Silphenylene polymer

Abstract

The subject of the present invention is of the formula (I): R a R 1 b Si[Y[(SiR 2 c R 3 d ) e f g YSiR a R 1 b (I) (wherein Y, R, R 1 , R 2 , R 3 , a, b, c, d, e, f and g have the definitions indicated in claim 1, provided that per silphenylene polymer of formula (I), at least one olefinically or acetylenically unsaturated radical R, R 1 , R 2 or R 3 must be present, based on the sum of all radicals R, R 1 , R 2 and R 3 bonded to Si as 100 mol%, the sum of all organic radicals bonded to the Si atom through an oxygen atom must be 10 mol% or less, and based on all crosslinking-forming radicals Y as 100 mol%, at least 55 mol% of the radicals Y are 2- to 12-valent aromatic, alkylaromatic and cycloalkylaromatic radicals) silphenylene polymers; processes for their preparation; and also their use as binders or as additives in preparations for the production of coating materials and impregnating systems and in the resulting coatings and coatings on substrates.​​

Description

Technical Field

[0001] The present invention relates to radical curable silphenylene polymers, methods for preparing them, and their use as binders in high frequency applications.

Background Art

[0002] Accompanying the progress in the development of high frequency technology for wireless communication is an increase in the demand for materials having the ability to implement this technology. This relates to all sectors of materials, such as copper foils, binders, glass fibers, etc. In the case of binders, the epoxy resins conventionally used for manufacturing copper laminates and subsequently for circuit board manufacturing can no longer be used because their dielectric loss factors are too high. Polytetrafluoroethylene, which has a very low dielectric loss factor and is very useful for high frequency applications based on this, has other drawbacks, particularly poor workability and poor adhesion characteristics, which make alternatives desirable. Polyphenylene ethers are currently being intensively utilized as binders for this application field, and they combine a low dielectric loss factor with good mechanical and thermal properties as well as water repellency. Currently, additionally, other organic polymers are also being considered in the current development activities for this application field. Examples include, in a listing that could be supplemented with further examples, bismaleimide polymers, bismaleimide-triazine copolymers, and hydrocarbon resins.

[0003]

[0004] ​These profiles of properties qualify not only the organic polymers described but also polyorganosiloxanes for use as binders for the manufacture of high-frequency compatible copper laminates as well as components (e.g. circuit boards and antennas). Thus, it is evident to utilize the positive properties of these classes of materials for modern high-frequency applications, and moreover they can be used in each case either alone or in combination with one another in order to achieve a synergistic increase in their performance capabilities. Experiments in this direction have already been reported in the prior art.

[0005] Here, the polar substituents are undesirable because they raise the dielectric loss factor. In this context, polyorganosiloxanes have inherent drawbacks compared to other organic binders because their frameworks are generally constructed from alternating silicon and oxygen atoms. The difference in electronegativity between silicon and oxygen is 3.50 - 1.74 = 1.76 according to the Allred and Rochow electronegativity scale. Here, the electronegativity of silicon is 1.74 and 3.5 is the electronegativity of oxygen. In contrast, the electronegativity difference between carbon and oxygen is only 3.5 - 2.5 = 1.0, where 2.5 is the electronegativity of carbon. For example, as in the case of polytetrafluoroethylene, which exhibits excellent dielectric properties despite the electronegativity difference between carbon and fluorine of 1.67, it is known that the difference in electronegativity can be sterically shielded and not externally manifested. A similar shielding effect can be assumed for symmetric polydiorganosiloxanes, such as polydimethylsiloxane. However, in contrast to polytetrafluoroethylene, polydimethylsiloxane does not have suitable working properties for use as a binder for high-frequency applications. When using polydiorganosiloxanes, for example, the production of prepregs and their subsequent curing are not possible, the achieved viscosities are not high enough, and the polydiorganosiloxanes are prevented from escaping due to the effect of heat from the molten tin as part of the soldering procedure. Crosslinking, for example, through radical polymerization of binders used for the production of metal laminates, etc., also does not enable polydiorganosiloxanes to achieve sufficient mechanical strength under heat exposure. Unlike the highly cross-linked elements that are dimensionally stable even under temperature load as required by this application, the crosslinking of polyorganosiloxanes under the influence of heat can produce a reversibly deformable, i.e., elastomeric, polymer. Furthermore, polydiorganosiloxanes are incompatible with organic polymers, thus severely limiting or even actually excluding the possibility of formulating suitable binder mixtures.

[0006] Candidate binders for high-frequency applications include polyorganosiloxanes that have a three-dimensional framework structure and, furthermore, can be chemically crosslinked to form a thermosetting resin. Corresponding examples are known from the patent literature: see, for example, US Patent Application Publication No. 2016 / 0244610 (composition of a mixture of an olefinically unsaturated MQ resin with a polyphenylene ether modified for unsaturation), US Patent Application Publication No. 2018 / 0220530 (composition of a mixture of a polyphenylene ether with MT, MDT, MDQ and MTQ silicone resins) or US Patent Application Publication No. 2018 / 0215971 (composition of a mixture of a polyphenylene ether with TT and TQ silicone resins).

[0007] The target dielectric loss factor in these inventions is <0.007. Newly manufactured specimens of the materials described therein meet this requirement but do not significantly fall below it, so this prior art leaves considerable room for improvement, and the materials are significantly removed from the dielectric properties of polytetrafluoroethylene, which achieves a dielectric loss factor in the region of 0.0001. Since complete shielding of the polarity of the Si-O-Si framework units in polyorganosiloxanes having a three-dimensional framework structure is not possible, this structural element is an inherent drawback of polyorganosiloxanes and always represents a barrier to their achieving a lower dielectric loss factor.

[0008] Attempts to replace parts of the polyorganosiloxane framework with other crosslink-forming units instead of Si-O-Si units have been reported, for example, in US Patent No. 3395168. However, what these inventions have in common is that a significant constituent of the polyorganosiloxane framework is nevertheless retained.

[0009] U.S. Patent No. 6,072,016 teaches linear, condensation crosslinkable silphenylene polymers as part of a condensation curable silicone preparation. The linear, condensation crosslinkable silphenylene polymers described therein are themselves condensable as a result of hydrolyzable end groups. While it is possible in principle for these linear, condensation crosslinkable silphenylene polymers not to have Si-O-Si units; their curing as intended results in a polyorganosiloxane where part of the linkage between adjacent silicon atoms is different from Si-O-Si units and the units crosslinking the Si atoms are present in the form of Si-C bonds. In addition to silphenylene units, the silphenylene polymers also contain silylene units, which are an inevitable side effect of their preparation by hydrosilylation reaction of silphenylene units with olefinically unsaturated ends. Pure polysilphenylene is thus not available and is not taught in U.S. Patent No. 6,072,016. It should also be noted that the starting materials for hydrosilylation in U.S. Patent No. 6,072,016 are only accessible through metal-mediated coupling reactions, such as Grignard reactions or Wurtz couplings. These synthetic methods are feasible on an industrial scale but are nevertheless difficult, so the overall cost and complexity of implementing this technology are significant, and it is inevitable to assume that the lack of profitability will doom this technology or that the price will be extremely high, thus only breaking through in a very small market. Regarding dielectric properties, an increase in the dielectric loss factor may be expected due to platinum residues in the products from hydrosilylation, which means that in any case, a technology that is already costly and inconvenient requires further steps to be made usable for high-frequency applications. In other words, the state-of-the-art according to U.S. Patent No. 6,072,016 needs to be further developed first in order to be industrially useful in the target applications of the present invention, apart from the additional economic drawbacks it poses.

[0010] U.S. Patent No. 10,982,053 describes a polymer comprising a linear aliphatic polyether modified with silphenylene units. The polymers described therein can have phenol or epoxide groups. The copolymers described therein are obtained by hydrosilylation of an olefinically unsaturated polyether with Si-H functional silphenylene units. According to the teachings of U.S. Patent No. 10,982,053, pure silphenylene polymers cannot be obtained. The essential structural unit of the polymers according to U.S. Patent No. 10,982,053 is a polyether unit.

[0011] U.S. Patent Application Publication No. 2011 / 0275768 provides teachings similar to those of U.S. Patent No. 10,982,053, but the organic units located between individual silphenylene units are different from the polyether units according to U.S. Patent No. 10,982,053. Also in the case of U.S. Patent Application Publication No. 2011 / 0275768, organosilicon polymers consisting exclusively or mainly of silphenylene units are not covered by the subject matter of the teachings described therein.

[0012] European Patent No. 0913420 teaches, similar to U.S. Patent No. 6,072,016, a silphenylene silalene polymer with an alternating configuration obtained by a hydrosilylation reaction of an olefinically unsaturated silphenylene unit with an Si-H terminated silphenylene unit. The profitability is the subject of the same statements as already described for U.S. Patent No. 6,072,016. Here again, costly and complex metal-mediated coupling reactions are required to produce the starting materials required. Hydrosilylation can only be carried out thereafter, and due to the platinum catalyst used, it is a synthesis that is itself expensive. Platinum remains in the product and increases the dielectric loss factor. For the dielectric properties with high-frequency compatibility to be achieved, platinum first needs to be removed. This requires further steps and improvements over the prior art of European Patent No. 0913420 that go beyond the teachings of European Patent No. 0913420.

[0013] In the copolymer according to European Patent No. 0913420, as already suggested by the fact that the polymer is called a silylphenylene silylalkylene polymer, phenylen and alkylene crosslink formations regularly alternate. Considering that the vinyl groups required for polymer synthesis, which become crosslink-forming alkanediyl units through hydrosilylation with Si-H units, regularly alternate with phenylene units in the completed polymer framework, this is inevitable. The phenylene units crosslinking the Si atoms can then only be obtained through a metal-mediated coupling reaction, either in the manner of a Grignard reaction or a Wurtz reaction, as described above. Thus, in the silylphenylene-silylalkylene copolymer according to European Patent No. 0913420, 50% of the crosslink-forming radicals crosslinking adjacent Si atoms are arylene radicals and 50% are alkylene radicals, or alkanediyl radicals. Since the starting units used have exclusively dual-symmetric functionalization, high molecular weight linear polymers terminated with residual Si-H and / or olefin groups are obtained. Here, it is also possible to use pure organic starting units with dual hydrosilyl potential, such as diolefins or acetylenes, instead of silylphenylene units with dual olefin unsaturation. The silylphenylene silylalkylene polymer described therein has sufficient solubility for use in target applications as a coating material only when there is a minimum ratio of 20 mol% of silicon-bonded phenyl substituents. Silylphenylene polymers with a random configuration are not described in European Patent No. 0913420 and are not accessible through the methods described in European Patent No. 0913420. Thus, the scope of structural chemistry accessible according to this prior art is very limited. Thus, no general access to any desired silylphenylene polymer is taught by European Patent No. 0913420. The incidental use of aliphatic units in the silylphenylene-silylalkylene copolymer according to European Patent No. 0913420 cannot be avoided.It is known that the thermal stability achieved with units bonded to aliphatic silicon is lower than that obtained with radicals bonded to aromatic silicon. When the silylene units in the silphenylene-silylene copolymers of European Patent No. 0913420 are replaced by siloxane units, it is possible to achieve high thermal stability, as described in part in the prior art already referenced. However, this results in drawbacks in terms of the achievable dielectric properties, so the known prior art always exhibits either reduced thermal stability or reduced performance capabilities in terms of reduced dielectric properties. The combination of high thermal robustness, as expected for pure silphenylene polymers, and optimal electrical insulation properties, which can be obtained in an economical way, cannot yet be derived from the existing prior art. This is the object addressed by the present invention.

[0014] U.S. Patent No. 9,751,989 teaches a condensable crosslinkable polyorganosiloxane having oligosilphenylene units for use as a material for encapsulating LEDs. U.S. Patent Application Publication No. 2017 / 051114 teaches a hydrosilylation curable preparation comprising Si-H terminated oligosilphenylene and alkenyl-functional polyorganosiloxane. In both cases, for the intended use, the final product is a polyorganosiloxane containing both polyorganosiloxane units and oligosilphenylene units. Olefinically unsaturated, radically curable silphenylene polymers are not part of the teachings of these two specifications. SUMMARY OF THE INVENTION

[0015] Object and Subject Matter of the Invention: The object was to provide a polymer crosslinkable by free radicals which combines the advantageous properties of 3-dimensionally crosslinkable polyorganosiloxanes, such as excellent heat resistance, weathering stability, water repellency and flame retardancy, with improved dielectric properties, more particularly a lower dielectric loss factor, and which is suitable for use as a binder for metal laminate for electronic applications and is economically accessible.

[0016] This is in that in the form of a pure binder they have a dielectric loss factor of 0.0030 or less at 10 GHz, effectively wet any filler present which reduces the dielectric loss factor, enables the production of tack-free prepregs, produces a formulation compatible with organic polymers, cures under the effect of heat to give dimensionally stable moldings, and has good solubility in typical application solvents. The object is achieved by the present invention.

[0017] The subject of the present invention is a silphenylene polymer of the formula (I). R a R 1 b Si[Y[(SiR 2 c R 3 d ) e f g YSiR a R 1 b (I) (wherein, R may be the same or different radicals, a hydrogen radical or an olefinically or acetylenically unsaturated, aliphatic or cycloaliphatic hydrocarbon radical, R 2 are, independently of one another, the same or different radicals, R 2 may be a hydrogen radical or a saturated or olefinically or acetylenically unsaturated C bonded to Si-C which may be substituted by heteroatoms 1 ~C 18 ​​It may be a hydrocarbon radical, and oxygen atoms and silicon atoms are preferably heteroatoms, and the same radical R 2 In two or more oxygen atoms in, are always separated from each other by hydrocarbon units, and oxygen atoms and silicon atoms, both types of heteroatoms are one radical R 2 When present simultaneously in, not bonded to each other to form a Si-O unit, instead always separated from each other by hydrocarbon units, while the same radical R 2 Two or more Si atoms in may be bonded to each other by a direct Si-Si bond, and the Si atom is always tetravalent, and the remaining valences of the Si atom can be olefinic or acetylenic unsaturation, further Si-C bonded substituents, preferably C 1 ~C 12 Saturated by alkyl, cycloalkyl or aryl radicals, and R 2 may also contain heteroatoms in the same way, and may comprise an olefinic or acetylenic unsaturated functional group, R 2 may also be a hydroxyl radical, or is bonded to a silicon atom through an oxygen atom, is unsubstituted or substituted by a heteroatom, and has 1 to 18 carbon atoms, a monovalent aliphatic, cycloaliphatic or aromatic, Si-C bonded, organic hydrocarbon radical. )

[0018] Radical R 2 may also, in particular, be of the formula (II) [Y[(SiR 2 c R 3 d ) e f g YSiR a R 1 b (wherein Y, R, R 1 , R 2 , R 3 , a, b, c, d, e, f and g have the definitions indicated in the text).

[0019] ​​ R 1 and R 3 may, independently of one another, be identical or different radicals, be a hydrogen radical, or be unsubstituted or substituted by heteroatoms and be a monovalent aliphatic, cycloaliphatic or aromatic, Si-C-bonded, hydrocarbon radical having 1 to 18 carbon atoms, and the hydrocarbon radical may also be an unsaturated hydrocarbon radical, and in the unsaturated hydrocarbon radical, R 1 and R 3 may also be a hydroxyl radical or be bonded to the silicon atom through an oxygen atom, be unsubstituted or substituted by heteroatoms and be a monovalent aliphatic, cycloaliphatic or aromatic, Si-C-bonded, hydrocarbon radical having 1 to 18 carbon atoms.

