Polyorganosiloxane copolymers with organic polymers

Abstract

The invention relates to polyarylene ether-polysiloxane copolymers containing olefinically unsaturated groups, of the formula (I) [O3-a / 2RaSi-Y1(SiRaO3 -a / 2)b]c(R1SiO3 / 2)d(R2 2SiO2 / 2)e(R3 3SiO1 / 2)f(SiO4 / 2)g (I), which contain polyarylene ether radicals selected from the formulae (II) or (III), where Y1, R, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 have the meanings indicated in claim 1; a process for preparing them and also the use thereof in the production of coating materials and impregnating systems and their resultant coatings and coverings on substrates, as a binder or as an additive in preparations.

Description

[0001] Polyorganosiloxane copolymers with organic polymers

[0002] The invention relates to hydrolysis-stable, curable copolymers of three-dimensionally crosslinked polyorganosiloxanes with polyarylene ethers, their preparation, and their use for the production of components for high-frequency applications.

[0003] With the progressive development of high-frequency technology for wireless communications, the demand for materials suitable for its implementation is increasing. This affects all areas of materials such as copper fillers, binders, glass fibers, etc. Regarding binders, the traditional binders used for the production of both flexible and rigid metal-clad laminates, especially copper-clad laminates, or the epoxy resins used in circuit board production are no longer suitable due to their high dielectric loss factors. Polytetrafluoroethylene, which has a very low dielectric loss factor and is well-suited for high-frequency applications in this respect, has other disadvantages, particularly poor processability and poor adhesion properties, which make an alternative desirable.Polyarylene ethers are currently intensively used as binders for this application area because they combine low dielectric loss factors with good mechanical and thermal properties and water repellency.

[0004] In addition, other organic polymers are currently being considered in development activities for this application area, such as bismaleimide polymers, bismaleimide triazine copolymers, and hydrocarbon resins, although this list could be expanded to include others. Polyorganosiloxanes generally possess excellent heat resistance, weathering stability, and hydrophobicity, are flame-resistant, and have low dielectric loss factors.

[0005] These property profiles qualify both the aforementioned organic polymers and the polyorganosiloxanes for use as binders in the production of high-frequency-capable copper-clad laminates and components, such as circuit boards and antennas. Therefore, it is logical to combine the positive properties of these material classes, in this case especially the polyarylene ethers, to symbiotically increase their performance. Corresponding experiments have already been documented in the state of the art.

[0006] A key challenge is combining the polysiloxanes and polyarylene ethers in such a way that they are compatible and do not separate. Physical mixtures often do not meet this requirement. Only highly aromatic substituted polysiloxanes are particularly suitable for such a mixing approach. Since aliphatic substituents often result in better dielectric properties, and especially small aliphatic silicon-bonded residues, such as the methyl residue, cause particularly low material shrinkage in the event of a fire or a particularly high mass fraction of the corresponding polysiloxanes remains as combustion residue, a method that allows any polysiloxane to be combined with polyarylene ethers offers clear advantages. One such method involves the copolymerization of polysiloxanes with polyarylene ethers. State of the art already exists for this. State of the art:

[0007] US 5357022 teaches flame-resistant thermoplastic polyorganosiloxane-polyarylene ether block copolymers of polydiorganosiloxane macromers, each containing two terminal 2-methoxy-4-trimethylenephenol groups, and 2,6-xylenol, obtained by oxidative coupling. It is demonstrated that polydiorganosiloxanes of different chain lengths can be used to achieve the flame-resistant effect according to the invention. The hydroxyaryl-terminated polydiorganosiloxanes used according to the invention for copolymer synthesis are obtained by hydrosilylation of an allyl-functional phenol, for example, eugenol, with an Si-H-terminal polydiorganosiloxane.

[0008] US 8017697 demonstrates that the yield of polyarylene ether polydiorganosiloxane block copolymers according to the process according to US 5357022 is quite low, resulting in predominantly physical mixtures of polyarylene ether and the silicone component used, which may only be miscible with each other to a limited extent and the inventive effect of flame resistance according to US 5357022 has considerable potential for improvement, which is to be realized according to the teaching of US 8017697.

[0009] The copolymers according to neither US 5357022 nor US 8017697 possess radically crosslinkable, olefinically unsaturated groups for chemical curing. Only the phenol group of the terminal 2,6-xylenol units remains for further chemical reaction.

[0010] Conventional methods for crosslinking and curing such polyarylene ethers include methods involving the addition of an excess of a thermosetting resin such as an epoxy resin or a crosslinking compound such as triallyl isocyanurate. However, the low dielectric loss factor, low dielectric constant, and high heat resistance inherent to polyarylene ethers cannot be achieved by these methods. For example, polyarylene ether / polyepoxide compositions are disclosed in JP 6-206984 A and JP 11-302529 A. Because crosslinking and curing are achieved by adding an excess of polyepoxide to polyarylene ether, the low dielectric loss factor, low dielectric constant, and high heat resistance inherent to polyarylene ethers cannot be achieved by these methods.JP 11-236430 A discloses a composition consisting of polyarylene ether, a brominated epoxy compound and an allyl compound, but there is a problem that the property of low dielectric loss factor, low dielectric constant and high heat resistance inherent in polyarylene ether is deteriorated due to the large proportion of the epoxy compound and the allyl compound in the composition.

[0011] The polydiorganosiloxane-polyarylene ether copolymers according to US 5357022 are therefore unsuitable for use in high-frequency applications due to their curing behavior. Furthermore, polydiorganosiloxanes themselves are soft structural elements that plasticize the copolymer and reduce its glass transition temperature. This results in a reduction in the glass transition temperature, which represents a processing disadvantage for a binder for electronic components such as copper-clad laminates for circuit board production. Binders with a low softening temperature tend to flow under soldering conditions and would leave holes in the electronic component. This would render the circuit board unusable. US20180155547 teaches thermoplastic preparations of polyarylene ethers, polyarylene ether-polysiloxane block copolymers, homopolystyrene, a flame retardant, and a reinforcing filler.According to US 20180155547, the preparations according to the invention exhibit a balanced balance of flame retardancy, heat resistance, rigidity, and melt flow properties. The polyarylene ether-polysiloxane block copolymers are structured similarly to those of US 5357022 and US 8017697, with US 20180155547 containing, in addition to C1-C, analogous to US 8017697. 12 hydrocarbon residues and C1-C 12 Halogenated hydrocarbon residues also contain silicon-bonded hydrogen on the polysiloxane chains of the structure permits. Similar to US 5357022, these are also linear polysiloxane blocks and thus essentially optionally water-substituted polydiorganosiloxanes. The polyorganosiloxane units used for the synthesis are also hydroxyaryl-terminated so that they are capable of oxidative coupling with other phenol units. In contrast to US 5357022, US 201801555047 also permits hydroxyaryl-terminated residues in the polysiloxane chain and not just at the end. Thus, according to US 20180155547, not only linear block copolymers are possible, as in US 5357022, but also branched block copolymer structures, which arise from the fact that polyarylene chains grow not only on the terminal hydroxyaryl residues but also on the chain-side hydroxyaryl residues as a result of the oxidative coupling.The polyorganosiloxanes according to US 201801555047, in turn, do not contain any organofunctional groups that would allow further chemical curing, in particular no olefinic groups that would allow radical curing. Due to the significant similarities between the polyorganosiloxane structures according to US 20180155547 and US 5357022, it is reasonable to assume that the hydroxyaryl-functional polyorganosiloxanes used to produce the polyarylene ether polysiloxane block copolymers according to US 20180155547 are also prepared by hydrosilylation from allyl-functional phenols and Si-H-functional polydiorganosiloxanes, especially since the same inventor explicitly states this in US 8017697 and the structures given therein, which correspond to those in US 20180155547. This is also obvious since US 20180155547 also allows Si-H groups in the polyorganosiloxane chains and chain-based hydroxyaryl residues.If chain-linked Si-H groups are present in the polydiorganosiloxanes, they will partially participate in this hydrosilylation reaction and thus lead to the chain-linked hydroxyaryl radicals, which are responsible for the branching permitted according to the invention through side-linked polyphenylene ether chains in the polyarylene ether polysiloxane block copolymers. Branches of the polyorganosiloxane unit through so-called T units of the general form RSiO. 3 / 2 or Q-units of the form SiC>4 / 2 are not contained in the block copolymers, but only the siloxane building blocks generally referred to as D-units of the above-mentioned and generalized as R2SiO 2 / 2 siloxane building blocks to be described.

[0012] The polyarylene ether polysiloxane block copolymers according to US 2018015547, like the polyarylene ether polysiloxane block copolymers according to US 5357022 and US 8017697, do not have any further functional groups capable of chemical curing, in particular radical curing, apart from the phenolic OH end groups, which is associated with the same disadvantages with regard to dielectric properties as already described above.

[0013] US8309655 describes the synthesis of polyarylene ether polysiloxane block copolymers which are not obtained by the oxidative coupling of hydroxyaryl-functional polysiloxanes and phenols, but by the reaction of alpha omega hydroxy-terminated polyarylene ethers with alpha omega hydroxyaryl-terminated polyorganosiloxanes and aromatic

[0014] Dicarboxylic acid chlorides .

[0015] The hydroxyaryl-terminated polyorganosiloxanes used have the following structure, where R 7 next to C1-C 12 hydrocarbon residues and C1-C 12 Halogenated hydrocarbon residues can also represent silicon-bonded hydrogen. In this case, a hydrosilylation reaction is stated as the formation reaction for the hydroxyaryl-terminated polysiloxanes.

[0016] The challenge in the reaction of alpha-omega hydroxy-terminated polyarylene ethers with alpha-omega hydroxyaryl-terminated polyorganosiloxanes and aromatic dicarboxylic acid chlorides is reaction control. The alpha-omega hydroxy-terminated polyarylene ethers and the alpha-omega hydroxyaryl-terminated polyorganosiloxanes exhibit different reactivities compared to the aromatic dicarboxylic acid chlorides, so that the composition of the copolymer can only be controlled with a certain degree of uncertainty and increased effort compared to the oxidative coupling method.

[0017] In this case too, the block copolymers contain only the remaining phenolic OH groups as functional groups and no further organofunctional, in particular radically curable olefinically unsaturated groups with the consequences and disadvantages for electronic high-frequency applications already described above.

[0018] There are many more examples of such alternatives to the oxidative coupling reaction as a formation reaction for polyarylene ether polysiloxane copolymers. For example, JP61252214 describes the preparation of polyarylene ether polysiloxane copolymers by reacting lithiated polyparylene ethers with mono-chloride-functional siloxane macromers. US4814392 describes the formation of polyarylene ether polysiloxane copolymers by reacting anhydride-functional polyarylene ethers with amino-terminated polysiloxanes. US20070208144 describes the synthesis of polyarylene ether polysiloxane copolymers by reacting polyarylene ethers with hydroxyaryl-terminated polysiloxanes in the presence of activated aromatic carbonates. All of these synthetic processes have their specific disadvantages.They sometimes require multiple reaction steps and the use of expensive and limited chemicals, the handling of which on an industrial scale would cause considerable problems and additional effort and costs. Alternatives to oxidative coupling as the process of choice for the preparation of polyarylene ethers and their derivatives or variants have therefore not become established. Furthermore, these publications and teachings also exclusively use linear polysiloxane structures, i.e., polydiorganosiloxanes with terminal functional groups. Neither crosslinked siloxane structures are obtained, nor are additional functional groups, particularly olefinically unsaturated ones suitable for radical curing, described.

[0019] Object of the invention:

[0020] The object of the invention is to provide hydrolysis-stable, chemically curable copolymers of three-dimensionally crosslinked polyorganosiloxanes with polyarylene ethers, as well as a process for their preparation and a teaching for their use in the production of components for

[0021] to provide high frequency applications.

