Method for preparing low silanol polyorganosiloxanes

Abstract

The present invention relates to a compound represented by formula (I) [O 3-a / 2 R a SiY(SiR a O 3-a / 2 ) b ] c (R 1 SiO 3 / 2 ) d (R 2 2SiO 2 / 2 ) e (R 3 3SiO 1 / 2 ) f (SiO 4 / 2 ) g [O 3-h / 2 R 4 h Si(SiR 5 2) i SiR 4 j O 3-j / 2 ] k (I) [In the formula, R, R 1 , R 2 , R 3 , R 4 , R 5 , Y, a, b, c, d, e, f, g, h, i and k have the definitions given in claim 1.], a process for bonding the polyorganosiloxane of formula (I) to a metal substrate, a process in which the polyorganosiloxane of formula (I) is crosslinked, and a metal clad laminate producible by one of the aforementioned processes.

Description

[Technical field]

[0001] The present invention relates to a process for the preparation of polyorganosiloxanes in which the polar Si-O-C bonds and silanol groups are reduced to a minimum, thus ensuring that the polyorganosiloxanes have suitable dielectric properties for radio frequency applications. [Background technology]

[0002] With the progressive opening of radio frequency technology for wireless communication, there is an increasing demand for materials that can realize this technology. This concerns the whole field of materials such as copper foils, binders, glass fibers, etc. In the case of binders, epoxy resins, which are traditionally used for the production of copper laminates and the subsequent production of circuit boards, can no longer be used because their dielectric loss factor is too high. Polytetrafluoroethylene has a very low dielectric loss factor and is therefore very useful for radio frequency applications, but has other drawbacks, in particular poor processing properties and poor adhesion properties, which make alternatives desirable. Polyphenylene ethers are currently intensively utilized as binders for this field of application, since they combine a low dielectric loss factor with good mechanical and thermal properties as well as water repellency. In addition, other organic polymers are currently being considered in the current development activities of this field of application, examples of which are bismaleimide polymers, bismaleimide-triazine copolymers and hydrocarbon resins, and this list can be supplemented with further examples.

[0003] Polyorganosiloxanes essentially have excellent heat resistance, weather stability, and hydrophobicity, are flame retardant, and have a low dielectric loss factor.

[0004] These property profiles qualify the described organic polymers as well as polyorganosiloxanes for use as binders for the manufacture of radio frequency compatible copper laminates and components, such as circuit boards and antennas. It is therefore clear to combine the beneficial properties of these classes of materials to achieve a symbiotic increase in their performance capabilities. Experiments in this direction have already been documented in the prior art.

[0005] Polar substituents in polyorganosiloxanes are undesirable in this context, since they increase the dielectric loss factor. According to the prior art, polyorganosiloxanes are preferably prepared by a process of hydrolysis and condensation. Alcohols can also be used in such a process. In this regard, see, for example, the following:

[0006] The combination of polyorganosiloxanes and polyphenylene ethers to improve flame retardancy is described in US 6258881. Particularly suitable for this purpose are solid polyorganosiloxanes having defined particle sizes.

[0007] Further examples of the use of compositions consisting of physical mixtures of polyphenylene ethers and polyorganosiloxanes to improve specific properties can be found in US 3,737,479 (improved impact strength), US 5,834,585 (mixtures of chemically curable polyphenylene ethers with improved processing properties), US 2004 / 0138355 (improved flame retardancy by blending with closed and partially open silsesquioxane cage structures), US 3,960,985 (improved thermal stability of mixtures of polyphenylene ethers and alkenyl aromatic polymers by the addition of small amounts of polydimethylsiloxanes with in-chain Si-H functional groups).

[0008] These examples are evidence of the interest and fundamental utility of polyorganosiloxanes as additives and co-binders for radio frequency applications.

[0009] US2016 / 0244610 describes a composition consisting of a mixture of olefinically unsaturated MQ resin and polyphenylene ether modified for unsaturation, the purpose of using MQ resin is to improve the dielectric and thermal properties of polyphenylene ether, but the examples of US2016 / 0244610 show a clearly high dielectric loss factor for the composition of the invention.

[0010] In describing the technology environment, US 2016 / 0244610 makes specific reference to future developments in communications technology and therefore the invention must be considered and evaluated with reference to the requirements of that environment.

[0011] For the requirements and performance capacities already achieved by modern materials suitable for use in 5G applications, see US2020 / 369855. In US2016 / 0244610, it is observed and claimed that the polyorganosiloxanes of the invention are prepared from monomers by a hydrolysis process. This process further uses alcohol as a solvent and alkoxylated precursors as reagents.

[0012] In the light of US2016 / 0244610, which cannot provide an analytical description of the MQ resin obtained, reference can be made at this point to US5548053, which is a more easily understood prior art that describes the synthesis of MQ resin in a hydrolysis process.The special feature of the process of US5548053 is that the MQ resin is prepared in a two-step process, with the number of residual silanol groups being reduced in the second step.Otherwise, this procedure is essentially the same as the procedure in the examples of US2016 / 0244610.

[0013] Since US2016 / 0244610 does not use the second step of the process of US5548053, there is no possibility of a silanol group reduction effect as achieved in US5548053. Therefore, in US2016 / 0244610, the assumption must be that of a higher number of silanol groups than shown in US5548053. Despite the targeted reduction of silanol groups by the process of the invention from US5548053, a significant amount of alkoxy groups remains, which are also Si-OC-bonded polar groups, and interfere with the achievement of a low dielectric loss factor. US 5,548,053 is prior art and, although earlier, is superior in terms of the synthesis of MQ resins, in terms of the reduction of polar groups, so that the MQ resins of US 2016 / 0244610 have inferior properties for use in radio frequency applications than those obtainable according to US 5,548,053, in terms of the number of silicon-bonded polar groups. The fact that the examples of US 2016 / 0244610 do not go back to the already existing prior art of US 5,548,053 is incomprehensible in this context. However, as maintained, in this case too there will be a significant amount of alkoxy groups remaining in the resin as well as residual amounts of silanol groups.

[0014] A further weakness of the teachings of US2016 / 0244610 is the unsatisfactory results of the inventive compositions in the results of this application due to the incompatibility of the MQ resins used in the polyphenylene ether matrix. This situation is clearly recognized and documented in the examples, and therefore the nature of the inventive problem solving in US2016 / 0244610 is not clear, and as a result US2016 / 0244610 misses its target and does not provide the teaching or benefit of the proposed combination to the field of radio frequency communication technology.

[0015] However, US2016 / 0244610 shows the fact that a homogeneous physical composition of silicone, in this case a silicone resin of MQ resin type, with polyphenylene ether is not easily possible. In particular, the selection of a suitable silicone resin that is compatible, has good processing properties, is available in a suitable presentation form, and allows a synergistic enhancement of the beneficial properties of both the organic component of the polyphenylene ether and the silicone component poses a particular challenge. For optimal results, it is further necessary to prepare the inventively useful polyorganosiloxanes by a suitable process that reduces polar groups to a minimum. This type of process is not found in either US2016 / 0244610 or US5548053.

[0016] Like US2016 / 0244610, US2018 / 0220530 also describes compositions consisting of mixtures of silicone resins, in this case mixtures of MT, MDT, MDQ and MTQ types, which are claimed as a class in a large scale manner, without more strict limitations. The claimed silicone resins are all prepared by a hydrolysis process.

[0017] Like US2016 / 0244610 and US2018 / 0220530, US2018 / 0215971 teaches compositions consisting of silicone resins with vinyl- or (meth)acrylate-functional polyphenylene ethers, in this case mixtures of TT and TQ types, which are again claimed as a class in a broad manner, without more strict limitations, and all silicone resins of the invention are claimed to be prepared by a hydrolysis process from starting monomers.

[0018] US 2018 / 0215971 and US 2018 / 0220530 also do not provide any analytical data, but may indicate to what extent Si-O-C-bonded polar and silanol groups are retained in the synthetic processes used.

[0019] The loss factor targeted in both inventions is less than 0.007. This requirement is achieved in freshly produced samples of the inventive materials without significant shortfalls, thus leaving significant room available for improvement in the prior art of US2018 / 0215971 and US2018 / 0220530.

[0020] It is noteworthy that, when measured in terms of the dielectric loss factor of the solutions of the inventions according to US2018 / 0215971 and US2018 / 0220530, the compositions of US2018 / 0215971 and US2018 / 0220530 are significantly more expensive than solutions already available in the prior art that achieve comparable dielectric loss factors with substantially better economy. These inventions therefore also lack teachings that constitute a future development of the prior art, making the realization of the inventions of US2016 / 0244610, US2018 / 0215971 and US2018 / 0220530 seem unlikely.

[0021] An alternative to the hydrolysis preparation process for the synthesis of polyorganosiloxanes is taught by US2019359774. In this case, an alkali metal siliconate is obtained from the reaction of an organosilanol or alkoxy-functional silane or siloxane precursor with an alkali metal hydroxide, which is reacted with a chlorosilyl component in an anhydrous condensation process. The alkali metal siliconate reacted in the process of the invention is prepared in a separate upstream synthesis step. This process uses an auxiliary base to bind the hydrogen chloride formed during the reaction. The salt is removed by filtration or as an aqueous solution in an aqueous work-up. In this way, a silanol-free, alkoxy-free linear polyorganosiloxane is obtained.

[0022] The possibility of applying this synthesis to silanol-functional polyorganosiloxanes without the detour route involving alkali metal siliconates has not been demonstrated. Moreover, the synthesis is still limited to linear polyorganosiloxanes. [Prior art documents] [Patent documents]

[0023] [Patent Document 1] U.S. Patent No. 6,258,881 [Patent Document 2] U.S. Pat. No. 3,737,479 [Patent Document 3] U.S. Patent No. 5,834,585 [Patent Document 4] US Patent Application Publication No. 2004 / 0138355 [Patent Document 5] U.S. Pat. No. 3,960,985 [Patent Document 6] US Patent Application Publication No. 2016 / 0244610 [Patent Document 7] US Patent Application Publication No. 2020 / 369855 [Patent Document 8] U.S. Pat. No. 5,548,053 [Patent Document 9] US Patent Application Publication No. 2018 / 0220530 [Patent Document 10] US Patent Application Publication No. 2018 / 0215971 [Patent Document 11] US Patent Application Publication No. 2019 / 359774 Summary of the Invention

[0024] The present invention aims to provide crosslinkable polyorganosiloxanes with dielectric properties suitable for use as binders for radio frequency applications, in a water-free process, which can be obtained economically, particularly without the detours that require the production of metal siliconates or other raw materials in separate steps, which crosslinkable polyorganosiloxanes have a minimum of Si-O-C bonded polar groups in sufficient structural diversity for use, including particularly three-dimensional structures. Part of this requirement is that, as a pure binder, the polyorganosiloxane has a dielectric loss factor at 10 GHz of 0.0040 or less, provides effective wetting of any fillers present that reduce the dielectric loss factor, allows the production of tack-free prepregs, and provides a formulation that is compatible with organic polymers.