[0020] Per silphenylene polymer of formula (I), at least one olefinically or acetylenically unsaturated radical R, R 1 , R 2 or R 3 must always be present, which is a condition of the present invention. Per silphenylene polymer of formula (I), preferably at least two such olefinically or acetylenically unsaturated radicals R, R 1 , R 2 or R 3 are present. The olefinically or acetylenically unsaturated radicals R and R 1 are always bonded here at the ends; the olefinically or acetylenically unsaturated radicals R 2 and R 3It is always bonded to the Si atoms (i.e., internally) present inside the polymer framework. Whether the olefinic or acetylenic unsaturated groups are present at the ends or internally is not particularly limited. Both are possible, and optionally, a hybrid form is also possible. However, it is a condition of the present invention that preferably at least two olefinic or acetylenic unsaturated groups are present on different Si atoms and not bonded to the same Si atom.

[0021] Radicals R, R bonded to oxygen 1 , R 2 and R 3 Regarding the number of, the total of all organic radicals bonded to the Si atom through the oxygen atom is 10 mol% or less, more preferably 8 mol% or less, more particularly 5 mol% or less, and particularly preferably less than 1 mol% based on the total of all radicals R, R 1 , R 2 and R 3 bonded to all Si. It should be noted that the fact that the radicals bonded to the Si atom through the oxygen atom are not desired in the silphenylene polymer of formula (I) of the present invention is to be considered here. They do not contribute to the improvement of the performance capabilities of the silphenylene polymer of the present invention, but instead, on the contrary, result in reduced performance capabilities. Therefore, it is most preferred that there are no radicals bonded to the Si atom through the oxygen atom in the silphenylene polymer of the present invention. However, the formation of such radicals cannot always be completely suppressed due to secondary reactions during synthesis. Therefore, although not preferred, a limited amount is tolerated according to the present invention. The best performance capabilities are achieved with complete avoidance of any Si-O bonds in the silphenylene polymer of the present invention.

[0022] The silphenylene polymer of the present invention preferably contains a structural group linked to Si—O of less than 10 mol %, more preferably less than 8 mol %, particularly preferably less than 5 mol %, and especially preferably less than 1 mol % of a structural group linked to Si—O. Here, the structural group linked to Si—O means not only the Si—O—Si framework unit but also an Si—O unit in which an oxygen atom is bonded to a silicon atom on one side and the radical bonded to the second oxygen is not bonded to oxygen through the silicon atom. It is more particularly preferred that the silphenylene polymer of the present invention does not contain Si—O—Si units. The silphenylene polymer of the present invention may be blended with a polyorganosiloxane and / or a polysiloxane-polysilphenylene copolymer and / or an organic polymer, and optionally used together with them if it is advantageous for the selected application. Such mixtures, and also mixtures containing an organic polymer, additives, fillers, dyes, etc. in addition to the silphenylene polymer of the present invention, are likewise according to the present invention.

[0023] Y is a chemical bond or a divalent to dodecavalent aromatic, alkylaromatic or cycloalkylaromatic or divalent to dodecavalent aliphatic or alicyclic radical having 1 to 48 carbon atoms and whose main chain does not contain heteroatoms, so the main chain does not have, for example, an ether or polyether structure, such a structure can instead only exist as a pendant radical optionally bonded to the main chain, Y may also contain an olefinic or acetylenic unsaturated functional group which may contain heteroatoms other than carbon atoms, such as N, P, O and S atoms, an oxygen atom is particularly preferred as a heteroatom in the functional group, and the presence of two or more oxygen atoms directly bonded to each other is excluded.

[0024] When the radical Y is not a chemical bond, it is always bonded to the silicon atom it crosslinks by an Si-C linkage. Y is preferably an aromatic, alkylaromatic, cycloalkylaromatic radical having a valence of 2 to 12. It is always the case that there are a greater number of such aromatic, alkylaromatic and cycloalkylaromatic radicals having a valence of 2 to 12 than aliphatic or alicyclic radicals having a valence of 2 to 12, and that the aliphatic or alicyclic radicals having a valence of 2 to 12 are present randomly and not in a regular arrangement with the aromatic, alkylaromatic, cycloalkylaromatic radicals having a valence of 2 to 12. This also means that the aromatic, alkylaromatic, cycloalkylaromatic radicals having a valence of 2 to 12 and the aliphatic or alicyclic radicals having a valence of 2 to 12 may be present in blocks, each case consisting of a greater number of aromatic, alkylaromatic, cycloalkylaromatic radicals having a valence of 2 to 12 or aliphatic or alicyclic radicals having a valence of 2 to 12 respectively.

[0025] A further condition imposed on the silphenylene polymers of the present invention is that there are always a greater number of radicals Y which are aromatic, alkylaromatic and cycloalkylaromatic radicals having a valence of 2 to 12 than radicals Y which are chemical bonds. Based on all crosslink-forming radicals Y as 100 mol%, at least 55 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, particularly at least 80 mol% are radicals Y which are aromatic, alkylaromatic and cycloalkylaromatic radicals having a valence of 2 to 12. In one particularly preferred form of the present invention, all radicals Y are aromatic, alkylaromatic and cycloalkylaromatic radicals having a valence of 2 to 12.

[0026] The silphenylene polymers of the present invention have an arbitrary composition, i.e., a random composition. The condition of a random composition is automatically achieved by the synthetic method used, which does not promote the formation of silphenylene polymers having aromatic unit-containing radicals Y that regularly alternate with aliphatic or alicyclic radicals Y.

[0027] Two or more radicals Y may have their definitions independently of each other. Therefore, two or more radicals Y may have different radicals within the range of the indicated definitions in the silylphenylene polymer of formula (I).

[0028] The definitions of the symbols are as follows: a is a number having a value of 1 or 2, preferably 1. b is a number having a value of 1 or 2, preferably 2, and the sum a + b = 3. c is a number having a value of 0, 1 or 2. d is a number having a value of 0, 1 or 2, and the sum c + d = 2. e is a number from 1 to 12, preferably from 1 to 6, more preferably from 1 to 3, and particularly 1. [(SiR 2 c R 3 d ) e When e in is a number greater than 1, two or more units of formula (SiR 2 c R 3 d ) are bonded to each other via Si-Si bonds to generate polysilane units such as disilane units and trisilane units according to the value of e. f is a number having a value of 1 to 12, particularly 1. g is a number having a value of 3 to 250, more preferably 4 to 150, and particularly 5 to 50.

[0029] Examples of radicals R other than hydrogen atoms are alkenyl radicals such as 7-octenyl, 5-hexenyl, 3-butenyl, allyl and vinyl radicals. Also included are acryloyloxy or methacryloyloxy radicals from acrylic acid or methacrylic acid, and also acrylic acid esters or methacrylic acid esters of unbranched or branched alcohols having from 1 to 15 carbon atoms. Preferred such radicals 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, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate and norbornyl acrylate. These radicals are preferably not directly bonded to the silicon atom, but instead are bonded via a hydrocarbon spacer which may comprise from 1 to 12 carbon atoms, preferably 1 or 3 carbon atoms, and which does not comprise heteroatoms other than the heteroatoms present in the acryloyloxy and / or methacryloyloxy radicals.

[0030] Radical R other than hydrogen atom 1 , R 2 and R 3Examples include saturated or unsaturated hydrocarbon radicals which may contain aromatic or aliphatic double bonds, such as alkyl radicals, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl radicals, hexyl radicals, for example n-hexyl radicals, heptyl radicals, for example n-heptyl radicals, octyl radicals, for example n-octyl radicals and isooctyl radicals, for example 2,2,4-trimethylpentyl and 2-ethylhexyl radicals, nonyl radicals, for example n-nonyl radicals, decyl radicals, for example n-decyl radicals, dodecyl radicals, for example n-dodecyl radicals, tetradecyl radicals, for example n-tetradecyl radicals, hexadecyl radicals, for example n-hexadecyl radicals, and octadecyl radicals, for example n-octadecyl radicals, cycloalkyl radicals, for example cyclopentyl, cyclohexyl and 4-ethylcyclohexyl radicals, cycloheptyl radicals, norbornyl radicals and methylcyclohexyl radicals, aryl radicals, for example phenyl, biphenyl, naphthyl and anthryl and phenanthryl radicals; alkaryl radicals, for example o-, m- and p-tolyl radicals, xylyl radicals and ethylphenyl radicals; aralkyl radicals, for example benzyl radicals, alkenyl radicals, for example 7-octenyl, 5-hexenyl, 3-butenyl, allyl and vinyl radicals, and also alpha- and beta-phenylethyl radicals.

[0031] Radical R 1 , R 2 and R 3 Preferred heteroatoms which may be present in R, R and R are oxygen atoms.

[0032] Furthermore, nitrogen atoms, phosphorus atoms, sulfur atoms and halogen atoms, for example chlorine atoms and fluorine atoms are also possible but are not preferred.

[0033] Preferred heteroatom-containing organic radicals R, R 1 , R2 and R 3 Examples of 2 and 3 are acryloyloxy or methacryloyloxy radicals from acrylic acid or methacrylic acid, and also acrylate or methacrylate esters of unbranched or branched alcohols having 1 to 15 carbon atoms. Preferred such radicals 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, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate and norbornyl acrylate.

[0034] These radicals are preferably not directly bonded to the silicon atom, but instead are bonded via a hydrocarbon spacer which may comprise 1 to 12 carbon atoms, preferably 1 or 3 carbon atoms, and which does not comprise heteroatoms other than those heteroatoms contained in the acryloyloxy and / or methacryloyloxy radicals.

[0035] Radical R 1 、R 2 and R 3 are preferably selected from methyl, phenyl, vinyl, acryloyloxy and methacryloyloxy radicals, and also acrylate or methacrylate esters of unbranched or branched alcohols having 1 to 15 carbon atoms.

[0036] More preferably, radicals R 1 、R 2 and R 3 which comprise further preferred heteroatoms are radicals of formula (III).

[0037] [Chemical formula]

[0038] In formula (III), R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are, independently of one another, a hydrogen radical, a hydrocarbon group or a hydrocarbon group substituted by a heteroatom, and always, at least one of the radicals R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is a hydrocarbon group bonded to a silicon atom via an Si-C bond, and this hydrocarbon group to which the radical of formula (III) is bonded via the silicon atom is preferably a C3 hydrocarbon group containing no heteroatom. Alternatively, the radicals R 4 , R 5 , R 6 , R 7 , R 8 and R 9 may also be chemical bonds, such that the radical of formula (III) is directly bonded to the silicon atom via an Si-C bond to an aromatic ring.

[0039] The radicals R 4 , R 5 , R 6 , R 7 , R 8 and R 9Examples include hydrogen radicals, saturated hydrocarbon radicals such as methyl, ethyl, n-propyl, isopropyl, primary, secondary and tertiary butyl radicals, hydroxyethyl radicals, aromatic radicals such as phenylethyl radicals, phenyl radicals, benzyl radicals, methylphenyl radicals, dimethylphenyl radicals, ethylphenyl radicals, heteroatom-containing radicals such as hydroxymethyl radicals, carboxyethyl radicals, methoxycarbonylethyl radicals and cyanoethyl radicals, and acrylate and methacrylate radicals such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate, and olefinically or acetylenically unsaturated hydrocarbon radicals.

[0040] Adjacent radicals R 4 and R 6 And also adjacent radicals R 5 and R 7 may also optionally be joined to each other to form the corresponding cyclic saturated or unsaturated radical to produce a fused polycyclic structure.

[0041] Examples of the phenol radicals of formula (III) are phenol radicals, ortho-, meta- or para-cresol radicals, 2,6-, 2,5-, 2,4- or 3,5-dimethylphenol radicals, 2-methyl-6-phenylphenol radicals, 2,6-diphenylphenol radicals, 2,6-diethylphenol radicals, 2-methyl-6-ethylphenol radicals, 2,3,5-, 2,3,6- or 2,4,6-trimethylphenol radicals, 3-methyl-6-tert-butylphenyl radicals, thymol radicals and 2-methyl-6-allylphenol radicals, which may optionally be substituted on the oxygen atom.

[0042] Preferred examples of the fluorine-containing radicals are trifluoropropyl, nonafluorohexyl and heptadecafluorooctyl radicals.

[0043] Y is preferably a crosslink-forming organic unit, preferably a crosslink-forming aromatic unit having from 1 to 24 carbon atoms between 2 and 12 carbosilyl units. Y is preferably divalent, trivalent or tetravalent, more particularly divalent.

[0044] Preferred crosslink-forming aromatic radicals Y are the radicals of formulae (IVa), (IVb) and (IVc).

[0045]

Chemical formula

[0046] (wherein the radicals R 10 , R 11 , R 12 and R 13 may be hydrogen radicals or hydrocarbon radicals which may be substituted or groups of the formula OR 14 (wherein R 14 is a hydrocarbon radical)). Here, adjacent radicals, for example, for example R 10 and R 12 or R 11 and R 13 in formula (IVa) may be linked to each other to form a cyclic radical and generate a fused ring system. Similar comments apply to adjacent radicals in formulae (IVb) and (IVc).

[0047] Typical examples of such crosslink-forming aromatic radicals are p-, m- or o-phenylene radicals, 2-methyl-1,4-phenylene radicals, 2-methoxy-1,4-phenylene radicals, and the p-phenylene radical is particularly preferred.

[0048] Optionally, two or more such radicals can also be linked to each other. For example, two or more units of formula (IVa), (IVb) and (IVc) are linked to each other, and this oligomeric crosslink-forming structural element exists through the bond of the corresponding carbon atom of the terminal aromatic ring to the silicon atom. Hybrid forms are also conceivable here. In other words, it consists not only of only one type of unit of formula (IVa), (IVb) or (IVc), but instead, oligomeric crosslink-forming units consisting of two or more, i.e., two or three, different types of repeating units corresponding to formula (IVa), (IVb) and (IVc) are also conceivable. The aromatic units in this case may be directly bonded to each other, or they may be linked to each other through a crosslink-forming group, such as an alkanediyl unit, such as a methylene group, 1,2-ethanediyl group, 1,1-ethanediyl group, 2,2-dimethylpropyl group or a sulfone group, etc.

[0049] Further examples of aromatic crosslink-forming units that may also contain heteroatoms are those in which two optionally substituted phenol rings are crosslinked via an alkanediyl or other unit. Typical representative examples are the 2,2-bis(4-hydroxyphenyl)propane radical (substituted bisphenol A radical), 2,2-bis(4-hydroxyphenyl)methane radical (substituted bisphenol F radical), bis(4-hydroxyphenyl)sulfone radical (bisphenol S radical) together with substitution on the phenolic oxygen. The phenolic oxygen atom is typically substituted by a radical of the -(C 3 H 6 )- type, and the -(C 3 H 6 )- radical forms a crosslink by Si-C bonding to the silicon atom.

[0050] Preferred radicals Y that are not crosslinked by aromatic units are, in addition to chemical bonds, alkanediyl, alkenediyl, and alkynediyl radicals, which may optionally contain heteroatoms and may contain aromatic groups as substituents, but do not undertake or contribute to the crosslinking formation function in these radicals.

[0051] Typical examples are the methylene radical, methine radical, quaternary carbon, 1,1-ethanediyl and 1,2-ethanediyl groups, 1,4-butanediyl and 1,3-butanediyl groups, 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 groups, 1,2-diphenylethanediyl group, 1,2-phenylethanediyl group, 1,2-cyclohexylethanediyl group. If the linear crosslink-forming unit has more than one carbon atom and the substitution pattern allows it, each of these groups may also exert its crosslinking effect not only through alpha-omega connection, i.e., through the first and last atoms of each linear unit, but also through any other connection, i.e., through the use of other chain carbon atoms, for crosslinking formation. Further, typical examples are not only the linear representative examples of the crosslink-forming hydrocarbons described, but also their isomers, which may then exert their crosslinking effect through the bonding of different carbon atoms of the hydrocarbon structure to silicon atoms.