[0022] The invention relates to polyarylene ether polysiloxane copolymers containing olefinically unsaturated groups of the formula (I)

[0023] [O 3-a / 2 R a Si-Y 1 (SiR a O 3-a / 2 ) b ] c (R 1 SiO 3 / 2 ) d (R 2 2SiO 2 / 2 ) e (R 3 3SiO 1 / 2 ) f (SiO 4 / 2 ) g (I), where

[0024] Y 1a chemical bond or a divalent to dodecavalent organic unsubstituted or heteroatom-substituted aliphatic, cycloaliphatic or aromatic organic radical having 1 to 24 C atoms and bonded to the silicon atoms by a Si-C bond, R, R 1 , R 2 and R 3 are independently of one another identical or different and are either a hydrogen radical, a hydroxy radical or a Si-C-bonded or Si-O-bonded monovalent, unsubstituted or heteroatom-substituted and optionally organofunctional organic hydrocarbon radical having 1 to 18 C atoms or a Si-C-bonded polyarylene ether radical, where the proportion of the hydroxy radicals and the Si-O-bonded radicals is based on the sum of all radicals R, R 1 , R 2 and R 3than 100% by weight is at most 5% by weight, wherein the proportion of Si-C-bonded polyarylene ether radicals based on the sum of all radicals R, R 1 , R 2 and R 3 than 100% by weight is at least 10% by weight, wherein the proportion of olefinically or acetylenically unsaturated radicals based on all radicals R, R 1 , R 2 and R 3 than 100 mol% is at least 0.5 mol%, wherein the polyarylene ether radical is selected from a radical of the formula (II) or (III) where the residues R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 independently of one another, a hydrogen radical, a monovalent hydrocarbon group, a hydrocarbon group substituted with heteroatoms, an organofunctional radical or a silyl group of the form (R 40 3Si-), where R 40the meanings of R 3 and the residues R 4 to R 12 may also be bound to the aromatic ring via a heteroatom, where the radicals R 4 , R 5 and R 6 also a chemical bond or a divalent aliphatic, cycloaliphatic or aromatic hydrocarbon radical with 1 to 12

[0025] Carbon atoms, by which the bond of the radicals of formula (II) to the polyorganosiloxane framework is produced, wherein at least one radical R 4 , R 5 or R 6 is such a radical which forms a bond to the polyorganosiloxane framework, wherein, as far as chemically possible, adjacent radicals from the group of radicals R 4 to R 12may also be bonded to each other to form the same cyclic saturated or unsaturated radical, so that fused polycyclic structures are formed which comprise both cycloaliphatic and cycloaromatic structures or mixed forms thereof, wherein the radical R 14 a chemical bond or a divalent, optionally substituted arylene radical of the form (-C6R 15 4-) where R 15 independently of these have the same meaning as the residues R 9 , R 10 , R 11 or R 12 or an alkylene radical of the form -CR 16 2 _ means, where R 16 independent of R 15 the same meanings as R 15 may have a divalent glycol residue of the form - [(OCH2)2O]1- or - [ (OCH2CH (CH3)2)O] m-, where 1 and m each independently represent integers ranging from 1 to 50 inclusive, a divalent silyloxy radical of the form - Si (R 17 )2O 2 / 2 -, a divalent siloxane residue of the form -[(CH2)3Si- [O-Si (R 18 )2] n O-Si(CH2)3-, a divalent silyl radical of the form - Si(R 19 )2 _ , where R 17 , R 18 and R 19 independently of each other and independently of R 15 can have the same meanings as R 15and n is an integer with a value from 0 to 500 inclusive, where a is an integer with a value of 0, 1 or 2, where the indices a on both sides of the group Y can assume their meaning independently of one another, so that different a can independently of one another have different values ​​within the specified value range, h has a value from 0 to 1000, b is an integer with a value of 1 to 11, c has a value from 0 to 0.9, d has a value from 0 to 1, e has a value from 0 to 0.5, f has a value from 0 to 0.6 and g has a value from 0 to 0.2, where c+d+e+f+g = 1 and at least c or d has a value other than 0 and the sum c+d of the sum c+d+e+f+g accounts for at least 40%, i, j and k are integers, where i is an integer with a value from 0 to 50 inclusive meansj is an integer having a value from 0 to 10 inclusive, and k is an integer having a value from 0 to 50 inclusive, with the proviso that at least one polyarylene ether radical of the,

[0026] Formula (II) or (III) each polyarylene ether polysiloxane copolymers of formula (I) are present.

[0027] The polyarylene ether polysiloxane copolymers of formula (I) are copolymers of three-dimensionally crosslinked polyorganosiloxanes with polyarylene ethers that can be chemically cured to thermosets by means of olefinically unsaturated groups. They overcome the disadvantages recognized in the prior art and improve upon it, since the addition of auxiliary polymers or other substances that negatively influence the dielectric properties, i.e., increase the dielectric loss factor and the dielectric constant, can be dispensed with for curing. By curing the polyarylene ether polyorganosiloxane copolymers according to the invention as the sole binder, usable materials suitable for use in high-frequency applications are obtained.

[0028] If several polyarylene ether radicals are present per polyarylene ether polysiloxane copolymer of formula (I), these can either be only those of formula (II) or only those of formula (III) or mixtures of those of formula (II) and formula (III).

[0029] The arrangement of the modules can be random or block-wise. This means that modules [O 3-a / 2 R a Si-Y 1 (SiR a O 3-a / 2 ) b ] c , (R 1 SiO 3 / 2 ) d , (R 2 2SiO 2 / 2 )e, (R 3 3SiO 1 / 2 ) f and (SiO 4 / 2 ) g in the molecular structure alternate statistically with each other, or there are blocks of several repeating units of the same form, i.e. of [O 3-a / 2 R a Si-Y 1 (SiR a O 3-a / 2 ) b ] c or (R 1 SiO 3 / 2 ) d or (R 2 2SiO 2 / 2 )e or (R 3 3SiO 1 / 2 ) f or (SiO 4 / 2 ) g , in addition to blocks made up of several repeating units of the other modules, whereby at least 3 identical modules must be combined to form a block in order to obtain an effective block structure.

[0030] Preferably, the value of d is at least 4, c+f is at least 9, preferably at least 15, in particular 20 to 100, and g is at least 1, independently of one another.

[0031] Preferably, the proportion of hydroxyl radicals and Si-O-bonded radicals based on the sum of all radicals R, R 1 , R 2 and R 3 than 100% by weight at most 4% by weight, particularly preferably at most 3% by weight, in particular at most 2% by weight. The proportion of Si-C-bonded polyarylene ether radicals, based on the sum of all radicals R, R 1 , R 2 and R3 as 100 percent by weight, at least 12 percent by weight, particularly preferably at least 14 percent by weight, in particular at least 15 percent by weight. It has proven particularly useful to adjust the proportion of polyarylene ether residues to at least 30 percent by weight, since this achieves particularly good adhesion properties of the polyorganosiloxane polyarylene ether copolymers of formula (I) according to the invention when used according to the invention as binders for high-frequency-capable metal layer laminates.

[0032] Preferably, based on all radicals R, R 1 , R 2 and R 3 than 100 mol% at least 2 mol%, particularly preferably at least 3 mol%, in particular at least 4 mol% olefinically or acetylenically unsaturated radicals.

[0033] A preferred divalent hydrocarbon radical selected from R 4 , R 5 and R 6 is the -(CH2)3- residue.

[0034] The polyarylene ether radicals of formula (III) can be bonded to the polyorganosiloxane skeleton of the polyorganosiloxane polyarylene ether copolymers of formula (I) at only one or at both ends.

[0035] Preferred residues R 14 are the chemical bond, the -CH2- residue, the C(CH3)2- residue, the -C(C6H5)2- residue and the - [(CH2)3Si-[0- Si (R 18 )2]O-Si(CH2)3- residue.

[0036] Preferred values ​​of h are 1 to 500, more preferably from 1 to 300 and especially preferably from 1 to 150.

[0037] A preferred value of b is 1. Preferred values ​​of e are 0 to 0.2.

[0038] Preferred values ​​of f are 0 to 0.5.

[0039] Preferred values ​​of g are < 0.2.

[0040] Preferably, the sum c+d of the sum c+d+e+f+g is

[0041] Share of at least 50%.

[0042] Preferably, i is from 1 to 40, more preferably from 1 to 30 and especially preferably from 1 to 25.

[0043] Preferably, j is a value from 0 to 5.

[0044] Preferably, k is between 1 and 40, more preferably between 1 and 30 and especially preferably between 1 and 25.

[0045] As pure substances, the polyorganosiloxane polyarylene ether copolymers of the formula (I) according to the invention preferably have average molecular weights Mw in the range from 500 to 750,000 g / mol, preferably from 600 to 600,000 g / mol, particularly preferably from 800 to 500,000 g / mol, in particular from 800 to 40,000 g / mol, wherein the polydispersity is at most 50, preferably at most 45, particularly preferably at most 40, in particular at most 35. The polyorganosiloxane polyarylene ether copolymers of the formula (I) according to the invention are solid or liquid at 25°C with viscosities at 25°C of 20 to 8,000,000 mPas, preferably of 20 to 5,000,000 mPas, in particular of 20 to 3,000,000 mPas, the solid polyorganosiloxanes containing phenyl groups having glass transition temperatures in the uncrosslinked state in the range from 25°C to 350°C, preferably from 30°C to 300°C, in particular from 30°C to 280°C.Polyorganosiloxane polyarylene ether copolymers of formula (I) which are solid at 25°C and have a glass transition temperature of 30 - 280°C have proven particularly suitable.

[0046] The polyorganosiloxane polyarylene ether copolymers of formula (I) according to the invention are soluble in aromatic solvents in a proportion of at least 30 percent by weight of the solution. This means that in a solution consisting of a total of 100 parts of solvent and polyorganosiloxane polyarylene ether copolymers of formula (I) according to the invention, at least 30 parts of polyorganosiloxane polyarylene ether copolymers of formula (I) according to the invention are soluble. Examples of suitable solvents are aromatic solvents such as toluene, xylene, ethylbenzene, or mixtures thereof. The solubility in other solvents varies depending on the solvent selected and the particular polyorganosiloxane polyarylene ether copolymers of formula (I) according to the invention and can vary from insoluble to highly soluble.

[0047] Selected examples of preferred alkyl, cycloalkyl, aryl and alkaryl radicals R, R 1 , R 2 , R 3are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2,2,4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical, and octadecyl radicals such as the n-octadecyl radical, cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, the Phenyl, naphthyl, anthryl and phenanthryl radicals, tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals such as the benzyl radical, the α- and the β-phenylethyl radical.

[0048] For the unsubstituted radicals R, R 1 , R 2 , R 3These are predominantly hydrocarbon radicals having 1 to 12 carbon atoms, particularly preferably the methyl, ethyl, n-propyl, and phenyl radicals, in particular the methyl, n-propyl, and phenyl radicals. The methyl and phenyl radicals are particularly preferred.

[0049] Preferred heteroatoms in the radicals R, R 1 , R 2 and R 3 may be present are oxygen atoms. Furthermore, nitrogen atoms, phosphorus atoms, sulfur atoms, and halogen atoms such as chlorine atoms and fluorine atoms are also preferred. Examples of preferred heteroatom-substituted radicals R, R 1 , R 2 , R 3 are glycol residues such as polypropylene glycol residues and polyethylene glycol residues.

[0050] Selected examples of preferred organofunctional residues R, R 1 , R 2 , R 3are 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, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, and norbornyl acrylate, with methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate being particularly preferred. Further examples of radicals R 2 are olefinically or acetylenically unsaturated hydrocarbon radicals of the formulas (IV) and (V)

[0051] Z-CR 19 =CR 20 R 21 (IV) ZC=CR 22(V), where Z represents a chemical bond or a divalent linear or branched hydrocarbon radical having up to 30 carbon atoms, where Z may also contain olefinically unsaturated groups or heteroatoms, and the atom directly bonded to the silicon by the radical Z is a carbon. Heteroatom-containing fragments that may typically be present in the radical Z are -COC-, -C(=O)-, -OC(=O)-, -O- C(=O)-O-, where asymmetric radicals may be incorporated into the radical Z in both possible directions, where R 19 , R 20 , R 21 and R 22 a hydrogen atom or a Cl - C8 hydrocarbon radical which may optionally contain heteroatoms, with heteroatom-free hydrocarbon radicals being preferred and with the hydrogen atom being the most preferred radical for R 19 , R 20 , R 21 and R 22Particularly preferred radicals (IV) are the vinyl radical, the allyl radical, the propenyl radical, and the butenyl radical, especially the vinyl radical. The radical (IV) can also be a dienyl radical bonded via a spacer, such as the 1,3-butadienyl or isoprenyl radical bonded via a spacer.

[0052] Further examples of residues R, R 1 , R 2 , R 3 are the hydridic silicon-bonded hydrogen.

[0053] The residues R, R 1 , R 2 , R 3 Except for the hydrogen atom, which is always bonded to silicon, they are generally not directly bonded to the silicon atom. The exception to this are the olefinic or acetylenic groups, which can also be directly bonded to silicon, especially the vinyl group. The other functional groups R, R 1 , R 2 , R 3are bonded to the silicon atom via spacer groups, with the spacer always present in a Si-C bond. The spacer is a divalent hydrocarbon radical comprising 1 to 30 carbon atoms, in which non-adjacent carbon atoms may be replaced by oxygen atoms, and which may also contain other heteroatoms or heteroatom groups, although this is not preferred.

