. These are either mixed in advance in step 1) with the silanes (iii) and / or the disiloxanes (iv) or added in a separate step. It is preferable that they are mixed in particular with the silanes (iii) in advance in step 1). Examples of such further reactive silanes are those of

Formula (V) and for reactive siloxanes those of repeating units of the formula (VI),

R _e Si (OH) f (V), R ⁶ _{g of} Si (OH) hO (4-gh) / 2 (VI), where R ⁴ and R ⁶ each independently have the meaning of R ¹ and several radicals R ⁴ and R ⁶ on the same silicon atom independently of one another or being different means

e and f are each 0, 1, 2, 3 or 4, with the proviso that e + f = 4,

g and h are each a number in the value of 0, 1, 2 or 3, where g + h ^ 3 and the siloxanes comprising repeating units of the formula (VI) comprise at least 3 repeat units of the formula (VI).

It is a further special feature and advantage of the process according to the invention that no organic solvent is used. There is also no organic solvent during the synthesis, since only chloride or hydroxyl radicals are used as hydrolyzable radicals. Hydrochloric acid is formed from the chloride residues during the reaction with water, and water from the hydroxyl radicals, and thus no organic solvent.

The inventive method is also characterized by the fact that is waived any phase mediator between the silicone phase and the water phase.

The process according to the invention therefore leads to soluble silicone resins (i) because the monochlorosilanes (iii) on contact with water form disiloxanes which serve as solvents for the silicone resins (i) which are formed and protect them from excessive hydrolysis and condensation to form the insoluble gel. At the same time, the disiloxanes so formed serve as reagents which introduce the terminating units into the silicone resin (i) and thereby limit the molecular weight. The same function is exercised by the disiloxanes (iv). It is preferred to use a PH neutral water blank in step 2) so that no acid is present in the water phase before step 3). The reaction proceeds autocatalytically through the hydrochloric acid which forms.

The reaction takes place in step 4) by hydrolysis of the chlorosilanes (ii) and (iii) when introduced into the water mixture followed by the condensation of the silanols that form to the silicone resins (i) according to the invention.

The water phase in step 2) can be chosen so that it can not completely absorb the resulting hydrochloric acid, so that hydrochloric acid can be used up as gas and possibly caught up for recycling. But the water phase can also be chosen so that the hydrochloric acid is completely dissolved in it and no hydrochloric acid gas is used. The design of the water phase is essentially determined by the apparatus used and the technical embodiment. If the formation of a fuming hydrochloric acid can not be tolerated in terms of apparatus, it is preferable to select the water phase such that a 5-35% particularly preferred 10 to 35%, particularly preferably a 20-33% aqueous hydrochloric acid solution arises.

In the process according to the invention, the silicone phase forms a water-immiscible phase. At the end of the reaction in step 4), a biphasic reaction mixture is obtained, which is subsequently purified in step 5). These process steps for work-up 5) may be carried out in any convenient order, the convenience being determined by the intervening properties of the silicone phase, such as viscosity, phase arrangement, etc. Here, reference may be made to the experiences and procedures of the commonly known art Technology used become. Work-up 5) takes place, for example, by separating off the aqueous phase from the silicone phase, then washing the silicone phase neutral with neutral or basic water and then distilling the silicone phase. This purification 5) completes the process according to the invention. The basification of the washing water can be carried out, for example, by adding sodium bicarbonate, sodium hydroxide, ammonia, sodium methoxide or another base, preferably in the form of its salt. If insoluble solids have formed in the silicone phase, they are separated by filtration through suitable filter media prior to distillation.

In the process according to the invention for the preparation of silicone resins (i), the reaction of at least one is preferably carried out

Silane (ii) of the formula (II) only with at least one silane (iii) of the formula (III).

The process according to the invention gives liquid silicone resins (i). The viscosities of these silicone resins (i) are between 20 and 100,000 mPas, preferably between 30 and 75,000 mPas, more preferably between 50 and 30,000 mPas, in particular between 50 and 10,000 mPas.

 All information on viscosity is valid at 25 ° C and at normal pressure of 1013 mbar.

From the silanes (iii) and / or disiloxanes (iv), the terminal units of the formula (VII) are formed in an aqueous hydrochloric medium by cleavage of the siloxane bond and reaction of the liberated silicon valence.

The amount of silanes (iii) or the amount of disiloxane (iv) or the mixture of the two should be chosen so that the resulting silicone resins (i) at least 5 mol% of the units of the formula (VII), preferably at least 7 mol%, particularly preferably at least 9 mol%, in particular at least 11 mol%.

The silicone resins (i) prepared by the process according to the invention consist at least of repeating units of the formula (Ia) and (VII) or (Ib) and (VII).

Repeating units of the formula (Ia) account for at least 20 mol%, preferably at least 25 mol%, particularly preferably at least 30 mol%, in particular at least 35 mol%, of the units of silicone resins (i). In a particularly preferred embodiment, the silicone resins (i) prepared according to the invention are composed only of repeating units of the formulas (Ia) and (VII).

The silicone resins (i) prepared according to the invention contain repeating units of the formula (Ib) in an amount of at most 20 mol%, preferably at most 15 mol%, in particular at most 10 mol%. In a particularly preferred embodiment, no units (Ib) are contained in the silicone resins (i).

Repeating units of the formula (Id) may be present in an amount of up to 80 mol%, preferably up to 70 mol%, more preferably up to 60 mol%, in particular up to 50 mol%, in the silicone resins (i). In a further embodiment, no units (Id) are contained in the silicone resins (i) prepared according to the invention. A further embodiment of the process according to the invention leads to silicone resins (i) which contain only randomly distributed units of the formula (Id). Another embodiment leads to silicone resins prepared according to the invention (i) containing the units of the formula (Id) only as chain segments. The silicone resins (i) produced by the process according to the invention are preferably those which have a molecular weight Mw of at least 500, preferably at least 600, more preferably at least 700, in particular at least 800, the polydispersity being at most 20, preferably at most 18, especially preferably at most 16, in particular at most 15.