[0052] Examples of particularly preferred radicals from the group of non-aromatic, heteroatom-free hydrocarbon radicals are -CH 2 CH 2 -,-CH(CH 3 )-,-CH=CH-,-C(=CH 2 )-and -C≡C-.

[0053] Examples of typical fluorine-substituted crosslink-forming radicals Y are -C(CF 3 ) 2 -,-C(H)F-C(H)F-and -C(F2 )-C(F 2 ) is a radical.

[0054] Examples of typical heteroatom-containing, non-aromatic crosslink-forming radicals are, for example, divalent hydrocarbon radicals containing a secondary or tertiary alcohol functional group, a keto and carboxylic acid and an ester functional group, or having a pendant ether chain. Here, pendant means that each radical has its origin in the carbon atom of radical Y, but the end of the radical is not bonded to the Si atom that is bonded to a further Si atom via the crosslink-forming radical. As a result, this radical does not contribute to the network structure.

[0055] All descriptions should be understood only as illustrative and non-limiting.

[0056] As will be described later, a preferred method for preparing the silphenylene polymers of the present invention lies in the application of synthesis in the manner of the Grignard reaction. Although described herein as an example, radicals that are not inert to magnesium are not tolerated and are correspondingly converted in such reactions. Nevertheless, in order to obtain them in the silphenylene polymers of the present invention, the radicals used in the Grignard reaction are initially only radicals that are inert to magnesium, which are subsequently generated in the precursors obtained from the Grignard reaction according to the known prior art. Examples of such radicals are radicals containing a carbonyl group, such as acrylic or methacryloyloxy radicals.

[0057] The silphenylene polymers of the present invention may vary in viscosity over a wide range or, alternatively, may be solid, depending on the average number of structural units forming them per molecule.

[0058] The liquid silphenylene polymer of the present invention in the uncrosslinked state at 25 °C has a viscosity of 20 to 8,000,000 mPas, preferably 200 to 5,000,000 mPas, more particularly 250 to 3,000,000 mPas.

[0059] The solid silphenylene polymer of the present invention in the uncrosslinked state has 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.

[0060] The silphenylene polymer of the present invention may, in principle, be obtained by any method leading to the formation of a bond between Si atoms and carbon atoms. Typical representatives of such reactions are the Grignard reaction, the coupling reaction in the Wurtz synthesis mode, optionally accompanied by adaptation in the synthesis profile, and the hydrosilylation reaction. All of these types of reactions are basically prior art and are thus known to those skilled in the art. For a basic overview of further organometallic reactions for the formation of Si-C bonds, reference may be made to the silicon chemistry module of the University of Freiburg, accessible using the following link: https: / / tu-freiberg.de / sites / default / files / media / institut-fuer-anorganische-chemie-10441 / lehre / kroke / siliciumchemie5.pdf

[0061] Hints and information regarding the procedure in the case of Grignard synthesis can be found, for example, in Synthesis of Silphenylene-Containing Siloxane Resins Exhibiting Strong Hydrophobicity and High Water Vapor Barriers, Xunjun Chen, Minghao Yi, Shufang Wu, Lewen Tan, Yixin Xu, Zhixing Guan, Jianfang Ge and Guoqiang Yin, Coatings 2019, 9, 481.

[0062] For the preparation of the silphenylene polymer of the present invention, it is necessary to pay attention to the appropriate selection of reaction conditions and raw materials.

[0063] As already pointed out in the prior art discussion, the hydrosilylation reaction is not preferred for the preparation of the silphenylene polymers of the present invention. European Patent No. 0913420 describes the raw materials required to effect the hydrosilylation reaction for obtaining the silphenylene-silalkylene polymers described in European Patent No. 0913420. These are dicyclophenylsilane and cyclophenylsilane having olefinically unsaturated ends, or diunsaturated silanes. The corresponding cyclophenyl starting materials are then accessible through Grignard reactions. This is no different in the case of the cyclophenyl polymers of the invention herein. This means that hydrosilylation represents a disadvantage due to additional steps, increased costs and complexity, and hence reduced profitability, compared to Grignard synthesis or Wurtz synthesis or any other procedure that directly supplies the cyclophenyl polymers of the present invention. In the case of the present invention, furthermore, considering that there are no regularly alternating structural elements in the polymer framework and that, as in the case of European Patent No. 0913420, the polymer instead has a random composition, a relatively large number of suitable raw materials are required for a successful hydrosilylation route to the cyclophenyl polymers of the present invention and, perhaps, for a specific synthetic strategy that enables a composition according to the present invention. Overall, therefore, the hydrosilylation reaction is in principle applicable for obtaining the cyclophenyl polymers of the present invention, but it requires considerably more additional cost and complexity compared to methods such as Wurtz or Grignard synthesis.

[0064] The hydrosilylation reaction is thus not preferred as a synthetic route to the cyclophenyl polymers of the present invention, in contrast to the cyclophenyl-silalkylene polymers and cyclophenyl-siloxane copolymers described in the known prior art. The novel state of the art described herein is best realized using a method different from the preferred methods according to the already known prior art.

[0065] A preferred method for preparing the silphenylene polymer of the present invention involves magnesium-mediated Si-C bond formation in the manner of a Grignard reaction. Through this method, it is possible to obtain the silphenylene polymer of the present invention in a single process step and thus with maximum profitability at the required purity.

[0066] For the preferred method for preparing the silphenylene polymer of the present invention, silicon-containing compounds of formulas (IV), (V), and (VI) are used: R 15 h R 16 i Si (IV), R 15 j R 16 k Si[SiR l 17 R m 18 n SiR j 15 R k 16 (V), R 15 j R 16 k Si[SiR l 17 R m 18 n -X 1 -[SiR l 17 R m 18 n SiR 15 j R 16 k (VI) (wherein R 15 is a halogen atom or a C1-C3 alkoxy group, preferably a chlorine, bromine or iodine atom or a methoxy radical, more particularly a Cl atom or a methoxy radical, and two or more radicals R 15 may be different radicals from the group described; in particular, two or more radicals R 15 ​​​may be both a halogen radical and an alkoxy radical, and R 16 、R 17 and R 18 are, independently of one another, radicals from the group of radicals R, R 1 、R 2 or R 3 but not radicals of formula (II), and R 18 may additionally be a halogen radical or a C1-C3 alkoxy radical, and the radicals R 16 、R 17 and R 18 do not contain a functional group comprising a carbonyl or carboxyl group, a hydroxyl group, a double-bonded nitrogen atom, a primary, secondary or tertiary amine group or a thiol group, and as a result, the radicals R 16 、R 17 and R 18 are inert towards magnesium).

[0067] X 1 is a chemical bond or does not contain a functional group comprising a carbonyl or carboxyl group, a hydroxyl group, a double-bonded nitrogen atom, a primary, secondary or tertiary amine group or a thiol group, and the hydro-silylation of an olefinically or acetylenically unsaturated precursor Z of formula R 19 -X 2 -R 19 (wherein R 19 is an olefinically or acetylenically unsaturated, hydro-silylatable C2-C8 radical, and X 2 is a radical X 1 shortened on either side by C2-C8) gives a magnesium-inert divalent crosslink-forming aliphatic, cycloalkylaliphatic, cycloalkylaromatic or alkylaromatic hydrocarbon radical. Examples of alicyclic, cyclic aromatic or aromatic hydrocarbon radicals X 2 are those already described for Y, X 2Regarding, the radical from the group of acceptable radicals Y is subject to the limitation that it is only a radical that is inert to magnesium. h is an integer having a value of 1, 2, 3 or 4, preferably 1, 2 or 3, and i is an integer having a value of 0, 1, 2 or 3, and the sum h + i = 4. j is a number having a value of 0, 1, 2 or 3. For at least one terminal Si atom of the di-, oligo- or polysilane of formula (V), j has a value of 1, and there is always at least one radical R per molecule of formula (V) 15 present, k is an integer having a value of 0, 1, 2 or 3, and k + j = 3. l and m are each numbers having a value of 0, 1 or 2, and l + m = 2. n is a number having a value of 0 to 50, preferably 0 to 30.

[0068] The radical X bonded to the Si atom at its boundary through hydrosilylation 1 The compound of formula (VI) containing is preferably obtained by hydrosilylation of the precursor Z with a Si-H functional, silicon-containing compound of formula (VII): R 15 j R 16 k Si[SiR l 17 R m 18 n -H (VII) (wherein R 15 , R 16 , R 17 and R 18 , and also j, k, l and m have the definitions indicated above, and H is a hydrogen atom). For n = 0, (VII) is a halosilane or alkoxysilane; for n > 0, (VII) is a halogenated or alkoxylated di-, oligo- or polysilane. Hybrid forms are also conceivable, in which case R 15 ​is both a halogen radical and an alkoxy radical in the same molecule.

[0069] Similar to the raw materials for the preparation of the compound of formula (VI), the compounds of formula (VII) may also be used to prepare the silphenylene polymers of the present invention, in which case they can participate in the Grignard reaction preferably used to prepare the silphenylene polymers of the present invention through halogen radicals and / or alkoxy radicals.

[0070] Typical examples of the silanes of formula (IV) are methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldichlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylsilanol, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldichlorosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, triphenylethoxysilane, diphenylmethylchlorosilane, diphenylmethoxysilane, diphenylmethyldiethoxysilane, phenyldimethylchlorosilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane and vinyldimethylethoxysilane, trichlorosilane, trimethoxysilane, triethoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, dimethylchlorosilane, dimethylmethoxysilane, dimethylethoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane and tetrachlorosilane. Particularly preferred silanes of formula (IV) are methyltrichlorosilane, methyltrimethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenylmethyldichlorosilane and phenylmethyldimethoxysilane. The silanes of formula (IV) may also be used in the form of a mixture. For example, it is preferred to use a mixture of silanes which is mixed with a terminating silane for chain formation and crosslinking. The description of the examples should be understood as illustrative and not limiting.

[0071] Typical examples of the di-, oligo- and polysilanes of formula (V) are hexachlorodisilane, hexamethoxydisilane, hexaethoxydisilane, dimethyltetrachlorodisilane, dimethyltetramethoxydisilane, dimethyltetraethoxydisilane, trimethyltrichlorodisilane, trimethyltrimethoxydisilane, trimethyltriethoxydisilane, tetramethyldichlorodisilane, tetramethyldimethoxydisilane, tetramethyldiethoxydisilane, dimethylvinyltrichlorodisilane, dimethylvinyltrimethoxydisilane, dimethylvinyltriethoxydisilane, diphenyltetrachlorodisilane, diphenyltrimethoxydisilane, diphenyltetraethoxydisilane, diphenylvinyltrichlorodisilane, diphenylvinyltrimethoxydisilane, diphenylvinyltriethoxydisilane, tetravinyldichlorodisilane, tetravinyldimethoxydisilane, tetravinyldiethoxydisilane, divinyltetrachlorodisilane, tetravinyldimethoxydisilane, tetravinyldiethoxydisilane, trimethyldichlorodisilane, trimethyldimethoxydisilane, trimethyldiethoxydisilane, octachlorotrisilane, octamethoxytrisilane, octaethoxytrisilane, tetramethyltetrachlorotrisilane, tetramethyltetramethoxytrisilane, tetramethyltetraethoxytrisilane, hexamethyldichlorotrisilane, hexamethyldimethoxytrisilane, hexamethyldiethoxytrisilane, pentamethyltrichlorotrisilane, pentamethyltrimethoxytrisilane, pentamethyltriethoxytrisilane, diphenyldivinyltetrachlorotrisilane, diphenyldivinyltetramethoxytrisilane, diphenyldivinyltetraethoxytrisilane, diphenyldimethylvinyltrichlorotrisilane, diphenyldimethylvinyltrimethoxytrisilane, diphenyldimethylvinyltriethoxytrisilane, tetramethyltrichlorotrisilane, tetramethyltrimethoxytrisilane, tetramethyltriethoxytrisilane, hexamethylchlorotrisilane, hexamethylmethoxytrisilane, hexamethylethoxytrisilane, pentamethyldichlorotrisilane, pentamethyldimethoxytrisilane, pentamethyldiethoxytrisilane, diphenyldivinyltrichlorotrisilane,Diphenyldivinyltrimethoxysilane, diphenyldivinylethoxysilane, diphenyldimethylvinyltrichlorosilane, diphenyldimethylvinyldimethoxysilane, diphenyldimethylvinyldiethoxysilane, nonamethylnonachlorooctasilane, nonamethylnonamethoxyoctasilane, nonamethylnonaeethoxyoctasilane, heptamethyldiphenylnonachlorooctasilane, heptamethyldiphenylnonamethoxyoctasilane, heptamethyldiphenylnonaeethoxyoctasilane, heptamethyldiphenyldivinylheptachlorooctasilane, heptamethyldiphenyldivinylheptamethoxyoctasilane, heptamethyldiphenyldivinylheptaeethoxyoctasilane, heptamethyltetraphenylheptachlorooctasilane, heptamethyltetraphenylheptamethoxyoctasilane, heptamethyltetraphenylheptaeethoxyoctasilane, wherein the methyl, phenyl, ethyl, vinyl and Si-H groups and chloro and / or methoxy and ethoxy groups, with compliance with the rule that each Si atom is tetravalent, may be randomly distributed over the silicon atoms. The description should be understood as illustrative and not limiting. Instead of the Si atoms being substituted purely by Cl atoms or by methoxy or ethoxy groups only, representative examples with mixed Cl, methoxy and / or ethoxy functionality are also possible in the exemplary molecules of formula (V) and belong to typical examples as well.,

[0072] Typical examples of the di, oligo and polycarbosilanes of formula (VI) are as follows: Cl(CH 3 ) 2 Si-CH 2 CH 2 -Si(CH 3 ) 2 Cl, Cl 2 (CH 3 )Si-CH 2 CH 2 -Si(CH 3 ) 2 Cl, Cl 2 (CH 3 )Si-CH 2 CH 2-Si(CH 3 )Cl 2 、Cl 3 Si-CH 2 CH 2 -SiCl 3 、Cl(CH 3 ) 2 Si-CH=CH-Si(CH 3 ) 2 Cl、Cl 2 (CH 3 )Si-CH=CH-Si(CH 3 ) 2 Cl、Cl 2 (CH 3 )Si-CH=CH-Si(CH 3 )Cl 2 、Cl 3 Si-CH=CH-SiCl 3 、Cl(CH 3 ) 2 Si-(CH 2 ) 3 (C 6 H 4 )(CH 2 ) 3 -Si(CH 3 ) 2 Cl、Cl 2 (CH 3 )Si-(CH 2 ) 3 (C 6 H 4 )(CH 2 ) 3 -Si(CH 3 ) 2 Cl、Cl 2 (CH 3 )Si-(CH 2 ) 3 (C 6 H 4 )(CH 2 ) 3 -Si(CH 3 )Cl 2 、Cl 3 Si-(CH 2 ) 3 (C 6 H 4 )(CH 2 ) 3 -SiCl 3 、Cl(CH 3)Si-Si(CH 3 ) 2 -(CH 2 ) 3 (C 6 H 4 )(CH 2 ) 3 -(CH 3 ) 2 Si-Si(CH 3 ) 2 Cl、Cl(CH 3 ) 2 Si-(CH 2 ) 3 (C 6 H 4 )-(C 6 H 4 )(CH 2 ) 3 -Si(CH 3 ) 2 Cl、Cl 2 (CH 3 )Si-(CH 2 ) 3 (C 6 H 4 )-(C 6 H 4 )(CH 2 ) 3 -Si(CH 3 ) 2 Cl、Cl 2 (CH 3 )Si-(CH 2 ) 3 (C 6 H 4 )-(C 6 H 4 )(CH 2 ) 3 -Si(CH 3 )Cl 2 、Cl 3 Si-(CH 2 ) 3 (C 6 H 4 )-(C 6 H 4 )(CH 2 ) 3 -SiCl 3 、Cl(CH 3 ) 2 Si-CH 2 CH 2 -Si(CH3 )(CH=CH 2 )Cl、Cl(CH 3 )(CH=CH 2 )Si-CH 2 CH 2 -Si(CH 3 )(CH=CH 2 )Cl、Cl(CH 3 )(CH=CH 2 )Si-(CH 2 ) 3 (C 6 H 4 )(CH 2 ) 3 -Si(CH 3 )(CH=CH 2 )Cl、Cl(CH=CH 2 ) 2 Si-(CH 2 ) 3 (C 6 H 4 )(CH 2 ) 3 -Si(CH=CH 2 ) 2 Cl、Cl(CH 3 )(H)Si-(CH 2 ) 3 (C 6 H 4 )(CH 2 ) 3 -Si(CH 3 )(H)Cl、Cl(H) 2 Si-(CH 2 ) 3 (C 6 H 4 )(CH 2 ) 3 -Si(H) 2 Cl、 In each case, instead of a chlorine atom, a methoxy group or an ethoxy group may be included in the exemplary molecules of formula (VI), and optionally, mixed Cl, methoxy and / or ethoxy functionality may be present, and representative examples belonging to typical examples may also be formed. The description should be understood by way of example and not by way of limitation.