[0025] The subject of the present invention is a process for the preparation of polyorganosiloxanes of formula (I), [O 3-a / 2 R a SiY(SiR a O 3-a / 2 ) b ] c (R 1 SiO 3 / 2 ) d (R 2 2SiO 2 / 2 ) e (R 3 3SiO 1 / 2 ) f (SiO 4 / 2 ) g [O 3-h / 2 R 4 h Si(SiR 5 2) i SiR 4 j O 3-j / 2 ] k (I) [wherein the groups R may be the same or different and are either hydrogen or a monovalent Si-C bonded unsubstituted or heteroatom-substituted organic hydrocarbon radical having 1 to 18 carbon atoms, which may also be an unsaturated hydrocarbon radical; Y is a chemical bond, an oxygen atom, or a divalent to dodecavalent organic unsubstituted or heteroatom-substituted organic group having 1 to 24 carbon atoms and bonded to a silicon atom by a Si-C bond; base R 1 , R 2 and R 3 are each independently a hydrogen group, a saturated or unsaturated Si-C bonded C1 to C18 hydrocarbon group which may be unsubstituted or substituted with a heteroatom, a C1 to C12 hydrocarbon group bonded via an oxygen atom and which may contain a heteroatom, or a silanol group; 1 , R 2 and R 3 can in each case adopt their definitions independently of one another, and therefore two or more groups R bonded to the same silicon atom 1 , R 2 and / or R 3 may be a group different from the defined groups, base R 4 are each independently a hydrogen group, a silanol group, or a monovalent Si-C bonded or Si-O-C bonded unsubstituted or heteroatom-substituted organic hydrocarbon group having 1 to 18 carbon atoms which may be an unsaturated hydrocarbon group; base R 5 are each independently a hydrogen group, a monovalent Si-C bonded unsubstituted or heteroatom-substituted organic hydrocarbon group having 1 to 18 carbon atoms which may be an unsaturated hydrocarbon group, or a group of the following formula (II): [O 3-a / 2 R a SiY(SiR a O 3-a / 2 ) b ] c (R 1 SiO 3 / 2 ) d (R 2 2SiO 2 / 2 ) e (R 3 3SiO 1 / 2 ) f (SiO 4 / 2 ) g (II), [Wherein, all groups Y, R, R 1 , R 2 , R 3 , R 4 and R 5 based on 100 mol %, at least 0.1 mol %, preferably at least 3 mol %, more preferably at least 5 mol %, and more specifically at least 7 mol % must be olefinically or acetylenically unsaturated groups; All groups Y, R, R 1 , R 2 , R 3 , R 4 and R 5 based on 100% by weight, a total of at most 3% by weight, preferably at most 2.5% by weight, more particularly at most 2% by weight, are Si-O-C bond groups and silanol groups, In addition, all groups Y, R, R 1 , R 2 , R 3 , R 4 and R 5 %. In total, up to 0.5% by weight, preferably up to 0.2% by weight, more particularly up to 0.1% by weight, of 100% by weight are silanol groups, a is 0, 1 or 2, the subscripts a on both sides of the group Y can independently adopt their definitions, so that different subscripts a, independently of each other, can have different values ​​within the stated range of values, b is a number having a value of 1 to 11, preferably 1; c has a value of 0 to 0.9, d has a value of 0 to 0.8, e has a value of 0 to 0.5, f has a value of 0.01 to 0.6, g has a value of 0 to 0.6, h and j are each independently 0, 1 or 2; i is an integer having a value from 0 to 50; k has a value between 0 and 0.9; c+d+e+f+g+k=1, with at least one value c, d or k being >0 and e+g being ≦0.6, preferably <0.5, more particularly <0.4; In the formula (I) and the formula (II), the groups R and R 1 , R 2 , R 3 , R 4 and R 5 and the subscripts a, b, c, d, e, f, g, h and i may each independently have the same definitions and may each independently adopt these definitions within the stated range of values. In a first step, a silane of formula (III) R 6 l SiR 7 4-l (III), [In the formula, R 7 is a hydrolyzable group, l is an integer having a value of 0, 1 or 2; For l=1, R 6 is the group R 1 For l=2, R 6 is the group R 2 It is.] and / or di-, oligo- or polysilanes of formula (IV) R 7 3-h R 4 h Si(SiR 5 2) i SiR 4 j R 7 3-j (IV) [Wherein, R 7 is a hydrolyzable group, R 4 , R 5 , h, i and j have the same definitions as above.] and / or organyl-crosslinked silicones of formula (V) R 7 3-a R a SiY(SiR a R 7 3-a ) b (V) [In the formula, R 7 , R, Y, a and b have the definitions previously given.] with water and a hydrolyzable group R 7 is not a halogen group, the reaction is carried out in the presence of a water-immiscible aprotic solvent using a catalytic amount of one or more acids that promote hydrolysis and condensation of the components of formulas (III), (IV) and (V), the water-immiscible aprotic solvent being particularly not and does not contain an alcohol; After the reaction has taken place, both the water and the remaining amount of acid in the organic phase are reduced to technically relevant minimum values, more specifically to less than 10000 ppm each, preferably less than 5000 ppm each, more specifically to less than 2000 ppm each, so that they are present, if at all, only as undesirable impurities, In the second step, the reaction product from the first step is reacted in a solution in an inert organic solvent, without water, in the presence of an auxiliary base, preferably a basic metal salt and a nitrogen compound, with a compound of formula (VI) R 3 3SiR 8 (VI), [In the formula, R 3 has the same definition as above, and R 8 is a halogen atom, preferably a chlorine atom. This is a process in which a silane is reacted with a halosilane. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Surprisingly, it has been found that the above object is achieved by a process for the preparation of polyorganosiloxanes of formula (I), consisting of two steps, the first of which corresponds to a hydrolytic condensation and, in a second step, the silanol groups present from the first step are reduced by anhydrous condensation, so that a polyorganosiloxane composition is obtained in a non-hydrolytic process, without the use of a metal silicate intermediate.

[0027] The polyorganosiloxanes of formula (I) obtained according to the process of the present invention are notable in that they are substantially free of silanol groups and silicon-bonded alkoxy groups.

[0028] Alkoxy groups and silanol groups, especially those with short alkyl groups, result in a higher dielectric loss factor and further cause an increase in the dielectric loss factor by forming attack points for moisture.

[0029] Polyorganosiloxanes of formula (I) in the context of the present invention include both polymeric and oligomeric organosiloxanes.

[0030] Included structures include, in particular, those of formulae (Ia), (Ib) and (Ic): [O 3-a / 2 R a SiY(SiR a O 3-a / 2 ) b ] c (R 3 3SiO 1 / 2 ) f (Ia) (R 3 3SiO 1 / 2 ) f [O 3-h / 2 R 4 h Si(SiR 5 2) i SiR 4 j O 3-j / 2 ] k (Ib) [O 3-a / 2 R a SiY(SiR a O 3-a / 2 ) b ] c (R 3 3SiO 1 / 2 ) f [O 3-h / 2 R 4 h Si(SiR 5 2) i SiR 4 j O 3-j / 2 ] k (I C) [Wherein, in (Ia), d, e, g and k are each 0, in (Ib), c, d, e and g are each 0, and in (Ic), d, e and g are each 0.] In these structures, the proportion of Si-O units is most favorably reduced to Si-C and Si-Si units.

[0031] The difference between the electronegativity of silicon and oxygen according to the Allred and Rochow electronegativity scale is 1.76, which is one greater than the difference between the electronegativity of silicon and carbon according to the same table, so Si-C bonds have a lower polarity than Si-O bonds. Therefore, it is expected that replacing Si-O bonds with Si-C bonds will further contribute to reducing the overall polarity of organopolysiloxanes, and therefore further contribute to reducing the dielectric loss factor of the corresponding components. The more Si-O bonds that can be replaced with Si-C or Si-Si bonds, the more pronounced this effect is. Therefore, for example, reducing the polarity in the organopolysiloxane backbone by introducing Si-C or Si-Si bonds instead of Si-O bonds significantly contributes to the wide utility of such organopolysiloxanes, and is the most preferred embodiment of the present invention.

[0032] Form (R 3 3SiO 1 / 2 ) units are used in the anhydrous second step with the aim of reducing the silanol groups remaining after hydrolysis, so these groups are always present. In the nomenclature for classifying silicone building blocks according to M, D, T and Q units, depending on the number of oxygen atoms that bond the silicon atom to a further silicon atom, the M units are correspondingly represented by the formula R 3 SiO 1 / 2 and correspondingly the D unit has the formula RSiO 2 / 2 and correspondingly the T unit has the formula R 1 SiO 3 / 2 and correspondingly the Q unit has the formula SiO 4 / 2The polyorganosiloxanes of the present invention are therefore in the broadest sense a combination of T, D and Q units with M units, and therefore M resins, MD resins, MT resins, MDT resins, MDTQ resins, MTQ resins and MDQ resins, without any distinction between M, D and T units with different compositions. M resins consisting of different M units are understood from formula (Ia) when the value of 2 is assumed for all a and Y is either a chemical bond or a Si-C bonded bridging group. In that case, each silicon atom in the bridging unit is surrounded by only one oxygen atom, which maintains its bond to the adjacent silicon atom, and therefore, in the sense of the general M, D, T, Q nomenclature, it can be understood as an M2 building block in which two M units are bonded to each other or coupled to each other via a bridging group. In this case, the structural peculiarities of the chain-forming M units consisting of both organic bridging units and di-, oligo- and / or polysilane units must be taken into account.

[0033] Formula (R 3 SiO 1 / 2 ) f Simple M units, as used in US20180220530, of the type corresponding to the synthetic equivalent of a unit of formula (R), are not used in the first step of the synthesis, the hydrolysis reaction step. While this is possible in principle, it does not provide the same effect in terms of the reduction of silanol groups as the use of these groups in the second anhydrous synthesis step. Thus, 3 SiO 1 / 2 ) fare used only in the second anhydrous reaction step to reduce the number of silanol groups and thus achieve an improvement over the prior art according to US20180220530. This is an important feature of the procedure according to the invention. In US20180220530, all building blocks forming the polyorganosiloxane of the invention react with each other in only one hydrolysis step, in which case there is no possibility to achieve a further reduction of the silanol groups formed in the condensation and, as a result, no possibility to further improve the binder for its target application as a binder for radio frequency applications. No attention is paid in US20180220530 to the fact that after hydrolysis condensation, silanol groups are inadvertently present that are bonded to the polyorganosiloxane backbone, and this lack of attention is easily evident from the fact that there is no meaningful analytical description of the polyorganosiloxane of the invention in this respect. Apparently, the inventors were not aware of the importance of the exact composition of the polyorganosiloxanes according to US20180220530 and the resulting explainable structure-activity relationships, as well as starting points for improvements, if they considered them to be so unimportant that they would not disclose them as relevant to the invention.

[0034] The present invention represents a further improvement over the prior art according to US20180220530, since it does not employ the possibility of using Si-Si bonded or Si-C bridged units to reduce the proportion of polar bonds in the polyorganosiloxane backbone.

[0035] In structures (Ia), (Ib) and (Ic), the proportion is particularly high, since the Si-C bonded bridging organic groups and / or the Si-Si bonds are of course likewise non-polar, and the structures are essentially 3 3SiO 1 / 2 ) f It is closed only by

[0036] The group R of formula (II) 5 Excluding R, R 1 , R 2 , R 3 , R4 and group R 5 Examples of are saturated or unsaturated hydrocarbon groups which may contain aromatic or aliphatic double bonds, examples being methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl groups, hexyl groups such as n-hexyl group, heptyl groups such as n-heptyl, octyl groups such as n-octyl group and isooctyl groups such as 2,2,4-trimethylpentyl and 2-ethylhexyl groups, nonyl groups such as n-nonyl group, decyl groups such as n-decyl group, dodecyl groups such as n-dodecyl group, tetradecyl groups such as n-tetradecyl group, n-hexadecane groups, cycloalkyl groups such as cyclopentyl, cyclohexyl and 4-ethylcyclohexyl groups, cycloheptyl, norbornyl and methylcyclohexyl groups; aryl groups such as phenyl, biphenylyl, naphthyl and anthryl and phenanthryl groups; alkaryl groups such as o-, m-, p-tolyl, xylyl and ethylphenyl groups; aralkyl groups such as benzyl groups; alkenyl groups such as 7-octenyl, 5-hexenyl, 3-butenyl, allyl and vinyl groups, and also α- and β-phenylethyl groups.

[0037] Group R, R 1 , R 2 , R 3 , R 4 and R 5 Preferred heteroatoms which may be present in are oxygen atoms. In addition, nitrogen atoms, phosphorus atoms, sulfur atoms, halogen atoms such as chlorine atoms and fluorine atoms are also possible, but are not preferred.

[0038] Preferred heteroatom-containing organic groups R, R 1 , R 2 , R 3 , R 4 and R 5Examples of are groups containing acryloyloxy and methacryloyloxy groups from acrylic acid or methacrylic acid, respectively, and also acrylic or methacrylic acid esters of unbranched or branched alcohols having 1 to 15 carbon atoms. Preferred such groups are those derived from 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.

[0039] These groups are preferably not directly bonded to the silicon atom, but instead are bonded via a hydrocarbon spacer, which may contain from 1 to 12 carbon atoms, preferably containing 1 or 3 carbon atoms, and which do not contain any heteroatoms other than those present in the acryloyloxy or methacryloyloxy groups. 1 , R 2 , R 3 , R 4 and R 5 is preferably selected from methyl, phenyl, vinyl, acryloyloxy and methacryloyloxy groups and acrylic or methacrylic esters of unbranched or branched alcohols having 1 to 15 carbon atoms.

[0040] Further preferred heteroatom-containing groups R, R 1 , R 2 and R 3 is of formula (VII).

[0041] [ka]

[0042] In formula (VII), R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently a hydrogen group, a hydrocarbon group or a hydrocarbon group substituted with heteroatoms, and are always the radical R 9 , R 10 , R 11 , R 12 , R 13 and R 14 At least one of the groups R is a hydrocarbon group bonded to the silicon atom via a Si-C bond or a Si-O-C bond, and it is preferred that the hydrocarbon group to which the group of formula (VII) is bonded to the silicon atom is a C3 hydrocarbon group that does not contain heteroatoms. 9 , R 10 , R 11 , R 12 , R 13 and R 14 may also be a chemical bond, and thus the group of formula (II) is directly bonded to the silicon atom via a Si-C bond by this group representing a chemical bond.

[0043] base R 9 , R 10 , R 11 , R 12 , R 13 and R 14Examples of these are hydrogen groups, saturated hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, primary, secondary and tertiary butyl groups, hydroxyethyl groups, aromatic groups such as phenylethyl, phenyl, benzyl, methylphenyl, dimethylphenyl, ethylphenyl groups, heteroatom-containing groups such as hydroxymethyl, carboxyethyl, methoxycarbonylethyl and cyanoethyl groups, and acrylate and methacrylate groups 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, as well as olefinically or acetylenically unsaturated hydrocarbon groups.