The silicone resins (i) produced by the process according to the invention are soluble in suitable organic solvents, the selection of the suitable solvent depending on the particular organic functional group R ² . Appropriately, solvents are selected which are not reactive towards the organic functional group, in which case the well-documented chemical reactivities, as known from standard works of the chemical literature, are to be observed. Examples of suitable solvents are aromatic solvents, such as toluene, xylene, ethylbenzene or mixtures thereof and also organic esters of acetic acid, such as ethyl acetate, butyl acetate, methoxypropyl acetate and hydrocarbons or mixtures thereof, for example commercial isoparafine mixtures.

Examples of organofunctional radicals R ² are, for example, glycol radicals and functional organic groups from the group of phosphoric esters, phosphonic acid esters, epoxide functions, methacrylate functions, carboxyl functions, acrylate functions, olefinically or acetylenically unsaturated hydrocarbons or a hydridic silicon-bonded hydrogen.

The respective functional groups may optionally be substituted. Acid-sensitive groups R ² will react in the formation reaction of silicone resins (i), so that at the end of the reaction only their reaction products are present as radicals. An epoxide function will thus for example react to the diol and correspondingly present as diol function at the end of the reaction.

The radicals R ² may optionally be hydroxyl-, alkyloxy- or trimethylsilyl-terminated. In the main chain, non-adjacent carbon atoms may be replaced by oxygen atoms.

The functional groups R ² except for the hydrogen atom, which is always silicon-bonded, are generally not bound directly to the silicon atom. An exception to this are the olefinic or acetylenic groups, which may also be present directly silicon-bonded, especially the vinyl group. The remaining functional groups R ² are bonded to the silicon atom via spacer groups, the spacer always being Si-C bonded. The spacer is a divalent hydrocarbon radical which comprises 1 to 30 carbon atoms and in which non-adjacent carbon atoms may be replaced by oxygen atoms and which may also contain other heteroatoms or heteroatom groups, although this is not preferred.

The methacrylate group, the acrylate group and the epoxy group are preferably bonded via a spacer, the spacer comprising from 3 to 15 carbon atoms, preferably in particular 3 to 8 carbon atoms, in particular 3 carbon atoms and optionally beyond at most 1 to 3 oxygen atoms, preferably at most 1 oxygen atom bivalent hydrocarbon radical is bonded to the silicon atom.

The carboxyl group is preferably via a spacer of preferably 3 to 30 carbon atoms, in particular 3 to 20 carbon atoms, in particular 3 to 15 carbon atoms and optionally beyond at most one to 3 oxygen atoms, preferably at most 1 oxygen atom, in particular comprising no oxygen atom containing bivalent hydrocarbon radical, bonded to the silicon atom. Hydrocarbon radicals R ² which contain heteroatoms are, for example, carboxylic acid radicals of the general formula (VIII)

Y ¹ - COOH (VIII), wherein Y ^{1 is} preferably a divalent linear or branched hydrocarbon radical having up to 30 carbon atoms, wherein Y ^{1 may} also contain olefinically unsaturated groups or heteroatoms and the radical Y ¹ directly bonded to the silicon atom is a carbon is. Heteroatom-containing fragments which may typically be included in the radical Y ¹ are

-N (R ⁵ ) -C (= O) -, -COC-, -N (R ⁵ ) -, -C (= O) -, -O-C (= O) -, -CSC-, -O -C (= O) -O-, -N (R ⁵ ) -C (= O) -N (R ⁵ ) -, where asymmetric radicals can be incorporated into the radical Y ¹ in both possible directions, where R ^{5 represents} a hydrocarbon radical or hydrogen.

When the radical of formula (VIII) is e.g. produced by ring opening and condensation of a maleic anhydride to a silanol function, it would mean a radical of the form (cis) -C = C-C00H.

Hydrocarbon radicals R ² which contain heteroatoms are furthermore, for example, carboxylic acid ester radicals of the general formula (IX)

Y ¹ - C (= O) O-Y ² (IX), wherein Y ^{1 has} the meaning given above. The radical Y ² is preferably hydrocarbon radicals and, accordingly, independently of R ^1, preferably has the meaning of R ¹ . Y ² may also contain other heteroatoms and organic functions such as double bonds or oxygen atoms, although this is not preferred.

The Carbonsäureesterrest R ² can also be bound are inversely upstream, ie, a radical of the form

Y ¹ - OC (= 0) Y ² .

Examples of carboxylic anhydride radicals R ² are those of the general formulas (X) or (XI)

Y ¹ - CC (= 0) -O-C (= 0) (X), Y ¹ - R ¹⁴ CC (= 0) -O-C (= 0) R ^ls (XI),

wherein Y ^{1 has} the abovementioned meaning and R ¹⁴ and R ¹⁵ independently of one another each represent a C ¹ -C 8 hydrocarbon radical which may optionally contain heteroatoms, although this is not preferred. Examples of phosphonic acid radicals and phosphonic ester radicals R ² are those of the general formula (XII)

Y ^x -P (= O) (OR ^1S ) ₂ (XII), wherein the radicals R ^{16 are} preferably independently of one another hydrogen or hydrocarbon radicals having up to 18 carbon atoms. Preferred phosphonic acid radicals are those in which R ^{16 is} hydrogen. Preferred phosphonic acid ester radicals are those in which R ^{15 is} methyl or ethyl, although this list is not intended to be limiting. Examples of further organofunctional radicals R ² are acryloxy or methacryloxy radicals of the methacrylic acid esters or acrylic acid esters, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate , t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate.

Examples of preferred olefinically unsaturated hydrocarbon radicals R ² are those of the formula (XIII) and (XIV) Y ¹ -CR ⁷ = CR ⁸ R ⁹ (XIII)

Y ¹ -C ^ CR ¹⁰ (XIV), wherein Y ^{1 has} the abovementioned meaning and may additionally denote a chemical bond, which is particularly preferred in formula (IX) and the radicals R ⁷ , R ⁸ , R ⁹ and R ^{10 is} preferably a hydrogen atom or a C 1 -C 8 hydrocarbon radical which may optionally contain heteroatoms, where the hydrogen atom is the most preferred radical. A particularly preferred radical (XIII) is the vinyl radical, the propenyl radical and the butenyl radical, in particular the vinyl radical. The radical (XIII) can also be a dienyl radical bound via a spacer, such as the 1,3-butadienyl or the isoprenyl radical bonded via a spacer.