[0073] Suitable organic raw materials for the preparation of the silphenylene of the present invention are organic raw materials of formula (VIII): [Hal] o -Y (VIII) (wherein Hal is a Cl, Br or iodine atom, preferably a Cl or Br atom, o is a number from 2 to 12, preferably 2, and Y has the definition indicated above therefor).

[0074] Typical examples of the organic raw material of formula (VIII) result from the description of the examples for radical Y, together with a free valence saturated by a halogen atom. Particularly preferred representative examples of formula (VIII) are dihalobenzenes such as 1,4-dibromobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene, 1,2-dibromobenzene, 1,2-dichloroethane, 1,2-dibromoethane, 1,1-dichloroethane, 1,1-dibromoethane, 1,4-dichlorobutane, 1,4-dibromobutane, 1,3-dichlorobutane, 1,3-dibromobutane, 1,5-dichloropentane, 1,5-dibromopentane, 1,6-dichlorohexane, 1,6-dibromohexane, 1,7-dichloroheptane, 1,7-dibromoheptane, 1,8-dichlorooctane, 1,8-dibromooctane, 1,9-dichlorononane, 1,9-dibromononane, 1,10-dichlorodecane, 1,10-dibromodecane, 1,11-dichloroundecane, 1,11-dibromoundecane, 1,12-dichlorododecane, 1,12-dibromododecane, 1,2-dichlorodiphenylethane, 1,2-dibromodiphenylethane, 1,2-dichlorocyclohexylethane, 1,2-dibromocyclohexylethane, 2-methyl-1,4-dichlorobenzene, 2-methyl-1,4-dibromobenzene, 2-methoxy-1,4-dichlorobenzene, 2-methoxy-1,4-dibromobenzene, 2-ethyl-1,4-dichlorobenzene, 2-ethyl-1,4-dibromobenzene, 2-ethoxy-1,4-dichlorobenzene, 2-ethoxy-1,4-dibromobenzene, 2-n-propyl-1,4-dichlorobenzene, 2-n-propyl-1,4-dibromobenzene, 2-n-propoxy-1,4-dichlorobenzene, 2-n-propoxy-1,4-dibromobenzene, 2-isopropyl-1,4-dichlorobenzene, 2-isopropyl-1,4-dibromobenzene, 2-n-butyl-1,4-dichlorobenzene, 2-n-butyl-1,4-dibromobenzene, 2-sec-butyl-1,4-dichlorobenzene, 2-sec-butyl-1,4-dibromobenzene, 2-tert-butyl-1,4-dichlorobenzene, 2-tert-butyl-1,4 - dibromobenzene, polyhalogenated biphenylenes such as dibromobiphenyl, tribromobiphenyl, tetrabromobiphenyl, pentabromobiphenyl, hexabromobiphenyl, heptabromobiphenyl, octabromobiphenyl, nonabromobiphenyl, decabromobiphenyl and the corresponding polychlorinated biphenylene analogs, 4 - chlorobenzhydryl chloride, 4 - bromobenzhydryl bromide, diphenyldichloromethane, diphenyldibromomethane, 1,2 - diphenyl - 1,2 - dichloroethane, 1,2 - diphenyl - 1,2 - dibromoethane, 1,1'-(2,2,2 - trichloroethane - 1,1 - diyl)bis(4 - chlorobenzene), hexachlorocyclohexane, 1,2,4,5,6,7,8,8 - octachloro - 3a,4,7,7a - tetrahydro - 4,7 - methanoindane (chlordane), 1,2,3,4,10,10 - hexachloro - 6,7 - epoxy - 1,4,4a,5,6,7,8,8a - octahydro - 1,4 - endo - 5,8 - exo - dimethanonaphthalene (dieldrin), 1 - bromo - 4 - chlorobenzene, 4,4'-(propane - 2,2 - diyl)bis(2,6 - dibromophenol) (tetrabromobisphenol A), 3,5,3',5' - tetrachlorobisphenol A.,

[0075] Preferred representative examples of formula (VIII) are 1,4 - dibromobenzene, 1,4 - dichlorobenzene, 1,2 - dichloroethane and 1,2 - dibromoethane. Optionally, mixtures of different representative examples of formula (VIII) can be used.,

[0076] The description, like all other descriptions of typical examples, should be understood as illustrative rather than limiting.,

[0077] Magnesium is preferably used in a form having a large surface area, i.e., as a metal in the form of, for example, turnings, granules or powder. Magnesium is preferably used in a minimum amount defined by the following equation: p=(q / 2)+r.,

[0078] Here, p represents the number of moles of magnesium, q is the number of halogen and alkoxy equivalents from compounds (IV), (V), (VI), (VII) and (VIII), and r is a value between 0 and half of the halogen and alkoxy equivalents used respectively from compounds (IV), (V), (VI), (VII) and (VIII), and an r value of 0 is not included. In other words, r is always greater than 0 and has a maximum value of q / 2. Magnesium is used in excess compared to the number of halogen atoms and alkoxy groups.

[0079] To promote the reaction, a solvent inert to the reactants is used in a preferred method for preparing the silylphenylene polymer of the present invention. Here, it is in principle possible to use substances typically used as inert solvents in the reaction of a metal with an organic halogen compound, and these are, more particularly, ethers such as diethyl ether, di-n-butyl ether, tert-butyl methyl ether, tetrahydrofuran, 1,4-dioxane, or hexamethylphosphoramide, and these may optionally also be used in mixtures with each other and optionally also in mixtures with further inert solvents such as toluene, xylene or ethylbenzene. However, in that case, it should be ensured that the solvent used is actually inert to the reactants. For example, the Si-Cl containing components of formulas (IV), (V), (VI) and (VII) react with THF upon ring opening to form butoxy groups, and the butoxy groups are inserted into the silylphenylene polymer by reaction when they are formed, and form unwanted alkoxy groups which can in principle react for hydrolysis to form silanol groups, and the silanol groups can then undergo condensation to form similarly unwanted Si-O-Si units. As will be seen later, since the workup is carried out aqueously, optionally using an acid such as hydrochloric acid, this reaction can occur during the workup. This secondary reaction produces silylphenylene-polysiloxane copolymers which are not in accordance with the present invention.

[0080] In the prior art directed to the preparation of silphenylene-polysiloxane polymers containing polysiloxane units, for example according to US Patent No. 3,350,350, this situation has not been paid attention to, because in that case the formation of the siloxane units is not inconsistent with the invention. However, in the case of the present application, this is different. In the present application, in particular, the selected method for preparing the silphenylene polymer of the present invention is novel. In the case of the present application, together with the Si-Cl-containing components of formulas (IV), (V), (VI) and (VII), the candidate solvents are only those that are inert to chlorosilanes, such as 1,4-dioxane and hexamethylphosphoramide. For example, the use of THF is actually possible, but only in the case of being used together with the alkoxy-functional components of formulas (IV), (V), (VI) and (VII).

[0081] A preferred method for preparing the silphenylene polymer of the present invention is preferably carried out at a temperature of -78 °C to 150 °C under atmospheric pressure. Optionally, higher or lower pressures may also be used. The method is conveniently carried out in an atmosphere inert to the reaction participants, composed of nitrogen or argon, and the best possible implementation is to apply means of suitable prior art, such as baking under reduced pressure, etc., to specifically exclude the entry of water as a coating on liquids, vapors or containers and also on magnesium.

[0082] A preferred method for preparing the silphenylene polymer of the present invention is preferably carried out stepwise by first reacting component (VIII) with magnesium and, in a second step, adding the required selections of components (IV), (V), (VI) and (VII) respectively. However, the method may also be carried out in one step, and the component of formula (VIII) may be reacted in the presence of the required selections from the components of formula (IV), (V), (VI) and optionally (VII). To activate the magnesium, it is advantageous first to combine, for example, 10 weight percent of the total amount of component (VIII), a portion of component (VIII) with the magnesium.

[0083] The reaction product obtained in the preferred method may be isolated in the same manner as is usually done for the isolation of reaction products obtained in organometallic synthesis, particularly Grignard synthesis. The resulting reaction mixture is preferably mixed with water at 0 to 30 °C. In this case, hydrochloric acid is formed from the still present Si-Cl groups and silanol groups are generated leading to condensation and the formation of Si-O-Si units, both of which are undesirable, so that complete or very nearly complete conversion of all of the halogen radicals involved in the reaction should be ensured prior to work-up. The same applies to the alkoxy groups bonded to Si that are still present during the addition of water. These groups can also be hydrolyzed to form silanol groups having the ability to condense. For this reason, in contrast to the prior art Grignard-like synthesis for the preparation of polysilarylene siloxanes, for example according to US Patent No. 3350350, the amount of magnesium used in the case of the present application is not an amount equivalent to the amount of halogen atoms and alkoxy groups used; instead, an excess of magnesium is used. Optionally, it is also possible to use, for example, an acid for work-up, such as hydrochloric acid, for example to adjust the pH or to promote the formation of magnesium halide.

[0084] The water-soluble salt components are subjected to aqueous extraction, while the insoluble fraction, in the case of solids such as magnesium or salts of magnesium, is removed by methods of the prior art, such as filtration or centrifugation.

[0085] The volatile components of the reaction mixture are removed by means of the prior art, such as continuous or batch distillation, for example, to obtain the reaction product in pure form. If the reaction products are desired as preparations in a solvent, they may subsequently be dissolved in a selected solvent or, alternatively, may be obtained directly as the desired preparation by solvent exchange from the reaction solvent. Solvent exchange is also carried out according to known prior art.

[0086] If it is desired that the silylphenylene polymer obtained as the primary product from a preferred method be further modified, for example, through the introduction of functional groups that are not stable under the conditions of a Grignard synthesis, it may be advantageous to introduce suitable functional groups into the primary silylphenylene polymer in a Grignard-like synthesis step. In this case, it should be noted that the initially obtained silylphenylene polymer already fulfills all the features of the invention as it is and is thus invention-compliant according to the present invention. From the prior art, it is known that the carbonyl groups of aldehydes, ketones and carboxylic acids, as well as also their esters, are converted to alcohols by the Grignard reaction. Thus, if a carbinol group is desired for the subsequent introduction of functional groups, one possibility for this is to use a correspondingly carbinol-functional starting material and, for example, by the selection of suitable components of formula (VIII), to use a carbonyl or epoxy-functional starting material. Since the Grignard reagent is consumed both in the presence of alcohol and in the reaction of the carbonyl group, additional requirements for the Grignard reagent must be taken into account. Considering that this procedure may endanger the economy of the method in certain situations, this procedure is not preferred but is possible in principle and is thus included as according to the present invention.

[0087] Through the reaction of this type of carbonyl group with acryloyl, methacryloyl or chloropropionyl chloride, for example, acrylate groups or methacrylate groups can be introduced into the silphenylene polymers of the present invention. In the case of the reaction of methacrylic acid and acrylic acid with acyl chlorides, the corresponding methacrylic acid or acrylic acid esters are formed after the elimination of HCl, which may be optionally promoted using a suitable amine, such as a tertiary amine. In the case of chloropropionyl chloride, the product of the first step is an ester of chloropropionic acid, and from this ester, acrylic acid radicals are formed in the second step, for example, by a basic workup using a tertiary amine and by the elimination of HCl from the propionyl chloride radical. All of the reactions are themselves prior art and thus not novel per se. However, their use for the preparation of the silphenylene polymers which are the subject of the present invention is novel, and consequently these steps are included within the scope of the present invention as components of a preferred method for preparing the silphenylene polymers of the present invention.

[0088] All of the silphenylene polymers of formula (I) have at least olefinically or acetylenically unsaturated functional groups through which they can be chemically crosslinked. Possible chemical crosslinking reactions here may be initiated by known prior art reactions, more particularly by means of a suitable radiation source, such as UV light, or by means of unstable chemical compounds which decompose into radicals, radical crosslinking, and addition crosslinking, for example, by means of hydrosilylation of olefinically unsaturated groups with Si-H functional groups in the presence of a suitable hydrosilylation catalyst. Si-H functional groups may also be bonded to the silphenylene polymers of the present invention.

[0089] To achieve sufficient curing, a sufficient amount of functional groups must be present. To achieve sufficient curing, there must be at least an average of 1.0 functional groups per silphenylene polymer molecule used in the present invention; preferably, there are at least an average of 1.1, more particularly at least an average of 1.2 per silphenylene polymer molecule of the present invention. The functional groups here may be different. For example, some of the functional groups are Si-H groups, and some of the other functional groups represent olefinically unsaturated groups that are radically curable or suitable for hydrosilylation. 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 that is radically curable is present, for example, only a functional group having olefin or acetylene unsaturation, then a corresponding number of these functional groups must be present. In the sense of copolymerization to form a homogeneous matrix, it should be ensured here that there is sufficient copolymerizability in the selected portions of the olefin and acetylene groups. Combinations of olefin groups that are not copolymerizable with each other are also possible, provided that the resulting matrix, which comprises two or in some cases more individual polymers, remains mutually compatible and does not form separate phases that are distinguishable as separate domains from each other.

[0090] Here, examples of suitable initiators for initiating 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 peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl cumyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butyl peroxycyclohexane, 2,2-di(tert-butyl peroxy)butane, bis(4-tert-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dibenzyl peroxydicarbonate, diisopropylbenzene dihydroperoxide, [1,3-phenylenebis(1-methylethylidene)]bis[tert-butyl] peroxide, 2,5-dimethyl-2,5-di-(tert-butyl peroxy)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 peroxypivalate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl monoperoxymaleate. This listing is not limiting and is merely illustrative. Optionally, it is also possible to use a mixture of different initiators for the radical reaction.

[0091] The suitability of an initiator or initiator mixture for a radical reaction depends on its decomposition kinetics and the requirements to be met. By paying sufficient attention to these boundary conditions, a person skilled in the art can appropriately select an initiator.

[0092] In the case of preparations that also contain hydrogen bonded to silicon, in addition to olefinic and acetylenic unsaturated groups, there is a possibility of curing through a hydrosilylation reaction. Suitable catalysts for promoting the hydrosilylation reaction are known catalysts from the prior art.