[0044] Adjacent group R 9 and R 11 and adjacent group R 10 and R 12 may also be optionally linked to each other to the same cyclic saturated or unsaturated group, thus forming a fused polycyclic structure.

[0045] Examples of phenol groups of formula (VII) are phenol, ortho-, meta- or para-cresol, 2,6-, 2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3,6- or 2,4,6-trimethylphenol, 3-methyl-6-tert-butylphenol, thymol and 2-methyl-6-allylphenol, which may optionally be substituted on the oxygen atom.

[0046] Preferred examples of fluorine-containing groups are trifluoropropyl, nonafluorohexyl and heptadecafluorooctyl groups.

[0047] Y is preferably a linked organic unit having 1 to 24 carbon atoms between 2 to 12 siloxanyl units. Y is preferably divalent, trivalent or tetravalent, more particularly divalent.

[0048] Preferred bridging aromatic groups Y are of formulae (VIIIa), (VIIIb) and (VIIIc).

[0049] [ka] [In the formula, the group R 15 , R 16 , R 16 and R 18 is a hydrogen group, or an optionally substituted hydrocarbon group, or a group of the formula OR 19 (In the formula, R 19 is a hydrocarbon group). 15 and R 16 or R 16 and R 18 Adjacent groups such as, for example, may be coupled together to form a cyclic group, thus forming a fused ring system.

[0050] Typical examples of such bridging aromatic groups are p-, m- or o-phenylene groups, 2-methyl-1,4-phenylene groups, 2-methoxy-1,4-phenylene groups, with the p-phenylene group being particularly preferred.

[0051] For example, two or more such groups may be coupled together such that two or more units of formula (IIIa) are coupled together and the oligomeric bridge structural element is present on the silicon atom by the connection of corresponding carbon atoms of the terminal aromatic rings. The aromatic units here may be directly bonded to each other or may be coupled to each other via a bridging group such as an alkanediyl unit, for example a methylene group, a 1,2-ethanediyl group, a 1,1-ethanediyl group, a 2,2-dimethylpropyl group, or a sulfone group.

[0052] Further examples of aromatic bridging units are those in which two optionally substituted phenol rings are bridged via an alkanediyl unit or other unit.Typical representatives are the following groups with substitution on the phenolic oxygen: 2,2-bis(4-hydroxyphenyl)propane group (substituted bisphenol A group), 2,2-bis(4-hydroxyphenyl)methane group (substituted bisphenol F group) and bis(4-hydroxyphenyl)sulfone group (bisphenol S group), in which the phenolic oxygen atom is typically replaced by a group of the -(C3H6)- type, in which the group -(C3H6)- is Si-C bonded to a silicon atom, thereby generating a bridge.

[0053] Preferred groups Y that are not bridged by aromatic units are alkanediyl, alkenediyl and alkynediyl groups, which may optionally contain heteroatoms and may contain aromatic groups as substituents in these groups that do not assume or contribute to the function of bridging.

[0054] Typical examples are methylene, methine, tetravalent carbon, 1,1-ethanediyl and 1,2-ethanediyl, 1,4-butanediyl and 1,3-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl, 1,11-undecanediyl and 1,12-dodecanediyl, 1,2-diphenylethanediyl, 1,2-phenylethanediyl and 1,2-cyclohexylethanediyl. If the linear bridging unit has more than one carbon atom and the substitution pattern allows it, each of these groups can result in bridging through alpha-omega connectivity, in other words bridging through the first and last respective atoms of the linear unit by any other connectivity, in other words using different linear carbon atoms. Also typical examples are not only linear representatives of the bridged hydrocarbons mentioned, but also their isomers, which may produce bridges by linking different carbon atoms of the hydrocarbon structure to the silicon atom.

[0055] Particularly preferred examples of groups from the group of non-aromatic heteroatom-free hydrocarbon groups are -CH2CH2-, -CH(CH3)-, -CH=CH-, -C(=CH2)- and

[0056] [ka] It is.

[0057] Examples of typical fluorine-substituted bridging groups Y are -C(CF3)2-, -C(H)FC(H)F- and -C(F2)-C(F2)- groups.

[0058] Typical examples of heteroatom-containing bridging groups are, for example, ethyleneoxypropylene and ethyleneoxybutylene groups. Other typical examples are -(CH2) n - or -CH2-CH(R 15 )-C(=O)O-terminated phenylene ether or glycol group, n is typically 3 to 8, R 15 is a hydrogen atom or a methyl group, and is bonded to the silicon atom via this terminal group.

[0059] All descriptions should be understood as illustrative only and not limiting.

[0060] With regard to their viscosity, the organopolysiloxanes used in the present invention can vary over a wide range or be solid, depending on the average number of their constituent structural units per molecule.

[0061] The liquid organopolysiloxanes useful in the present invention have a viscosity at 25° C. in the uncrosslinked state of 20 to 8,000,000 mPas, preferably 20 to 5,000,000 mPas, more specifically 20 to 3,000,000 mPas.

[0062] The solid organopolysiloxanes useful in the present invention in the non-crosslinked state have a glass transition temperature in the range of 25° C. to 250° C., preferably 30° C. to 230° C., more particularly 30° C. to 200° C. Organopolysiloxanes that have proved particularly suitable are those which have bridged phenylene units and have an aromatic fraction of at least 20 mol % in total, taking all Si-C bonded substituents as 100 mol %, where phenylene units are understood to mean both substituted and unsubstituted phenylene units, both monomeric and oligomeric, as the nature of this type of bridged substituent is exemplarily described in the examples.

[0063] The group R of formula (II) 5 Selected examples of are linear and cyclic structures with the following average compositions: [O 2 / 2 MeSi-CH2-CH2-SiMeO 2 / 2 ][(CH2=CH)(Me)2SiO 1 / 2 ]3, [O 2 / 2 MeSi-CH2-CH2-SiMeO 2 / 2 ][(H)(Me)2SiO 1 / 2 ]3, [O 2 / 2 MeSi-CH2-CH2-SiMeO 2 / 2 ]2[(CH2=CH)(Me)2SiO 1 / 2 ]5, [O 2 / 2 MeSi-CH2-CH2-SiMeO 2 / 2 ]2[(H)(Me)2SiO 1 / 2 ]5, [O 2 / 2 PhSi-C6H4-SiPhO 2 / 2 ][(CH2=CH)(Me)2SiO 1 / 2 ]3, [O 2 / 2 PhSi-C6H4-SiPhO 2 / 2 ][(H)(Me)2SiO 1 / 2 ]3, [O 2 / 2 PhSi-C6H4-SiPhO 2 / 2 ]2[(CH2=CH)(Me)2SiO 1 / 2 ]5, [O 2 / 2 PhSi-C6H4-SiPhO 2 / 2 ]2[(H)(Me)2SiO 1 / 2 ]5, [O 2 / 2 PhSi-C6H4-SiMeO 2 / 2 ][(CH2=CH)(Me)2SiO 1 / 2 ]3, [O 2 / 2 PhSi-C6H4-SiMeO 2 / 2 ][(H)(Me)2SiO 1 / 2 ]3, [O 2 / 2 MeSi-CH2-CH2-SiMe2O 1 / 2 ]8[(CH2=CH)(Me)2SiO 1 / 2 ]9, [O 2 / 2 MeSi-CH2-CH2-SiMeO 2 / 2 ]8[(CH2=CH)(Me)2SiO 1 / 2 ]8[(H)(Me)2SiO 1 / 2 ]9, (CH2=CH)(Me)2SiO 1 / 2 , (H)(Me)2SiO 1 / 2 , (CH3-CH(=CH2)C(=O)O-CH2CH2CH2)(Me)2SiO 1 / 2 , (Me)3SiO 1 / 2 , (CH2=CH)3SiO 1 / 2 , (CH2=CH)Ph2SiO 1 / 2 .

[0064] Preferred hydrolyzable groups R 7 and R 8 Examples of are halogen, acid or alkoxy groups, more preferably chlorine, acetate, formate, methoxy or ethoxy groups.

[0065] Compounds (VI) are obtained by prior art processes, the type of reaction used being highly dependent on the composition of the respective compound (VI). Compounds (VI) are typically obtained, for example, by hydrosilylation, from olefinically unsaturated organic precursors, such as acetylene, diallyl or divinyl compounds and Si-H functional silicone building blocks.

[0066] The process considered here also includes Grignard reaction from halogenated organic precursor and then reaction with halogenated or alkoxylated organosilane.It is also possible to use optionally metal halide exchange reaction of halogenated organic precursor with alkyl alkali metal compound, for example butyl lithium, and known subsequent reaction for bonding to silicone building block.Those skilled in the art are aware of such processes, which are easily accessible and understandable from available literature.Since these processes are not the subject of the present invention, at this point, only reference is made to the prior art that is documented and searchable.

[0067] The first process step, i.e. the cohydrolysis, is preferably carried out by metering the mixture of compounds (III), (IV), (V) and (VI) into water or dilute acid, if they are used, with cooling. In the case of gaseous acids such as HCl, metering into concentrated aqueous HCl is likewise expedient, provided that the liberated acid is recovered as gas. The hydrolyzable group R 7 Depending on the nature of the hydrolysis, it is more or less exothermic and therefore requires cooling for the safe performance of the reaction and, where appropriate, to avoid secondary reactions in the corresponding sequence of the synthesis. Conversely, it may be advantageous and necessary to use high temperatures to drive the reaction to completion.

[0068] The reaction times for chlorosilanes are generally very short, so that the time required to carry out the process in batch operation depends mainly on the cooling capacity. Alternatively, the cohydrolysis of (III), (IV) and / or (V) can be carried out continuously, for which loop reactors, but also column and tubular reactors, are suitable.

[0069] Effective washing with water, clean phase separation and purification of the hydrolysis product under reduced pressure are advantageous to deplete the residual acid.

[0070] The process can be carried out under atmospheric pressure. However, depending on the objective, higher or lower pressures are equally practical. At the end of the first process step, it is essential that the amount of water present is reduced to such an extent that at most there is a residual amount of water that can no longer be further depleted by the methods of the prior art as an unintended impurity. Ideally, the amount of residual water remaining is reduced to below the detection limit, so that an anhydrous medium can be envisaged. This depletion of water is necessary for the successful implementation of the process of the invention, since if conditions exist in which polyorganosiloxanes can react with water, i.e. typically acidic or basic conditions, water essentially entails the option of the formation of silanol groups. The presence of water in the next step is detrimental, since the intention is to deplete the silanol groups. In the remainder of the text, the reaction mixture from the first step depleted of water is referred to as anhydrous.

[0071] The second process step is carried out with the water-free reaction mixture from the first step. The silanol groups on the polyorganosiloxane from the first step are reacted with the silane of formula (VI) by metering the silane as a solution in an inert solvent, if appropriate. To initiate and accelerate the reaction, an auxiliary base is advantageously used. In principle, the reaction between the silanol groups and the silane of formula (VI) is possible without an auxiliary base, but in that case the reaction would be uneconomical on an industrial scale or would result in inadequate conversion, due to the very slow reaction rate and long reaction times. The group R 8is a halogen radical, more specifically a chlorine radical.

[0072] The suitability as an auxiliary base for capturing the hydrogen halide formed is possessed by basic salts or nitrogen-containing compounds, such as amines, ureas, imines, guanidines and amides. Examples of basic salts are sodium hydride, sodium amide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate, calcium oxide, magnesium oxide, magnesium carbonate. Examples of nitrogen-containing compounds are ammonia, ethylamine, butylamine, triethylamine, trimethylamine, tributylamine, N,N-dimethyldecylamine, triisooctylamine, urea, tetramethylurea, guanidine, tetramethylguanidine, N-methylimidazole, N-ethylimidazole, piperidine, pyridine, picoline, N-methylmorpholine. Preferably, amine compounds are used in which the nitrogen atom does not have any hydrogen atom.

[0073] The auxiliary base is preferably used in at least equimolar amounts relative to the halosilane. Preferably, at least 0.5, more preferably at least 1.0, more preferably at least 2.0 base equivalents are used per molar equivalent of halosilane. It is also possible to use a larger amount of auxiliary base added, for example, when it is intended to serve as a solvent at the same time. However, this usually does not provide any advantage, but instead reduces the space-time yield and therefore the economic viability of the process. The halosilane is preferably added to the anhydrous reaction mixture from the first step of the process, and then the auxiliary base is metered in. This procedure may also be optionally reversed, so that the auxiliary base is first added to the reaction mixture from the first synthesis step, followed by the metering in of the halosilane.

[0074] A mixture of two or more auxiliary bases may also be used.

[0075] One or more halosilanes of formula (VI) are preferably used such that the amount of halogen groups present is equimolar to the silanol groups in the polyorganosiloxane species from the first reaction step.