Examples of preferred epoxy-functional radicals R ² are those of the formulas (XV) and (XVI),

 0 formula (XV)

 / \

 1 11 12 13

Y - CR CR R 0

1 13 formula (XVI)

Y -

wherein Yl has the meanings given above, wherein Yl here is not a chemical bond and it is preferred that Yl is a C3 to C18 hydrocarbon radical and the radicals R ¹¹ , R ¹² and R ¹³ independently of one another may have the meaning of R ⁷ , wherein the preferred meaning for all radicals R ¹¹ , R ¹² and R ^{13 is} the hydrogen radical, in particular it is preferred that all three simultaneously represent a hydrogen radical. Particularly preferred organofunctional radicals R ² are carboxylic acid-functional, vinyl-functional and epoxy-functional radicals and the hydrogen radical. In particular, the vinyl and hydrogen radical.

In principle, it is conceivable that the silicone resins (i) carry different organofunctional groups. However, this is only possible if the selected organic groups do not react with each other under the conditions of regular storage, ie storage for 6 months at 23 ° C., 1013 mbar in airtight and moisture-tight containers. For example, combinations of vinyl groups and Si-H groups are possible because they require significantly different conditions than the regular storage for their reaction, for example, a catalyst and elevated temperature. A suitable selection of combinations of functional groups will be readily apparent to those skilled in the art from the published literature on the chemical reactivity of organofunctional groups. A particularly preferred combination of various organofunctional groups is that of hydridic hydrogen and olefinically unsaturated group, wherein in the particularly preferred form thereof the olefinically unsaturated group is directly silicon-bonded. The most preferred olefinically unsaturated group is the vinyl group.

If more radicals R ¹ or R ^{2 are present} in a unit of the formula (VII), these may be, independently of one another, different radicals within the stated group of possible radicals, it being necessary to observe the abovementioned conditions for the organofunctional groups.

R ¹⁷ has the meaning of R ¹ or may be an -OH. Preferred hydrocarbon radicals R ¹ are unsubstituted hydrocarbon radicals having 1 to 16 carbon atoms. Selected examples of hydrocarbon radicals R ¹ are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert. Pentyl radical, hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2, 2, -trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical, cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, aryl radicals, such as phenyl, naphthyl, anthryl and phenanthryl radical, alkaryl radicals, such as tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals, such as the benzyl radical and the .beta.-phenylethyl radical. Particularly preferred hydrocarbon radicals R ¹ are the methyl, the n-propyl and the phenyl radical.

Examples of preferred disiloxanes (iv) are [(cyclo-H ₂ C (O) CH) -O- (CH ₂ ) ₃ -Si (CH ₃ ) ₂ ] ₂ O = bis (propylglycidyl) tetramethyldisiloxane

[H ₂ C = CH-Si (CH ₃ ) ₂ ] ₂ O

[H-Si (CH ₃ ) ₂ ] ₂ O

[HOOC- (CH ₂ ) ₁₃ -Si (CH ₃ ) ₂ ] ₂ O

-O- (CH ₂ ) ₃ -Si (CH ₃ ) ₂ ] ₂ O

[H ₂ C = CH-C (= O) -O- (CH ₂ ) ₃ -Si (CH ₃ ) ₂ ] ₂ O

[H ₂ C = C (CH ₃ ) -C (= O) -O- (CH ₂ ) ₃ -Si (CH ₃ ) ₂ ] ₂ O, where this list is exemplary and should not be considered as limiting.

The following disiloxanes (iv) are particularly preferred

[H ₂ C = CH-Si (CH ₃ ) ₂ ] ₂ O

[H-Si (CH ₃ ) ₂ ] ₂ O

[H ₂ C = CH-C (= O) -O- (CH ₂ ) ₃ -Si (CH ₃ ) ₂ ] ₂ O

[H ₂ C = C (CH ₃ ) -C (= O) -O- (CH ₂ ) ₃ -Si (CH ₃ ) ₂ ] ₂ O,

in particular [H ₂ C =CH-Si (CH ₃ ) ₂ ] ₂ O and [H-Si (CH ₃ ) ₂ ] ₂ O. A further subject of the present invention are silicone resins (i) obtainable by the reaction according to the process of the invention , It is a particular feature of these silicone resins (i) that the units (VII) carrying the organofunctional groups R ² bear no alkoxy groups and no hydroxy groups. This is due to the invention Production process conditionally and deliberately brought about so. This also has its advantage over the prior art processes which use alkoxy-functional silanes to introduce organofunctional groups, in which case only part of the silane-bonded alkoxy groups present reacts and a residual amount of alkoxy groups is still present after the synthesis. This is precisely what is avoided by the method according to the invention. It is avoided in the process according to the invention in particular that the reduction of the alkoxy groups must be carried out in a subsequent further reaction step, if desired. In addition, the use of exclusively terminal functionalities ensures that the introduced organofunctional groups R ^{2 are} preferably in an exposed position in the outer edge region of the silicone resins (i) prepared according to the invention and thus readily available and available for chemical reactions with a complementarily functionalized reactant. This ensures that only a minimum of functional groups R ^{2 is} needed to get to a hardened solid. Since organofunctional groups R ^{2 are} generally more expensive than standard hydrocarbon groups without heteroatoms, the synthesis is thus also advantageous from an economic point of view, which makes them much cheaper. The inventive method is characterized in that it is very easy to perform. It comprises a simple step sequence that can be easily implemented on an industrial scale. It can be operated both discontinuously and continuously, in which case the usual systems can be used, such as coal plants, loop systems, agitator plants, which can optionally be combined and interconnected.

The inventive method is also robust and fault-tolerant and therefore also from a safety-relevant point of view unproblematic. The reactions usually proceed without significant energy release.

The silicone resins (i) prepared according to the invention can be formulated by blending and blending them with suitable liquid or solid components by means of state-of-the-art techniques.

A further subject matter comprises blends containing silicone resins (i) prepared according to the invention and other suitable liquid or solid constituents selected from the group of fillers, such as reinforcing and non-reinforcing fillers, plasticizers, adhesion promoters, soluble dyes, inorganic and organic pigments, fluorescent dyes - Substances, solvents as already stated above, fungicides, fragrances, dispersing aids, rheological additives, corrosion inhibitors, antioxidants, light stabilizers, heat stabilizers, flame retardants, agents for influencing the electrical properties and means for improving the thermal conductivity.