[0093] Examples of such catalysts are compounds or complexes from the group of noble metals, preferably metal catalysts from the group of platinum metals or compounds and complexes from the group of platinum metals, including platinum, ruthenium, iridium, rhodium and palladium. Examples of such catalysts may be present on supports such as silicon dioxide, aluminum oxide or activated carbon, metallic and finely divided platinum, as well as compounds or complexes of platinum, such as platinum halides, e.g., PtCl 4 、H 2 PtCl 6 x6H 2 O、Na 2 PtCl 4 x4H 2 O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-aldehyde complexes, H 2 PtCl 4 x6H 2Platinum-ketone complexes, platinum-vinyl-siloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, bis(γ-picoline)platinum chloride, trimethylenedipyridine platinum chloride, dicyclopentadiene platinum dichloride, dimethylsulfoxyethenylplatinum(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 in a solution of 1-octene with sec-butylamine, or ammonium-platinum complexes, which contain the reaction product of O and cyclohexane. A further embodiment of the method of the present invention uses a complex of iridium with cyclooctadiene, such as μ-dichlorobis(cyclooctadiene)diiridium(I).

[0094] This description is merely illustrative and not limiting.

[0095] The development of hydrosilylation catalysts is an active research area that constantly yields new active species, which may of course also be used in the present invention.

[0096] The hydrosilylation catalyst preferably comprises a platinum compound or complex, preferably a platinum chloride and a platinum complex, more particularly a platinum-olefin complex, and particularly preferably a platinum-divinyltetramethyldisiloxane complex.

[0097] In the method of the present invention, the hydrosilylation catalyst is used in an amount of 2 to 250 ppm by weight, preferably 3 to 150 ppm by weight, more particularly 3 to 50 ppm by weight.

[0098] In one preferred embodiment, the silphenylene polymer of formula (I) in the third step is applied to a metal substrate.

[0099] The silphenylene polymer of formula (I) is particularly suitable for use as a binder and / or as an adhesion promoter for the production of metal-coated laminates, especially for electronic applications, in particular for metal surface laminates, and especially for high-frequency applications, in particular for high-frequency applications operating at frequencies above 1 GHz. In particular, the production of metal surface electro-laminates of the type used for the production of circuit boards in electronic devices for high-frequency applications is particularly preferred.

[0100] The above metal surface electro-laminates may contain a reinforcing material, but do not necessarily require it. This means that they may or may not contain, for example, a reinforcing fabric, such as a fiber woven fabric or non-woven fabric. If a reinforcing material is included, it is preferably arranged in a layer. In this case, the reinforcing layer may be constructed from multiple different fibers.

[0101] These types of reinforcing layers help control shrinkage characteristics and provide enhanced mechanical strength.

[0102] If a reinforcing layer is used, the fibers forming this layer may be selected from multiple different possibilities. Non-limiting examples of such fibers are glass fibers, such as E-glass fibers, S-glass fibers, and D-glass fibers, silica fibers, polymer fibers, such as polyetherimide fibers, polysulfone fibers, polyetherketone fibers, polyester fibers, polycarbonate fibers, aromatic polyamide fibers, etc., or liquid crystalline fibers. The fibers may 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.

[0103] One preferred form of the application is the use of the silphenylene polymer of formula (I) as a binder or co-binder together with an organic binder for the production of a metal surface laminate comprising a glass fiber composite for further production of a circuit board. The preferred metal is copper.

[0104] For the use of the silphenylene polymers of formula (I) according to the invention, they may be used as the sole binder. They may also be used in a blended form with organic monomers, oligomers and polymers.

[0105] Organic monomers, oligomers and polymers typically used for this purpose include polyphenylene ether, bismaleimide, bismaleimide-triazine copolymers, for example both aliphatic, such as polybutadiene and aromatic, such as polystyrene, and also hydrocarbon resins having both aliphatic and aromatic characteristics, such as styrene-polyolefin copolymers, etc., and there is no principle limitation in the form of copolymers; epoxy resins, cyanate ester resins, and optionally others, and the selection is illustrative and non-limiting.

[0106] Preferred organic monomers, oligomers and polymers are oligomers and polymer polyphenylene ether, monomers, oligomers and polymer bismaleimide, oligomers and polymer hydrocarbon resin, and bismaleimide-triazine copolymers. Here, the organic monomers, oligomers and polymers may optionally be used as a mixture with each other.

[0107] The proportion of the organic monomers, oligomers and polymers in the preparation containing the silphenylene polymer of formula (I) is 10% to 90%, preferably 20% to 90%, more particularly 30% to 80% based on the silphenylene polymer of formula (I) as 100% and the mixture of the organic monomers, oligomers and polymers if the organic component is also used.

[0108] Furthermore, not only the silylenepolymer of formula (I), but also its mixtures with organic monomers, oligomers or polymers may be dissolved in further organic monomers optionally having olefinic or acetylenic unsaturated groups as reactive diluents, for example, styrene, alpha-methylstyrene, para-methylstyrene and vinylstyrene, chloro- and bromostyrene, etc.

[0109] It is also possible to use typical non-reactive solvents for dissolving the silylenepolymer of formula (I) and optionally its mixtures with organic monomers, oligomers and polymers, for example, aliphatic or aromatic solvents, for example aliphatic mixtures having a defined boiling range, toluene, xylene, ethylbenzene or mixtures of these aromatic compounds, ketones, for example acetone, methyl ethyl ketone, cyclohexanone, carboxylic acid esters, for example ethyl acetate, methyl acetate, ethyl formate, methyl formate, methyl propionate, ethyl propionate; in particular, effective solubility of mixtures of the silylenepolymer of formula (I) with organic monomers, oligomers and polymers is most likely to be achieved in aromatic solvents, for example toluene, xylene, ethylbenzene and mixtures thereof.

[0110] When the silylenepolymer of formula (I) is used in combination with an organic oligomer or polymer or mixtures thereof, it is essential to use a silylenepolymer of formula (I) that is compatible with the selected organic component and does not lead to phase separation. In these cases, generally, a more phenyl-rich silylenepolymer of formula (I) should be used, because the phenyl group increases the compatibility with the organic component. When using relatively aromatic-rich organic polymers, such as polyphenylene ether or aromatic hydrocarbon resin, in particular, a more aromatic-rich silylenepolymer of formula (I) should be used, and both the crosslink-forming aromatic groups and the aromatic substituents bonded to the ends on the silyl units contribute to establishing compatibility.

[0111] The precise amount of aromatic groups required to establish the compatibility of the silphenylene polymers of formula (I) with a defined selection of organic binders must be determined depending on the choice of organic binder.

[0112] It is possible to mix two or more organic polymers, optionally selected from different polymer classes, and use them in a binder preparation, in the same way it is also possible to combine two or more silphenylene polymers of formula (I) with each other in a binder preparation. In other words, according to the present invention, only a single silphenylene polymer of formula (I) may be used as the binder, or alternatively, two or more silphenylene polymers of formula (I) may be combined with each other to form a binder preparation. It is also done according to the present invention to combine one or more organic polymers with only one silphenylene polymer of formula (I) to form a binder preparation. It is also done according to the present invention to combine one or more different organic polymers with two or more silphenylene polymers of formula (I) to form a binder preparation.

[0113] The determination of the compatibility of one or more silphenylene polymers of formula (I) with one or more organic oligomers or polymers is advantageously carried out by mixing a mixture of one or more organic binders with one or more silphenylene polymers of formula (I) in a solvent that dissolves all of the preferably selected components, and then removing the solvent by prior art methods such as distillation or spray drying, and subjecting the resulting residue to visual evaluation or evaluation with the aid of microscopic techniques, optionally electron microscopic techniques. A compatible mixture is evident from the separation of the organic components and the absence of any silphenylene polymer domains that can be recognized as separate phases.

[0114] Further formulation components, such as additives, such as antifoaming agents and degassing agents, wetting and dispersing agents, flow control agents, compatibilizers, adhesion promoters, curing initiators, catalysts, stabilizers, fillers containing pigments, dyes, inhibitors, flame retardants, crosslinking aids, etc., which may optionally also contain silane, are used in accordance with the present invention, and there is no principle limitation in the selection of such components. In addition to testing for compatibility in the sense of suitable miscibility behavior, testing for compatibility from the perspective of reactivity is also necessary, both to prevent premature gelation and to ensure sufficiently rapid polymerization or copolymerization of all components with each other during curing, and also testing for sufficient wetting properties and optionally further properties may also be necessary. This may need to be noted and considered when formulating the preparation.

[0115] Examples of fillers that can be used are ceramic fillers, such as silica, such as precipitated silica or fumed silica, which may be either hydrophilic or hydrophobic, preferably hydrophobic, and furthermore may also optionally have organic groups functionally and optionally reactively on their surfaces, etc.; quartz which may optionally be surface-treated or surface-functionalized to be enabled to have reactive functional groups on its surface; aluminum oxide, aluminum hydroxide, calcium carbonate, talc, mica, alumina, kaolin, magnesium sulfate, carbon black, titanium dioxide, zinc oxide, antimony trioxide, barium titanate, strontium titanate, corundum, wollastonite, zirconium tungstate, hollow ceramic beads, aluminum 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 silicone resin beads having a silica surface coating, and elastomer particles having a polymer coating, etc., in the latter case, the elastomer particles may also optionally be silicone elastomers, and a typical example of the surface coating on this type of elastomer particle is a polymethyl methacrylate shell. The ceramic filler preferably has a D of 0.1 μm to 10 μm.90 It has a particle size represented as. The filler is preferably present in an amount of 0.1 to 60 weight percent, more preferably 0.5 to 60 weight percent, and particularly 1 to 60 weight percent, based on the overall binder formulation consisting of one or more binders, reactive monomers, additives, and fillers as 100%. This means that the amount of any non-reactive solvent used is not included.

[0116] Among the fillers, those having thermal conductivity should be particularly emphasized. These are aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, zinc oxide, zirconium silicate, magnesium oxide, silicon oxide, and aluminum oxide.

[0117] In principle, the binder preparation may typically comprise a flame retardant additive in an amount of 5 to 25 weight percent. However, a particular feature of the silphenylene polymer of formula (I) is that it reduces the requirement for flame retardant additives since the silphenylene polymer of formula (I) itself already exhibits flame retardant properties. Polyorganosiloxanes and siloxanes are known to exhibit flame retardant properties, and these are also encountered with the silphenylene polymers of the present invention and can therefore be used as flame retardant additives themselves. Thus, it is a particular advantage of the present invention that in this case the function of the binder can be linked to the function of flame retardancy. Depending on the amount of the silphenylene polymer of formula (I) used, the amount of the flame retardant additive can therefore be reduced. Based on the total mixture of all binders and reactive organic monomers used, for an amount of at least 20 weight percent, the amount of the flame retardant additive is preferably only 0 to 10 weight percent, more preferably 0 to 8 weight percent, and particularly 0 to 5 weight percent; in other words, when using the silphenylene polymer of formula (I), depending on its selection and the amount used, it is possible to omit the use of the flame retardant additive.

[0118] 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. The flame retardant additives may be surface treated, in which case they may optionally have reactive groups on the surface. The flame retardant additives may also be halogenated organic flame retardant additives, such as hexachlorendomethylene tetrahydrophthalic 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 fine particle melamine polyphosphate.

[0119] Further examples of bromine-containing flame retardant additives are bispentabromophenyl ethane, ethylenebistetrabromophthalimide, tetradecabromodiphenoxybenzene, decabromodiphenyl oxide or brominated polysilsesquioxane. For certain flame retardant additives, their effects are synergistically boosted. This applies, for example, to combinations of halogenated flame retardant additives with antimony trioxide.

[0120] Further examples of other components are antioxidants, stabilizers against degradation by weathering, lubricants, plasticizers, colorants, phosphors or other agents for labeling and traceability, and antistatic agents.

[0121] The silylphenylene polymer of formula (I) is preferably crosslinked as part of the production of a metal laminate.

[0122] The crosslinking aids used include, in particular, polyunsaturated, radically curable or hydrosilylatable monomers and oligomers, as shown in the following non-limiting examples. They include, for example, diolefinically unsaturated components such as symmetrically olefinically unsaturated disubstituted disilanes such as 1,1,2,2-tetramethyl-1,2-divinyldisilane, 1,1,2,2-tetramethyl-1,2-dipropylmethacryloyldisilane, diolefinically unsaturated disubstituted organic monomers or oligomers having, for example, diallyl, divinyl, diacryloyl or dimethacryloyl substitution, such as conjugated and non-conjugated dienes such as 1,9-decadiene, 1,3-butadiene, etc. 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.

[0123] Also included herein are monomers and oligomers having unsaturated substitution, such as 2,2-bis[[(2-methyl-1-oxoallyl)-oxy]-methyl]-1,3-propanediyl bis methacrylate (pentaerythritol tetramethacrylate), tetraallyl cis,cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylate, tetraallylsilane, glyoxal bis(diallyl acetal), etc.

[0124] Due to the possible possibility of hydrosilylation curing in addition to radical curing, a plurality of Si-H functional components may also act as crosslinkers, which are, for example, 1,1,2,2-tetramethyl-1,2-disilane, 1,4-bis(dimethylsilyl)benzene or oligo- and polyorganosilanes having Si-H functionality in a plurality of chains and / or at the ends.

[0125] Suitable catalysts and initiators for the radical curing of the silphenylene polymers of formula (I) and binder preparations composed of organic monomers, oligomers and polymers are the same as those already identified above and are, in particular, peroxides. Furthermore, there are suitable further radical initiators for initiating the radical curing of both the silphenylene polymers of formula (I) alone and the described binder preparations, which are, for example, 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 and the like.

[0126] The silphenylene polymers of formula (I) and preparations comprising them may be used for the uses according to the invention either as solvent-free or solvent-containing preparations. Generally, they are used as solvent-containing preparations in order to promote a homogeneous distribution of all the components of the formulation with each other and to promote the wetting and saturation of any reinforcing layer used. Generally, a reinforcing layer is also used. It is preferably a glass fiber fabric. Saturation of the reinforcing layer may be achieved by an impregnating application of the preparation, for which purpose, optionally, various technical solutions including continuous processing are available and the choice thereof for the purpose of manufacturing the metal area laminate of the present invention is not limited in any way. Non-limiting examples of application techniques are dipping, spraying, flow coating, knife coating, etc. of a web of reinforcing material via a roller system in continuous processing, where appropriate. It is an advantage of the present invention that all available techniques can be used without limitation and modification, and that no special new methods are required for the use of the silphenylene polymers of formula (I). Thus, in the manufacture of metal area laminates, the present invention is well within the scope of available state-of-the-art techniques. The new feature is the use of the silphenylene polymers of formula (I) for manufacturing the intended metal area laminate, which has not been known hitherto.

[0127] Following the impregnation, a drying process is carried out, in which any solvent used is removed. For the drying operation, prior art is also used. These techniques include, in particular, thermally induced evaporation with or without a reduction in pressure. By appropriate setting of the reactivity and the adhesiveness of the binder mixture used, the product of this process under suitable conditions, for example under cooling, is a storable composite material, which may optionally be further processed at a later point in time.

[0128] In the last step of the above method, the binder preparation is polymerized again according to the prior art. Any initiator of radical polymerization used here is heated above its decomposition temperature, thus decomposing to form radicals and initiating the radical polymerization of the binder preparation. In principle, radiation curing techniques can also be used.

[0129] When hydrosilylation curing is used instead of radical polymerization, the temperature used in this step is suitable for deactivating the inhibitor used together with the hydrosilylation catalyst and for releasing the catalytic activity of the hydrosilylation catalyst.

[0130] This step is generally carried out at an elevated temperature of preferably 100 to 390 °C, more preferably 100 to 250 °C, and particularly 130 to 200 °C, and the temperature is effective over a time of preferably 5 to 180 minutes, more preferably 5 to 150 minutes, and particularly 10 to 120 minutes. It is also customary to use elevated pressure in this step. The customary pressure is in the range of 1 to 10 MPa, more preferably 1 to 5 MPa, and particularly 1 to 3 MPa.

[0131] The lamination of the composite material using the conductive metal layer is carried out in this second step by applying at least one 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 curing occurs. In other words, between the first step consisting of impregnation and drying and the second step comprising the chemical curing of the binder preparation, the composite from the first step is laminated using at least one type of conductive metal.