[0076] The reaction of the one or more halosilanes of formula (VI) with the silanol groups of the polyorganosiloxane species from the first reaction step is preferably carried out at a temperature of at least -20° C., more preferably at least 0° C., more particularly at least 10° C. The maximum permissible temperature is further determined by the boiling points of the solvent used and the one or more halosilanes of formula (VI), the reaction temperature preferably does not exceed 200° C., more preferably does not exceed 175° C., more preferably does not exceed 150° C.

[0077] The reaction mixture may be cooled or heated as necessary, and the individual reactants may be adjusted to a certain temperature before reacting with each other, for example, in order to utilize the heat of reaction. The process may be carried out batchwise in a stirred reactor, or continuously in a column, loop, fluidized bed or tubular reactor. Any low molecular weight siloxanes formed during the reaction may be removed from the reaction mixture by distillation as necessary. The halide salts formed in the reaction may be decanted off, filtered off, or removed by centrifugation, or dissolved in water and separated. For aqueous workup, the amount of solvent already present may be adapted as necessary, or additional solvent may be added, for example, to promote phase separation by establishing density differences, and the solubility or miscibility of the solvent with water is very low, more specifically 5% by weight or less at 25°C.

[0078] Preferably, excess halosilane of formula (VI) is removed by distillation prior to the aqueous workup, which avoids the presence of aqueous acidic solutions that may again result in the formation of silanol groups on the polyorganosiloxane.

[0079] The second reaction step is preferably carried out in the absence of water, i.e. under a dry atmosphere or under reduced pressure, more preferably under an inert gas such as argon, nitrogen, carbon dioxide or diluted air, preferably at 900-1100 hPa.

[0080] Aprotic solvents suitable for both the first and second steps include, in particular, aromatic hydrocarbon solvents, such as benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene or mixtures thereof. Depending on the group selected, it may also be possible to use aliphatic or cycloaliphatic solvents, and / or linear or cyclic ethers. The suitability of a solvent is determined by its solubility for the resulting polyorganosiloxane. The solvent must dissolve the resulting polyorganosiloxane sufficiently well, must not be miscible with water, i.e. it must not be able to dissolve more than 5% by weight of water itself, and must not participate in the reaction.

[0081] The suitability of the solvent can optionally be determined by appropriate experimentation. Aromatic solvents best meet the conditions described and are therefore preferred.

[0082] At this point, it should be noted that the use of disiloxanes, generally used in the form of symmetrical disiloxanes, with the aim of reducing the number of silanol groups, is excluded as not in accordance with the present invention. Disiloxanes are cleaved in the presence of acids by breaking the Si-O-Si bond, but acids for this purpose are generally used as aqueous preparations, which intentionally introduce water into the second step of the synthesis, with the result that the tendency of the silanol groups to reform cannot be eliminated, and the second step is no longer anhydrous, reducing its efficiency.

[0083] The polyorganosiloxanes of formula (I) are chemically curable, which means that they can be cured by chemical reaction to form a crosslinked insoluble network.Cure occurs by the olefinic unsaturated groups described above.Typically, radical polymerization reaction is used here for curing, or when silicon-bonded hydrogen exists as radical, as well as olefinic or acetylenic unsaturated functional groups, hydrosilylation cure is used.

[0084] The polyorganosiloxane of formula (I) has all the olefinic functional groups through which it can be chemically crosslinked.Possible chemical crosslinking reactions here include known reactions such as those in the prior art, in particular radical crosslinking, which can be initiated by using suitable radiation sources such as UV light and unstable compounds that decompose to form radicals, and addition crosslinking is carried out, for example, by the hydrosilylation of olefinic unsaturated groups with Si-H functional groups in the presence of suitable hydrosilylation catalysts.

[0085] Sufficient curing requires the presence of a sufficient amount of functional groups. To achieve sufficient curing, at least an average of 1.0 functional groups must be present per molecule of the polyorganosiloxane used in the present invention, preferably an average of at least 1.1, more particularly an average of at least 1.2 functional groups per molecule of the polyorganosiloxane of the present invention. Here, the functional groups may be different, for example, one part of the functional groups is a Si-H group, and another part of the functional groups represents a radically curable or hydrosilylatable olefinically unsaturated group. Further combinations of complementary functional groups are also conceivable, where complementary means that the selected combination of functional groups can react with each other. If only one type of functional group is present, for example, only olefinic or acetylenically unsaturated functional groups that are radically curable, then a corresponding number of these functional groups must be present. In the context of copolymerization to form a homogeneous matrix, it must be ensured here that the selected olefinic and acetylenic groups have sufficient copolymerizability. Combinations of olefinic groups that are not copolymerizable with each other are also possible, provided that the resulting matrices of the two or more individual polymers remain compatible with each other and do not form distinct phases that are separate from each other in distinct domains.

[0086] Examples of suitable initiators for initiating the radical polymerization include, in particular, examples from the field of organic peroxides, such as di-tert-butyl peroxide, dilauryl peroxide, dibenzoyl peroxide, dicumyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylcumyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxycyclohexane, 2,2-di(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, Examples include tetradecyl peroxydicarbonate, dibenzyl peroxydicarbonate, diisopropylbenzene dihydroperoxide, 1,3-phenylene bis(1-methylethylidene) bis(tert-butyl) peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, dicetyl peroxydicarbonate, acetylacetone peroxide, acetylcyclohexanesulfonyl peroxide, tert-amyl hydroperoxide, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxyisopropyl carbonate, tert-amyl peroxyneodecanoate, tert-amyl peroxy-3,5,5-trimethylhexanoate, and tert-butyl monoperoxymaleate, which are merely illustrative and not limiting. Optionally, it is also possible to use a mixture of different initiators for the radical reaction. The suitability of an initiator or initiator mixture for a radical reaction depends on its decomposition kinetics and the requirements that must be met. If due attention is paid to these boundary conditions, the skilled person will be able to select the initiator appropriately.

[0087] In the case of preparations containing silicon-bonded hydrogen as well as olefinically and acetylenically unsaturated groups, the possibility of curing by hydrosilylation reactions exists. Suitable catalysts for promoting the hydrosilylation reaction are the catalysts known from the prior art.

[0088] Examples of such catalysts are compounds or complexes from the group of noble metals including platinum, ruthenium, iridium, rhodium and palladium, preferably metal catalysts from the group of platinum metals or compounds and complexes from the group of platinum metals. Examples of such catalysts are finely divided platinum of the metal, which may be present on a support such as silicon dioxide, aluminum oxide or activated carbon, platinum compounds or complexes, for example platinum halides, such as PtCl4, HPtCl6×6H2O, Na2PtCl4×4H2O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alkoxide complexes, platinum ether complexes, platinum aldehyde complexes, platinum ketone complexes (including the reaction product of HPtCl4×6H2O and cyclohexanone), platinum-vinylsiloxane complexes (for example platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane), (detectable Examples of suitable platinum complexes include bis(γ-picoline)platinum chloride (with or without inorganically bound halogen), trimethylenedipyridine platinum chloride, dicyclopentadiene platinum dichloride, dimethylsulfoxyethenyl platinum(II) dichloride, cyclooctadiene platinum dichloride, norbornadiene platinum dichloride, γ-picoline platinum dichloride, cyclopentadiene platinum dichloride, and reaction products of platinum tetrachloride with olefins and primary or secondary amines or primary and secondary amines, such as the reaction product of platinum tetrachloride with sec-butylamine in 1-octene solution, or ammonium-platinum complexes. A further embodiment of the process of the invention uses complexes of iridium with cyclooctadiene, such as μ-dichlorobis(cyclooctadiene)diiridium(I).

[0089] This description is merely illustrative and not limiting: the development of hydrosilylation catalysts is the subject of kinetic studies, which of course continually generate new active species that can be used here as well.

[0090] The hydrosilylation catalyst preferably comprises a platinum compound or complex, more preferably platinous chloride and platinum complexes, more preferably platinum-olefin complexes, and most preferably platinum-divinyltetramethyldisiloxane complexes.

[0091] In the process of the present invention, the hydrosilylation catalyst is used in an amount of from 2 to 250 ppm by weight, preferably from 3 to 150 ppm, and more specifically from 3 to 50 ppm.

[0092] In a preferred embodiment, the polyorganosiloxane of formula (I) is bonded to a metal substrate in a third step.

[0093] The polyorganosiloxanes of formula (I) are particularly suitable for use as binders and / or adhesion promoters for producing metal clad laminates, especially for electronic applications, more particularly for metal surface laminates, especially for radio frequency applications, especially for applications operating at frequencies above 1 GHz.Particularly preferred is the production of metal surface electrolaminates of the type used for producing printed circuit boards in electronic devices, especially for radio frequency applications.

[0094] The metal-faced electrolaminates may, but do not have to, contain reinforcing materials. This means that they may or may not contain reinforcing fabrics, such as woven or nonwoven fiber fabrics. If reinforcing materials are included, they are preferably arranged in layers. The reinforcing layers in this case can be composed of a number of different fibers.

[0095] These types of reinforcing layers help to control shrinkage properties and provide improved mechanical strength.

[0096] If a reinforcing layer is used, the fibers forming this layer can be selected from a number of different possibilities. Non-limiting examples of such fibers are glass fibers, such as E-glass, S-glass and D-glass fibers, silica fibers, polymer fibers, such as polyetherimide fibers, polysulfone fibers, polyetherketone fibers, polyester fibers, polycarbonate fibers, aromatic polyamide fibers, or liquid crystal fibers. The fibers can have a diameter of 10 nm to 10 μm. The reinforcing layer has a thickness of up to 200 μm, preferably up to 150 μm.

[0097] One of the preferred forms of application is the use of polyorganosiloxanes of formula (I) as binders or co-binders together with organic binders to produce metal surface laminates containing glass fiber composites for the further production of printed circuit boards. The preferred metal is copper.

[0098] For the use of the polyorganosiloxanes of formula (I) in the present invention, they can be used as the sole binder or they can be used in the form of blends with organic monomers, oligomers and polymers.

[0099] Organic monomers, oligomers and polymers typically used for these purposes include polyphenylene ethers, bismaleimides, bismaleimide-triazine copolymers, hydrocarbon resins, both aliphatic resins such as polybutadiene and aromatic resins such as polystyrene, and also hybrid systems having both aliphatic and aromatic characteristics such as styrene-polyolefin copolymers (the morphology of the copolymers is in principle not limited), epoxy resins, cyanate ester resins, and optionally others, the selection being exemplary and non-limiting.

[0100] Preferred organic monomers, oligomers and polymers are oligomeric and polymeric polyphenylene ethers, monomeric, oligomeric and polymeric bismaleimides, oligomeric and polymeric hydrocarbon resins, and bismaleimide-triazine copolymers. These organic monomers, oligomers and polymers can be used as mixtures with one another, if desired. The proportion of organic monomers, oligomers and polymers in the preparations containing the polyorganosiloxane of formula (I) is between 10 and 90%, preferably between 20 and 90%, more specifically between 30 and 80%, based on the mixture of the polyorganosiloxane of formula (I) and the organic monomers, oligomers and polymers, taken as 100%, if the organic components are used as well.

[0101] Furthermore, the polyorganosiloxanes of formula (I) as well as their mixtures with organic monomers, oligomers or polymers can be dissolved in further organic monomers, optionally bearing olefinically or acetylenically unsaturated groups, as reactive diluents, such as, for example, styrene, α-methylstyrene, para-methylstyrene and vinylstyrene, chloro- and bromostyrene.

[0102] It is also possible to use typical non-reactive solvents for dissolving the polyorganosiloxane of formula (I) and its mixtures, optionally with organic monomers, oligomers and polymers, such as aliphatic or aromatic solvents, such as aliphatic mixtures having a defined boiling range, such as toluene, xylene, ethylbenzene, or mixtures of these aromatics, ketones such as acetone, methyl ethyl ketone and cyclohexanone, carboxylic acid esters such as ethyl acetate, methyl acetate, ethyl formate, methyl formate, methyl propionate and ethyl propionate, and in particular effective solubility of the polyorganosiloxane of formula (I) and its mixtures with organic monomers, oligomers and polymers is most likely to be achieved in aromatic solvents such as toluene, xylene, ethylbenzene and mixtures thereof.

[0103] When the polyorganosiloxane of formula (I) is used in combination with an organic oligomer or polymer or mixtures thereof, it is essential that the polyorganosiloxane of formula (I) is used which is compatible with the selected organic component and does not cause phase separation. In these cases, generally, the polyorganosiloxane of formula (I) which is more phenyl-rich should be used, since the phenyl group enhances the compatibility with the organic component. In particular, the polyorganosiloxane of formula (I) which is more aromatic should be used in relatively aromatic-rich organic polymers such as polyphenylene ethers or aromatic hydrocarbon resins, and both the bridging aromatic group and the aromatic substituents attached to the end of the silyl unit contribute to establishing compatibility. The exact amount of aromatic group required to establish the compatibility of the polyorganosiloxane of formula (I) with a defined selection of organic binder must be ascertained according to the selection of organic binder.