The silicone resins (i) obtainable by the process according to the invention can react with chemically cross-linked reaction products with suitable functionalized reactants, which may for example themselves be polyorganosiloxanes, organic polymers, functional surfaces of solids, at least two monomers bearing suitable functional groups. The reactants of the silicone resins (i) not only have to bear functional groups which can react with the silicone resins (i), but they can additionally also carry those with which they can react further with other reactants. An example of this is, for example, trialkoxy-functional silanes, which at the fourth silicon valency carry an organofunctional group which is reactive toward an organofunctional group of silicone resins (i). With The alkoxy groups can react the corresponding silane after hydrolysis by condensation with other silanes of its kind to a silicone resin network. The chemically crosslinked reaction products produced in this way can be hard, solid products, such as shaped bodies, planar structures, such as coatings, fillers for filling cavities or the like, and this list is to be understood only as an example and not by way of limitation.

For such further reactions of the silicone resins (i), for example, mixtures of several silicone resins (i) are used. Preferably, they are mixtures of at most 3 different silicone resins (i), particularly preferably only two silicone resins (i), but in particular only one silicone resin (i), which has the molecular weight distribution given for a polymer.

The crosslinking of the silicone resins (i) is carried out by reaction with suitable functionalized reactants, depending on the reactivity of the selected functional groups, where appropriate, the use of catalysts, temperature, activating radiation or other measures according to the prior art are required to initiate the reactions put. Depending on the choice of organofunctional groups, the reactions which are suitable for crosslinking are addition reactions including hydrosilylation, condensation reactions, polymerization reactions, etc. If the silicone resins (i) prepared according to the invention have organofunctional groups capable of reacting with one another, they are suitable under suitable conditions Self-networking capable. The invention furthermore relates to moldings or coatings produced by crosslinking of the silicone resins (i) according to the invention with themselves or with functionalized reaction partners.

The silicone resins (i) prepared according to the invention are suitable both for impregnation of porous materials, as described e.g. be used in the electrical insulation (such as glass fabric, mica) as well as potting and investment materials. The formulations according to the invention comprising silicone resins (i) have advantages in comparison with the known non-organofunctional silicone resins, especially when processed together with temperature-sensitive components (for example electronic components, casting molds) due to the generally milder curing conditions.

In addition, the silicone resins (i) prepared according to the invention may also be used to manipulate further properties of preparations containing them or of solids or films obtained from silicone resins (i) prepared according to the invention, such as, for example:

 Control of electrical conductivity and electrical

resistance

 Control of the flow properties of a preparation

 Control of the gloss of a wet or cured film or object

 Increase the weathering resistance

 Increase in chemical resistance

 Increase in color stability

 Reduction of the tendency to chalk

Reduction or increase in static friction and sliding friction on solids or films obtained from preparations comprising a composite preparation according to the invention Stabilization or de-stabilization of foam in the preparation containing silicone resins (i) prepared according to the invention

 Improvement of the adhesion of the preparation containing a silicone resin (i) prepared according to the invention to substrates on or between the preparation containing a silicone resin (i) prepared according to the invention, control of the filler and pigment wetting and dispersing behavior,

 Control of the rheological properties of the preparation containing a silicone resin (i) prepared according to the invention,

 Control of mechanical properties, e.g. Flexibility, scratch resistance, elasticity, extensibility, bendability, tear behavior, rebound behavior, hardness, density, tear propagation resistance, compression set, behavior at different temperatures, coefficient of expansion, abrasion resistance and other properties such as heat conductivity, flammability, gas permeability, resistance to water vapor, hot air, chemicals, Weathering and radiation, the sterilizability, of solids or films he holds of preparations, containing a silicone resin according to the invention (i) containing,

 Control of electrical properties, e.g. Dielectric strength, creep resistance, arc resistance, surface resistance, resistivity,

Flexibility, scratch resistance, elasticity, extensibility, Bie ability, tear, rebound, hardness, density, tear propagation resistance, compression set behavior at various temperatures of solids or films available from the preparation containing the silicone resins according to the invention (i). Examples of applications in which the silicone resins (i) according to the invention can be used to manipulate the abovementioned properties are the preparation of coating materials and impregnations and coatings and coatings to be obtained therefrom on substrates, such as metal, glass, wood, mineral substrate, artificial and natural fibers for the production of textiles, carpets, floor coverings, or other fiber-fabricated goods, leather, plastics such as films, moldings. The silicone resins (i) produced according to the invention can also be used as additives for defoaming, flow-promoting, hydrophobing, hydrophilization, filler and pigment dispersion, filler and pigment wetting, substrate wetting, promotion of surface smoothness, reduction of the Adhesion and sliding resistance can be used on the surface of the hardened composition obtainable from the additized preparation. The preparations according to the invention can be incorporated in liquid or in hardened solid form in elastomer compositions. Here, they may be used for the purpose of enhancing or improving other utility properties such as control of transparency, heat resistance, yellowing tendency, weathering resistance. Examples:

Examples of silicone resins (i) prepared according to the invention are given below, but these are not to be understood as limiting the present invention.

All percentages are by weight. Unless otherwise stated, all manipulations are carried out at room temperature of 23 ° C and under normal pressure (1.013 bar). The devices are commercially available laboratory equipment as they are commercially available from numerous equipment manufacturers. Ph is a phenyl radical = C ₆ H ₅ - Me is a methyl radical = CH ₃ -,

Me ₂ correspondingly means two methyl radicals.

Me ₂ (CH ₂ -) SiOi / 2 means that, due to side reactions, additional ethylene bridging takes place between two silicon atoms.

Example 1: Preparation of a Si-H and Si-vinyl functional phenyl resin with balanced functionality

As an apparatus for carrying out the reaction, a 1 1 4 - necked glass flask with spout, with KPG stirrer, intensive condenser and dosing (dropping funnel) is used. The air in the apparatus is not replaced by nitrogen.

300 g of demineralized water are poured into the glass flask. 60 g (0.5 mol) vinyldimethylchlorosilane (silane VM2, molecular weight 120.5 g / mol), 135 g (0.63 mol) phenyltrichlorosilane (P-silane, molecular weight 211.5 g / mol) and 30 g (0.31 mol) of dimethylchlorosilane (silane HM2, molecular weight 94 g / mol) were mixed with a magnetic stirrer and then transferred to the dosing vessel.