[0132] Suitable conductive metals include, in particular, at least one of the following selections: copper, stainless steel, gold, aluminum, silver, zinc, tin, lead, and transition metals. In principle, there are no limitations regarding the thickness or its shape, size, or surface texture of the conductive layer. The conductive metal layer preferably has a thickness of 3 to 300 μm, more preferably 3 to 250 μm, and even more particularly 3 to 200 μm. When two layers are used, the thicknesses of the two layers of at least one type of conductive metal may vary and do not need to be the same. In a particularly preferred case, the conductive metal is copper, and when two conductive layers of the conductive metal are used, both layers are copper. The conductive metal is preferably used in the form of a foil of the desired metal. The average roughness Ra of the metal foil used is preferably at most 2 μm, more preferably at most 1 μm, and even more particularly at most 0.7 μm. The lower the surface roughness, the better the suitability of each foil for use in high-frequency applications, which is a preferred objective of the present invention. To improve the adhesion between the conductive metal layer and the composite composed of the binder preparation and the reinforcing layer, various techniques from the prior art can optionally be used, such as the use of an adhesion-promoting layer, electrochemical deposition of the metal layer on the composite composed of the binder preparation and the reinforcing layer, or vapor deposition. The layer of conductive metal may be located directly on the composite composed of the binder preparation and the reinforcing layer or may be joined thereto via an adhesion-promoting layer.

[0133] In the case where the reinforcing layer is not used, the layer of the binder preparation comprising the silylenepolymer of formula (I) is produced by deposition of the layer of the binder preparation onto a carrier, for example a release film or a release plate, and materials suitable for the carrier are, in principle, any materials from which the dried or cured binder preparation can be detached again later, for example polytetrafluoroethylene, and polyesters and the like. The releasability on each carrier material and also the film-forming properties have to be determined individually depending on the binder composition. The statements made with respect to the method remain equally valid for this reinforcement-free variant.

[0134] From the reinforced or non-reinforced composite material from the first step and the laminated composite material from the second step, a plurality of plies of the composite material from the first step are stacked, for example, alternately and in sequence, with the area laminate from the second step, and then the still uncured composite material from the first step is cured in an operation substantially corresponding to the procedure for producing a metal area laminate, making it possible to produce a multilayer system. To produce thicker layers, it is also possible here to stack a plurality of plies of the reinforced or non-reinforced composite from the first step in a direct order in sequence.

[0135] In addition to being used for producing a metal area laminate, the silylenepolymer of formula (I) may also be additionally used in corrosion protection preparations, more particularly in corrosion protection preparations for use in preventing corrosion at elevated temperatures.

[0136] Furthermore, the silphenylene polymers of formula (I) and preparations comprising them may also be used for the corrosion protection of reinforcing steel in steel-reinforced concrete. The corrosion inhibition effect in steel-reinforced concrete is achieved in that case both when the silphenylene polymers of formula (I) and preparations comprising them are introduced into the mixture before the concrete mixture is shaped and cured, and when the silphenylene polymers of formula (I) or preparations comprising them are applied to the surface of the concrete after the concrete has cured.

[0137] In addition to the purpose of corrosion prevention on metals, the silphenylene polymers of formula (I) may also serve to manipulate further properties of preparations comprising the silphenylene polymers of the invention, or solids or films obtained from preparations comprising the silphenylene polymers of formula (I), examples of which are as follows: - Control of electrical conductivity and electrical resistance - Control of the flow properties of the preparation - Control of the gloss of wet or cured films or objects - Increase in weather resistance - Increase in chemical resistance - Increase in hue stability - Reduction of the choking tendency - Reduction or increase of static and sliding friction on solids or films obtained from preparations comprising the polyorganosiloxane of formula (I) - Stabilization or destabilization of bubbles in preparations comprising the preparation - Improvement of the adhesion of preparations comprising the polyorganosiloxane of formula (I) to the substrate - Control of the wetting and dispersion behavior of fillers and dyes - Control of the rheological properties of preparations comprising the silphenylene polymers of the invention - Obtainable from a silphenylene polymer of formula (I) or a preparation comprising them, and mechanical properties of solids or films comprising them, such as flexibility, scratch resistance, elasticity, extensibility, bendability, fracture behavior, elastic behavior, hardness, density, tear resistance, compression set, behavior at different temperatures, coefficient of expansion, abrasion resistance, and also further properties, such as thermal conductivity, flammability, gas permeability, resistance to water vapor, warm air, chemicals, weathering and radiation, control of sterility - Control of electrical properties, such as dielectric loss factor, decomposition resistance, dielectric constant, leakage current resistance, arc resistance, surface resistance, specific decomposition resistance, etc. - Flexibility, scratch resistance, elasticity, extensibility, bendability, fracture behavior, elastic behavior, hardness, density, tear resistance, compression set, behavior at different temperatures of solids or films obtainable from a preparation comprising a silphenylene polymer of formula (I).

[0138] Examples of applications in which a silphenylene polymer of formula (I) can be used to manipulate the properties specified above are the manufacture of coating materials and impregnation systems, and also for the manufacture of synthetic and natural fibers, leather, plastics, such as films, and resulting coatings and coverings on moldings for other products that can be manufactured from substrates such as metals, glass, wood, mineral substrates, textiles, carpets, floor coverings or fibers. Together with an appropriate selection of preparation components, furthermore, the silphenylene polymer of formula (I) can be used in the preparation as an additive for the purposes of 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 obtainable from the preparation with additives. The silphenylene polymers of formula (I) may be incorporated into the elastomer composition in liquid form or in cured solid form. In that case, they may be used for reinforcement or to improve other service properties, such as controlling transparency, heat resistance, yellowing tendency or weathering stability.

[0139] All of the symbols in the above formula each have their definitions independently of one another in each case. In all formulas, the silicon atom is tetravalent.

Examples

[0140] The following examples are useful for the explanation of the present invention. They should be understood as illustrative and not limiting.

[0141] Unless otherwise indicated, all manipulations are carried out at room temperature of 23 °C and atmospheric pressure (1.013 bar).

[0142] Unless otherwise indicated, all data describing product characteristics are valid at room temperature of 23 °C and atmospheric pressure (1.013 bar).

[0143] The apparatus is of the kind of commercially conventional laboratory apparatus commercially available from a number of apparatus manufacturers.

[0144] Ph is phenyl radical = C 6 H 5 represents a - bond.

[0145] Me is methyl radical = CH 3 represents a - bond. Me 2 correspondingly represents two methyl radicals.

[0146] PPE represents polyphenylene ether.

[0147] HCl represents hydrogen chloride.

[0148] In the present text, substances are characterized by reports of data obtained through instrumental analysis. The underlying measurements are performed according to publicly available standards or verified according to specially developed methods. To ensure the clarity of the given instructions, the methods used are indicated below.

[0149] In all examples, numerical values for parts and percentages are by weight, unless otherwise indicated.

[0150] Viscosity: Viscosity is determined by rotational viscometry in accordance with DIN EN ISO 3219, unless otherwise indicated. Unless otherwise indicated, all viscosity data are valid at 25 °C and an atmospheric pressure of 1013 mbar.

[0151] Refractive index: The refractive index is determined at 589 nm within the wavelength range of visible light at 25 °C and an atmospheric pressure of 1013 mbar in accordance with standard DIN 51423, unless otherwise indicated.

[0152] Transmittance: Transmittance is determined by UV-VIS spectroscopy. An example of a suitable instrument is the Analytik Jena Specord 200.

[0153] The measurement parameters used are as follows: Range: 190 - 1100 nm Step size: 0.2 nm, integration time: 0.04 s, measurement mode: step operation. A reference measurement (background) is carried out first. A quartz plate (quartz plate dimensions: H × W approx. 6 × 7 cm, thickness approx. 2.3 mm) fixed to the sample holder is placed in the sample beam path and measured against air.

[0154] The sample measurement is then carried out as follows: A quartz plate layer fixed to and having the applied sample (thickness of the layer of the applied sample approx. 1 mm) is placed in the sample beam path and measured against air. Internal calculation compared to the background spectrum yields the transmission spectrum of the sample.

[0155] Molecular composition: The molecular composition is 1 H nuclei and 29Determined using nuclear magnetic resonance spectroscopy (for academic terms, refer to ASTM E 386: High-resolution nuclear magnetic resonance (NMR) spectroscopy: terms and symbols) along with the measurement of the Si core.

[0156] 1 Explanation of H-NMR measurement: Solvent: CDCl3, 99.8% d Sample concentration: Approximately 50 mg per 1 ml of CDCl3 in a 5 mm NMR tube Measurement without the addition of TMS, reference to the spectrum of residual CHCl3 in CDCl3 at 7.24 ppm Spectrometer: Bruker Avance I 500 or Bruker Avance HD 500 Probe: 5 mm BBO probe or SMART probe (Bruker)

[0157] Measurement parameters: Pulse program (Pulprog) = zg30 TD = 64k NS = 64 or 128 (depending on probe sensitivity) SW = 20.6 ppm AQ = 3.17 seconds D1 = 5 seconds SFO1 = 500.13 MHz O1 = 6.175 ppm Processing parameters: SI = 32k WDW = EM LB = 0.3 Hz

[0158] Individual adaptation of the measurement parameters may be necessary according to the type of spectrometer used.

[0159] 29 Explanation of Si-NMR measurement: Solvent: 1 weight percent of Cr(acac) as a relaxation reagent 3C6D6 99.8% d / CCl4 1:1 v / v with Sample concentration: Approximately 2 g per 1.5 ml of solvent in a 10 mm NMR tube Spectrometer: Bruker Avance 300 Probe: 10 mm 1H / 13C / 15N / 29Si glass-free QNP probe (Bruker)

[0160] Measurement parameters: Pulse program = zgig60 TD = 64k NS = 1024 (depending on probe sensitivity) SW = 200 ppm AQ = 2.75 seconds D1 = 4 seconds SFO1 = 300.13 MHz O1 = -50 ppm Processing parameters: SI = 64k WDW = EM LB = 0.3 Hz

[0161] Individual adaptation of the measurement parameters may be necessary according to the type of spectrometer used.

[0162] Molecular weight distribution: The molecular weight distribution is determined as weight average Mw and number average Mn using gel permeation chromatography (GPC or size exclusion chromatography (SEC)) with polystyrene standards and a refractive index detector (RI detector). Unless otherwise specified, THF is used as the eluent and DIN 55672-1 is applied. The polydispersity is the ratio Mw / Mn.

[0163] Glass transition temperature: The glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, in an open crucible, with a heating rate of 10 K / min.

[0164] Determination of particle size: The particle size was measured by the method of dynamic light scattering (DLS) involving the determination of zeta potential.

[0165] The auxiliaries and reagents used for the determination were as follows: 10×10×45 mm polystyrene cuvette, Pasteur pipette for single use, ultrapure water.

[0166] The sample for measurement is homogenized and introduced into the measurement cuvette without bubbles.

[0167] The measurement is carried out at 25 °C after a 300 - second equilibration time, with high resolution and automatic measurement time adjustment.

[0168] The reported value is always based on the D(50) value. D(50) should be understood as the volume - averaged particle diameter, such that 50% of all the measured particles have a volume - averaged diameter smaller than the value specified for D(50).

[0169] 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 following the split - cylinder resonator method at 10 GHz.

[0170] Procedure of microscopy: The micro / nano structures were characterized by optical microscopy and transmission electron microscopy respectively.

[0171] Optical microscopy: Sample preparation: 1 drop of sample (neat) on a slide; covered with a cover glass Equipment: LEICA DMRXA2 with a LEICA DFC420 CCD camera (2592×1944 pixels) Imaging: Transmitted light - interference contrast, various magnification stages Transmission electron microscopy: Sample preparation: 1 drop of sample (dilution 1:20, adaptation required if necessary) on a coated TEM grid; addition of contrast agent if required; drying at RT Equipment: ZEISS LIBRA 120 with Sharp Eye CCD camera (1024×1024 pixels) Imaging: Excitation voltage 120 kV; TEM bright field; various magnification stages

[0172] Peel strength test for adhesion: The adhesion of the metal layer laminated on the composite layer with or without reinforcement material was determined in the "standard" (as received) version, i.e., without heat load or exposure, according to IPC-TM 650 method 2.4.8 "Peel Strength of Metallic Clad Laminates".

[0173] Mass 285 ± 10 g / m 2 A 35-μm copper foil with roughness depth Rz ≦ 8 μm and average roughness Ra ≦ 0.4 μm was laminated on both sides of a composite layer with a thickness of 100 μm, and curing and lamination were carried out at 200 °C, 2.0 MPa, and 30 mmHg column for 180 minutes.

[0174] Combustibility test: The test was conducted as a vertical burning test in accordance with the UL 94-V specification of Underwriters Laboratories. Prior to the test, the specimens were conditioned as follows: storage for 2 days at 23°C and 50% relative humidity, followed by 7 days at 70°C in a hot air oven. The application of the flame was carried out with the flame of a Tirill burner. The flame application time was 2 × 10 seconds in each case. The second flame application time starts immediately when the ignited sample is consumed. If the sample does not ignite, the second flame application is carried out immediately after the first flame application. The length of the test specimen is 5” (127 mm), and the width is 0.5” (12.7 mm). The plate under test had a thickness of 0.4” (10.2 mm). The plate was fixed at the upper 1 / 4” length in the vertical position. A mesh coated with surgical cotton was placed 12” (305 mm) below the test plate. The burner was adjusted to produce a blue flame with a length of 3 / 4”. The flame was directed at the lower end of the plastic plate from a distance of 3 / 8” (9.5 mm). After 10 seconds of exposure, the flame is removed. The flame extinction time of the test specimen is recorded. Immediately after the generation of the flame stops, the burner flame is placed under the test specimen again for 10 seconds. After the removal of the flame, the flame extinction time and glow time of the specimen are recorded. The test is carried out on 5 different test specimens.

[0175] Synthesis example 1: Preparation of silphenylene polymers by the method of the present invention from chlorosilanes: 48 g of shaved magnesium (2 mol) is introduced into a 2 l three-necked flask glass apparatus equipped with a valve condenser and a dropping funnel. The apparatus is then evacuated to an internal pressure of 10 -3 millibar, and at the same time, the glass wall is subjected to a temperature of 270°C using a warm air blower to remove the residue of water adhering to the magnesium and the glass wall. The vacuum is then broken with argon until the pressure spreading inside the apparatus reaches 1013 millibar. The apparatus is cooled to room temperature at 23°C.

[0176] Charge the apparatus with 250 ml of dry 1,4-dioxane purged with nitrogen. Add iodine grains having a mass of about 50 mg and heat to an internal temperature of 60 °C. Dissolve 118 g (0.5 mol) of 1,4-dibromobenzene in dry nitrogen atmosphere in 400 ml of dry nitrogen-purged 1,4-dioxane and transfer the mixture to a dropping funnel. Meter the mixture at a uniform pace over a period of 3 hours and concomitantly heat to ensure the exothermic warming that occurs does not exceed an internal temperature of 65 °C. Subsequently, stir at 65 °C for 7 hours to complete the reaction to form the 1,4-dibromobenzene Grignard reagent. A gray, turbid preparation is obtained.