[0054] The methacrylate group and the acrylate group are preferably bonded via a spacer, wherein the spacer is bonded to the silicon atom from 3 to 15 carbon atoms, preferably in particular 3 to 8 carbon atoms, in particular 3 carbon atoms and optionally furthermore at most one to 3 oxygen atoms, preferably at most one divalent hydrocarbon radical comprising 1 oxygen atom.

[0055] In principle, the term "olefinically unsaturated residues" refers to all residues that contain at least one double bond, regardless of whether this double bond is part of a functional group with a different name, such as an acrylate group or a methacrylate group. In this sense, an acetylenically unsaturated residue is one that contains a triple bond. Residues that contain both double and triple bonds can be included under both terms and are also included.

[0056] If the remainder Y 1 does not mean a chemical bond, it is always bound exclusively to the silicon atoms by a Si-C bond, which is formed by the residue Y 1 Typical examples of bridging residues Y 1 are connecting organic units with 1 to 24 C atoms between preferably two to twelve siloxanyl units. Y is preferably 1divalent, trivalent, or tetravalent, especially divalent. The residue Y 1 can also be a bridging organic radical which contains a polyarylene ether radical of the formula (II) or (III).

[0057] Preferred bridging aromatic residues Y 1 are those of

[0058] Formula (VI) where the residues R 23 , R 24 , R 25 , R 26 , R 27 and R 28 a

[0059] hydrogen radical or an optionally substituted hydrocarbon radical or a group of

[0060] Formula OR 29 where R 29 a hydrogen residue or a

[0061] Polyarylene ether radical of formula (II) or (III) or an aliphatic or cycloaliphatic optionally

[0062] Heteroatom-containing hydrocarbon radical, with oxygen atoms being preferred as heteroatoms. Neighbouring radicals in formula (VI) can react with one another to form cyclic

[0063] residues are coupled to form fused ring systems. In particular, two residues from the

[0064] Group of residues R 23 , R 24 , R 25 , R 26 , R 27 and R 28 either a chemical bond or a divalent organic

[0065] Hydrocarbon radical having 1 to 12 carbon atoms, preferably an aliphatic radical of the form -(CH2)3- with three

[0066] carbon atoms, which combines a silicon atom with the aromatic

[0067] Ring. Typical examples of such bridging aromatic radicals are the p-, m-, or o-phenylene radical, the 2-methyl-1,4-phenylene radical, and the 2-methoxy-1,4-phenylene radical, with the p-phenylene radical being particularly preferred.

[0068] Optionally, several such radicals can be coupled together, so that, for example, two or more units of formula (VI) are coupled together and this oligomeric bridging structural element is present by bonding the corresponding carbon atoms of the terminal aromatic rings to silicon atoms. The aromatic units can be directly bonded to one another or they can be connected by a bridging group such as an alkanediyl unit, for example the methylene group, the

[0069] 1,2-ethanediyl group, 1,1-ethanediyl group, 2,2-dimethylpropyl group or a sulfone group.

[0070] Further examples of aromatic bridging units are those in which two substituted phenol rings are bridged via an alkanediyl or other unit.

[0071] Typical representatives are 2,2-bis(4-hydroxyphenyl)propane residues substituted on the phenol oxygen or on the aromatic ring (substituted bisphenol A residues),

[0072] 2,2-Bis(4-hydroxyphenyl)methane residues (substituted bisphenol F residues), bis(4-hydroxyphenyl)sulfone residues (bisphenol S residues), where either the phenol oxygen atoms or the aromatic rings of the parent structure are typically substituted with residues of the type -(C3H6)-, where the residues -(C3H6)- are bonded to silicon atoms Si-C, thereby forming the bridge. Unsubstituted phenol groups of the bisphenol parent structure in such bridging units can be substituted by residues of the formula (II) or (III) during the synthesis of the polyorganosiloxane polyarylene ether copolymers according to the invention, so that the bridging residues Y 1not only represent a structural feature of the polyorganosiloxane framework, but can also contribute to the formation of copolymers according to the invention, or the building group containing them alone is sufficient to form polyorganosiloxane polyarylene ether copolymers of the formula (I) according to the invention, provided that it additionally contains the required minimum amount of crosslinkable unsaturated radicals.

[0073] Preferred residues Y not bridged by an aromatic unit 1 are alkanediyl, alkenediyl and alkynediyl radicals which may optionally contain heteroatoms and which may contain aromatic groups as substituents, but which do not take over or contribute to the bridging function in these radicals.

[0074] Typical examples are the methylene radical, the methine radical, the tetravalent carbon, the 1,1-ethanediyl and the 1,2-ethanediyl group, the 1,4-butanediyl and the 1,3-butanediyl group, the 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonadiyl, 1,10-decanediyl, 1,11-undecanediyl and the 1,12-dodecanediyl group, the 1,2-diphenylethanediyl group, the 1,2-phenylethanediyl group, the 1,2-cyclohexylethanediyl group. If a linear bridging unit has more than one carbon atom and the substitution pattern allows it, each of these groups can act as a bridge not only through alpha-omega connectivity, i.e. bridging through the first and last atom of a linear unit, but also through any other connectivity, i.e. the use of other chain carbon atoms.In addition, typical examples are not only the linear representatives of the bridging hydrocarbons mentioned, but also their isomers, which in turn can have a bridging effect by binding different C atoms of the hydrocarbon structure to silicon atoms.

[0075] Examples of particularly preferred radicals from the group of non-aromatic heteroatom-free hydrocarbon radicals are -CH2CH2-, -CH(CH3)-, -CH=CH-, -C(=CH2)- and -C=C-.

[0076] Examples of typical fluorine-substituted bridging residues Y 1 are the -C(CF3)2-, the -C(H)FC(H)F- and the -C(F2)-C(F2)- residue.

[0077] Examples of typical heteroatom-containing bridging radicals are the ethyleneoxypropylene radical and the ethyleneoxybutylene radical. Also, on both sides -(CH2) n - or -CH2- CH (R 30 )-C (=O)O-terminated, where n is typically 3 to 8 and R 30represents a hydrogen atom or a methyl group and glycol residues or phenylene ether residues bonded to the silicon atoms via this terminal group are typical examples.

[0078] Another typical example of a remainder Y 1 is the chemical bond that directly connects two Si atoms.

[0079] Typical examples of residues R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 and R 23 , R 24 , R 25 , R 26 , R 27 and R 28are the hydrogen radical, saturated hydrocarbon radicals such as methyl, ethyl, n-propyl, iso-propyl, the primary, secondary and tertiary butyl radical, the hydroxyethyl radical, aromatic radicals such as the phenylethyl radical, the phenyl radical, the benzyl radical, the methylphenyl radical, the dimethylphenyl radical, the ethylphenyl radical, heteroatom-containing radicals such as the hydroxymethyl radical, the carboxyethyl radical, the methoxycarbonylethyl radical and the cyanoethyl radical 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, iso-butyl acrylate, iso-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate, olefinic or acetylenically unsaturated hydrocarbon residues .

[0080] If necessary, adjacent residues can also be bonded to form the same cyclic saturated or unsaturated residue, thus forming fused polycyclic structures. The possibility that certain residues from the group of residues R 4 , R 5 , R 6 , R 7 , R 8 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 It has been pointed out above that these can mean a chemical bond or a divalent hydrocarbon residue.

[0081] If the index h in formula (II) is 0 and R 13is a hydrogen radical, the radical of formula (II) represents a substituted or unsubstituted phenol radical. Typical examples of such phenol residues of the formula (II) are the phenol residue, the ortho-, meta- or para-cresol residue, 2,6-, 2,5-, 2,4- or 3,5-dimethylphenol residue, 2-methyl-6-phenylphenol residue, 2,6-diphenylphenol residue, 2,6-diethylphenol residue, 2-methyl-6-ethylphenol residue, 2,3,5-, 2,3,6- or 2,4,6-trimethylphenol residue, 3-methyl-6-tertiary-butylphenol residue, thymol residue, 2-methyl-6-allylphenol residue and the 4-allyl-2-methoxyphenol (= eugenol) residue, which may optionally be substituted on the oxygen atom and which can be formed by direct bonding of an aromatic ring carbon atom or by a C3 spacer of the form — (CH2)3— to the Polyorganosiloxane framework can be bound.

[0082] All examples of typical radicals are illustrative but in no way limiting. The polyorganosiloxane polyarylene copolymers of formula (I) are preferably used as binders for the production of metal-clad laminates. The polyorganosiloxane polyarylene copolymers of formula (I) are crosslinked during the production of the laminates. The laminates are preferably metal-clad laminates. The laminates are preferably used in electronic components, preferably in high-frequency applications, especially those operating at frequencies of 1 GHz and above.

[0083] Surprisingly, it has been found that suitable unsaturated organic functional group-bearing polyorganosiloxane polyarylene copolymers of the formula (I) or preparations thereof are particularly suitable for this purpose.

[0084] The polyorganosiloxane polyarylene copolymers of formula (I) have a dielectric loss factor of not more than 0.0040 at 10 GHz.

[0085] The polyorganosiloxane polyarylene copolymers of formula (I) in the context of the present invention also include in particular the preferred structures of formula (Ia), (Ib), (Ic) and (Id)

[0086] [O 3-a / 2 R a Si-Y 1 (SiR a O 3-a / 2 ) b ] c (R 3 3SiO 1 / 2 ) f (la)

[0087] [O 3-a / 2 R a Si-Y 1 (SiRaO 3-a / 2 ) b ] c (R 1 SiO 3 / 2 ) d (R 3 3SiO 1 / 2 ) (Ib)

[0088] (R 1 SiO3 / 2) d (R 3 3SiO 1 / 2 ) f (Ic)

[0089] (R 1 SiO 3 / 2 ) d(Id). These are particularly suitable for practicing the invention. They do not contain any units of the formula (R 2 2SiO 2 / 2 ) ei which represent the main, if not exclusive, building blocks in the polyorganosiloxanes according to the prior art. This is a structurally particularly striking distinguishing feature of the present invention from the known prior art.

[0090] In a particularly preferred embodiment of (Ia) and (Ib), the value for a = 2 and b = 1. All meanings for the radicals and indices in the formulas (Ia), (Ib), (Ic) and (Id) are the same as already indicated above.

[0091] The preferred preparation of the polyorganosiloxane polyarylene ether copolymers of formula (I) according to the invention is carried out from hydroxyaryl-functional polyorganosiloxane compounds of formula (VII) by oxidative coupling of the arylhydroxy radicals of the polyorganosiloxane compounds of formula (VII)

[0092] [O 3-a / 2 R 31 a Si-Y 2 (SiR 31 a O 3-a / 2 ) b ] c (R 32 SiO 3 / 2 ) d (R 33 2SiO 2 / 2 )he 34 3SiO 1 / 2 ) f

[0093] (SiO 4 / 2 ) g

[0094] (VII), where

[0095] R 31 a residue R, R 32 a remainder R 1 , R 33 a remainder R 2 , R 34 a remainder R 3 and Y 2 a remainder Y 1 means, with the difference that if R 31 , R 32 , R 33 or R 34a radical of formula (II) or if Y 2 comprises such a radical of formula (II), in this radical of formula (II) the index h is always 0 and the radical R 13 is always a hydrogen residue and that R 31 R 32 , R 33 and R 34 cannot represent a polyarylene ether radical of the formula (III), and that Y 2 may not contain a radical of formula (III), with the proviso that at least 1 mol-% of all Si-bonded

[0096] residues a residue of formula (II) with h = 0 and R 13 = hydrogen, with phenols of the formula (VIlla) or (VIllb) or a mixture of (VIlla) and (VIllb) where the residues R 9 , R 10 , R 11 , R 12 and R 14 and j have the meanings given above.

[0097] In the process, residues of formula (II) with h = 0 and R 13= Hydrogen must be present in the polyorganosiloxanes of formula (VII) in sufficient quantity to provide sufficient reactants for the phenols of formula (VIII) to form the copolymers of formula (I) according to the invention. This is the case when at least 1 mol%, preferably at least 2 mol% of all Si-bonded radicals contain a radical of formula (II) with h = 0 and R 13 = hydrogen. Therefore, this is an essential condition for the polyorganosiloxanes of formula (VII).

[0098] The phenols for oxidative coupling with the polyorganosiloxanes of formula (VII) are those of formula (VIlla) to produce a radical of formula (II).

[0099] The phenols for oxidative coupling with the polyorganosiloxanes of formula (VII) are bisphenols of formula (VIllb) to produce a radical of formula (III).