The chlorosilane mixture is metered into the water feed over 2 hours with the temperature rising from 21.3 ° C to 46.0 ° C. After the end of the dosing, stirring is continued for 1 hour without heating or cooling. Thereafter, another 19 g (0.2 mol) of silane HM2 are added to the dosing vessel and added over a period of 10 minutes. When the dosage is complete, the temperature is 32 ° C. It is stirred for 20 minutes. A biphasic reaction mixture is obtained. The lower phase is the hydrochloric acid water phase, which is drained from the flask. 500 g of demineralized water are added to the remaining product phase and the mixture is heated to 60.degree. In the biphasic mixture now obtained, the upper phase is the water phase, which in turn is separated. Repeat the washing process a total of three times. Then 15 g filter aid Seitz EF are added to the product phase, 15 Stirred minutes and filtered with a pressure filter chute on a Seitz K 100 filter plate.

 The filtrate is heated on a rotary evaporator at 160 ° C and 10 mbar pressure for 2 hours. This gives 110 g of a slightly cloudy product having a viscosity of 133 mPas.

The contained resin has, according to SEC (eluent THF), a molecular weight of Mw = 1900 g / mol and Mn = 1000 g / mol.

The silanol content is determined in ^ ^"H NMR to 195 ppm.

The vinyl content is 2.64 mmol / g, the silicon-bonded hydrogen content 2.54 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

Me ₂ Si0 _2/2 : 1.2%

Me ₂ (CH ₂ -) SiO _1/2 : 1.1%

Ph (OR) ₂ Si0 _{1 2} : 0.0%

Ph (OR) Si0 _2/2 : 8.3%

PhSi0 _3/2: 36.5%

where R is hydrogen here. The product is free of alkoxysilyl groups.

Example 2 Non-functional Phenyl Resin According to the Invention

 As apparatus for carrying out the reaction, a 500 ml 3-necked glass flask with outlet, with KPG stirrer, intensive cooler and dosing (dropping funnel) is used. The air in the apparatus is not replaced by nitrogen.

148 g of demineralized water and 176 g of 25% strength aqueous hydrochloric acid solution are introduced into the glass flask. 70.58 g (0.44 mol) of hexamethyldisiloxane (molecular weight 162 g / mol), 135.36 g (0.63 mol) of phenyltrichlorosilane (P-silane, molecular weight 211.5 g / mol ) and 21.67 g (0.20 mol) of trimethylchlorosilane (silane M3, molecular weight 108.5 g / mol) were mixed with a magnetic stirrer and then transferred to the dosing vessel. The chlorosilane mixture is metered into the water feed over 4 hours, with the temperature rising from 21.5 ° C to 40.1 ° C. After the end of the dosing, stirring is continued for 10 minutes without heating or cooling. A two-phase reaction mixture is obtained. The lower phase is the hydrochloric acid water phase, which is drained from the flask. 400 g of demineralized water are added to the remaining product phase and then left to stir for 10 minutes without stirring to separate the phases. In the biphasic mixture now obtained, the upper phase is the water phase, which in turn is separated. One repeats the washing process a total of twice. Then 15 g filter aid Seitz EF are added to the product phase, stirred for 15 minutes and filtered through a Seitz K 100 filter plate with a pressure filter.

The filtrate is heated on a rotary evaporator at 160 ° C and 10 mbar pressure for 2 hours. This gives 123 g of a slightly cloudy product having a viscosity of 2057 mPas.

According to SEC (eluent THF), the contained resin has a molecular weight of Mw = 1300 g / mol and Mn = 1000 g / mol.

The silanol content is determined in ¹ H-NMR to be 10800 ppm.

According to ⁹ Si NMR, the molar composition is:

Me ₂ Si0 _2/2 : 0.1%

Ph (OR) ₂ Si0 _1/2 : 0.6%

Ph (OR) Si0 _2/2 : 14.0%

PhSi0 _3/2 : 32.6%

where R is hydrogen here. The product is free of alkoxysilyl groups.

Example 3 Non-functional Phenyl Resin According to the Invention

The apparatus used was a glass loop reactor consisting of a glass tube of 5 cm internal diameter and a volume of 1.5 liters. Connected to the loop are two metering pumps which can convey substances into the loop at a distance of 30 cm from each other. NEN. The loop reactor is filled with 5% aqueous hydrochloric acid solution. In a metering vessel, 494 g (3.05 mol) of hexamethyldisiloxane (molecular weight 162 g / mol), 948 g (4.48 mol) of phenyltrichlorosilane (P-silane, molecular weight 211.5 g / mol) and 303 g (2 , 79 mol) of trimethylchlorosilane (silane M3, molecular weight 108.5 g / mol).

 This silane mixture is fed into the loop at a rate of 870 ml / h, at the same time retracting demineralized water at a rate of 5900 ml / h. The selected dosing rates result in an average residence time of 15 minutes in the loop reactor. The loop content is circulated by a centrifugal pump. The temperature may be limited to 40 ° C by cooling. The phase separation is carried out continuously by coalescers. The water dosage is selected so that a constant hydrochloric acid concentration of 5% is maintained during the entire loop travel. The resulting crude product after phase separation is stirred for 15 minutes with 15 g filter aid Seitz EF per 250 ml product phase and filtered through a Seitz K 100 filter plate with a pressure filter.

The filtrate is heated on a rotary evaporator at 160 ° C and 10 mbar pressure for 2 hours. This gives 123 g of a slightly cloudy product having a viscosity of 637 mPas. The 0H content determined by Zerevitinov is 3.33%.

According to SEC (eluent THF), the contained resin has a molecular weight of Mw = 1200 g / mol and Mn = 1000 g / mol.

According to ²⁹ Si NMR, the molar composition is:

Me ₃ Si0 _1/2 : 44.6%

Ph (OR) ₂ Si0 _1/2 : 0.8%

Ph (OR) Si0 _2/2 : 29.7%

PhSi0 _3/2 : 24.9%

where R is hydrogen here. The product is free of alkoxysilyl groups.

Example 4 Non-functional Phenyl Resin According to the Invention

The procedure corresponds to that of Example 2. Here, a 2 1 glass flask was used.