[0104] Likewise, it is possible to mix two or more organic polymers, optionally selected from different polymer classes, and use them in the binder preparation. It is also possible to combine two or more polyorganosiloxanes of formula (I) with each other in the binder preparation. That is, according to the present invention, only one polyorganosiloxane of formula (I) can be used as binder, or two or more polyorganosiloxanes of formula (I) can be combined with each other to form the binder preparation. It is also possible according to the present invention to combine only one polyorganosiloxane of formula (I) with one or more organic polymers to form the binder preparation. It is also according to the present invention to combine two or more polyorganosiloxanes of formula (I) with one or more different organic polymers to form the binder preparation.

[0105] The compatibility of one or more polyorganosiloxanes of formula (I) with one or more organic oligomers or polymers can be easily achieved by mixing one or more organic binders with one or more polyorganosiloxanes of formula (I) in a solvent that dissolves all of the selected components, then removing the solvent by prior art methods, such as by distillation or spray drying, and subjecting the resulting residue to visual evaluation or evaluation using microscopy, and in some cases electron microscopy.A compatible mixture is evident from the absence of silicone domains that are separate from the organic components and can be recognized as a separate phase.

[0106] The use of further compounding components, such as defoamers and degassing agents, wetting and dispersing agents, flow control agents, compatibilizers, adhesion promoters, curing initiators, catalysts, stabilizers, fillers, such as pigments, dyes, inhibitors, flame retardants and crosslinking coagents, additives that may optionally include silanes, is in accordance with the present invention, and in principle there is no restriction on the choice of such components. Apart from testing compatibility in the sense of appropriate miscibility behavior, testing compatibility in terms of reactivity may also be necessary to prevent premature gelation and to ensure that there is a sufficiently rapid polymerization or copolymerization of all components with each other during curing, as well as to test for sufficient wetting and optionally other properties. This may need to be borne in mind and taken into account when preparing the compound.

[0107] Examples of fillers which can be used are ceramic fillers, such as silica, for example precipitated silica or fumed silica, which may be hydrophilic or hydrophobic, preferably hydrophobic, and furthermore may be provided with organic groups on their surface, functionally and optionally reactively, quartz, which may optionally be surface-treated or surface-functionalized, making it possible to carry reactive functional groups on the surface, aluminium oxide, aluminium hydroxide, calcium carbonate, talc, mica, alumina, kaolin, magnesium sulphate, carbon black, titanium dioxide, zinc oxide, antimony trioxide, barium titanate, strontium titanate, corundum, wollastonite, zirconium tungstate, hollow ceramic beads, aluminium nitride, silicon carbide, beryllium oxide, magnesium oxide, magnesium hydroxide, solid glass beads, hollow glass beads and boron nitride. Further fillers used may be core-shell particles of various materials, such as, for example, silicone resin beads with a surface coating of silica, and elastomeric particles with a polymeric coating (in this case, the elastomeric particles may optionally be silicone elastomers, a typical example of a surface coating on such elastomeric particles being a polymethylmethacrylate shell). The ceramic fillers are preferably D 90 The filler has a particle size, expressed as 0.1 μm to 10 μm. The filler is preferably present in an amount of 0.1 to 60 weight percent, more preferably 0.5 to 60 weight percent, and more specifically 1 to 60 weight percent, based on 100 percent of the total binder formulation consisting of binder(s), reactive monomer, additives, and filler. This does not include the amount of any non-reactive solvent used.

[0108] Among the fillers, particular attention should be paid to those that have thermal conductivity: these are aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, zinc oxide, zirconium silicate, magnesium oxide, silicon oxide and aluminum oxide.

[0109] In principle, the binder preparation may contain a flame retardant additive, typically in an amount of 5 to 25 percent by weight. However, a particular feature of the polyorganosiloxane of formula (I) is that it reduces the need for a flame retardant additive, since the polyorganosiloxane of formula (I) itself already exhibits flame retardant properties. Polysilsesquioxanes and siloxanes are known to exhibit flame retardant properties, and their use as a flame retardant additive is itself part of the prior art. A particular advantage of the present invention is therefore that in this case the function of the binder can be associated with the function of flame retardancy. Thus, depending on the amount of polyorganosiloxane of formula (I) used, the amount of flame retardant additive can be reduced. The amount of flame retardant additive is preferably only 0-10 weight percent, more preferably 0-8 weight percent, more specifically 0-5 weight percent, for a total mixture of at least 20 weight percent of all binders and reactive organic monomers used; in other words, when using polyorganosiloxanes of formula (I), it is possible to omit the use of a flame retardant additive, depending on the choice of organopolysiloxane and the amount used.

[0110] Typical examples of flame retardant additives are hydrates of metals Al, Mg, Ca, Fe, Zn, Ba, Cu or Ni, and borates of Ba and Zn. Flame retardant additives may be surface-treated, in which case they may optionally have reactive groups on the surface. Flame retardant additives may be halogenated organic flame retardant additives, such as hexachloroendomethylenetetrahydrophthalic acid, tetrabromophthalic acid or dibromoneopentyl glycol. Further examples of flame retardant additives are melamine cyanurate, phosphorus-containing components such as phosphinates, diphosphinates, phosphazenes, vinylphosphazenes, phosphonates, phosphaphenanthrene oxide, and finely divided melamine polyphosphate. Further examples of bromine-containing flame retardant additives are bispentabromophenylethane, ethylenebistetrabromophthalimide, tetradecabromodiphenoxybenzene, decabromodiphenyl oxide or brominated polysilsesquioxane. Certain flame retardant additives are synergistically enhanced in their effectiveness, such as the combination of a halogenated flame retardant additive with antimony trioxide.

[0111] Further examples of other components are antioxidants, stabilizers against degradation due to weathering, lubricants, plasticizers, colorants, phosphorescence or other agents for marking and traceability, and antistatic agents.

[0112] The polyorganosiloxane of formula (I) is preferably crosslinked in a fourth step.

[0113] The crosslinking coagents used include, in particular, polyunsaturated, radically curable or hydrosilylatable monomers and oligomers, as illustrated in the following non-limiting examples. These include, for example, diolefinically unsaturated components, such as symmetrical olefinically unsaturated disubstituted disiloxanes, such as 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-tetramethyl-1,3-dipropylmethacryloyldisiloxane, diolefinically unsaturated disubstituted organic monomers or oligomers, such as conjugated and non-conjugated dienes, such as 1,9-decadiene, 1,3-butadiene, with diallyl, divinyl, diacryloyl or dimethacryloyl substitutions. They also include triolefinically unsaturated monomers or oligomers, such as 1,2,4-trivinylcyclohexane, triallyl cyanurate or triallyl isocyanurate, tri(meth)acrylates, such as trimethylolpropane trimethacrylate.

[0114] Also included herein are tetraunsaturated substituted monomers and oligomers such as 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetraphenyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,2-bis[[(2-methyl-1-oxoallyl)oxy]methyl]-1,3-propanediylbismethacrylate (pentaerythritol tetramethacrylate), tetraallyl orthosilicate, tetraallyl cis,cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylate, tetraallylsilane, glyoxal bis(diallyl acetal), and the like.

[0115] Due to the possible possibility of hydrosilylation curing in addition to radical curing, multiple Si-H functional components such as 1,1,3,3-tetramethyl-1,3-disiloxane, 2,4,6,8-tetramethyl-cyclotetrasiloxane, 1,4-bis(dimethylsilyl)benzene, or oligo- and polyorganosiloxanes with multiple intrachain and / or terminal Si-H functional groups may also act as crosslinkers.

[0116] Suitable catalysts and / or initiators for the radical curing of the binder preparations composed of polyorganosiloxanes of formula (I) and organic monomers, oligomers and polymers are the same as those already specified above, and are therefore in particular peroxides.Furthermore, there are suitable further radical initiators, such as azo components such as α,α'-azobis(isobutyronitrile), redox initiators such as combinations of peroxides such as hydrogen peroxide and iron salts, or azides such as acetyl azide, to initiate the radical curing of both the polyorganosiloxanes of formula (I) alone and the binder preparations described.

[0117] The polyorganosiloxanes of formula (I) and / or preparations containing them can be used either as solvent-free or solvent-containing preparations for use according to the invention. Generally, they are used as solvent-containing preparations in order to promote homogeneous distribution of all the components of the formulation with each other and to promote wetting and saturation of any reinforcing layer used. Generally, a reinforcing layer is used. It is preferably a glass fiber fabric. Saturation of the reinforcing layer can be achieved by impregnation application with the preparation, for which various technical solutions are available, optionally including continuous processes, the choice of which is in no way limited for the purpose of producing the metal surface layer of the invention. Non-limiting examples of application techniques are, where appropriate, immersion, spraying, flow coating, knife coating, etc. of a web of reinforcing material via a roller system in a continuous operation. The advantage of the present invention is that all available techniques can be used without restrictions and modifications and that the use of polyorganosiloxanes of formula (I) does not require special new processes. In the production of metal surface layers, the present invention is therefore entirely within the scope of the available state of the art. A new feature is the use, hitherto unknown, of polyorganosiloxanes of formula (I) for producing the metal surface layers in question.

[0118] Impregnation is followed by a drying step to remove any solvent used. For the drying operation, prior art methods are also used. These methods include, in particular, thermally induced evaporation with or without vacuum. With the appropriate setting of the reactivity and viscosity of the binder mixture used, the product of this step under appropriate conditions, for example cooling, is a storable composite material, which can optionally be further processed at a later point in time.

[0119] In the last step of the process, the binder preparation is polymerized according to the methods of the prior art. Any initiator of radical polymerization used here is heated above its decomposition temperature, so that it decomposes to form radicals and initiates the radical polymerization of the binder preparation. The method of radiation curing can also be used in principle.

[0120] When hydrosilylation curing is used instead of radical polymerization, the temperature to be used in this step is a temperature suitable for deactivating the hydrosilylation catalyst used with the inhibitor used, thus deactivating the catalytic activity of the hydrosilylation catalyst.

[0121] This step is usually carried out at high temperatures, preferably 100-390°C, more preferably 100-250°C, more preferably 130-200°C, and the temperature is effective for preferably 5-180 minutes, more preferably 5-150 minutes, more preferably 10-120 minutes. It is also customary to use high pressure in this step. Customary pressures are in the range of 1-10 MPa, more preferably 1-5 MPa, more specifically 1-3 MPa.

[0122] The lamination of the composite material with the conductive metal layer is carried out in this second step by applying a layer of at least one selected metal to one or both sides of the composite material composed of the reinforcing layer and the binder preparation before the curing takes place. In other words, between the first step consisting of impregnation and drying and the second step which involves the chemical curing of the binder preparation, the composite from the first step is faced with at least one conductive metal.

[0123] Suitable conductive metals include, in particular, at least one from the following selection: copper, stainless steel, gold, aluminum, silver, zinc, tin, lead and transition metals. In principle, there are no restrictions on the thickness of the conductive layer or its shape, size or surface texture. The conductive metal layer preferably has a thickness of 3 to 300 μm, more preferably 3 to 250 μm, even more preferably 3 to 200 μm. If two layers are used, the thickness of the two layers of at least one conductive metal may vary and need not be the same. Particularly preferably, the conductive metal is copper, and if two conductive layers of a conductive metal are used, both layers are copper. The conductive metal is preferably used in the form of a foil of said metal. The average roughness Ra of the metal foil used is preferably at most 2 μm, more preferably at most 1 μm and especially at most 0.7 μm. The smaller the surface roughness, the better the suitability of the respective foil for use in radio frequency applications, which is a preferred object of the present invention. To improve the adhesion between the conductive metal layer and the composite composed of the binder formulation and the reinforcing layer, various methods from the prior art can be optionally used, such as, for example, the use of an adhesion-promoting layer, electrochemical deposition of the metal layer on the composite composed of the binder formulation and the reinforcing layer, or vapor deposition. The layer of conductive metal can be placed directly on the composite composed of the binder formulation and the reinforcing layer or can be joined to it by an adhesion-promoting layer.

[0124] If no reinforcing layer is used, the layer of binder preparation comprising polyorganosiloxane of formula (I) is produced by depositing the layer of binder preparation on a carrier such as a release film or release plate, for example, suitable materials for the carrier are in principle any material from which the dried or cured binder preparation can be peeled off again later, such as polytetrafluoroethylene, polyester, etc. The peelability and film-forming properties on the carrier material must be determined individually depending on the binder composition. The description made regarding this process remains equally valid for this variant that does not contain a reinforcing material.

[0125] From the reinforced or unreinforced composite material from the first step and the laminated composite material from the second step, a multi-layer system can be built up by laminating several plies of the composite material from the first step, alternating, for example, with the opposing laminates from the second step, and then curing the still uncured composite material from the first step in an operation that substantially corresponds to the procedure for manufacturing metal surface laminates. To produce thicker layers, it is also possible here to stack several plies of reinforced or unreinforced composite material from the first step one after the other in a direct sequence.

[0126] As well as for producing metal surface layers, the polyorganosiloxanes of formula (I) can also be used in anticorrosive preparations, in particular for use in preventing corrosion at high temperatures.