[0100] Preferably, j is 0 or 1, in particular 1.

[0101] Depending on the tolerance of the chosen production process toward olefinically and acetylenically unsaturated groups, these groups, which are essential for the invention, are introduced in further process steps after the copolymerization. How this is possible and the options available for selecting olefinic and acetylenic groups with only limited hydrosilylatability in the preparation of the inventive copolymers of formula (I) are explained below.

[0102] Oxidative coupling is known per se. The process of oxidative copolymerization of phenolic compounds to produce polyphenylene ethers is described by way of example in US Pat. No. 3,306,874. This reference is to be understood as illustrative and not restrictive, i.e., any other prior art suitable for producing polyarylene ethers is equally relevant here. The further steps for subsequent functionalization are also already prior art in themselves. However, they are not described in combination, which makes the processes described here new overall. It is surprising that this novel combination of known processes can solve a previously unsolved problem.If this had been obvious, the problem would have been solved earlier, because as the discussion of the state of the art shows, the production of corresponding copolymers for commercial purposes has been a subject of research for more than 20 years.

[0103] The polyorganosiloxane compounds of formula (VII) can vary in viscosity over a wide range depending on the average number of structural units per molecule forming them or can also be solids.

[0104] Liquid organopolysiloxane compounds of the formula (VII) have, in the uncrosslinked state at 25°C, viscosities of preferably 20 to 8,000,000 mPas, particularly preferably 20 to 5,000,000 mPas, in particular 20 to 3,000,000 mPas.

[0105] Solid organopolysiloxane compounds of the formula (VII) have, in the uncrosslinked state, glass transition temperatures in the range of preferably 25°C to 250°C, particularly preferably from 30°C to 230°C, in particular from 30°C to 200°C.

[0106] The organopolysiloxane compounds of formula (VII) can be prepared by any method. A preferred method for preparing these compounds is hydrolysis and cocondensation of compounds of general formula (IX).

[0107] Hal 3-a R 31 a Si-Y 2 (SiR 31 a Hal 3-a ) b (IX) with compounds of formula (X)

[0108] R 36 m SiHal 4-m (X), where Hal is a hydrolyzable group,

[0109] R 31 and Y 2 have the meanings already given above, m is an integer with a value from 0 to 3, where R 31 for m = 1 a residue R 1, for m = 2 a residue R 2 and for m = 3 a residue R 3 and a and b have the meanings already given for formula (VII).

[0110] The compounds (IX) are obtained by state-of-the-art processes, whereby the reaction types to be used depend heavily on the composition of the respective compound (IX). Typically, compounds (IX) are obtained, for example, from olefinically unsaturated organic precursors, such as acetylene, diallyl or divinyl compounds, and Si-H-functional silicone building blocks by hydrosilylation.

[0111] Grignard reactions from halogenated organic precursors and subsequent reaction with halogenated or alkoxylated organosilanes are also conceivable processes. Metal halide exchange reactions of halogenated organic precursors with alkyl alkali metal compounds, such as butyllithium, and known subsequent reactions for linking with silicone building blocks can also be used. Such processes are known to the person skilled in the art and are easily accessible and understandable from the available literature. Since these processes are not the subject of the invention, only a reference to the documented and searchable prior art is provided here.

[0112] The relative proportions in which the connections of the

[0113] Formula (IX) are cocondensed with the compounds of formula (X) are given by the values ​​of the indices c, d, e, f and g in formula (VII).

[0114] Hal is preferably a halogen, acid or alkoxy group, particularly preferably a chlorine, acetate, formate, methoxy or ethoxy group.

[0115] The organosiloxanes thus obtained can optionally be further modified and altered by further reactions, such as equilibration, so that almost any branched siloxane oligomers and polymers and silicone resins can be prepared by applying known processes according to the prior art, all of which are understood to be organopolysiloxanes in the context of the present invention.

[0116] The cohydrolysis is preferably carried out by dosing a mixture of compounds (IX) and (X), optionally together with a preferably aromatic solvent, into water or dilute acids while cooling. For gaseous acids such as HCl, dosing into a concentrated aqueous HCl solution is also useful if the released acid is to be recovered as a gas. Depending on the nature of the Hal group, the hydrolysis is more or less exothermic, so cooling is necessary both to ensure safe conduct of the reactions and, where appropriate, to avoid side reactions in corresponding synthesis sequences. However, to complete the reactions, it may be advantageous and necessary to use elevated temperatures.

[0117] Reaction times are generally very short in the case of chlorosilanes, so the time required to carry out the process in batch mode depends primarily on the cooling capacity. Alternatively, the cohydrolysis of (XI) and (XII) can also be carried out continuously, for which loop, column, and tubular reactors are suitable. To remove residual acids, thorough washing with water, clean phase separation, and vacuum purification of the hydrolysis product are advantageous.

[0118] The process can be performed at normal pressure. However, depending on the objective, higher or lower pressure is also practical.

[0119] By using the groups of the formula (R 3 3SiO 1 / 2 ) fIf necessary, both the molecular weight control and the reduction of the alkoxy and silanol groups can be achieved during the synthesis. The latter are formed during the synthesis if it is carried out in a hydrolytic process, which is the preferred embodiment. To generate the groups of the formula (R 3 3SiO 1 / 2 ) fIf a chlorosilane precursor is used, symmetrical disiloxanes are also formed from them during the synthesis. However, these disiloxanes can be cleaved again under the conditions of acid hydrolysis and are therefore still available as terminating groups for reactions with silanol groups, since starting materials are formed on the organopolysiloxane formed after hydrolysis of the chlorosilanes. This achieves the reduction of the silanol groups. Since alkoxy groups, particularly those with small alkyl radicals, also form silanol groups under the conditions of acid hydrolysis with the elimination of short-chain alcohols, the alkoxy groups are also reduced by the use of the terminating building blocks. These can also be used in excess, since any remaining disiloxanes can usually be distilled off after the synthesis is complete, especially if they are exclusively or predominantly substituted with short-chain alkyl radicals, especially methyl radicals.

[0120] The chlorosilanes or disiloxanes forming these terminal groups can also be added separately in a final step of the synthesis, and the silanol groups can be reduced using acidic hydrolytic conditions. It is advantageous to always use an excess of terminating chlorosilanes and to remove the resulting disiloxanes by distillation. Vinyldimethylchlorosilane, dimethylchlorosilane, or trimethylchlorosilane are particularly advantageous for this purpose, as the resulting disiloxanes are particularly easy to separate by distillation. Alternatively, it is of course also possible to use the disiloxanes directly and select hydrolytic conditions; in this case, the addition of a sufficient amount of catalytic acid, preferably hydrochloric acid, is required. Typically, between 50 and 1000 ppm of hydrochloric acid is used in this case, based on the amount of siloxane in the reaction mixture.

[0121] Functional groups that are not tolerated by the formation reaction of the polyorganosiloxanes (VII) can be subsequently introduced into the polyorganosiloxane structure, for example, by hydrosilylation. For example, a 4-allyl-2-methoxyphenol (eugenol) or a 2-allylphenol function is introduced in this way, as typical examples of the obligatory hydroxyaryl residues in (VII).

[0122] Since the copolymers according to the invention must be capable of radical crosslinking by suitable olefinically unsaturated groups during application, it is important, particularly when using a hydrosilylation reaction that consumes olefinic groups, to ensure that a sufficient number of olefinically unsaturated groups is present in the copolymer of formula (I). This can be achieved most easily by adjusting the stoichiometry between olefinically unsaturated groups and Si-H groups, i.e., by using an appropriate excess of olefinic groups. If only one type of olefinic group is used, the sterically easiest to reach olefinic groups will react first, leaving the more difficult-to-access olefinic groups for subsequent radical curing.This not only leads to random copolymers, but potentially also to disadvantages in radical curing, such as a slower reaction rate or a less complete reaction. To compensate for this, one can, for example, use two different types of olefinically unsaturated groups that are hydrosilylated at different rates, such as allyl groups or vinyl groups, as examples of rapidly hydrosilylatable groups, combined with acrylate groups or methacrylate groups, as examples of more difficultly hydrosilylatable olefinically unsaturated groups. Thus, hydrosilylation will occur primarily or exclusively at the more rapidly hydrosilylatable groups, leaving a larger number of the more slowly hydrosilylatable groups available for subsequent radical curing. This provides the opportunity to influence the molecular architecture and reaction rates.

[0123] In principle, the subsequent introduction of the hydrosilylatable or radically curable groups required for the copolymers of formula (I) can be achieved using known methods of organic chemistry, either by functionalization of the polyarylene ether moiety or the polysiloxane moiety, or of these two components forming the copolymers of formula (I). Thus, the introduction of the hydrosilylatable groups to the polyarylene ether units can occur, for example, at their optionally terminal phenolic OH groups. Reference should be made here to the chemistry of phenols in general, and, as an example, to the introduction of allyl groups to form allylphenyl ether groups, which can be converted to allylphenols by subsequent Claisen rearrangement. Since publicly available knowledge can be used here, the synthesis routes to the raw materials used here are known to the person skilled in the art and will not be discussed further here.It should also be noted that natural substances, such as eugenol (4-allyl-2-methoxyphenol), can also be used as building blocks for the polyarylene ether units in order to insert suitable olefinically unsaturated groups into the polyarylene ether residues.

[0124] As an example, the introduction of an acrylate group should also be mentioned here. This can be achieved by reacting a phenolic OH group with 3-chloropropionyl chloride to form a 3-chloropropionic acid ester, followed by HCl elimination from the chloropropyl residue by adding, for example, trialkylamine to the reaction mixture, whereby the acrylate group is formed by creating the double bond, since the acrylate group represents a relevant radically curable group. This reaction sequence is also described in the literature and is therefore known to the person skilled in the art.

[0125] As a further example, the introduction of olefinic groups by subsequent silylation with olefinically unsaturated chlorosilanes or olefinically unsaturated disiloxanes is explained below as another option. Another possibility to ensure that a sufficient number of olefinically unsaturated, radically curable functional groups is present in the copolymer according to formula (I) is to subsequently functionalize the copolymer after oxidative coupling in the case of the combination of formula (VII) with formula (V11a) and formula (V11b) by proceeding in the same way as already described above for controlling the molecular weight of the polyorganosiloxanes (VII). This means that further groups of the formula (R 3 3SiO 1 / 2 )f, where R 3can have the meanings given above and for this process step in particular those precursors are used for which at least one radical R 3 is an olefinically unsaturated group, for example a vinyl group.

[0126] This can be achieved both in a hydrolytic process, as described above, and in an anhydrous process.

[0127] Used to generate the groups of formula (R 3 3SiO 1 / 2)fIf a chlorosilane precursor according to formula (X) is used under hydrolytic conditions, symmetrical disiloxanes are also formed from them in the course of the synthesis, which, however, can be cleaved again under the conditions of acid hydrolysis and are therefore still available as terminating groups for reactions with silanol and silicon-bonded alkoxy groups or carbinol groups, whereby the silanol groups and the silicon-bonded alkoxy groups are formed on the organopolysiloxane when it is produced by a hydrolytic process and the carbinol groups can be present as phenolic OH groups.

[0128] One can use the chlorosilane precursors for the groups of the formula (R 3 3SiO 1 / 2)fmay also be used in excess, since any remaining disiloxanes can usually be distilled off after the synthesis has been completed, especially if they are exclusively or predominantly substituted with short-chain alkyl radicals, especially methyl radicals.

[0129] The chlorosilanes or disiloxanes forming these terminal groups can also be added separately in a final step of the synthesis, and the silanol groups can be reduced specifically using acidic hydrolytic conditions. It is advantageous to always use an excess of terminating chlorosilanes and to remove the resulting disiloxanes by distillation. Vinyldimethylchlorosilane, divinylmethylchlorosilane, trivinylchlorosilane, methacryloyloxypropyldimethylchlorosilane, bismethacryloyloxypropylmethylchlorosilane, trismethacryloyloxypropylchlorosilane, acryloyloxypropyldimethylchlorosilane, bismethacryloyloxypropylmethylchlorosilane, and trismethacryloyloxypropylchlorosilane are particularly advantageous for this purpose, since the resulting disiloxanes are particularly easily separated by distillation.Alternatively, it is of course also possible to use the disiloxanes directly and select hydrolytic conditions. In this case, the addition of a sufficient amount of catalytic acid, preferably hydrochloric acid, is required. Typically, between 50 and 1000 ppm of hydrochloric acid is used in this case, based on the amount of siloxane in the reaction mixture.