 In contrast to Example 2, the following starting materials were used here:

 5% aqueous hydrochloric acid solution: 352 g

demineralized water: 296 g

Hexamethyldisiloxane: 328.08 g

P-silane: 514.44 g

 In this experiment, unlike Example 2, no trimethylchlorosilane was used.

This gives 519 g of a slightly cloudy product having a viscosity of 2437 mPas.

 The silanol content is 3600 ppm by NMR.

 The contained resin has, according to SEC (eluent THF), a molecular weight of Mw = 1400 g / mol and Mn = 1000 g / mol.

According to ²⁹ Si NMR, the molar composition is:

Me ₃ Si0 _1/2 : 55.6%

Ph (OR) Si0 _2/2: 8.9%

PhSi0 _3/2 : 35.2%

where R is hydrogen here. The product is free of alkoxysilyl groups.

Example 5 Non-functional phenyl resin according to the invention

The procedure corresponds to that of Example 2. Here, a 0.5 1 glass flask was used.

 In contrast to Example 2, the following starting materials were used here:

 5% aqueous hydrochloric acid solution: 88 g

demineralized water: 74 g

Hexamethyldisiloxane: 70.58 g

P-silane: 135.36 g

 Dimethyldichlorosilane (M2 ~ silane; Mw = 129 g / mol): 25.82 g (0.2 mol)

In this experiment, unlike Example 2, no trimethylchlorosilane was used. This gives 101 g of a slightly cloudy product with a viscosity of 522 mPas.

 The silanol content is 1524 ppm by NMR.

 According to SEC (eluent THF), the contained resin has a molecular weight of Mw = 2300 g / mol and Mn = 1200 g / mol.

According to ²⁹ Si NMR, the molar composition is:

Me ₂ Si0 _2/2 : 12.5%

Ph (OR) Si0 _{2 2} : 5.6%

PhSi0 _3/2 : 36, 1%

where R is hydrogen here. The product is free of alkoxysilyl groups.

Example 6 Comparative Example: Phenyl resin not according to the invention

 The procedure corresponds to that described in Example 2 with the following differences:

Apparatus: 2 1 three-necked discharge flask

Starting materials:

demineralized water: 296 g

no aqueous hydrochloric acid

 Hexamethyldisiloxane: 141.16 g (0.88 mol)

Phenyltriethoxysilane: 307.72 g (1.28 mol)

Trimethylchlorosilane: 43.34 g (0.40 mol)

The silanes and the disiloxane are mixed in advance and added to the water reservoir. Due to exothermic temperature increase, the temperature only rises to 30 ° C. Phase inversion already occurred during the first phase separation. The water phase evidently contained significantly less HCl and thus had a lower density than the resin phase.

This gives 240 g of clear, colorless product having a viscosity of 472 mm ² / s. The silanol content is 15062 ppm by NMR, the alkoxy content is 3.3 wt .-%.

According to SEC (eluent THF), the contained resin has a molecular weight of Mw = 1300 g / mol and Mn = 1000 g / mol. According to ²⁹ Si NMR, the molar composition is:

Ph (OR) ₂ Si0 _1/2 : 0.3%

PhSi0 _3/2 : 24.5%

where R is hydrogen and ethoxy.

Example 7 Inventive vinyl-functional phenyl resin

The procedure corresponds to that of Example 2, with the following differences:

 Apparatus: 500 ml three-necked outlet flask

 Starting materials and quantities:

 5% aqueous hydrochloric acid solution: 88 g

demineralized water: 74 g

1, 3-divinyl-1,1,3,3-tetramethyldisiloxane [(CH ₂ = CH) Me ₂ Si] ₂ O (186 g / mol): 82.02 g (0.44 mol)

 Phenyltrichlorosilane: 135.36 g (0.64 mol)

 Trimethylchlorosilane: 21.67 g (0.20 mol)

 56 g of clear product with a viscosity of 4325 mPas are obtained.

 The silanol content is 1380 ppm by NMR.

 The contained resin has, according to SEC (eluent THF), a molecular weight of Mw = 2600 g / mol and Mn = 1600 g / mol.

According to ²⁹ Si NMR, the molar composition is:

Me ₂ (CH ₂ = CH) SiO _1/2 : 22.6%

Ph (OR) Si0 _2/2 : 8.7%

PhSi0 _3/2 : 53.5%

where R is hydrogen here. The product is free of alkoxysilyl groups.

Example 8: Functional Phenyl Resin According to the Invention

 The procedure corresponds to that described in Example 2 with the following differences:

Apparatus: 2 1 four-necked flask Starting materials and quantities:

1, 3-divinyl-1,1,3,3-tetramethyldisiloxane [(CH ₂ = CH) Me ₂ Si] ₂ O (186 g / mol): 164.04 g (0.88 mol)

1, 1, 3, 3-tetramethyldisiloxane [(H) Me ₂ Si] ₂ O (136 g / mol): 53.72 g (0.40 mol)

 Phenyltrichlorosilane: 270.72 g (1.28 mol)

 This gives 316 g of product with a viscosity of 1425 mPas. The silanol content is 1217 ppm by NMR.

 According to SEC (eluent THF), the contained resin has a molecular weight of Mw = 2800 g / mol and Mn = 1100 g / mol.

According to ²⁹ Si NMR, the molar composition is:

Me ₂ (CH ₂ -) SiO _1/2 : 3.0%

Me ₂ (H) Si0 _1/2 : 24.6%

Me ₂ (CH ₂ = CH) SiO _1/2 : 22.4%

Me ₂ Si0 _2/2 : 0.2%

Ph (OR) Si0 _2/2 : 11.2%

PhSi0 _3/2 : 38.6%

where R is hydrogen here. The product is free of alkoxysilyl group.

Example 9: RW 69: functional methyl resin according to the invention

The procedure is analogous to Example 2 with the following differences:

 Apparatus: 2 1 four-neck glass flask

quantities

 5% aqueous hydrochloric acid 176 g

demineralized water: 148 g

1, 3-divinyl-1,1,3,3-tetramethyldisiloxane [(CH ₂ = CH) Me ₂ Si] ₂ O (186 g / mol): 164.04 g (0.88 mol)

Methyltrichlorosilane: 174.08 g (1.28 mol)

1, 1, 3, 3-tetramethyldisiloxane [(H) Me ₂ Si] ₂ O (136 g / mol): 38.95 g (0.28 mol)

There are obtained 176 g of a clear resin, which according to SEC (eluent THF) has a molecular weight of Mw = 2200 g / mol and Mn = 1000 g / mol. The silanol content is determined to be 173 ppm in 1 H-NMR.