[0177] Cool the reaction mixture to 2 °C. Introduce into a dropping funnel an 89.8 g mixture of 0.14 mol of vinyldimethylchlorosilane and 0.57 mol of dimethyldichlorosilane. This step is also carried out under dry nitrogen as the inert gas. With cooling to again keep the temperature below 5 °C, meter the silane mixture at a uniform pace over a period of 3 hours. At the end of the metering, continue stirring at 2 °C for an additional 3 hours. Subsequently, filter the reaction mixture through a filter plate having a pore size of 1.2 μm. The filtrate is clear and of low viscosity. Evaporate off the 1,4-dioxane next under reduced pressure of 120 °C and 20 mbar. The product is a slightly reddish-yellow solid which is then dissolved in toluene for further work-up to form a solution of slightly over 50% strength. Add 200 ml of fully desalted water to the toluene solution with stirring, switch off the stirrer and let the preparation stand to separate the aqueous and organic phases from each other. Drain off the aqueous phase and repeat the washing procedure 3 more times in the same manner. Mix the remaining organic phase with 30 g of sodium sulfate, stir for 5 minutes and then isolate by filtration through a 1.2 μm filter plate. Distill off the toluene completely at 120 °C and a reduced pressure of 20 mbar to obtain an orange solid. SEC: Mw = 1050 g / mol, Mn = 713 g / mol, polydispersity PD = 1.47.

[0178] The silanol and alkoxy groups are1 Undetectable by H-NMR. 29 According to Si-NMR, the molar composition of the silicon-containing fraction of the preparation is as follows: (CH 2 =CH)Me 2 Si(C 6 H 4 )-: 21.8% -(C 6 H 4 )(Me 2 )Si(C 6 H 4 )-: 78.2%

[0179] Here, half of each crosslink-forming -(C 6 H 4 )- radical is counted for each Si atom to which it is attached.

[0180] This product is readily soluble in toluene. An 80% strength toluene solution consisting of 80% of the reaction product in 20% toluene can be easily prepared. The numerical values of the percentages are based on mass. However, in the examples of use, a 50% strength toluene solution has been used, the reason being that the counterexamples have a lower solubility and this is intended to ensure comparability in this way. The 50% preparation is identified as 1.1 below.

[0181] The silphenylene polymers prepared here are not accessible according to the European Patent No. 0913420, the reason being that they are not preparable by hydrosilylation.

[0182] Synthesis example 2: Preparation of silphenylene polymers by the method of the invention from alkoxysilanes: The procedure corresponds to the procedure described in Synthesis Example 1, with the following differences: Instead of 1,4-dioxane, the solvent used is THF. Instead of the mixture of chlorosilanes, an 84.6 g mixture of 0.14 mol of vinyldimethylmethoxysilane (116 g / mol) and 0.57 mol of dimethyldimethoxysilane (120 g / mol) is used.

[0183] In the resulting product, the silanol groups are 1 not detectable by 1H-NMR. 1 According to 1H-NMR, the methoxy groups are present in an amount of about 0.1 weight percent.

[0184] By SEC (eluent: toluene), the following molecular weights were determined: Mw = 1134 g / mol, Mn = 803 g / mol, polydispersity PD = 1.41. 29 According to Si-NMR, the molar composition of the silicon-containing fraction of the preparation is as follows: (CH 2 =CH)Me 2 Si(C 6 H 4 )-: 22.1% -(C 6 H 4 )(Me 2 )Si(C 6 H 4 )-: 77.9%

[0185] Here, half of each crosslink-forming -(C 6 H 4 )- radical is counted for each Si atom to which it is attached.

[0186] This product is readily soluble in toluene. An 80% strength toluene solution consisting of 80% of the reaction product in 20% toluene is easily prepared. The percentage values are based on mass. However, in the examples of use, a 50% strength toluene solution is used, the reason being that the counterexamples have lower solubility and this is intended to ensure comparability in this way. The 50% preparation is identified as 2.1 below.

[0187] The silphenylene polymers prepared herein are not accessible according to the specifications of European Patent No. 0913420, because they cannot be prepared by hydrosilylation.

[0188] Synthesis example 3: Preparation of the silphenylene polymers of the invention from alkoxysilanes using multi-halogenated organic raw materials: The procedure corresponds to the procedure described in Synthesis Example 1, with the following differences: Instead of 1,4-dioxane, the solvent used is THF. Instead of the mixture of chlorosilanes, a 67.8 g mixture of 0.14 mol of vinyldimethylmethoxysilane (116 g / mol) and 0.43 mol of dimethyldimethoxysilane (120 g / mol) is used. Instead of 1,4-dibromobenzene, 0.25 mol (118 g) of 3,3’,5,5’-tetrabromo-1,1’-biphenyl is used.

[0189] In the resulting product, the silanol groups are 1 not detectable by 1H-NMR. 1 According to 1H-NMR, the methoxy groups are present in an amount of <0.1 weight percent.

[0190] By SEC (eluent: toluene), the following molecular weights were determined: Mw = 1347 g / mol, Mn = 941 g / mol, polydispersity PD = 1.43.

[0191] 29 According to Si-NMR, the molar composition of the silicon-containing fraction of the preparation is as follows: (CH 2 =CH)Me 2 Si(C 12 H 8 )-: 21.3% -(C 12 H 8 )(Me 2 )Si(C 12 H 8 )-: 78.7%

[0192] Here, 1 / 4 of each crosslink-forming -(C 12 H 8 )-radical is counted for each Si atom to which it is attached.

[0193] This product is readily soluble in toluene. An 80% strength toluene solution consisting of 80% of the reaction product in 20% toluene is readily prepared. The numerical values of the percentages are based on mass. However, in the examples of use, a 50% strength toluene solution is used, the reason being that the counterexamples have a lower solubility and this is intended to ensure comparability. The 50% preparation is identified as 3.1 below. The silylphenylene polymer prepared here is not accessible according to the specification of European Patent No. 0913420, since it is not preparable by hydrosilylation.

[0194] Synthesis example 4: Preparation of a prior art silylphenylene-silalkylene copolymer according to Example 1 in the specification of European Patent No. 0913420 as a non-inventive comparative example.

[0195] 1,4-Bis(phenylmethylvinylsilyl)phenylene and 1,4-bis(dimethylsilyl)phenylene starting materials were prepared by Grignard synthesis. A suitable procedure for this is the same as the procedure described in Synthesis Example 1.

[0196] Here, in the case of 1,4-bis(phenylmethylvinylsilyl)phenylene, in the first step, a di-Grignard reagent in THF is generated from 4-fold molar amount of shaved magnesium based on 1,4-dibromobenzene, and the amount of 1,4-dibromobenzene used, and in the second step, this reagent is reacted with 2-fold molar amount of phenylmethylvinylmethoxysilane based on dibromobenzene as described in the examples. This gives the desired 1,4-bis(phenylmethylvinylsilyl)phenylene, the elemental composition of which is 1 H and 29It was analytically confirmed by Si-NMR spectroscopy. This time, the same procedure was used to prepare 1,4-bis(dimethylsilyl)phenylene using an equivalent amount of dimethylmethoxysilane instead of phenylmethylvinylmethoxysilane. Again, the acquisition of the desired chemical composition can be demonstrated by NMR spectroscopy. At this point, a significant substantial difference between this prior art and the invention described herein is already apparent, because the cost and complexity for simply performing the preparation for the experiment according to Example 1 of European Patent No. 0913420 is already twice as high as the cost and complexity involved in the preparation of the silphenylene polymers of the present invention. Further execution of the experiment corresponds in all details to the description according to Example 1 in European Patent No. 0913420. As a result, a solid reaction product with a weight average molecular weight of Mw = 19900 g / mol is obtained according to SEC. European Patent No. 0913420 does not give numerical values for Mn and PD, so a comparison is not possible here. In this case, the values obtained were as follows: Mn = 3042 g / mol and PD = 6.54. 1 Both H-NMR and 29 In Si-NMR, the expected signals for the structural groups were found, so the product obtained here is undoubtedly chemically identical to the product according to Example 1 in European Patent No. 0913420. The product obtained is soluble in xylene and toluene at a maximum concentration of 50%. In contrast to the silphenylene polymers of the present invention, a higher solubility is not achieved, so this material is used at a concentration of 50% in toluene for comparison of properties.

[0197] This 50% preparation in toluene is referred to hereinafter as 4.1.

[0198] Synthesis example 5: Preparation of a prior art silphenylene-polysiloxane copolymer according to Example 1 of US Patent No. 6072016 as a non-inventive comparative example: For Example 1 according to U.S. Patent No. 6,072,016, an initial polymer is required that is made from 1,4-bis(phenylmethylvinylsilyl)phenylene and 1,4-bis(dimethylsilyl)phenylene, which are the same starting materials already described in Synthesis Example 4, and additionally vinyltrimethoxysilane, according to Reference Example 1 from the specification of U.S. Patent No. 6,072,016. The preparation of 1,4-bis(phenylmethylvinylsilyl)phenylene and 1,4-bis(dimethylsilyl)phenylene has already been described in Synthesis Example 4. It was prepared according to the description in Reference Example 1 from the specification of U.S. Patent No. 6,072,016 to obtain the initial polymer for Example 1 according to the specification of U.S. Patent No. 6,072,016. The relative amounts of 1,4-bis(phenylmethylvinylsilyl)phenylene and 1,4-bis(dimethylsilyl)phenylene here are different from those in Synthesis Example 4 and Example 1 according to the specification of European Patent No. 0,913,420. Thus, vinyltrimethoxysilane is terminally hydrosilylated onto the residual Si-H of 1,4-bis(dimethylsilyl)phenylene, which is used in excess. Also in this case, the chemical properties of the obtained product can be elucidated by NMR and SEC analysis to ensure that the obtained product is the same as that described in Reference Example 1 from the specification of U.S. Patent No. 6,072,016. For the product in the experiment reproduced here, the weight-average molecular weight determined by SEC is Mw = 9675 g / mol. The specification of U.S. Patent No. 6,072,016 does not give numerical values for the number-average molecular weight Mn and the polydispersity index PD. In this case, they were found to be Mn = 6365 g / mol and PD = 1.52.

[0199] Additionally, to stay precisely within the prior art of U.S. Patent No. 6,072,016, the obtained bistrimethoxysilyl-terminated silphenylene was cured according to the procedure described in Example 1 of U.S. Patent No. 6,072,016, i.e., curing was carried out using methyltri(methylethylketoxime)silane in toluene. For this purpose, a 50% strength toluene solution of bistrimethoxysilyl-terminated silphenylene according to Reference Example 1 from U.S. Patent No. 6,072,016 was prepared as described in Example 1 of U.S. Patent No. 6,072,016. This 50% strength toluene solution composed of toluene and bistrimethoxysilyl-terminated silphenylene according to Reference Example 1 of U.S. Patent No. 6,072,016 is referred to as 5.1 below.

[0200] Usage example 1: Use of the silphenylene polymers 1.1, 2.1, and 3.1 of the present invention and the contrasting non-inventive examples 4.1 and 5.1 for manufacturing a copper laminate: The silphenylene polymers 1.1, 2.1, and 3.1 of the present invention, the non-inventive silphenylene-silalkylene copolymer 4.1, and likewise the non-inventive alkoxysilyl-terminated silphenylene-silalkylene copolymer 5.1, prepared according to Synthesis Examples 1 to 5, were used as binders for manufacturing a copper laminate having a glass fiber-reinforced composite layer. The materials used were as follows: Copper foil: A 35-μm thick copper foil (285 ± 10 g / m 2 ) from Jiangtong-yates Copper Foil Co Ltd, having a roughness depth of Rz ≤ 8 μm and an average roughness depth of Ra ≤ 0.4 μm, and a purity ≥ 99.8%. Glass fiber: E-glass fiber type 1080 E manufactured by Changzhou Xingao Insulation Materials Co., Ltd. With a thickness of 0.055 ± 0.012 mm, 47.5 ± 2.5 g / m 2 。

[0201] To ensure the comparability of the binders, all of the binders in this example were used as 50% strength solutions in toluene.

[0202] To initiate curing, the vinyl-functional silphenylene polymers 1.1, 2.1, and 3.1 of the present invention and the non-inventive silphenylene-silalkylene copolymer 4.1 were each mixed with 1 weight percent dicumyl peroxide based on the amount of silphenylene polymer 1.1, 2.1, and 3.1 or silphenylene-silalkylene copolymer 4.1 used, and the peroxide was uniformly distributed in the resin matrix by stirring. 5.1 was cured by adding methyltri(methylethylketoxime)silane in the amounts indicated in Example 1 according to U.S. Patent No. 6,072,016.

[0203] A 30×30 cm glass fiber layer was used for each ply, with the assistance of an air removal roller, for bubble-free impregnation with the respective organopolysiloxane as a toluene solution where appropriate, to produce the laminate. In this procedure, the glass fiber layer was mounted on a flat, dimensionally stable stainless steel support, and after applying one ply of copper foil to the support, the first ply of glass fiber was placed. In total, three plies of glass fiber fabric were successfully impregnated in each case. To remove the solvent, the impregnated fabric was dried to a constant weight in a vacuum drying oven at 10 mbar and 60 °C where appropriate. Thereafter, a second layer of copper foil was applied over the impregnated glass fiber layer, and a further dimensionally stable stainless steel plate was placed. The laminate was baked in a hot press at a pressure of 2 MPa for 120 minutes at 200 °C and a reduced pressure of 30 mbar. This produced a copper-clad laminate with an overall thickness of 260 ± 20 µm.

[0204] 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: [Table 1]

[0205] D of copper laminates made from silphenylene polymers and from silphenylene-silalkylene copolymers of the present invention f and D. k The values ​​are the D values ​​obtained with ketoxime-cured silphenylene-silalkylene copolymers according to U.S. Pat. No. 6,072,016, which have a significant organopolysiloxane ratio and therefore a higher polarity due to the ketoxime silane used. f and D. k values. Considering that high frequency applications require extremely low dielectric loss factors and relative dielectric constants, this is undesirable, and the silphenylene polymers of the present invention are an improvement over this prior art in terms of dielectric properties. Non-inventive silphenylene-silalkylene polymers are more similar to the silphenylene polymers of the present invention in terms of dielectric properties, but are not comparable to them. They are comparable to the silphenylene polymers of the present invention in terms of the degree of avoidance of polar siloxane bonds, but it is nevertheless the case that in non-inventive silphenylene-silalkylene copolymers, as a result of the selected mode of preparation by hydrosilylation, platinum residues remain in the product, adversely affecting the dielectric properties and causing an increase in the dielectric loss factor. Thus, although the chemical composition of the silphenylene-silalkylene copolymers is in principle suitable per se for achieving the dielectric properties according to the present invention, it can only be utilized if the platinum residues are successfully removed. This causes additional costs and complexity, thus reducing the profitability of this technology compared to the silphenylene polymers that are the subject of the present invention.Furthermore, in the fourth synthesis example, it has already been indicated that the starting material for the hydrosilylation can only be obtained by two upstream Grignard syntheses, thereby doubling the overall costs and complexity compared to the technology of the present invention, making it uneconomical and no longer commercially viable.