[0130] This final step can also be carried out without water by adding the selected chlorosilane, preferably vinyldimethylchlorosilane, divinylmethylchlorosilane, trivinylchlorosilane, methacryloyloxypropyldimethylchlorosilane, bismethacryloyloxypropylmethylchlorosilane, trismethacryloyloxypropylchlorosilane, acryloyloxypropyldimethylchlorosilane, bismethacryloyloxypropylmethylchlorosilane or trismethacryloyloxypropylchlorosilane to the copolymer from the oxidative coupling of (VII) with (VIIa) or (VIIb) dissolved in an inert organic solvent, and carrying out the reaction without water in the presence of an auxiliary base, wherein basic metal salts and nitrogen compounds are preferably used as auxiliary bases.

[0131] Suitable auxiliary bases for capturing the hydrogen halide formed include basic salts or nitrogen-containing compounds such as amines, ureas, imines, guanidines, and amides. Examples of basic salts are sodium hydride, sodium amide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate, calcium oxide, magnesium oxide, and magnesium carbonate. Examples of nitrogen-containing compounds are ammonia, ethylamine, butylamine, triethylamine, trimethylamine, tributylamine, N,N-dimethyldecylamine, triisooctylamine, urea, tetramethylurea, guanidine, tetramethylguanidine, N-methylimidazole, N-ethylimidazole, piperidine, pyridine, picoline, and N-methylmorpholine. Amine compounds in which the nitrogen atoms do not carry hydrogen atoms are preferably used.

[0132] The auxiliary base is preferably used in at least equimolar amounts with respect to the halosilane. At least 0.5, more preferably at least 1.0, in particular at least 2.0 base equivalents of auxiliary base are used per mole equivalent of halosilane. Larger additional amounts of auxiliary base can also be used, e.g. if it is to serve simultaneously as a solvent. In most cases, however, this does not provide any advantage but rather reduces the space-time yield and thus the economics of the process. The halosilane is preferably added to the anhydrous reaction mixture from the first step of the process and the auxiliary base is then metered in. If desired, this procedure can also be reversed, so that the auxiliary base is first added to the reaction mixture from the first synthesis step and the halosilane is then metered in.

[0133] Mixtures of several auxiliary bases can also be used. The reaction of the halosilane(s) of formula (XII) with the silanol radicals of the polyorganosiloxane species or the phenolic OH radicals of the copolymer from the oxidative coupling of (VII) with (VIIa) or (VIIb) is preferably carried out at a temperature of at least -20°C, more preferably at least 0°C, in particular at least 10°C. The maximum permissible temperature also results from the boiling point of the solvent used and of the halosilane(s) of formula (X), with the reaction temperature preferably not exceeding 200°C, more preferably 175°C, in particular 150°C.

[0134] The reaction mixture can be cooled or heated as required; if necessary, individual reaction components can be adjusted to temperature beforehand before they are reacted with one another, e.g. to utilize the heat of reaction. The process can be carried out batchwise in stirred reactors or continuously in column, loop, fluidized bed or tubular reactors. Any low molecular weight siloxanes formed during the reaction can be separated from the reaction mixture by distillation if required. The halide salts formed during the reaction can be decanted, filtered off or centrifuged off, or dissolved in water and separated off. For the subsequent aqueous work-up, the amount of solvent present can be adjusted as required, e.g. to facilitate phase separation by adjusting density differences, or further solvents can be added whose solubility orMiscibility with water is as low as possible, in particular a maximum of 5 wt% at 25°C.

[0135] Preferably, any excess of halosilane of formula (X) is removed by distillation before the aqueous workup.

[0136] Particularly suitable aprotic solvents are aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, or mixtures thereof. The suitability of the solvent is determined by its solubility for the resulting copolymers of formula (I). The solvent must dissolve the resulting copolymer of formula (I) sufficiently well and must not be miscible with water, i.e., it must not itself be able to dissolve more than 5 wt.% water and must not participate in the reaction.

[0137] If necessary, the suitability of the solvent should be determined through appropriate experiments. Aromatic solvents best meet the above conditions and are therefore preferred.

[0138] The copolymers of formula (I) are chemically curable, i.e., they can be cured by a chemical reaction to form a crosslinked, insoluble network. Curing occurs via the olefinically unsaturated groups described above. Possible chemical crosslinking reactions include the known reactions according to the prior art, in particular radical crosslinking, which can be initiated using suitable radiation sources such as UV light, as well as by unstable chemical compounds that decompose to form radicals, and addition crosslinking, for example, by hydrosilylation of the olefinically unsaturated group with an Si-H function in the presence of a suitable hydrosilylation catalyst. To achieve adequate curing, a sufficient amount of functional groups must be present.

[0139] At least 1.0 functional groups must be present on average per polyorganosiloxane molecule used according to the invention to achieve sufficient curing; preferably, at least 1.1 functional groups are present on average, and in particular at least 1.2 functional groups are present on average per polyorganosiloxane molecule according to the invention. The functional groups can be different, so that, for example, some of the functional groups are an Si-H group and another part of the functional groups is an olefinically unsaturated group that is radically curable or hydrosilylatable. It should be noted that, according to the invention, a minimum proportion of olefinically or acetylenically unsaturated groups must always be present.If only one type of functional group is present, for example only olefinically or acetylenically unsaturated functional groups that are radically curable, the appropriate number of these functional groups must be present. In order to copolymerize to form a homogeneous matrix, it is important to ensure that the selected olefinic and acetylenic groups are sufficiently copolymerizable. The combination of olefinic groups that are not copolymerizable with one another is also possible, provided that the resulting matrix of two or more individual polymers remains compatible with one another and does not form separate phases that separate into distinguishable domains. It must be ensured that each of the individual polymers is itself chemically curable, so that the entire resulting matrix is ​​chemically cured after crosslinking has taken place.Examples of suitable initiators for starting the radical polymerization include, in particular, examples from the field of organic peroxides, such as di-tert-butyl peroxide, dilauryl peroxide, dibenzoyl peroxide, dicumyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl cumyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-ditert-butylperoxycyclohexane, 2,2-di(tert-butylperoxy)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-butylperoxy)hexane, dicetylperoxydicarbonate, acetylacetone peroxide, acetylcyclohexanesulfonyl peroxide, tert.Amyl hydroperoxide, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxyisopropyl carbonate, tert-amyl peroxyneodecanate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl monoperoxymaleate; this list is merely illustrative and not restrictive. If necessary, mixtures of different initiators can also be used for free-radical reactions. The suitability of an initiator or initiator mixture for free-radical reactions depends on its decomposition kinetics and the requirements to be met. With sufficient consideration of these general conditions, the skilled person will be able to select a suitable initiator.

[0140] For preparations containing silicon-bonded hydrogen in addition to olefinically and acetylenically unsaturated groups, there is the possibility of curing by a hydrosilylation reaction. Suitable catalysts for promoting the hydrosilylation reaction are the known

[0141] State-of-the-art catalysts.

[0142] Examples of such catalysts are compounds or complexes of the noble metal group containing platinum, ruthenium, iridium, rhodium, and palladium, preferably metal catalysts from the platinum group or compounds and complexes from the platinum group. Examples of such catalysts are metallic and finely divided platinum, which can be on supports such as silicon dioxide, aluminum oxide, or activated carbon, compounds or complexes of platinum such as platinum halides, e.g.PtCl4, H2PtCl6x6H2O, Na2PtCl4x4H2O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H2PtCl4x6H2O and cyclohexanone, platinum-vinyl-siloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane, with or without detectable inorganic halogen, bis-(gamma-picoline)platinum chloride, trimethylenedipyridineplatinum chloride, dicyclopentadieneplatinum dichloride, dimethylsulfoxyethenylplatinum (II) dichloride, cyclooctadieneplatinum dichloride, norbornadieneplatinum dichloride, gammapicolineplatinum dichloride, cyclopentadieneplatinum dichloride, as well as reaction products of platinum tetrachloride with olefin and primary or secondary amine or primary and secondary amine such as the reaction product of platinum tetrachloride dissolved in 1-octene with sec-butylamine or ammonium platinum complexes.In a further embodiment of the process according to the invention, complexes of iridium with cyclooctadienes, such as p-dichlorobis(cyclooctadiene)diiridium (I), are used. This list is illustrative only and not limiting. The development of hydrosilylation catalysts is a dynamic field of research that continually produces new, effective species that can naturally also be used here.

[0143] The hydrosilylation catalyst preferably comprises compounds or complexes of platinum, preferably platinum chlorides and platinum complexes, in particular platinum-olefin complexes, and particularly preferably platinum-divinyltetramethyldisiloxane complexes. In the process according to the invention, the hydrosilylation catalyst is used in amounts of 2 to 250 ppm by weight, based on the total composition, preferably in amounts of 3 to 150 ppm, in particular in amounts of 3 to 50 ppm.

[0144] In a preferred application, the copolymers of formula (I) are applied to a metal substrate.

[0145] The copolymers of formula (I) are particularly suitable for use as binders and / or adhesion promoters for the production of metal-clad laminates, particularly for electronic applications, especially for metal-clad laminates and especially for use in high-frequency applications, especially those operating at frequencies of 1 GHz and above. Particular preference is given to the production of metal-clad electrical laminates, such as those used for the manufacture of printed circuit boards in electronic devices, particularly for high-frequency applications.

[0146] These metal-clad electrical laminates may, but do not have to, contain reinforcing materials. This means they may, for example, contain reinforcing fabrics such as fiber fabrics or nonwovens, or they may be free of them. If a reinforcing material is included, it is preferably arranged in layers. A reinforcing layer can be composed of a variety of different fibers.

[0147] Such reinforcing layers help to control shrinkage behavior and provide increased mechanical strength.

[0148] If a reinforcing layer is used, the fibers forming this layer can be selected from a wide variety of options. Non-limiting examples of such fibers include 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, or liquid crystalline fibers. The fibers can have a diameter of 10 nm to 10 pm. The reinforcing layer has a thickness of at most 200 pm, preferably at most 150 pm.

[0149] A preferred application is the use of the copolymers of formula (I) as binders or cobinders together with organic binders for the production of metal-clad laminates from glass fiber composites for the further production of printed circuit boards. The preferred metal is copper.

[0150] For the inventive use of the copolymers of formula (I), they can be used as the sole binder. They can also be used blended with polyorganosiloxanes, organic monomers, oligomers, and polymers.

[0151] Typically used organic monomers,

[0152] Oligomers and polymers include polyphenylene ethers,

[0153] Bismaleimides, bismaleimide triazine copolymers, hydrocarbon resins, both aliphatic such as polybutadiene, and aromatic such as polystyrene, as well as hybrid systems which have both aliphatic and aromatic character such as styrene-polyolefin copolymers, whereby the form of the copolymers is in principle not restricted, epoxy resins, cyanate ester resins and optionally others, whereby the selection is to be understood as illustrative and not restrictive.

[0154] Preferred organic monomers, oligomers, and polymers are oligomeric and polymeric polyphenylene ethers, monomeric, oligomeric, and polymeric bismaleimides, oligomeric and polymeric hydrocarbon resins, and bismaleimide triazine copolymers. The organic monomers, oligomers, and polymers can optionally be used in admixture with one another.

[0155] The proportion of organic monomers, oligomers and polymers in the preparations with the copolymers of formula (I), if the organic components are used, is between 10 and 90% based on the mixture of the copolymers of formula (I) and the organic monomers, oligomers and polymers as 100%, preferably 20 - 90%, in particular 30 - 80%.

[0156] In addition, both the copolymers of formula (I) and the mixtures thereof with organic monomers, oligomers or polymers can be dissolved in further organic monomers, optionally with olefinically or acetylenically unsaturated groups, as reactive diluents, such as, for example, styrene, alpha-methylstyrene, para-methylstyrene and vinylstyrene, chloro- and bromostyrene.

[0157] Likewise, typical non-reactive solvents can be used to dissolve the copolymers of the formula (I) and optionally mixtures thereof with organic monomers, oligomers and polymers, such as, for example, aliphatic or aromatic solvents such as aliphatic mixtures with certain boiling ranges, toluene, xylene, ethylbenzene or mixtures of the same aromatics, ketones such as acetone, methyl ethyl ketone, cyclohexanone, carboxylic acid esters such as ethyl acetate, methyl acetate, ethyl formate, methyl formate, propionic acid methyl ester, propionic acid ethyl ester, wherein good solubility in particular of the mixtures of polyorganosiloxanes of the formula (I) with organic monomers, oligomers and polymers is most easily achieved in aromatic solvents such as toluene, xylene, ethylbenzene and mixtures thereof.