[0127] The polyorganosiloxanes of formula (I) and preparations containing them can also be used for the corrosion protection of reinforcing steel in steel-reinforced concrete.In this case, the corrosion-inhibiting effect in steel-reinforced concrete is achieved both when the polyorganosiloxanes of formula (I) and preparations containing them are introduced into the concrete mixture before the mixture is molded and hardened, and when the polyorganosiloxanes of formula (I) or preparations containing them are applied to the surface of the concrete after the concrete has hardened.

[0128] As well as for corrosion protection on metals, the polyorganosiloxanes of formula (I) may also be used to manipulate further properties of the formulations containing the organopolysiloxanes of the invention or of the solids or films obtained from the formulations containing the polyorganosiloxanes of formula (I), examples of which are as follows: - Control of electrical conductivity and electrical resistance - Control of the flow properties of the preparation - Controlling the gloss of wet or cured films or objects - Improved weather resistance - Improved chemical resistance - Improved hue stability - Reduced tendency to choke - reduction or increase in static and sliding friction for solids or films obtained from preparations containing polyorganosiloxanes of formula (I) - stabilization or destabilization of foam in preparations containing polyorganosiloxanes of formula (I) - improving the adhesion of preparations containing polyorganosiloxanes of formula (I) to substrates; - Control of the wetting and dispersing behavior of fillers and pigments - Control of the rheological properties of formulations containing the organopolysiloxanes of the invention control of the mechanical properties, such as flexibility, scratch resistance, elasticity, extensibility, bending, fracture behavior, resilience behavior, hardness, density, tear resistance, compression set, behavior at different temperatures, expansion coefficient, abrasion resistance, and / or further properties, such as thermal conductivity, flammability, gas permeability, stability against water vapor, hot air, chemicals, weathering and radiation, sterilizability, of the solids or films obtainable which contain the polyorganosiloxanes of formula (I) or preparations which contain them; - Control of electrical properties such as dielectric loss factor, breakdown resistance, dielectric constant, leakage current resistance, arc resistance, surface resistance, specific breakdown resistance - flexibility, scratch resistance, elasticity, extensibility, bending, fracture behavior, resilience behavior, hardness, density, tear resistance, compression set, behavior at different temperatures of the solids or films obtained from the preparations containing the polyorganosiloxanes of formula (I).

[0129] Examples of applications in which the polyorganosiloxanes of formula (I) can be used to manipulate the above properties are the manufacture of coating materials and impregnations, and coatings obtainable therefrom, on substrates such as metal, glass, wood, mineral substrates, synthetic and natural fibers, leather, and plastics, such as films and moldings, for the manufacture of textiles, carpets, floor coverings, or other articles that can be manufactured from fibers. By appropriate selection of the components of the formulation, the polyorganosiloxanes of formula (I) can further be used in the formulation as additives for defoaming, flow promotion, hydrophobization, hydrophilization, filler and pigment dispersion, filler and pigment wetting, substrate wetting, promotion of surface smoothness, reduction of static and sliding friction on the surface of the cured material obtained from the additive formulation. The polyorganosiloxanes of formula (I) can be incorporated into the elastomeric composition in liquid form or in cured solid form. They can then be used for reinforcement or to improve other service properties, such as transparency, heat resistance, yellowing tendency, or weather stability control.

[0130] All of the above symbols in the above formulas have their definitions independent of each other. In all formulas, the silicon atom is tetravalent. EXAMPLES

[0131] All percentages are by weight. Unless otherwise indicated, all operations are carried out at room temperature of 23° C. and under standard pressure (1.013 bar).

[0132] Unless otherwise indicated, all data relating to the description of the product properties are valid at room temperature of 23° C. and standard pressure (1.013 bar).

[0133] The equipment used is standard commercially available laboratory equipment of the type available from a number of instrument manufacturers.

[0134] Ph represents the phenyl group =C6H5-.

[0135] Me represents a methyl group =CH3-. Thus, Me2 represents two methyl groups.

[0136] PPE stands for polyphenylene ether.

[0137] HCl stands for hydrogen chloride.

[0138] In this document, materials are characterized by data obtained using instrumental analysis. The underlying measurements are performed according to publicly available specifications or are determined according to specially developed methods. To ensure clarity of the teachings given, the methods used are specified below.

[0139] In all examples, parts and percentages are by weight unless otherwise indicated.

[0140] <Viscosity> Unless otherwise indicated, viscosities are determined by rotational viscometry according to DIN EN ISO 3219. Unless otherwise indicated, all reported viscosities are for 25° C. and a standard pressure of 1013 mbar.

[0141] <Refractive index> The refractive index is measured in the wavelength range of visible light, according to standard DIN 51423, at 589 nm, at 25° C. and a standard pressure of 1013 mbar, unless otherwise indicated.

[0142] <Transmittance> The transmittance is determined by UV VIS spectroscopy. An example of a suitable instrument is the Analytik Jena Specord 200.

[0143] The measurement parameters used were as follows: Range: 190~1100nm Step width: 0.2 nm, integration time: 0.04 sec, measurement mode: step mode. First, a reference measurement (background) is performed. A quartz plate fixed to a sample holder (quartz plate dimensions: H×B approx. 6×7 cm, thickness approx. 2.3 mm) is placed in the sample beam path and measured against air.

[0144] Then the sample measurement is performed: a quartz plate fixed in a sample holder and carrying the applied sample (layer thickness of applied sample approx. 1 mm) is placed in the sample beam path and measured against air. By internal calculation against the background spectrum the transmission spectrum of the sample is obtained.

[0145] <Molecular composition> Molecular composition was determined using nuclear magnetic resonance spectroscopy (see ASTM E 386 for terminology: High Resolution Nuclear Magnetic Resonance (NMR) Spectroscopy: Terminology and Symbols) and was 1 H nucleus and 29 Determined using Si nuclei.

[0146] < 1 Explanation of H-NMR measurement> Solvent: CDCl3, 99.8%d Sample concentration: Approximately 50 mg / 1 ml of CDCl3 in a 5 mm NMR tube

[0147] Measurements without added TMS, reference spectrum of residual CHCl3 in CDCl3 at 7.24 ppm

[0148] Spectrometer: Bruker Avance I 500 or Bruker Avance HD 500 Probe: 5mm BBO probe or SMART probe (Bruker)

[0149] Measurement parameters: Pulprog=zg30 TD=64k NS=64 or 128 (depending on probe sensitivity) SW=20.6ppm AQ=3.17 seconds D1=5 seconds SFO1=500.13MHz O1=6.175ppm

[0150] Processing parameters: SI=32k WDW=EM LB=0.3Hz

[0151] An individual adaptation of the measurement parameters may be necessary according to the type of spectrometer used.

[0152] < 29 Explanation of Si-NMR measurement> Solvent: C6D6 99.8%d / CCl4 1:1v / v containing 1wt% Cr(acac)3 as relaxation agent Sample concentration: approximately 2 g / 1.5 ml of solvent in a 10 mm NMR tube Spectrometer:Bruker Avance 300 Probe: 10mm 1H / 13C / 15N / 29Si glass-free QNP probe (Bruker)

[0153] Measurement parameters: Pulprog=zgig60 TD=64k NS=1024 (depends on probe sensitivity) SW=200ppm AQ=2.75 seconds D1=4 seconds SFO1=300.13MHz O1=-50ppm

[0154] Processing parameters: SI=64k WDW=EM LB=0.3Hz

[0155] An individual adaptation of the measurement parameters may be necessary according to the type of spectrometer used.

[0156] <Molecular weight distribution> The molecular weight distribution is determined as weight average Mw and number average Mn using the method of gel permeation chromatography (GPC or size exclusion chromatography (SEC)) with polystyrene standards and a refractive index detector (RI detector). Unless otherwise stated, THF is used as the eluent and DIN 55672-1 is used. Polydispersity is the quotient Mw / Mn.

[0157] <Glass transition temperature> The glass transition temperature is determined by differential scanning calorimetry (DSC) in accordance with DIN 53765 in a perforated crucible at a heating rate of 10 K / min.

[0158] <Determination of particle size> The particle size was measured by dynamic light scattering (DLS) along with the determination of the zeta potential.

[0159] The following auxiliary agents and reagents were used in the determination: 10 x 10 x 45 mm polystyrene cuvettes, single-use Pasteur pipettes, and ultrapure water.

[0160] The sample for the measurement is homogenized and bubble-free and introduced into the measuring cuvette.

[0161] Measurements are performed at 25° C. after an equilibration time of 300 seconds with high resolution and automatic measurement timing.

[0162] The reported values ​​always relate to the D(50) value, which should be understood as the volume-average particle size at which 50% of all particles measured have a volume-average diameter smaller than the specified value of D(50).

[0163] <Determination of dielectric properties: Df, Dk> The dielectric properties are determined according to IPC TM 650 2.5.5.13 using a Keysight / Agilent E8361A network analyzer according to the Split-Cylinder Resonator method at 10 GHz.

[0164] <Microscopy Procedure> The micro / nanostructures were characterized by optical microscopy and transmission electron microscopy, respectively.

[0165] Optical microscopy: Sample preparation: 1 drop of sample (solvent-free) on a slide, covered with a coverslip Equipment: LEICA DMRXA2 with LEICA DFC420 CCD camera (2592 x 1944 pixels) Imaging: Transmitted light - interference contrast, various magnification steps

[0166] Transmission electron microscopy: Sample preparation: 1 drop of sample on a coated TEM grid (dilution 1:20, adaptation required if necessary), add contrast agent if necessary, allow to dry at room temperature Equipment: ZEISS LIBRA 120 with Sharp Eye CCD camera (1024 x 1024 pixels) Imaging: Excitation voltage 120 kV, TEM bright field, various magnification steps

[0167] <Peel strength test for adhesion> The adhesion of metal layers laminated on composite layers with or without reinforcing material was measured according to the "received" version of IPC-TM 650 method 2.4.8 "Peel Strength of Metallic Clad Laminates", i.e. without thermal load or exposure.

[0168] Mass 285±10g / m 2 A 35 μm copper foil having a roughness depth Rz≦8 μm and an average roughness Ra≦0.4 μm was laminated on both sides of the 100 μm thick composite layer, and curing and lamination were performed under conditions of 200°C, 2.0 MPa, and 30 mmHg column for 180 minutes.

[0169] <Synthesis Example 1: Production of organopolysiloxane by the process of the present invention> A mixture of 1267.8 g (6 mol) phenyltrichlorosilane, 372.6 g (1.5 mol) 3-(trimethoxysilyl)propyl methacrylate and 780 g xylene is metered into an initial quantity of 3600 g water over a period of 4 hours. The reaction of the chlorosilanes in water is exothermic and produces hydrochloric acid, which dissolves in the initial quantity of water. Care is taken to ensure that the temperature as a result of the exothermic temperature rise does not exceed 50°C and, if appropriate, the metering rate is reduced so that this temperature limit is not exceeded.

[0170] After the metering is complete, stirring is continued for 15 minutes and the agitator is stopped. The reaction mixture contains hydrochloric acid and separates into an aqueous phase at the bottom of the reaction vessel and an organosilicone phase at the top. The aqueous phase is drained.

[0171] One liter of water is added to the remaining organic phase, the mixture is stirred for 30 minutes, then the stirrer is stopped again. The aqueous phase is again separated at the bottom and drained. This procedure is repeated until the residual HCl content of the organic phase, determined by acid-base titration according to the prior art, is less than 20 ppm.

[0172] When the aqueous phase settles to the top, washing is carried out not with fully demineralized water but instead with an aqueous solution containing 10% sodium chloride, or 100 g of sodium chloride are added and the mixture is stirred again for 30 minutes, after which the phase separation is carried out again.

[0173] The organic phase is then distilled on a water separator at ambient pressure until no further water is separated and therefore the organic phase is technically free of water.

[0174] The residual water content of the organic preparation is determined by Karl Fischer titration and is 856 ppm.

[0175] The amount of silanol groups expressed as OH groups with a molecular weight of 17 g / mol 1 1.6 weight percent as determined by H-NMR. Given that the molecular weight of the intermediate from the first reaction step is Mw=3347 g / mol, this means that the silanol content is 3.2 mol OH.

[0176] The reaction mixture is cooled to 40° C. and initially 318 g (3.2 mol) dimethyldichlorosilane are metered in, followed by 261 g (3.3 mol) pyridine. The first metering lasts 30 min, the second metering lasts 45 min. An exothermic temperature rise is observed. Here too, the temperature is limited to 50° C. by adapting the metering rate. After metering is complete, stirring is carried out for 60 min in order to complete the reaction.

[0177] After the reaction is over, the reaction mixture is washed 3 times with 1 liter of fully demineralized water and the aqueous phase is in each case separated off as described above.

[0178] After the final phase separation, the residual HCl content of the organic phase is less than 20 ppm. The solvent fraction is reduced by distillation to establish a solids content of 80% resin, i.e. the final resin solution consists of 20% xylene and 80% polyorganosiloxane.

[0179] Methoxy groups are not detectable by NMR. The residual silanol content is 1 0.05 weight percent as determined by H-NMR spectroscopy.