[0206] Usage example 2: Use of the silphenylene polymers 1.1, 2.1 and 3.1 of the present invention and the contrasting examples 4.1 and 5.1 not of the invention for producing a copper laminate via a prepreg The silphenylene polymers 1.1, 2.1 and 3.1 of the present invention and the non-inventive silphenylene-silalkylene copolymer 4.1, prepared according to Synthesis Examples 1 to 5, and likewise the non-inventive alkoxysilyl-terminated silphenylene-silalkylene copolymer 5.1 were used as binders for producing a copper laminate having a glass fiber reinforced composite layer

[0207] Instead of constructing the laminate directly without an intermediate prepreg stage as in Use Example 1, this time, as individual plies in each case on a polytetrafluoroethylene film, the glass fiber plies were impregnated with a resin preparation and then prepregs were produced by drying them to a constant weight in a vacuum drying oven. A set of three plies of the thus-produced impregnated glass fiber fabric was subsequently successively deposited on a copper foil, and the stack was completed using the plies of copper foil. This multilayer structure was pressed and cured under the conditions indicated in Example 1 between two dimensionally stable stainless steel plates in a vacuum press, as in Use Example 1

[0208] The resulting laminate had a thickness of 290 ± 20 μm

[0209] The dielectric properties measured in the resulting laminate were as follows

Table 2

[0210] D of copper laminates made from the silphenylene polymers of the present invention and from silphenylene-silalkylene copolymers f and D kThe values are much lower than those of D cured with a ketoxime-cured silphenylene-silalkylene copolymer according to U.S. Patent No. 6,072,016, which has a significant organopolysiloxane ratio and thus higher polarity due to the ketoxime silane used. f and D k This is undesirable considering that high-frequency applications require extremely low dielectric loss factors and relative permittivities, and the silphenylene polymers of the present invention represent an improvement over this prior art in terms of dielectric properties. Non-inventive silphenylene-silalkylene polymers are somewhat similar to the silphenylene polymers of the present invention in terms of dielectric properties but are not comparable. They are equivalent to the silphenylene polymers of the present invention in terms of the degree of avoidance of polar siloxane bonds, yet in non-inventive silphenylene-silalkylene copolymers, as a result of the chosen mode of preparation by hydrosilylation, residues of platinum remain in the product, detrimentally affecting the dielectric properties and causing an increase in the dielectric loss factor. Thus, the chemical composition of silphenylene-silalkylene copolymers is in principle suitable per se for achieving the dielectric properties according to the present invention, but it can only be utilized if the platinum residues are successfully removed. This causes additional cost and complexity and thus reduces the profitability of this technology compared to the silphenylene polymers which are the subject of the present invention. Furthermore, in the fourth synthesis example, the starting materials for hydrosilylation can only be obtained by two upstream Grignard syntheses, thereby doubling the overall cost and complexity compared to the technology of the present invention, which has already been shown to make it uneconomical and no longer commercially viable.

[0211] Usage example 3: Use of the silphenylene polymers 1.1, 2.1, and 3.1 of the present invention and the non-inventive opposite examples 4.1 and 5.1 in a mixture with an organic polymer for manufacturing a copper laminate The procedure substantially corresponds to the procedure described in Use Example 2, but this time, as a binder for producing a copper laminate having a glass fiber reinforced composite layer, an organic polymer was used in a mixture with the silphenylene polymers 1.1, 2.1 and 3.1 of the present invention, the non-inventive silphenylene-silalkylene copolymer 4.1, and similarly the non-inventive alkoxysilyl-terminated silphenylene-silalkylene copolymer 5.1.

[0212] The final solvent-free mixture always contained 30 weight percent of each of components 1.1, 2.1, 3.1, 4.1 and 5.1, mixed with 70 weight percent of the organic polymer. The organic polymers were triallyl isocyanurate, NORYL SA 9000, an alpha, omega-methacrylate-terminated polyphenylene ether obtained from SABIC, Mn = 2500 g / mol, Tg = 160 °C, and B 3000 from Nippon Soda, a liquid polybutadiene with Mn = 3200 having more than 85% 1,2-vinyl structure in the polymer chain and a viscosity of 210 poise at 45 °C.

[0213] The polymers were always used in the same proportions. They were dissolved or dispersed in xylene, and 30 parts by weight of SA 9000, 25 parts by weight of B 3000 and 15 parts by weight of triallyl isocyanurate were dispersed together with 100 parts by weight of xylene.

[0214] The resulting preparation was mixed, according to Use Example 2, with toluene solutions of components 1.1, 2.1, 3.1, 4.1 and 5.1 respectively, such that in each case the specified proportion of 30% of 1.1, 2.1, 3.1, 4.1 or 5.1 and 70% of the organic component was present in the resulting solution. As described in Use Example 2, these solutions were then used to produce copper laminates via prepregs.

[0215] The resulting laminate had a thickness of 290 ± 20 μm.

[0216] The dielectric properties measured in the obtained laminate were as follows:

Table 3

[0217] The D achieved for the copper laminates using the silphenylene polymers 1.1, 2.1 and 3.1 of the present invention k and D f values were much lower than the D achieved with the non-inventive silphenylene-silalkylene copolymer 4.1 and likewise the non-inventive alkoxysilyl-terminated silphenylene-silalkylene copolymer 5.1 f and D k values. Considering that high frequency applications require extremely low dielectric loss factors and relative permittivities, the effect according to the present invention is clearly evident.

[0218] Usage example 4: Conducting a fire test according to UL 94 V: The tests were carried out as vertical burning tests in accordance with the UL 94-V specifications of Underwriters Laboratories. Test specimens composed of the silphenylene polymers 1.1, 2.1, and 3.1 and the non-inventive silphenylene-silalkylene copolymer 4.1 of the present invention were each obtained from a toluene solution mixed with 2% dicumyl peroxide for curing, the percentage being by weight and based on the amount of the dissolved product as 100%. The overall 50% strength solution thus contained 1 weight percent of dicumyl peroxide. The solution was each poured into a suitable size and the solvent was then removed by evaporation in a forced air oven in stages, first at 80 °C for 4 hours and subsequently at 120 °C for 2 hours, after which the resulting evaporation residue was cured at 200 °C for 2 hours. The procedure for curing the non-inventive alkoxysilyl-terminated silphenylene-silalkylene copolymer 5.1 involved the addition of the ketoxime silane as already described above, as described in Example 1 of U.S. Patent No. 6,072,016. The procedure for producing the sample specimens corresponded otherwise to the procedure described for the specimens 1.1, 2.1, 3.1, and 4.1.

[0219] The obtained specimens were conditioned under the following conditions prior to testing: storage for 2 days at 23°C and 50% relative humidity, followed by 7 days at 70°C in a hot air oven. The flame was applied using the flame of a Tirill burner. The flame application time was 2 × 10 seconds in each case. The second flame application time starts immediately when the ignited sample is digested. If the sample does not ignite, the second flame application is performed immediately after the first flame application. The length of the test piece was 5” (127 mm), and the width was 0.5” (12.7 mm). The plate under test had a thickness of 0.4” (10.2 mm). The plate was fixed at the upper 1 / 4” length in the vertical position. A grid coated with surgical cotton was placed 12” (305 mm) below the test plate. Adjust the burner to produce a blue flame with a length of 3 / 4”. Direct the flame towards the lower end of the plastic plate from a distance of 3 / 8” (9.5 mm). After 10 seconds of exposure, remove the flame. Record the flame extinction time of the test piece. As soon as the formation of the flame stops, place the burner flame under the test piece again for 10 seconds. After removing the flame, record the flame extinction time and glow time of the piece. The test is performed on five different test pieces.

[0220] The results obtained were as follows:

Table 4

[0221] Flammability class V-0 is the highest flammability class under UL94-V. V-0 is a requirement for the target application of copper laminates for high-frequency applications. Only the silphenylene polymers of the present invention meet this requirement. Overall, both the synthesis examples and the use examples demonstrate that the desired effects of the present invention are achieved and that the existing prior art is improved as required by the present invention.

Claims

1. Formula (I): R ａ R １ ｂ Si[Y[(SiR ２ ｃ R ３ ｄ ) ｅ ｆ ｇ YSiR ａ R １ ｂ (I)​​ (wherein R may be the same or different radicals, a hydrogen radical, or an olefinically or acetylenically unsaturated, aliphatic or cycloaliphatic hydrocarbon radical, R ２ are, independently of one another, identical or different radicals, and R ２ may be a hydrogen radical or may be substituted by a heteroatom, a saturated or olefinically or acetylenically unsaturated C bonded to Si-C １ -C １８ hydrocarbon radical, and two or more oxygen atoms in the same radical R ２ are always separated from one another by hydrocarbon units, and the oxygen and silicon atoms are such that when both types of heteroatoms are present in one radical R ２ they are not bonded to one another to form an Si-O unit, but are instead always separated from one another by hydrocarbon units, while two or more Si atoms in the same radical R ２ may be bonded to one another by a direct Si-Si bond, and the Si atoms are always tetravalent, and the remaining valences of the Si atoms are saturated by further substituents bonded to Si-C which can be olefinically or acetylenically unsaturated, and R ２ may also contain olefinic or acetylenic unsaturated functional groups which may also contain heteroatoms, and R ２ may also be a hydroxyl radical, or is bonded to the silicon atom through an oxygen atom, is unsubstituted or substituted by a heteroatom, and is a monovalent aliphatic, alicyclic or aromatic, Si—C-bonded organic hydrocarbon radical having 1 to 18 carbon atoms, R １ and R ３ may each independently be the same or different radicals, a hydrocarbon radical, or unsubstituted or substituted by heteroatoms, a monovalent aliphatic, alicyclic or aromatic, Si—C-bonded, organic hydrocarbon radical having 1 to 18 carbon atoms, and said organic hydrocarbon radical may also be an unsaturated hydrocarbon radical, where R １ and R ３ may also be a hydroxyl radical, or be bonded to said silicon atom through an oxygen atom, unsubstituted or substituted by heteroatoms, a monovalent aliphatic, alicyclic or aromatic, Si—C-bonded, organic hydrocarbon radical having 1 to 18 carbon atoms, Y is a chemical bond or a divalent to dodecavalent aromatic, alkylaromatic or cycloalkylaromatic or divalent to dodecavalent aliphatic or cycloaliphatic radical having 1 to 48 carbon atoms and a main chain not containing heteroatoms, and when the radical Y is not a chemical bond, it is always bonded to the silicon atom to which it crosslinks by an Si-C linkage, a is a number having a value of 1 or 2, b is a number having a value of 1 or 2, and a + b = 3, c is a number having a value of 0, 1 or 2, d is a number having a value of 0, 1 or 2, and c + d = 2, e is a number from 1 to 12, f is a number having a value from 1 to 12, g is a number having a value from 3 to 250, provided that Per silphenylene polymer of the formula (I), at least one olefinic or acetylenic unsaturated radical R, R １ , R ２ or R ３ must be present, All radicals R, R bonded to all Si as 100 mol%, １ , R ２ and R ３ Based on the total of, the total of all organic radicals bonded to Si atoms through oxygen atoms must be 10 mol% or less, based on all crosslink-forming radicals Y as 100 mol%, at least 55 mol% of the radicals Y are divalent to dodecavalent aromatic, alkylaromatic and cycloalkylaromatic radicals) of the silphenylene polymer.

2. R ２ The silphenylene polymer according to claim 1, wherein the heteroatom in R is selected from an oxygen atom and a silicon atom.

3. The olefinic or acetylenic unsaturated radicals R, R １ , R ２ or R ３ is selected from alkenyl radicals, acryloyloxy and methacryloyloxy radicals of acrylic acid or methacrylic acid, and acrylic acid esters or methacrylic acid esters of unbranched or branched alcohols having 1 to 15 carbon atoms, the silylphenylene polymer according to any one of claims 1 to 2.

4. The silphenylene polymer according to any one of claims 1 to 3, wherein Y is a crosslink-forming aromatic unit having 1 to 24 carbon atoms in 2 to 12 carbosilyl units.

5. The crosslink-forming aromatic radical Y is of the formula (IVa), (IVb) and (IVc): 【Chemical 1】 (wherein the radical R １０ , R １１ , R １２ and R １３ are a hydrogen radical, a substituted or unsubstituted hydrocarbon radical, or a group of the formula OR １４ (wherein R １４ is a hydrocarbon radical), and adjacent radicals in the formulas (IVa), (IVb) and (IVc) may be linked to each other to form a cyclic radical and may form a fused ring system) The silphenylene polymer according to any one of claims 1 to 4, which is a radical of.

6. All radicals R, R １ , R ２ and R ３ bonded to Si as 100 mol% of all Si, based on the total of all organic radicals bonded to Si atoms by oxygen atoms, is 1 mol% or less. The silphenylene polymer according to any one of claims 1 to 5.

7. It is liquid in the uncrosslinked state and has a viscosity of 20 to 8,000,000 mPa·s as determined by rotational viscosity measurement according to DIN EN ISO 3219 at 25°C, or is solid and has a glass transition temperature determined by differential scanning calorimetry (DSC) according to DIN 53765, perforated crucible, heating rate 10 K / min in the range of 25°C to 250°C. The silphenylene polymer according to any one of claims 1 to 6.

8. The silphenylene polymer according to any one of claims 1 to 7, wherein g is a number having a value of at least 5.

9. A method for preparing the silphenylene polymer of formula (I) according to any one of claims 1 to 8: R ａ R １ ｂ Si[Y[(SiR ２ ｃ R ３ ｄ ) ｅ ｆ ｇ YSiR ａ R １ ｂ (I)​​ ​ Formula (VIII): [Hal] ｏ -Y(VIII) (wherein Hal is a Cl, Br or iodine atom, o is a number from 2 to 12, Y has the definition indicated therefor in claims 1 to 8) of the compound, with magnesium, and a silicon-containing compound selected from the compounds of formula (IV), (V) and (VI): R １５ ｈ R １６ ｉ Si (IV) R １５ ｊ R １６ ｋ Si[SiR ｌ １７ R ｍ １８ ｎ SiR ｊ １５ R ｋ １６ (V)​ R １５ ｊ R １６ ｋ Si[SiR ｌ １７ R ｍ １８ ｎ -X １ -[SiR ｌ １７ R ｍ １８ ｎ SiR １５ ｊ R １６ ｋ (VI)​​ (wherein R １５ is a halogen atom or a C1-C3 alkoxy group, R １６ , R １７ and R １８ are, independently of one another, radicals of the group of the radicals R, R １ , R ２ or R ３ but not the radical of the formula (II), and R １８ may additionally be a halogen radical or a C1-C3 alkoxy radical which does not contain a carbonyl or carboxyl group, a hydroxyl group, a double-bonded nitrogen atom, a primary, secondary or tertiary amine group or a thiol group-containing functional group X １ is a chemical bond or does not contain a functional group comprising a carbonyl or carboxyl group, a hydroxyl group, a doubly-bonded nitrogen atom, a primary, secondary or tertiary amine group or a thiol group, and has the formula R １９ -X ２ -R １９ (wherein R １９ is an olefinically or acetylenically unsaturated, hydrosilylatable C2-C8 radical, and X ２ is the radical X １ shortened on either side by said C2-C8), is a divalent crosslink-forming aliphatic, cycloalkylaliphatic, cycloalkylaromatic or alkylaromatic hydrocarbon radical produced by hydrosilylation of a hydrosilylatable, olefinically or acetylenically unsaturated precursor Z, h is an integer having a value of 1, 2, 3 or 4, i is an integer having a value of 0, 1, 2 or 3 and the sum h + i = 4, j is a number having a value of 0, 1, 2 or 3, and j has a value of 1 at at least one terminal Si atom of the di-, oligo- or polysilane of formula (V), with the result that there is always at least one radical R per molecule of formula (V) １５ is present k is an integer having a value of 0, 1, 2 or 3, where k + j = 3, l and m are each a number having a value of 0, 1 or 2 and l + m = 2, n is a number having a value from 0 to 50) and reacting with the compound of said formula (VIII): (wherein [Hal] ｏ -Y(VIII) Hal is a Cl, Br or iodine atom, o is a number from 2 to 12, Y has the definition indicated therefor in claims 1 to 7) of the compound, a method.

10. The method according to claim 9, wherein the compound of said formula (VIII) is selected from 1,4-dibromobenzene, 1,4-dichlorobenzene, 1,2-dichloroethane and 1,2-dibromoethane.

11. The method according to claim 9 or 10, which is carried out in an ether.

12. The method according to any one of claims 9 to 11, which is carried out stepwise by first reacting the component of said formula (VIII) with magnesium and adding in a second step the respective required selections of components (IV), (V), (VI) and (VII).

13. Use of the copolymer according to any one of claims 1 to 8 in the manufacture of coating materials and impregnants as binders or additives in preparations and of coatings and coverings produced therefrom on substrates.

14. Use of the copolymer according to any one of claims 1 to 8 for producing a metal laminate.

15. The use according to claim 14, wherein the metal is selected from copper, stainless steel, gold, aluminum, silver, zinc, tin, lead and transition metals. ​

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