[0158] In the case where polyorganosiloxanes are used as an additional mixture component together with the copolymers of formula (I) and optionally other organic monomers, oligomers, or polymers, it is essential that polyorganosiloxanes are used that are compatible with the organic components of choice and do not lead to phase separation. In these cases, polyorganosiloxanes richer in phenyl groups should generally be used, since phenyl groups increase compatibility with the organic components. Especially with organic polymers richer in aromatics, such as polyphenylene ethers or aromatic hydrocarbon resins, polyorganosiloxanes richer in aromatics should be used, with both the bridging aromatic groups and aromatic substituents terminally bonded to silyl units contributing to compatibility.

[0159] The exact amount of aromatic groups required to adjust the compatibility of the polyorganosiloxanes with a specific selection of organic binders must be determined depending on the selection of organic binders. It is also possible to mix several organic polymers, optionally selected from different polymer classes, and use them in the binder preparation. It is also possible to combine several polyorganosiloxanes with one another in a binder preparation. Furthermore, it is possible, and according to the invention, to mix several different copolymers of formula (I) together to form a binder.Mixtures of polyorganosiloxanes, copolymers of formula (I), and other organic polymers can also result from the formation reaction of the copolymers of formula (I) if, after the reaction has ended, portions of unreacted polyorganosiloxanes of formulas (VII) or (IX) are still present, possibly in addition to polyarylene ether units not bound to the polyorganosiloxane framework from the polymerization of the polyarylene ether precursors (VIIa) and (VIIIb) or non-hydrosilylated polyarylene ethers of formulas (Xa) and (Xb). Such mixtures and their use are also within the scope of the invention as long as they also contain copolymers of formula (I).

[0160] The compatibility of one or more polyorganosiloxanes with one or more organic oligomers or polymers can be easily determined by mixing a mixture of the organic binder(s) with the polyorganosiloxane(s), advantageously in a solvent that dissolves all selected components. The solvent is then removed using state-of-the-art methods, for example, by distillation or spray drying. The resulting residue is evaluated visually or using microscopic, optionally electron microscopic, methods. Compatible mixtures can be identified by the fact that no silicone domains separate from the organic components and are recognizable as a separate phase.The use of additional formulation components, such as additives, which may optionally also include silanes, such as antifoams and deaerating agents, wetting and dispersing agents, flow control agents, compatibilizers, adhesion promoters, curing initiators, catalysts, stabilizers, fillers including pigments, dyes, inhibitors, flame retardants, crosslinking aids, etc., is permitted according to the invention, and the selection of such components is fundamentally unrestricted. In addition to compatibility tests in the sense of suitable miscibility behavior, compatibility tests with regard to reactivity may also be necessary to prevent premature gelling and to ensure that sufficiently rapid polymerization or copolymerization of all components is achieved during curing, as well as tests for adequate wetting and, if appropriate, other properties.This must be taken into account when drafting the text.

[0161] Examples of usable fillers are ceramic fillers such as silicas, for example precipitated silicas or pyrogenic silicas, which can be both hydrophilic and hydrophobic and are preferably hydrophobic and which can furthermore also be functionally and optionally reactively provided with organic groups on their surface, quartz, which can optionally be surface-treated or surface-functionalized so that it can carry reactive functional groups on the surface, aluminum oxides, aluminum hydroxides, calcium carbonate, talc, mica, clay, kaolin, magnesium sulfate, carbon black, titanium dioxide, zinc oxides, antimony trioxide, barium titanate, strontium titanate, corundum, wollastonite, zirconium tungstate, ceramic hollow spheres, aluminum nitride, silicon carbide, beryllium oxide, magnesium oxide, magnesium hydroxide, solid glass spheres, hollow glass spheres and boron nitride.Core-shell particles made of various materials can be used as additional fillers, such as silicone resin spheres coated with silica on the surface, or polymer-coated elastomer particles, whereby the elastomer particles can optionally also be silicone elastomers, and a typical example of a surface coating of such an elastomer particle is a polymethyl methacrylate shell. The ceramic fillers preferably have particle sizes, expressed as a D90 value, of 0.1 μm to 10 μm. Fillers are preferably present in amounts of 0.1 to 60 percent by weight, preferably 0.5 to 60 percent by weight, in particular 1 to 60 percent by weight, based on the total binder formulation consisting of binder(s), reactive monomers, additives, and fillers as 100%. This means that the amount of any non-reactive solvent used is not counted.

[0162] Among the fillers, those that are thermally conductive are particularly noteworthy. These include aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, zinc oxide, zirconium silicate, magnesium oxide, silicon oxide, and aluminum oxide.

[0163] In principle, the binder preparations can contain flame-retardant additives in an amount of typically 5 to 25 percent by weight. However, a special feature of the copolymers of formula (I) is that they reduce the need for flame-retardant additives, since the polyorganosiloxane content in the copolymers of formula (I) already exhibits flame-retardant properties. Polysilsesquioxanes and siloxanes are known for their flame-retardant properties, as can be seen from the discussion of the prior art as background to this invention. It is part of the prior art that they themselves are used as flame-retardant additives. It is therefore a particular advantage of the present invention that it succeeds in combining the function of a binder suitable for high-frequency applications with the function of flame retardancy.Depending on the amount of polyorganosiloxanes used in the copolymers of formula (I), the amount of flame-retardant additives can therefore be reduced. At an amount of at least 20 percent by weight based on the total mixture of all binders and reactive organic monomers used, the amount of flame-retardant additives is preferably only 0 to 10 percent by weight, particularly preferably 0 to 8 percent by weight, and in particular 0 to 5 percent by weight. This means that, when using the copolymers of formula (I), it is possible to dispense with the use of a flame-retardant additive depending on the selection of the organopolysiloxane and the amount used.

[0164] Typical examples of flame-retardant additives are hydrates of the metals Al, Mg, Ca, Fe, Zn, Ba, Cu, or Ni, and borates of Ba and Zn. The flame-retardant additives can be surface-treated, in which case they may optionally possess reactive groups on the surface. The flame-retardant additives can also be halogenated organic flame-retardant additives, such as hexachloroendomethylenetetrahydrophthalic acid, tetrabromophthalic acid, or dibromoneopentyl glycol. Examples of other flame-retardant additives include melamine cyanurate, phosphorus-containing components such as phosphinates, diphosphinates, phosphazenes, vinylphosphazenes, phosphonates, phosphaphenanthrene oxides, and fine-grained melamine polyphosphates. Further examples of bromine-containing flame-retardant additives are bispentabromophenylethane, ethylenebistetrabromophthalimide, tetradecabromodiphenoxybenzene, decabromodiphenyl oxide or brominated polysilsesquioxanes.Some flame-retardant additives enhance their effect synergistically. This is the case, for example, with the combination of halogenated flame retardants with antimony trioxide.

[0165] Further examples of other components include antioxidants, stabilizers against degradation due to weathering, lubricants, plasticizers, coloring agents, phosphorescent or other agents for the purpose of marking and traceability and antistatic agents.

[0166] Preferably, the copolymers of formula (I) are crosslinked in a step of use as binders or cobinders.

[0167] Crosslinking aids used include, in particular, polyunsaturated, radically curable or hydrosilylatable monomers and oligomers, as illustrated in the following non-limiting examples. These include, for example, diolefinically unsaturated components such as, for example, symmetrically olefinically unsaturated disubstituted disiloxanes, such as 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-tetramethyl-1,3-dipropylmethacryloyldisiloxane, diolefinically unsaturated disubstituted organic monomers or oligomers, such as, for example, conjugated and non-conjugated dienes, such as 1,9-decadiene and 1,3-butadiene. This also includes triply olefinically unsaturated monomers or oligomers such as 1,2,4-trivinylcyclohexane, triallyl cyanurates or triallylisocyanurates, tri(meth)acrylates, such as trimethylolpropane trimethacrylate.

[0168] This also includes four-fold unsaturated substituted monomers and oligomers such as 2,4,6,8-tetramethyl-

[0169] 2.4.6.8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetraphenyl-

[0170] 2.4.6.8-tetravinylcyclotetrasiloxane, 2,2-bis[[(2-methyl-l-oxoallyl)oxy]methyl]-1,3-propanediylbismethacrylate

[0171] (Pentaerythritol tetramethacrylate), tetraallyl orthosilicate, tetraallyl-cia,cis,cis,cis-1, 2,3,4-cyclopentane tetracarboxylate, tetraallylsilanes, glyoxalbis(diallylacetal).

[0172] Since hydrosilylation curing is also conceivable in addition to radical curing, multiply Si-H-functional components can also act as crosslinkers, such as 1,1,3,3-tetramethyl-1,3-disiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 1,4-bis(dimethylsilyl)benzene or multiply chain and / or terminal Si-H-functional oligo- and polyorganosiloxanes.

[0173] Suitable catalysts or initiators for the radical curing of binder preparations composed of copolymers of formula (I) and polyorganosiloxanes, organic monomers, oligomers, and polymers are the same as those already mentioned above, i.e., in particular, peroxides. Furthermore, other radical initiators are suitable for initiating the radical curing of both the copolymers of formula (I) alone and the binder preparations described, such as, for example, azo components such as, for example, α,α'azobis(isobutyronitrile), redox initiators such as, for example, combinations of peroxides such as hydrogen peroxide and iron salts, or azides such as acetyl azide. The copolymers of formula (I) or the preparations containing them can be used for the application according to the invention both in solvent-free and solvent-containing forms.They are generally used as a solvent-based preparation to facilitate the homogeneous distribution of all components of the formulation and the wetting and saturation of any reinforcing layer used. A reinforcing layer is generally included. This is preferably a glass fiber fabric. The reinforcing layer can be impregnated by impregnating the preparation. Various technical solutions are available for this, including continuous processes where appropriate, and their selection for producing the metal-clad laminates according to the invention is in no way restricted. Non-limiting examples of application techniques include dipping, optionally of webs of the reinforcing material via roller systems in continuous processes, spraying, flooding, doctoring, etc.An advantage of the present invention is that all available technologies can be applied without restriction or modification, and no special new process is required for the use of the copolymers of formula (I). In this respect, the present invention is fully within the available state of the art in the production of metal-clad laminates. What is new is the use of the copolymers of formula (I) for the production of the metal-clad laminates in question, which was previously unknown.

[0174] Impregnation is followed by a drying step, in which any solvent used is removed. State-of-the-art methods are also used for the drying process. These include, in particular, thermally induced evaporation with or without vacuum. By appropriately adjusting the reactivity and tackiness of the binder mixture used, storable composite materials are obtained after this step under suitable conditions, such as cooling, which can be further processed at a later date if necessary.

[0175] In a final step of the process, the binder preparation is polymerized, again using state-of-the-art methods. Any initiators used for radical polymerization are heated above their decomposition temperature, causing them to decompose to form radicals and initiate radical polymerization of the binder preparation. Radiation curing methods are also generally applicable. If hydrosilylation curing is used instead of radical polymerization, a temperature suitable for deactivating the inhibitor used with the hydrosilylation catalyst and releasing the catalytic activity of the hydrosilylation catalyst must be used in this step.

[0176] This step is generally carried out at an elevated temperature of preferably 60 to 390°C, particularly preferably 70 to 250°C, in particular 80 to 200°C, wherein the temperature is effective for a time of preferably 5 to 180 minutes, particularly preferably 5 to 150 minutes, in particular 10 to 120 minutes. Furthermore, it is customary to apply elevated pressure in this step. Typical pressures are in the range of 1 to 10 MPa, particularly preferably 1 to 5 MPa, in particular 1 to 3 MPa. The lamination of the composite material with a conductive metal layer takes place in this second step by applying a layer of at least one selected metal to one or both sides of the composite material comprising the reinforcement layer and binder preparation before curing takes place. This meansBetween 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 with at least one type of conductive metal.

[0177] In particular, at least one of the following can be considered as conductive metals: copper, stainless steel, gold, aluminum, silver, zinc, tin, lead, and transition metals. The thickness of the conductive layer, its shape, size, or surface texture are not fundamentally restricted. The conductive metal layer preferably has a thickness of 3 to 300 μm, particularly preferably 3 to 250 μm, in particular 3 to 200 μm. The thickness of the two layers of at least one type of conductive metal, if two layers are used, can vary and does not have to be identical. It is particularly preferred that the conductive metal is copper, and if two conductive layers of conductive metal are used, both layers are copper. The conductive metal is preferably used in the form of a foil made of the metal in question.The average roughness Ra of the metal foil used is preferably at most 2 μm, more preferably at most 1 μm, in particular at most 0.7 μm. The lower the surface roughness, the better the suitability of the respective foil for use in high-frequency applications, which are the preferred goal of the present invention. To improve the adhesion between the conductive metal layer and the composite of binder preparation and reinforcing layer, various prior art methods can be used, such as the use of an adhesion-promoting layer, the electroplating of the metal layer on the composite of binder preparation and reinforcing layer, or vapor deposition. The layer of conductive metal can sit directly on the composite of binder preparation and reinforcing layer or be bonded to it by an adhesion-promoting layer.