[0180] Sc:Mw=4914g / mol, Mn=1904g / mol, polydispersity PD=2.58.

[0181] 29 According to Si-NMR the molar composition of the silicon-containing fraction of the preparation is as follows: Me2Si(H)O 1 / 2 :30.96% H2C=C(CH3)C(O)-O-(CH2)3-SiO 3 / 2 :13.89% PhSiO 3 / 2 :55.15%

[0182] This product is identified below as 1.1.

[0183] Synthesis Example 2: Preparation of a silphenylene-bridged organopolysiloxane by the process of the present invention and comparison with non-inventive hydrolysis procedures at both steps.

[0184] <Synthesis of silphenylene precursor> 1,4-Bis(dimethoxyphenylsilyl)benzene according to the literature protocol by Xunjun Chen, Minghao Yi, Shufang Wu, Lewen Tan, Yixin Xu, Zhixing Guan, Jianfang Ge and Guoqiang Yin: Synthesis of silphenylene-containing siloxane resins exhibiting strong hydrophobicity and high water vapor barriers, Coatings 2019, 9, 481;doi:10.3390 / coatins9080481www.mdpi.com / journal / coatings

[0185] The reaction of trimethoxyphenylsilane with the Grignard reagent obtained from 1,4-dibromobenzene according to the literature protocol specified in "2.2. Synthesis of the 1,4-bis(dimethoxyphenylsilyl)benzene (BDMPD)" gives 1,4-bis(dimethoxyphenylsilyl)benzene, whose structure is: 1 Confirmation was achieved by 1 H-NMR spectroscopy and comparison with prescribed literature.

[0186] The procedure for resin synthesis corresponds to that described in Synthesis Example 1, with the following differences. A mixture of 845.2g (=4mol) of phenyltrichlorosilane, 546.7 g (1.3 mol) of 1,4-bis(dimethoxyphenylsilyl)benzene, 198.7 g (0.8 mol) of 3-(trimethoxysilyl)propyl methacrylate and 820g xylene As well as an initial charge of 2400 g of fully demineralised water are used. The weighing time is 4 hours.

[0187] The intermediate obtained after the first step has a molecular weight of Mw=1247, 1It contains 3 weight percent silanol groups determined by H-NMR as OH with a molecular weight of 17 g / mol, i.e. 2.2 moles of OH.

[0188] This is the end point of the synthesis of US2018022053 and follows the text of the specification of US2018022053, following the examples reported therein as examples.

[0189] To reduce the silanol content, the same procedure as described in Synthesis Example 1 is used, but in this case, in contrast to Synthesis Example 1, the following is used: 265.1 g (2.2 mol) of vinyldimethylchlorosilane and 174g (2.2mol) of pyridine.

[0190] In the resulting product, the methoxy group is no longer 1 1H-NMR. This means that the methacrylate-functional trimethoxysilane was completely incorporated by condensation and the resulting methanol was removed during workup. The proportion of silanol groups was reduced to about 0.05 weight percent ( 1 1H-NMR).

[0191] The following molecular weights were determined by SEC (eluent: toluene): Mw=2347 g / mol, Mn=1503 g / mol, polydispersity PD=1.56.

[0192] 29 According to Si-NMR the molar composition of the silicon-containing fraction of the preparation is as follows: Me2Si(Vi)O 1 / 2 :26.54% H2C=C(CH3)C(=O)-O-(CH2)3-SiO 3 / 2 :9.98% O 2 / 2 (Ph)Si-C6H4-Si(Ph)O 2 / 2 :15.23% PhSiO 3 / 2 :48.25%

[0193] This product is hereinafter identified as 2.1.

[0194] As an alternative to the non-hydrolysis procedure of the present invention, the following hydrolysis procedure to reduce silanol groups is carried out, which is not mentioned in US2018022053, but can in principle fall within the scope of the invention since there is no limit to the number of steps in the hydrolysis process.

[0195] 200 g of water are metered into the previously completely distilled xylene reaction mixture up to the anhydrous initial amount from the first reaction step. 265.1 g (2.2 mol) of vinyldimethylchlorosilane are then metered in slowly, the metering rate being adapted so that the reaction temperature (internal temperature in the reaction vessel) remains limited to less than 50° C. After the metering is over, it is stirred for 60 minutes without heating or cooling in order to complete the reaction of the silanol groups with the vinyldimethylchlorosilane or the tetramethyldivinyldisiloxane formed therefrom.

[0196] The aqueous phase is separated as above and then washed three times with 1 liter of water as already described above. Phase separation can be improved in some cases by stopping the agitator and heating to a heating jacket temperature of 60° C. After washing, the HCl content of the xylene solution is less than 20 ppm.

[0197] The amount of toluene is reduced by distillation under reduced pressure (20 mbar) at 110° C. until a solution of 80% of the resin in 20% of xylene is obtained.

[0198] In the resulting product, the methoxy group is no longer 1 H-NMR. This means that the methacrylate-functional trimethoxysilane was again fully incorporated by condensation and the resulting methanol was removed during workup. However, the proportion of silanol groups was reduced by the workup, but ( 1 The decrease was only to 0.9 weight percent (as determined by H-NMR).

[0199] The following molecular weights were determined by SEC (eluent: toluene): Mw=7347 g / mol, Mn=2903 g / mol, polydispersity PD=2.53.

[0200] Here, a further difference is evident for the process of the invention. The vinyldimethylsilane used to partially reduce the silanol groups forms symmetrical disiloxanes, which are distilled off during the work-up and, as a result of the HCl formed in the reaction of the chlorosilanes with water, catalyze the reaction of the silanol groups, thus reducing these groups. However, as a result of the condensation, it leads to much higher molecular weights and therefore a significant increase in the risk that the polyorganosiloxanes obtained from the first step will polymerize into insoluble products and therefore become unusable. This effect is effectively avoided by the procedure according to the invention.

[0201] 29 According to Si-NMR the molar composition of the silicon-containing fraction of the preparation is as follows: Me2Si(Vi)O 1 / 2 :11.54% H2C=C(CH3)C(=O)-O-(CH2)3-SiO 3 / 2 :11.98% O 2 / 2 (Ph)Si-C6H4-Si(Ph)O 2 / 2 :19.23% PhSiO 3 / 2 :57.25%

[0202] The silanol group is PhSiO 3 / 2 is connected to the unit.

[0203] This product is hereinafter identified as 2.2.

[0204] Using the hydrolysis procedure, in the case of complete reaction to polyorganosiloxane from the first step, Me2Si(Vi)O 1 / 2Incomplete reaction of the chlorosilanes used is also discernible in the NMR data, since the proportion of units would have to be much higher. Thus, the anhydrous procedure is clearly shown to be superior to the aqueous procedure for the controlled reduction of polar silanol groups in a robustly controllable and manageable process.

[0205] Synthesis Example 3: Preparation of alkylene bridged organopolysiloxanes by the process of the present invention and comparison with non-inventive aqueous procedures. The synthesis according to Synthesis Example 1 is repeated, but with the following deviations from Synthesis Example 1: Phenyltrichlorosilane: 422.6g (=2mol) 1,2-Bis(dichloromethylsilyl)ethane: 341.35g (1.35mol) 198.7 g (0.8 mol) of 3-(trimethoxysilyl)propyl methacrylate 820g xylene and an initial amount of 2400 g of fully demineralized water.

[0206] The weigh-in time is 4 hours.

[0207] The intermediate obtained after the first step has a molecular weight of Mw=2247. 1 It contains 2.5 weight percent silanol groups determined by H-NMR as OH with a molecular weight of 17 g / mol, i.e. 3.3 moles of OH.

[0208] This is the end point of the synthesis of US2018022053 and follows the text of the specification of US2018022053, following the examples reported therein as examples.

[0209] To reduce the silanol content, the same procedure as described in Synthesis Example 1 is used, but in this case, in contrast to Synthesis Example 1, the following is used: 397.7 g (3.3 mol) of vinyldimethylchlorosilane and 261g (3.3mol) of pyridine.

[0210] Methoxy groups cannot be detected by NMR. The proportion of silanol groups is reduced to about 0.05 weight percent ( 1 1H-NMR).

[0211] The following molecular weights were determined by SEC (eluent: toluene): Mw=2954 g / mol, Mn=1919 g / mol, polydispersity PD=1.53.

[0212] 29 According to Si-NMR the molar composition of the silicon-containing fraction of the preparation is as follows: Me2Si(Vi)O 1 / 2 :44.29% H2C=C(CH3)C(=O)-O-(CH2)3-SiO 3 / 2 :10.78% O 2 / 2 (Me)Si-C2H4-Si(Me)O 2 / 2 :18.12% PhSiO 3 / 2 :26.81%

[0213] This product is hereinafter identified as 3.1.

[0214] As an alternative to the non-hydrolysis procedure of the present invention, the following hydrolysis procedure to reduce silanol groups is carried out, which is not mentioned in US2018022053, but can in principle fall within the scope of the invention since there is no limit to the number of steps in the hydrolysis process.

[0215] Similar to the procedure of Synthesis Example 2, 300 g of water is added to the anhydrous initial charge from the first reaction step.

[0216] Then 397.7 g (3.3 mol) vinyldimethylchlorosilane are slowly metered in and the subsequent procedure is as described in Synthesis Example 2.

[0217] In the resulting product, the methoxy group is no longer 1H-NMR. The proportion of silanol groups was reduced by post-treatment, but only to 1.0 weight percent ( 1 (determined by H-NMR).

[0218] Sc:Mw=6974g / mol, Mn=2812g / mol, polydispersity PD=2.48.

[0219] 29 According to Si-NMR the molar composition of the silicon-containing fraction of the preparation is as follows: Me2Si(Vi)O 1 / 2 :21.69% H2C=C(CH3)C(=O)-O-(CH2)3-SiO 3 / 2 :15.09% O 2 / 2 (Me)Si-C2H4-Si(Me)O 2 / 2 :25.47% PhSiO 3 / 2 :37.75%

[0220] The silanol group is PhSiO 3 / 2 is connected to the unit.

[0221] This product is hereinafter identified as 3.2.

[0222] Again, higher molecular weight and less complete silanol group reduction is achieved with the hydrolytic process than with the non-hydrolytic process of the present invention.

[0223] Synthesis Example 4: Preparation of organopolysiloxanes having Si-Si bonds by the process of the present invention compared to non-inventive aqueous procedures. The synthesis according to Synthesis Example 1 is repeated, except that the following starting materials and amounts are used, which deviate from Synthesis Example 1: Phenyltrichlorosilane: 422.6g (=2mol) 198.7 g (0.8 mol) of 3-(trimethoxysilyl)propyl methacrylate 296.4g (1.3mol) of 1,1,2,2-tetrachloro-1,2-dimethyldisilane 820g xylene and an initial amount of 2400 g of fully demineralized water.

[0224] The weigh-in time is 4 hours.

[0225] The intermediate obtained after the first step has a molecular weight of Mw=1867 g / mol. 1 It contains 2.9 weight percent silanol groups determined by H-NMR as OH with a molecular weight of 17 g / mol, i.e. 3.2 moles of OH.

[0226] This is the end point of the synthesis of US2018022053 and follows the text of the specification of US2018022053, following the examples reported therein as examples.

[0227] To reduce the silanol content, the same procedure as described in Synthesis Example 1 is used, but in this case, in contrast to Synthesis Example 1, the following is used: 385.6 g (3.2 mol) of vinyldimethylchlorosilane and 261g (3.3mol) of pyridine.

[0228] Methoxy groups cannot be detected by NMR. The proportion of silanol groups is reduced to about 0.05 weight percent ( 1 1H-NMR).

[0229] The following molecular weights were determined by SEC (eluent: toluene): Mw=2479 g / mol, Mn=1678 g / mol, polydispersity PD=1.47.

[0230] 29 According to Si-NMR the molar composition of the silicon-containing fraction of the preparation is as follows: Me2Si(Vi)O 1 / 2 :40.34% H2C=C(CH3)C(=O)-O-(CH2)3-SiO 3 / 2 :10.96% O 2 / 2(Me)Si-Si(Me)O 2 / 2 :21.31% PhSiO 3 / 2 :27.39%

[0231] This product is hereinafter identified as 4.1.

[0232] As an alternative to the non-hydrolysis procedure of the present invention, the following hydrolysis procedure to reduce silanol groups is carried out, which is not mentioned in US2018022053, but can in principle fall within the scope of the invention since there is no limit to the number of steps in the hydrolysis process.

[0233] Similar to the procedure of Synthesis Example 2, 300 g of water is added to the anhydrous initial charge from the first reaction step.

[0234] Then 385.6 g (3.2 mol) vinyldimethylchlorosilane are slowly metered in and the rest of the procedure is as described in Synthesis Example 2.

[0235] In the resulting product, the methoxy group is no longer 1 H-NMR. The proportion of silanol groups was reduced by post-treatment, but only to 1.1 weight percent ( 1 (determined by H-NMR).