The vinyl content is 4.43 mmol / g, the silicon-bonded hydrogen content 1.67 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

Me ₂ (H) Si0 _1/2 : 12.9%

Me ₂ (CH ₂ = CH) SiO _2/2 : 35.3%

Me ₂ Si0 _2/2: 1.4%

Me ₂ (CH ₂ -) Si0 _1/2: 2.3%

Me (OR) Si0 _2/2 : 1.3%

MeSi0 _3/2 : 46.8%

where R is hydrogen here. The product is free of alkoxysilyl groups.

Example 10 Functional Methyl Resin According to the Invention

The procedure corresponds to that described in Example 1. The quantities are chosen as follows:

demineralized water: 400 g

Silane VM2: 80 g (0.66 mol)

 Methyltrichlorosilane (Ml-silane, molecular weight 136 g / mol): 52 g (0.38 mol)

 Silane HM2 in the chlorosilane mixture: 40 g

 Silane HM2 for later dosing: 22.2 g (0.24 mol)

The washes are done at 23 ° C without heating. The product is volatilized at 80 ° C and 10 mbar on a rotary evaporator. This gives 107 g of a clear product having a viscosity of 57 mPas.

According to SEC (eluent THF), the contained resin has a molecular weight of Mw = 800 g / mol and Mn = 700 g / mol.

The silanol content is determined to <100 ppm in ¹ H-NMR.

The vinyl content is 2.54 mmol / g, the silicon-bonded hydrogen content 3.42 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

27,5 %

27.5%

Me (OR) ₂ Si0 _1/2 : 0.0%

Ph (OR) Si0 _2/2: 1.3%

PhSi0 _3/2 : 35.6%

where R is hydrogen here. The product is free of alkoxysilyl groups. Example 11 Inventive non-functional phenyl resin with random D units

 The procedure corresponds to that described in Example 1. The quantities are chosen as follows:

demineralized water: 300 g

Silane VM2: 60 g (0.66 mol)

 Phenyltrichlorosilane (P-silane, molecular weight 211.5 g / mol): 135 g (0.64 mol)

 Phenylmethyldichlorosilane (PM silane, molecular weight 191 g / mol): 54 g (0.28 mol)

Silane HM2 in the chlorosilane mixture: 30 g (0.43 mol)

Silane HM2 for later dosing: 19.0 g (0.20 mol)

The washes take place at 60 ° C. The product is volatilized at 100 ° C and 10 mbar on a rotary evaporator. This gives 137 g of a clear product having a viscosity of 657 mPas.

The contained resin has, according to SEC (eluent THF), a molecular weight of Mw = 1500 g / mol and Mn = 1000 g / mol.

The silanol content is determined to be 385 ppm in ¹ H-NMR.

The vinyl content is 2.25 mmol / g, the silicon-bonded hydrogen content is 1.99 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

(CH ₂ = CH) Me ₂ Si0 _1/2 : 26.7%

Me ₂ Si0 _{2 2} : 1.8% Ph (Me) Si0 _2/2 : 15.6%

Me ₂ (CH ₂ -) SiO _1/2 : 0.7%

Ph (OR) Si0 _2/2: 5.9%

PhSi0 _3/2 : 29.5%

where R is hydrogen here. The product is free of alkoxysilyl groups.

Example 12 Inventive Phenyl Resin with D-Chain Segments

The procedure corresponds to that described in Example 1. The quantities are chosen as follows:

demineralized water: 300 g

Silane VM2: 60 g (0.66 mol)

 Phenyltrichlorosilane (P-silane, molecular weight 211.5 g / mol): 135 g (0.64 mol)

short-chain alpha omega silanol-functional phenylmethyl oil having the average composition: HO-Si (Me) (Ph) [O-Si (Me) (Ph)] ₄ OSi (Me) (Ph) OH, thus comprising a total of 6 silicon repeating units, of which each substituted with a phenyl and a methyl group and of which the two terminal silicon atoms each carry a hydroxyl function and which has an average molecular weight of Mw = 800 g / mol at Mn = 700 g / mol, and a viscosity of 503 mPas 25 ° C and atmospheric pressure of 1013 mbar (PM siloxane): 54 g

Silane HM2 in the chlorosilane mixture: 49 g (0.63 mol)

Notwithstanding the procedure in Example 1, here silane HM2 is not added to the silane mixture, not even a part thereof. Silane HM2, due to its high reactivity on hydridic hydrogen, tends to react with hydrogen release compared to OH-rich compounds. To avoid this, silane HM2 is added to the reaction mixture here later. The PM siloxane is added to the silane mixture of VM2 silane and P-silane and added together with them. The washes take place at 60 ° C. The product is volatilized at 100 ° C and 10 mbar on a rotary evaporator. This gives 128 g of a clear product with a viscosity of 558 mPas. The contained resin has, according to SEC (eluent THF), a molecular weight of Mw = 2200 g / mol and Mn = 1200 g / mol.

The silanol content is determined to be 68 ppm in ¹ H-NMR.

The vinyl content is 2.21 mmol / g, the silicon-bonded hydrogen content 1.18 mmol / g.

According to ²⁹ Si NMR, the molar composition is:

(CH ₂ = CH) Me ₂ Si0 _1/2 : 25.8%

Ph (Me) Si0 _2/2 : 22.7%

Ph (OR) Si0 _2/2: 6.5%

PhSi0 _3/2 : 32.1%

where R is hydrogen here. The product is free of alkoxysilyl groups.