[0178] If no reinforcement layer is used, a layer of the binder preparation containing the polyorganosiloxanes of formula (I) is produced by depositing a layer of binder preparation on a carrier, such as a release film or release plate. In principle, any material from which the dried or cured binder preparation can be subsequently removed is suitable for the carrier, such as polytetrafluoroethylene, polyester, and the like. The removability and film-forming properties on the respective carrier material must be determined individually depending on the binder composition. The statements made regarding the process remain equally valid for this reinforcement-free variant.

[0179] Multilayer structures can be created from the reinforced or unreinforced composite materials from the first step and the laminated composite materials from the second step. For example, stacking multiple layers of the composite materials from the first step alternately with the laminated laminates from the second step. The uncured composite materials from the first step are then cured in a process that essentially corresponds to the procedure for producing metal-clad laminates. To create thicker layers, multiple layers of the reinforced or unreinforced composites from the first step can also be stacked one on top of the other in direct succession.

[0180] The copolymers of formula (I) can be used for the production of metal-clad laminates, in particular electrical laminates,

[0181] They can also be used in anti-corrosive preparations, particularly for use in corrosion protection at high temperatures.

[0182] In addition, the copolymers of formula (I) and

[0183] Preparations containing these can also be used for corrosion protection of reinforcing steel in reinforced concrete.

[0184] Corrosion-inhibiting effects in reinforced concrete are achieved both when the copolymers of formula (I) and preparations containing them are introduced into the concrete mixture before they are shaped and cured, and when the copolymers of formula (I) or

[0185] Preparations containing these on the surface of the

[0186] concrete after the concrete has hardened.

[0187] In addition to the purpose of corrosion protection on metals, the

[0188] Copolymers of formula (I) also for the manipulation of further

[0189] Properties of preparations containing the inventive

[0190] Organopolysiloxanes or solids or films obtained from preparations containing the copolymers of

[0191] Formula (I) contain, serve as for example:

[0192] -Control of electrical conductivity and electrical

[0193] resistance

[0194] -Control of the flow properties of a preparation

[0195] -Control of the gloss of a wet or cured film or object -Increase of weathering resistance

[0196] -Increase in chemical resistance

[0197] -Increase in color stability

[0198] -Reduction of chalking tendency

[0199] -Reduction or increase of static and sliding friction on

[0200] Solids or films obtained from preparations containing

[0201] Copolymers of formula (I) contain

[0202] - Stabilization or destabilization of foam in the

[0203] Preparation containing the preparation

[0204] - Improvement of the adhesion of the preparation containing the copolymers of formula (I) to substrates

[0205] - Control of filler and pigment wetting and

[0206] Dispersing behavior,

[0207] - Control of the rheological properties of the preparation containing the organopolysiloxanes according to the invention,

[0208] - Control of mechanical properties, such as

[0209] Flexibility, scratch resistance, elasticity, stretchability,

[0210] Flexibility, tear resistance, rebound behaviour, hardness,

[0211] Density, tear resistance, compression set, behavior at different temperatures, expansion coefficient,

[0212] Abrasion resistance and other properties such as

[0213] Thermal conductivity, flammability, gas permeability,

[0214] Resistance to steam, hot air, chemicals,

[0215] Weathering and radiation, sterilizability,

[0216] Solids or films containing the copolymers of

[0217] Formula (I) or preparations containing it

[0218] - Control of electrical properties, such as dielectric loss factor, dielectric strength,

[0219] Dielectric constant, tracking resistance,

[0220] Arc resistance, surface resistance, specific

[0221] breakdown resistance,

[0222] - Flexibility, scratch resistance, elasticity, stretchability,

[0223] Flexibility, tear behavior, rebound behavior, hardness, density, tear resistance, compression set, behavior at different temperatures of solids or films obtainable from the preparation containing the copolymers of formula (I).

[0224] Examples of applications in which the copolymers of formula (I) can be used to manipulate the properties described above are the production of coating materials and impregnations and the coatings and coverings obtainable therefrom on substrates such as metal, glass, wood, mineral substrates, synthetic and natural fibers for the production of textiles, carpets, floor coverings, or other goods producible from fibers, leather, plastics such as films, and molded parts. With appropriate selection of the preparation components, the copolymers of formula (I) can also be used in preparations as additives for the purposes of defoaming, promoting flow, hydrophobizing, hydrophilizing, filler and pigment dispersing, filler and pigment wetting, substrate wetting, promoting surface smoothness, and reducing adhesion and sliding resistance on the surface of the cured composition obtainable from the additized preparation.The copolymers of formula (I) can be incorporated into elastomer compositions in liquid or cured solid form. They can be used for reinforcement or to improve other performance properties, such as controlling transparency, heat resistance, yellowing tendency, or weathering resistance.

[0225] All symbols in the above formulas have their meanings independently of each other. In all formulas, the silicon atom is tetravalent. Examples:

[0226] The following examples serve to further explain the invention. They are to be understood as illustrative, not limiting.

[0227] All percentages are based on weight. Unless otherwise stated, all manipulations are carried out at room temperature (23°C) and under atmospheric pressure (1.013 bar).

[0228] Unless otherwise stated, all data describing product properties apply at room temperature of 23°C and under normal pressure (1,013 bar).

[0229] The devices are commercially available laboratory devices, such as those offered for sale by numerous device manufacturers.

[0230] Ph means a phenyl residue = C6H5-

[0231] Me means one methyl residue = CH3-. Me2 means two methyl residues.

[0232] PPE stands for polyphenylene ether.

[0233] HCl means hydrogen chloride.

[0234] In this text, substances are characterized by data obtained by instrumental analysis. The underlying measurements are either performed according to publicly available standards or determined using specially developed procedures. To ensure the clarity of the presented teaching, the methods used are listed below.

[0235] In all examples, parts and percentages are by weight unless otherwise stated.

[0236] Viscosity: Unless otherwise stated, viscosities are determined by rotational viscometric measurement in accordance with DIN EN ISO 3219. Unless otherwise stated, all viscosity data apply at 25°C and a standard pressure of 1013 mbar.

[0237] Refractive index:

[0238] The refractive indices are determined in the wavelength range of visible light, unless otherwise stated, at 589 nm at 25°C and normal pressure of 1013 mbar according to the standard DIN 51423.

[0239] Transmission:

[0240] The transmission is determined by UV-VIS spectroscopy. A suitable instrument is the Analytik Jena Specord 200.

[0241] The measurement parameters used are: Range: 190 - 1100 nm, Step size: 0.2 nm, Integration time: 0.04 s, Measurement mode: Step mode. First, the reference measurement (background) is performed. A quartz plate, attached to a sample holder (dimensions of the quartz plate: HxW approx. 6 x 7 cm, thickness approx. 2.3 mm), is placed in the sample beam path and measured against air.

[0242] Next, the sample is measured. A quartz plate with a sample applied to it (approximately 1 mm thick) is attached to the sample holder. It is placed in the sample beam path and measured against air. Internal comparison with the background spectrum yields the sample's transmission spectrum.

[0243] Molecule compositions:

[0244] The molecular compositions are determined by nuclear magnetic resonance spectroscopy (for terminology see ASTM E 386: High-resolution nuclear magnetic resonance spectroscopy (NMR): Terms and Symbols), where the 1 H-core and the 29 Si core can be measured.

[0245] Description 1 H-NMR measurement

[0246] Solvent: CDC13, 99.8%

[0247] Sample concentration: approx. 50 mg / 1 ml CDC13 in 5 mm NMR-

[0248] tube

[0249] Measurement without addition of TMS, spectra referencing of residual CHC13 in CDC13 to 7.24 ppm

[0250] Spectrometer: Bruker Avance I 500 or Bruker Avance HD 500 Probe head: 5 mm BBO probe head or SMART probe head (Fa.

[0251] Bruker)

[0252] Measurement parameters:

[0253] Pulprog = zg30

[0254] TD = 64k

[0255] NS = 64 or 128 (depending on the sensitivity of the probe head)

[0256] SW = 20.6 ppm

[0257] AQ = 3.17 s

[0258] Dl = 5 s

[0259] SFO1 = 500.13 MHz

[0260] 01 = 6.175 ppm

[0261] Processing parameters:

[0262] ST = 32k

[0263] WDW = EM

[0264] LB = 0.3 Hz Depending on the spectrometer type used, individual adjustments of the measurement parameters may be necessary.

[0265] Description 29 Si-NMR measurement

[0266] Solvent: C6D6 99.8%d / CC14 1:1 v / v with 1 wt% Cr(acac)3 as relaxation reagent

[0267] Sample concentration: approx. 2 g / 1.5 ml solvent in 10 mm NMR-

[0268] tube

[0269] Spectrometer: Bruker Avance 300

[0270] Probe head: 10 mm 1H / 13C / 15N / 29Si glass-free QNP probe head

[0271] (Bruker)

[0272] Measurement parameters:

[0273] Pulprog = zgig60

[0274] TD = 64k

[0275] NS = 1024 (depending on the sensitivity of the probe head)

[0276] SW = 200 ppm

[0277] AQ = 2.75 s

[0278] Dl = 4 s

[0279] SFO1 = 300.13 MHz

[0280] 01 = -50 ppm

[0281] Processing parameters:

[0282] ST = 64k

[0283] WDW = EM

[0284] LB = 0.3 Hz

[0285] Depending on the type of spectrometer used, individual adjustments of the measurement parameters may be necessary.

[0286] Molecular weight distributions:

[0287] Molecular weight distributions are determined as weight-average Mw and number-average Mn using gel permeation chromatography (GPC or size exclusion chromatography (SEC)) with a polystyrene standard and a refractive index detector (RI detector). Unless otherwise stated, THE is used as the eluent and DIN 55672-1 is applied. Polydispersity is the ratio Mw / Mn.

[0288] Glass transition temperatures:

[0289] The glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, perforated crucible, heating rate 10 K / min.

[0290] Determination of particle size:

[0291] Particle sizes were measured using the dynamic light scattering (DLS) method, determining the zeta potential. The following tools and reagents were used for the determination: 10 x 10 x 45 mm polystyrene cuvettes, disposable Pasteur pipettes, and ultrapure water.

[0292] The sample to be measured is homogenized and filled into the measuring cuvette without any bubbles.

[0293] The measurement is carried out at 25°C after an equilibration time of 300s with high resolution and automatic measurement time setting.

[0294] The specified values ​​always refer to the value D(50). D(50) is defined as the volume-averaged particle diameter where 50% of all measured particles have a volume-averaged diameter smaller than the stated value D(50).

[0295] Determination of dielectric properties: Df, Dk

[0296] The dielectric properties were determined according to IPC TM 6502.5.5.13 using a Keysight / Agilent E8361A network analyzer using the split-cylinder resonator method at 10 GHz. Microscopy procedure:

[0297] The micro- / nanostructure was examined using light microscopy or

[0298] characterized by transmission electron microscopy.

[0299] Light microscopy:

[0300] Sample preparation: 1 drop of sample (undiluted) on a slide; cover with a coverslip

[0301] Device: LEICA DMRXA2 with CCD camera LEICA DFC420 (2592x1944 pixels) Illustration: Transmitted light - interference contrast, various magnification levels

[0302] Transmission electron microscopy:

[0303] Sample preparation: 1 drop of sample (dilution 1:20, adjustment necessary if necessary) on coated TEM grid; addition of a contrast agent if necessary; drying at room temperature

[0304] Device: ZEISS LIBRA 120 with Sharp Eye CCD camera (1024x1024 pixels)

[0305] Figure: Excitation voltage 120 kV; TEM bright field; various magnification levels

[0306] Adhesion test by peel strength test:

[0307] The adhesion of the metal layers laminated to the composite layers with or without reinforcement material was determined according to the method IPC-TM 6502.4.8 "Peel Strength of Metallic Clad Laminates" in the "as received" version, ie without thermal stress or exposure.

[0308] A 35 pm copper foil, mass 285 ± 10 g / m 2 , surface roughness Rz ≤ 8 pm, mean roughness Ra ≤ 0.4 pm was laminated on both sides to a composite layer of 100 pm thickness, with 200°C, 2.0 MPa, 30 mm Hg for 180 min for curing and lamination

[0309] Column worked.