[0236] Sc:Mw=4974g / mol, Mn=2006g / mol, polydispersity PD=2.48.

[0237] 29 According to Si-NMR the molar composition of the silicon-containing fraction of the preparation is as follows: Me2Si(Vi)O 1 / 2 :18.96% H2C=C(CH3)C(=O)-O-(CH2)3-SiO 3 / 2 :15.13% O 2 / 2 (Me)Si-Si(Me)O 2 / 2 :28.08% PhSiO3 / 2 :37.83%

[0238] The silanol group is PhSiO 3 / 2 is connected to the unit.

[0239] This product is identified below as 4.2.

[0240] Again, higher molecular weight and less complete reduction of silanol groups is achieved with the hydrolytic process than with the nonhydrolytic process of the present invention.

[0241] <Use Example 1: Use of organopolysiloxanes produced according to the present invention and not according to the present invention in Synthesis Examples 1 to 4 for producing metal surface laminates> To produce a copper laminate having a glass fiber reinforced composite layer, the organopolysiloxanes produced according to Synthesis Examples 1 to 4 and the comparative examples contained therein were used as binders. The starting materials used were as follows:

[0242] Copper foil: 35 μm thick copper foil (285±10 g / m) manufactured by Jiangtong-yates Copper Foil Co Ltd, with a roughness depth of Rz≦8 μm and an average roughness depth of Ra≦0.4 μm, and a purity of ≧99.8%. 2 ).

[0243] Glass fiber: E-glass fiber type 1080E from Changzhou Xingao Insulation Materials Co. Ltd. Thickness 0.055±0.012mm, 47.5±2.5g / m 2 .

[0244] In this example, all organopolysiloxanes were used as solutions in xylene, each containing 80% organopolysiloxane and 20% xylene.

[0245] To initiate curing, the organopolysiloxanes were mixed with 1 weight percent of dicumyl peroxide, in each case based on the amount of polyorganosiloxane used, and the peroxide was uniformly dispersed in the resin matrix by stirring.

[0246] Laminates were produced by subjecting glass fibre layers measuring 30-30 cm to bubble-free impregnation, ply by ply, with the respective organopolysiloxane, where appropriate as a xylene solution, using an air removal roller. In this procedure, the glass fibre layer was mounted on a planar, dimensionally stable stainless steel support, to which one ply of copper foil was applied, after which the first ply of glass fibre was placed on top of it. A total of three plies of glass fibre fabric were impregnated successively in each case. To remove the solvent, where appropriate, the impregnated fabric was dried to constant weight at 10 mbar and 60 ° C in a vacuum drying oven. A second layer of copper foil was then applied on top of the impregnated glass fibre layer and a further dimensionally stable stainless steel plate was placed on top of it. The laminate was heated in a heatable press at 200 ° C, 30 mbar vacuum for 120 minutes at a pressure of 2 MPa. This results in a copper surface laminate with a total thickness of 260 ± 20 μm.

[0247] The dielectric properties were determined according to IPC TM 650 2.5.5.13 using a Keysight / Agilent E8361A network analyzer according to the Split-Cylinder Resonator method at 10 GHz. The values ​​obtained were as follows:

[0248] [Table 1]

[0249] The Df and Dk values ​​of the copper laminate containing the organopolysiloxane of the present invention are significantly lower than those achieved with organopolysiloxanes from the prior art procedures. Considering that extremely low dielectric loss factors and relative dielectric constants are desirable for radio frequency applications, the advantages of the present invention are highly evident.

[0250] <Use Example 2: Use of organopolysiloxanes produced according to the present invention and not according to the present invention in Synthesis Examples 1 to 4 for producing a metal surface laminate via a prepreg> For this example, the organopolysiloxanes from synthesis examples 1 to 4 according to both the inventive and non-inventive procedures were used as solutions in xylene, in each case using a formulation of 20% xylene and 80% polyorganosiloxane.

[0251] Instead of building a laminate directly without an intermediate prepreg stage, this time the prepregs were produced by impregnating the glass fiber plies, in each case as individual plies on a polytetrafluoroethylene film, with a resin preparation and then drying to constant weight in a vacuum drying oven. A set of three plies of the impregnated glass fiber cloth thus produced was then stacked one on top of the other on copper foil, and the laminate was finished with a ply of copper foil. This multilayer structure was pressed between two-dimensionally stable stainless steel plates in a vacuum press and cured under the conditions indicated in Example 1, as in Example 1.

[0252] The resulting laminate had a thickness of 290±20 μm.

[0253] The dielectric properties of the resulting laminate were measured and were as follows:

[0254] [Table 2]

[0255] The Dk and Df values ​​achieved for the copper laminates containing the organopolysiloxanes produced according to the present invention are significantly lower than the Df and Dk values ​​achieved for the organopolysiloxanes from the comparative examples. Considering that extremely low dielectric loss factors and relative dielectric constants are desirable for radio frequency applications, the advantages of the present invention are strikingly evident.

[0256] <Use Example 3: Use of the organopolysiloxanes produced according to the invention and not according to the invention according to Synthesis Examples 1 to 4 for the production of metal surface laminates in a mixture with an organic polymer> This procedure corresponds substantially to that described in Use Example 2, except that this time the organic polymer was mixed with the organopolysiloxane. The final solvent-free mixture always contained 30 weight percent of the organopolysiloxane and 70 weight percent of the organic polymer. The organic polymers were triallyl isocyanurate, NORYL SA 9000, an α,ω-methacrylate terminated polyphenylene ether obtained from SABIC, Mn=2500 g / mol, Tg=160° C., and B 3000, a liquid polybutadiene with Mn=3200, viscosity at 45° C.=210 poise, and more than 85% 1,2-vinyl structures in the polymer chain, from Nippon Soda.

[0257] The polymers were always used in the same proportions: they were dissolved or dispersed in xylene, 30 parts by weight of SA 9000, 25 parts by weight of B3000 and 15 parts by weight of triallyl isocyanurate were dispersed in 100 parts by weight of xylene.

[0258] The resulting preparations were mixed with xylene solutions of organopolysiloxanes according to Use Example 2 so that in each case 30% of organopolysiloxane and 70% of organic components were present in the resulting solutions. These solutions were then used as described in Use Example 2 to produce copper laminates via prepregs.

[0259] The resulting laminate had a thickness of 290±20 μm.

[0260] The dielectric properties of the resulting laminate were measured and were as follows:

[0261] [Table 3]

[0262] The Dk and Df values ​​achieved for the copper laminate using the organopolysiloxanes prepared according to the present invention are significantly lower than the Df and Dk values ​​achieved with the organopolysiloxanes from the comparative examples. Considering that extremely low dielectric loss factors and relative dielectric constants are desirable for radio frequency applications, the advantages of the present invention are strikingly evident.

Claims

1. A process for preparing a polyorganosiloxane of formula (I), [O ３－ａ／２ R ａ SiY(SiR ａ O ３－ａ／２ ) ｂ ｃ (R １ SiO ３／２ ) ｄ (R ２ ２ SiO ２／２ ) ｅ (R ３ ３ SiO １／２ ) ｆ (SiO ４／２ ) ｇ [O ３－ｈ／２ R ４ ｈ Si(SiR ５ ２ ) ｉ SiR ４ ｊ O ３－ｊ／２ ) ｋ [[ID=​ wherein the group R is a group which may be the same or different, and is either a hydrogen group or a monovalent Si—C bonded unsubstituted or heteroatom-substituted organic hydrocarbon group having 1 to 18 carbon atoms which may also be an unsaturated hydrocarbon group, Y is a chemical bond, an oxygen atom, or a divalent to dodecavalent organic group having 1 to 24 carbon atoms and bonded to a silicon atom by an Si—C bond, which is unsubstituted or substituted by a heteroatom, Group R １ , R ２ and R ３ are, independently of one another, a hydrogen group, or a saturated or unsaturated Si—C-bonded C1-C18 hydrocarbon group which may be unsubstituted or substituted by heteroatoms, or a C1-C12 hydrocarbon group bonded via an oxygen atom and which may contain heteroatoms, or a silanol group, and the groups R １ , R ２ and R ３ can each independently adopt their definitions in each case, and thus two or more groups R １ , R ２ and / or R ３ bonded to the same silicon atom may also be groups different from the defined groups. Group R ４ is, independently of one another, either a hydrogen group, a silanol group, or an unsaturated hydrocarbon group, and is any one of monovalent Si—C-bonded or Si—O—C-bonded unsubstituted or heteroatom-substituted organic hydrocarbon groups having 1 to 18 carbon atoms, Group R ５ is, independently of one another, a hydrogen group, a monovalent Si—C-bonded unsubstituted or heteroatom-substituted organic hydrocarbon group having 1 to 18 carbon atoms which may be an unsaturated hydrocarbon group, or any of the groups of the following formula (II): [O ３－ａ／２ R ａ SiY(SiR ａ O ３－ａ／２ ) ｂ ｃ (R １ SiO ３／２ ) ｄ (R ２ ２ SiO ２／２ ) ｅ (R ３ ３ SiO １／２ ) ｆ (SiO ４／２ ) ｇ (II),​ [wherein, all groups Y, R, R １ , R ２ , R ３ , R ４ and R ５ are 100 mol%, and at least 0.1 mol% must be an olefinic or acetylenic unsaturated group, All groups Y, R, R １ , R ２ , R ３ , R ４ and R ５ are 100% by weight, and in total at most 3% by weight are Si—O—C bonding groups and silanol groups, Also, for all groups Y, R, R １ , R ２ , R ３ , R ４ and R ５ being 100% by weight in total, at most 0.5% by weight in total is a silanol group, a is 0, 1 or 2, and the subscripts a on both sides of the group Y can independently adopt their definitions, and thus, the different subscripts a can have different values within the defined value range, b is a number having a value of 1 to 11, c has a value of 0 to 0.9, d has a value of 0 to 0.8, e has a value of 0 to 0.5, f has a value of 0.01 to 0.6, g has a value of 0 to 0.6, h and j are independently 0, 1 or 2, i is an integer having a value of 0 to 50, k has a value of 0 to 0.9, c + d + e + f + g + k = 1, at least one of the values c, d or k is >0, and e + g ≦ 0.6, In the formula, the groups R, R in formula (I) and formula (II) １ , R ２ , R ３ , R ４ , and R ５ as well as the subscripts a, b, c, d, e, f, g, h and i may independently of one another have the same definitions, and these definitions may be adopted independently of one another within the ranges of the values described.] In a first step, a silane of formula (III) R ６ ｌ SiR ７ ４－ｌ (III), [wherein, R ７ is a hydrolyzable group, l is an integer having a value of 0, 1 or 2, When l = 1, R ６ is the radical R １ and when l = 2, R ６ is the radical R ２ . and / or a di-, oligo- or polysilane of formula (IV) R ７ ３－ｈ R ４ ｈ Si(SiR ５ ２ ) ｉ SiR ４ ｊ R ７ ３－ｊ (IV) [In the formula, the above R ７ is a hydrolyzable group, R ４ 、 R ５ , h, i and j have the same definitions as described above. and / or an organically crosslinked silicone of formula (V) R ７ ３－ａ R ａ SiY(SiR ａ R ７ ３－ａ ) ｂ (V) [Wherein, R ７ , R, Y, a and b have the definitions already described.] with water and a hydrolyzable group R ７ When at least one of them is not a halogen group, the reaction is carried out in the presence of a non-aqueous miscible aprotic solvent using a catalytic amount of one or more acids that promote the hydrolysis and condensation of the components of formulas (III), (IV) and (V). After the reaction occurs, both the remaining amounts of acid in water and in the organic phase are each reduced to less than 10000 ppm, In a second step, the reaction product from the first step is reacted in a solution in an inert organic solvent, without water, in the presence of a secondary base, with a halosilane of formula (VI) R ３ ３ SiR ８ (VI), [Wherein, R ３ has the same definition as described above, and R ８ is a halogen atom.] Process.

2. Group R, R １ , R ２ , R ３ , R ４ , and R ５ are selected from a methyl group, a phenyl group, a vinyl group, an acryloyloxy group, a methacryloyloxy group, and an acrylate or methacrylate of an unbranched or branched alcohol having 1 to 15 carbon atoms, the process according to claim 1.

3. The process according to claim 1 or 2, wherein the aprotic solvent is an aromatic hydrocarbon.

4. The process according to any one of claims 1 to 3, wherein the secondary base is used in at least an equimolar amount relative to the halosilane.

5. The process according to any one of claims 1 to 4, wherein the secondary base is selected from basic metal salts and nitrogen compounds.

6. In a third step, the polyorganosiloxane of formula (I) is bonded to a metal substrate, the process according to any one of claims 1 to 5.

7. The process according to claim 6, wherein in the fourth step, the polyorganosiloxane of formula (I) is crosslinked. **Claim 8** A metal-clad laminate producible by the process according to claim 6 or 7, wherein in the second step, one or more halosilanes of formula (VI) are used such that the amount of halogen groups present is equimolar to the silanol groups in the polyorganosiloxane species from the first reaction step.