Claims

claims 1. Process for the preparation of silicone resins (i) from units of the formulas (Ia), (Ib), (VII) and (Id) [R ¹⁷ Si0 _3/2] [Si0 _4/2], [R ² _c R ¹ _(3-c) Si0 _1/2], [R ¹⁷ ₂ Si0 _2/2] (Ia) (Ib) (VII) (Id ) in which R ^{1 is the} same or independently different monovalent hydrocarbon radicals, R ^{17 is the} same or independently of one another the meaning of R ¹ or -OH, R ^{2 is} identical or independently different monovalent organofunctional hydrocarbon radicals, olefinically unsaturated hydrocarbon radicals or a hydrogen radical, where the radical R ^{2 is} bonded to the silicon atom via a carbon atom, or the hydrogen radical is bonded directly to the silicon atom, c = 0 or 1  mean,  with the stipulations that  at least 5 mol% of the formula (VII) are contained,  at least 20 mol% of the formula (Ia) are contained,  at most 20 mol% of the formula (Ib) are present, by reacting at least one silane (ii) of the formula (II) R ¹ _(4-a) Si (Cl) _a (II) where R ^{1 is the} same or independently of one another as defined above, and a is 2, 3 or 4  mean with at least one silane (iii) of the formula (III) R'O- _b jR _'b SiCl (III) wherein R ¹ and R ² has the meanings given above, and b values can have 0 or 1, with at least one disiloxane (iv) of the formula (IV) t R ¹ _{(3- b)} R ² _b Si] ₂ O (IV), where R ¹ and R ² and b have the meanings given above, and the disiloxanes (iv) are of symmetrical construction, so that the radicals R ¹ and R ² have the same meaning on both silicon atoms, or with a mixture of at least one silane (iii) and at least one disilioxane (iv) in a water master , with the stipulations that  always at least 5 mol% of a silane (ii) with a = 3 are used, based on the total reaction partners used,  no organic solvents are used, the reaction taking place via the following process steps: 1) Preparation of a starting material template by Case a) if only silanes (ii) or mixtures of silanes (ii) and disiloxanes (iv) are used: the silanes (ii) are mixed with all or part of the silanes (iii) or mixtures of silanes (iii) and Disilioxanes (iv) or  Case b) if only disiloxanes (iv) are used: presentation of only the silanes (ii) or mixing of the silanes (ii) with the total amount of disiloxanes (iv)  2) Prepare a water blank from PH neutral water or PH acidic water by adding additional water  Case a): mixing in of the residual amount of disiloxane (iv), if in step 1) only partial quantities were used,  Case b): mixing the total amount of disiloxanes (iv) if not done in step 1)  3) adding the educt template from step 1) into the water template from step 2) or vice versa,  4) Hydrolysis and condensation and  Case a): addition of the residual amount of silane (iii), if in step 1) only partial quantities were used,  5) Purification of the resulting silicone resin (i) from the forming silicone phase. 2. A process for the preparation of silicone resins (i) according to claim 1, characterized in that no units of formula (Ib) are included. 3. Process for the preparation of silicone resins (i) according to claim 1 or 2, characterized in that no units of the formula (Id) are contained. 4. A process for the preparation of silicone resins (i) according to claim 1 or 2, characterized in that units of formula (Id) are included only statistically distributed. 5. Process for the preparation of silicone resins (i) according to claim 1 or 2, characterized in that units of the formula (Id) are contained only as chain segments. 6. A process for preparing silicone resins (i) according to any one of claims 1 to 5, characterized in that the reaction of at least one silane (ii) of the formula (II) only with at least one silane (iii) of the formula (III). 7. A process for the preparation of silicone resins (i) according to any one of claims 1 to 6, characterized in that R ^{2 is} independently a vinyl or a hydrogen radical. 8. Silicone resins (i) from units of the formulas (Ia), (Ib), (VII) and (Id) [R ¹⁷ Si0 _3/2 ] [Si0 _4/2 ]

[R ¹⁷ ₂ Si0 _2/2 ] (Ia) (Ib) (VII) (Id) where R ^{1 is the} same or independently different monovalent hydrocarbon radicals, R ^{17 is the} same or independently of one another the meaning of R ¹ or -OH, R ^{2 is the} same or independently different monovalent organofunctional hydrocarbon radicals, olefinically unsaturated hydrocarbon radicals or a hydrogen radical, where the radical R ^{2 is} bonded to the silicon atom via a carbon atom, or the hydrogen radical is bonded directly to the silicon atom, c = 0 or 1 mean,  with the stipulations that  at least 5 mol% of the formula (VII) are contained,  at least 20 mol% of the formula (Ia) are contained, at most 20 mol% of the formula (Ib) are present, by reacting at least one silane (ii) of the formula (II)

where R ^{1 has the} same or the same meaning as defined above,  and a the values 2, 3 or 4,  mean with at least one silane (iii) of the formula (III)

where R ¹ and R ^{2 have} the meanings given above, and b may have the values 0 or 1, or with at least one disiloxane (iv) of the formula (IV)

where R ¹ and R ² and b have the meanings given above, and the disiloxanes (iv) have a symmetrical structure, so that the radicals R ¹ and R ² have the same meaning on both silicon atoms, or with a mixture of at least one silane (iii) and at least one disilioxane (iv), in a water template with the stipulations that  always at least 5 mol% of a silane (ii) are used with a = 3, based on the total reactants used,  no organic solvents are used, the reaction taking place via the following process steps:  1) Preparation of a starting material template by  Case a) if only silanes (ii) or mixtures of silanes (ii) and disiloxanes (iv) are used: the silanes (ii) are mixed with all or part of the silanes (iii) or mixtures of silanes (iii) and Disilioxanes (iv) or  Case b) if only disiloxanes (iv) are used: presentation of only the silanes (ii) or mixing of the silanes (ii) with the total amount of disiloxanes (iv)  2) Prepare a water blank from PH neutral water or PH acidic water by adding additional water  Case a): mixing in of the residual amount of disiloxane (iv), if in step 1) only partial quantities were used,  Case b): mixing the total amount of disiloxanes (iv) if not done in step 1)  3) adding the educt template from step 1) into the water template from step 2) or vice versa,  4) Hydrolysis and condensation and  Case a): addition of the residual amount of silane (iii), if in step 1) only partial quantities were used, 5) Purification of the resulting silicone resin (i) from the forming silicone phase. 9. blends containing at least one silicone resin (i) according to claim 8 and other suitable liquid or solid components selected from the group of fillers, plasticizers, adhesion promoters, soluble dyes, inorganic and organic see pigments, fluorescent dyes, solvents, fungicides, fragrances, dispersants , rheological additives, corrosion inhibitors, antioxidants, light stabilizers, heat stabilizers, flame retardants, electrical property modifiers, and thermal conductivity improvers.