WO2016116349A1 - Procédé de production de résines de silicone - Google Patents

Procédé de production de résines de silicone Download PDF

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Publication number
WO2016116349A1
WO2016116349A1 PCT/EP2016/050660 EP2016050660W WO2016116349A1 WO 2016116349 A1 WO2016116349 A1 WO 2016116349A1 EP 2016050660 W EP2016050660 W EP 2016050660W WO 2016116349 A1 WO2016116349 A1 WO 2016116349A1
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mol
formula
silanes
silane
iii
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PCT/EP2016/050660
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German (de)
English (en)
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Frank Sandmeyer
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Wacker Chemie Ag
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

Definitions

  • 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.
  • US5280098 describes the synthesis of epoxy-functional silicone resins using epoxy-functional alkoxy-carrying silanes, resulting in epoxy-functional alkoxy-bearing silicone resins.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the process is not tolerant to epoxide groups, carboxy groups, and amino groups as they would undergo transformations through chemical reactions during the process.
  • 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
  • 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:
  • 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.
  • 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.
  • Spectrometer Bruker Avance I 500 or Bruker Avance HD 500 Probe Head: 5 mm BBO Probe Head or SMART Probe Head (Fa.
  • Pulprog zg30
  • NS 64 or 128 (depending on the sensitivity of the sample head)
  • Probe head 10 mm lH / 13C / 15N / 29Si glass-free QNP probe head
  • Pulprog zgig60
  • 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.
  • the glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, perforated Tigel, heating rate 10 K / min.
  • 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)
  • 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
  • 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
  • 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 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.
  • siloxanes or silanes may be added which do not correspond to (ii), (iii) or (iv).
  • 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
  • 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).
  • 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.
  • 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.
  • step 4 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.
  • the silicone phase forms a water-immiscible phase.
  • 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.
  • 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.
  • 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.
  • 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%.
  • 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).
  • 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).
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • Carbonkladerrest R 2 can also be bound are inversely upstream, ie, a radical of the form
  • carboxylic anhydride radicals R 2 are those of the general formulas (X) or (XI)
  • 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.
  • 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)
  • 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.
  • 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.
  • methyl acrylate methyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate.
  • 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),
  • 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.
  • the silicone resins (i) carry different organofunctional groups.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • 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.
  • 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).
  • 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.
  • silicone resins (i) for example, mixtures of several silicone resins (i) are used.
  • 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.
  • 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.
  • the reactions which are suitable for crosslinking are addition reactions including hydrosilylation, condensation reactions, polymerization reactions, etc.
  • 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.
  • 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 properties e.g. Dielectric strength, creep resistance, arc resistance, surface resistance, resistivity,
  • silicone resins (i) according to the invention can be used to manipulate the abovementioned properties
  • 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:
  • silicone resins (i) prepared according to the invention are given below, but these are not to be understood as limiting the present invention.
  • 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
  • a 1 1 4 - necked glass flask with spout, with KPG stirrer, intensive condenser and dosing (dropping funnel) is used as an apparatus for carrying out the reaction.
  • the air in the apparatus is not replaced by nitrogen.
  • 300 g of demineralized water are poured into the glass flask.
  • silane HM2 dimethylchlorosilane
  • 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.
  • 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 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.
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl groups.
  • 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.
  • the upper phase is the water phase, which in turn is separated.
  • 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.
  • the silanol content is determined in 1 H-NMR to be 10800 ppm.
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl groups.
  • 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.
  • 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%.
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl groups.
  • Example 2 The procedure corresponds to that of Example 2. Here, a 2 1 glass flask was used.
  • the silanol content is 3600 ppm by NMR.
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl groups.
  • Example 2 The procedure corresponds to that of Example 2. Here, a 0.5 1 glass flask was used.
  • the silanol content is 1524 ppm by NMR.
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl groups.
  • Phenyltriethoxysilane 307.72 g (1.28 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.
  • the molar composition is:
  • R is hydrogen and ethoxy
  • the silanol content is 1380 ppm by NMR.
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl groups.
  • Phenyltrichlorosilane 270.72 g (1.28 mol)
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl group.
  • the vinyl content is 4.43 mmol / g, the silicon-bonded hydrogen content 1.67 mmol / g.
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl groups.
  • Silane VM2 80 g (0.66 mol)
  • Methyltrichlorosilane (Ml-silane, molecular weight 136 g / mol): 52 g (0.38 mol)
  • 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.
  • 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.
  • the molar composition is:
  • Example 11 Inventive non-functional phenyl resin with random D units
  • 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 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 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.
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl groups.
  • Silane VM2 60 g (0.66 mol)
  • Phenyltrichlorosilane (P-silane, molecular weight 211.5 g / mol): 135 g (0.64 mol)
  • 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 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.
  • the molar composition is:
  • R is hydrogen here.
  • the product is free of alkoxysilyl groups.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un procédé de fabrication sans solvants de résines de silicone exemptes d'alcoxy et éventuellement organofonctionnelles, ainsi que les résines organofonctionnelles obtenues selon ledit procédé et leur utilisation.
PCT/EP2016/050660 2015-01-19 2016-01-14 Procédé de production de résines de silicone WO2016116349A1 (fr)

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DE102017214382B4 (de) 2017-08-18 2022-09-08 Wacker Chemie Ag Verfahren zur Herstellung von Siloxanmischungen mit geringem Gehalt an Silanol- und Kohlenwasserstoffoxygruppen

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US20130289293A1 (en) * 2011-05-03 2013-10-31 Dow Corning Corporation Method Of Forming An MT-Propyl Siloxane Resin
EP2762518A1 (fr) * 2013-02-05 2014-08-06 Wacker Chemie AG Hydrolyse d'organochlorosilanes dans un réacteur à faisceau tubulaire

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EP1010714B1 (fr) 1998-12-15 2006-04-12 General Electric Company Procédé de préparation de siloxanes fonctionnalisés, compositions les contenant et produits obtenus à base ces dernières
DE10151264A1 (de) 2001-10-17 2003-04-30 Degussa Aminoalkylalkoxysiloxanhaltige Gemische, deren Herstellung und deren Verwendung
DE10242418A1 (de) 2002-09-12 2004-03-25 Wacker-Chemie Gmbh Verfahren zur Herstellung von Organopolysiloxanharz
DE10335178A1 (de) 2003-07-30 2005-03-31 Degussa Ag Zusammensetzung eines Gemisches aminoalkyl- und oligo-silylierter-aminoalkyl-funktioneller Siliciumverbindungen, deren Herstellung und deren Verwendung

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US20130289293A1 (en) * 2011-05-03 2013-10-31 Dow Corning Corporation Method Of Forming An MT-Propyl Siloxane Resin
EP2762518A1 (fr) * 2013-02-05 2014-08-06 Wacker Chemie AG Hydrolyse d'organochlorosilanes dans un réacteur à faisceau tubulaire

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CN113039246A (zh) * 2019-05-17 2021-06-25 瓦克化学股份公司 可进行交联以形成硅树脂复合材料的硅酮组合物
JP2022533643A (ja) * 2019-05-17 2022-07-25 ワッカー ケミー アクチエンゲゼルシャフト 架橋してシリコーン樹脂複合材料を形成できるシリコーン組成物

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