[0310] Example 1: Preparation of a copolymer according to the invention by oxidative coupling

[0311] 1.1. Preparation of a hydroxyaryl-functional three-dimensionally cross-linked polyorganosiloxane:

[0312] 700 g of a polyorganosiloxane with the percentage composition (in mol%)

[0313] [ (C6H5)SiO 3 / 2 ]55.8[(C6H5)(OH)2SiO 1 / 2 ]2,0[(C6H5)(OH)SiO 2 / 2 ] 32 ,9

[0314] [ (CH3)2(H)SiO 1 / 2 ]9.3, Mw = 4391 g / mol, Mn = 2014 g / mol are dissolved in 500 g of toluene. 90 g (=0.55 mol) of 4-allyl-2-methoxyphenol (eugenol, C) are added to this solution at room temperature of 23°C. 10 H 12O2, 164.2 g / mol) is added and homogenized by stirring with a laboratory paddle stirrer. The solution is heated to an internal temperature of 80°C, and the heating power on the heater is adjusted to maintain this temperature constant. At this temperature, 0.6 g of a 4% platinum(IV)-containing solution of hexachloroplatinic acid in propanediol is added, which means that 30 ppm of platinum(IV) based on the sum of the reactants (790 g) is available for catalysis. The solution is stirred for 2 hours, with the heating power on the heater remaining unchanged. The reaction mixture is then cooled to room temperature of 23°C and filtered through a filter plate with a pore size of 1 μm. The solution is adjusted to a concentration of 50% toluene. A clear, yellowish solution is obtained. The eugenol-functional silicone resin contained therein has, according to 29 Si-NMR the percentage composition (in mol-%)

[0315] [ (C6H5)SiO 3 / 2 ]67,7 [(C6H5)(OH)2SiO 1 / 2 ]1,0[(C6H5)(OH)SiO 2 / 2 ] 22 ,0 [(CH3)2(H)SiO 1 / 2 ] 4,0 [(CH3)2(C 10 H 13 O2)SiO 1 / 2 ] 5,3 and, according to SEC, a molecular weight of Mw = 5596 g / mol and Mn = 2281 g / mol. The number of hydroxyaryl-functional residues relative to all Si-bonded residues is 3.7 mol%.

[0316] 1.2. Oxidative coupling of the polyorganosiloxane from 1.1. with phenols:

[0317] A constant stream of 0.5 m 3 / h of pure oxygen. A mixture of 70 g of the polyorganosiloxane from 1.1 and 140 g (1.15 mol) of 2,6-xylenol (122.2 g / mol) in 200 ml of toluene is metered into this vessel at a rate such that an internal temperature of 30°C is not exceeded. After the addition is complete, the reaction mixture is stirred for a further 3 h without additional heating. The reaction is stopped by adding 60 ml of acetic acid, and the water-soluble components are then removed by washing three times with 200 ml of deionized water each time. After filtration through a 1 μm filter plate, the volatile components are removed at 120°C under vacuum. As soon as a final vacuum of 10 mbar is established, the vessel is heated for a further 2 h to remove all components that are volatile under these conditions.196 g of a brown, clear, room-temperature solid product is obtained, which dissolves easily in both toluene and xylene at a concentration of 50 wt% to form a brown, clear, low-viscosity solution. According to 29S1 NMR spectroscopy, the resulting copolymer has the following percentage composition (mol%):

[0318] [(C6H5)SiO 3 / 2 ] 66,3 [(C6H5)(OH)2SiO 1 / 2 ] 1,5 [(C6H5)(OH)SiO 2 / 2 ] 23,0 [(CH3)2(H)SiO 1 / 2 ] 3,8 [(CH3)2(C 10 H 13 O2)SiO 1 / 2 ] 0,3 [(CH3)2(poly-2,6-dimethylphenol)SiO 1 / 2 ] 5, 1 The molecular weight is determined to be Mw = 17234 g / mol, Mn = 6798 g / mol. The proportion of poly-2,6-dimethylphenol units in the polyorganosiloxane polyphenylene ether copolymer is 1H-NMR 62 wt.%. The proportion of OH groups in the copolymer (phenolic OH groups and silanol groups combined) is 0.9 wt.%. This means that with a molecular weight of 17 g / mol for OH, one molecule with Mw = 17234 g / mol contains 9 mol of OH.

[0319] This copolymer is referred to below as 1.2.1 and is not yet in accordance with the invention because it does not yet contain any olefinically unsaturated groups. These are introduced as described below.

[0320] A 50 wt.% solution of copolymer 1.2.1 is prepared by dissolving 100 g of this copolymer (5.8 mmol) in 100 g of toluene. The residual water content of this solution is determined by Karl Fischer titration and is 364 ppm.

[0321] First, 21.2 g (0.18 mol) of dimethylvinylchlorosilane are added, followed by 17.4 g (0.22 mol) of pyridine. The first addition takes 30 minutes, the second 45 minutes. An exothermic temperature rise is observed. Here, too, the temperature is limited to 40°C by adjusting the addition rate. After the addition is complete, the mixture is stirred for 60 minutes to complete the reaction.

[0322] After the reaction has ended, the mixture is washed three times with 200 ml of deionized water each time and the aqueous phase is separated each time.

[0323] To separate the phases, the mixture is stirred for 30 minutes, then the stirrer is turned off and the phases are allowed to separate. The aqueous phase separates to the bottom and is drained. This process is repeated until the residual HCl content in the organic phase is determined by acid-base.

[0324] Titration according to the state of the art is < 20 ppm.

[0325] If the aqueous phase settles to the top, wash with an aqueous solution containing 10% sodium chloride instead of demineralized water and otherwise proceed in the same way.

[0326] After the final phase separation, the residual HCl content in the organic phase is < 20 ppm. The solvent is removed by distillation at 120°C and 10 mbar vacuum, as described above. Distillation is continued under these conditions for 2 hours to remove all volatile components. A brown, clear solid reaction product with a molecular weight of Mw = 18843 g / mol, Mn = 6920 g / mol is obtained. According to 29S1 NMR spectroscopy, the resulting copolymer has the following percentage composition (mol%):

[0327] [(C6H5)SiO 3 / 2 ] 84,6 [(C6H5)(OH)SiO 2 / 2 ] 3,1 [(CH3)2(H)SiO 1 / 2 ] 3,5 [(CH3)2(C 10 H 13 O 1, 5 )SiO 1 / 2 ] 0, 3[(CH3)2(poly-2,6-dimethylphenol)SiO 1 / 2 ] 4,8 [(CH3)2(CH2=HC)SiO 1 / 2 ] 6,8 , where the 6.8 mol-% [(CH3)2(CH2=HC)SiO 1 / 2 ] units must be bound to the previous OH groups, since there is no alternative to this under the chosen reaction conditions.

[0328] The remaining OH content is 0.05 weight percent determined by 1 H-NMR spectroscopy.

[0329] This copolymer is referred to below as 1.2.2.

[0330] The copolymer 1.2.2 contains more than 30 weight percent polyarylene ether units, more than 0.5 mol% olefinically unsaturated groups, and the proportion of three-dimensionally crosslinked silicone building blocks in the polyorganosiloxane framework is more than 40 mol%, in particular more than 50 mol%. Thus, all criteria for inventiveness are met. Additionally, Si-H groups are present, allowing curing by both hydrosilylation and radical curing.

[0331] Example 2: Preparation of a copolymer according to the invention by oxidative coupling

[0332] 2.1. Preparation of a hydroxyaryl-functional three-dimensionally cross-linked polyorganosiloxane:

[0333] 700 g of a polyorganosiloxane with the percentage composition (in mol%)

[0334] [ (C6H5)SiO 3 / 2 ] 43 [(C6H5)(OH)2Si0 1 / 2 ] 0,7 [(C6H5)(OH)SiO 2 / 2 ] 29 ,3

[0335] [ (CH3)2(H)SiO 1 / 2] 27, 0 , Mw = 3419 g / mol, Mn = 1741 g / mol are dissolved in 500 g of toluene. 120 g (= 0.73 mol) of 4-allyl-2-methoxyphenol (eugenol, C) are added to this solution at room temperature of 23°C. 10 H 12 O2, 164.2 g / mol) and 100 g (= 0.82 mol) of allyl methacrylate (C7H 10 O2 (126.16 g / mol) is added and homogenized by stirring with a laboratory paddle stirrer. The solution is heated to an internal temperature of 80°C, and the heating power on the heater is adjusted to maintain this temperature. At this temperature, 0.69 g of a 4% platinum(IV)-containing solution of hexachloroplatinic acid in propanediol is added. This means that 30 ppm of platinum(IV) is available for catalysis, based on the total mass of the reactants (920 g). The procedure is as in Example 1.1, and the following result is obtained:

[0336] 29 Si-NMR the percentage composition (in mol-%)

[0337] [ (C6H5)SiO 3 / 2 ]44,9 [(C6H5)(OH)2SiO 1 / 2 ]0.7[(C6H5)(OH)SiO 2 / 2 ] 27 ,4

[0338] [ (CH3)2(H)SiO 1 / 2 ] 11,6 [(CH3)2SiO 2 / 2 ] 1,0 [(CH3)2(C 10 H 13 O2)SiO 1 / 2 ] 6,5 [(CH3)2(C

[0339] 7H 11 O2)SiO 1 / 2 ] 7, 9 , whereby the formation of [(CH3)281O 2 / 2 ] units can most likely be explained by hydrogen loss during the reaction and the formation of siloxane bonds. According to SEC, the molecular weight is Mw = 4369 g / mol and Mn = 2018 g / mol. The number of hydroxyaryl-functional residues relative to all Si-bonded residues is 3.6 mol%. The number of olefinically unsaturated groups is 4.3 mol%.

[0340] 2.2. Oxidative coupling of the polyorganosiloxane from 2.1. with phenols:

[0341] The procedure is the same as described in 1.2. 187 g of brown, clear product is obtained, which is solid at room temperature and can be easily dissolved in both toluene and xylene at a concentration of 50 wt% to form a brown, clear, low-viscosity solution. 29 Si-NMR spectroscopy shows that the obtained copolymer has the percentage composition (mol-%):

[0342] [(C6H5)SiO 3 / 2 ] 50,2 [(C6H5)(OH)2SiO 1 / 2 ] 0,5 [(C6H5)(OH)SiO 2 / 2 ] 22,4 [(CH3)2(H)S 10 1 / 2 ] 11,2 [(CH3)2SiO 2 / 2 ] 1,4 [(CH3)2(Cl0H 13 O2)SiO 1 / 2 ] 0,6 [(CH3)2(poly-2,6-dimethylphenol)SiO 1 / 2 ] 5,9 [(CH3)2(C7H 11 O2)SiO 1 / 2 ] 7,8 ,

[0343] The molecular weight is determined to be Mw = 12334 g / mol, Mn = 4987 g / mol. The proportion of poly-2,6-dimethylphenol units in the polyorganosiloxane polyphenylene ether copolymer is1 H-NMR 63 wt.%. The proportion of OH groups in the copolymer (phenolic OH groups and silanol groups together) is 0.8 wt.%.

[0344] This copolymer is referred to below as 2.2.

[0345] It contains more than 30 percent by weight

[0346] Polyarylene ether units, more than 0.5 mol% of olefinically unsaturated groups, and the proportion of three-dimensionally crosslinked silicone building blocks in the polyorganosiloxane framework is more than 40 mol%, in particular more than 50 mol%. Thus, all criteria for inventiveness are met.

[0347] Additionally, Si-H groups are present, so that curing can occur both by hydrosilylation and radically.

[0348] Example 3: Preparation of a copolymer according to the invention by oxidative coupling (methyl resin without excess Si-H)

[0349] 3.1. Preparation of a hydroxyaryl-functional three-dimensionally cross-linked polyorganosiloxane:

[0350] 700 g of a polyorganosiloxane with the percentage composition (in mol%)

[0351] [(CH3)SiO 3 / 2 ]56[(CH3)(OH)2SiO 1 / 2 ]i,7[(CH3)(OH)SiO 2 / 2 ] 28 ,3

[0352] [(CH3)2(H)SiO 1 / 2 ] 14 , Mw = 3965 g / mol, Mn = 1984 g / mol are dissolved in 500 g of toluene. 120 g (= 0.73 mol) of 4-allyl-2-methoxyphenol (eugenol, CIQHI2O2, 164.2 g / mol) and 100 g (= 0.82 mol) of allyl methacrylate (C7H10O2, 126.16 g / mol) are added to this solution at room temperature of 23°C and homogenized by stirring with a laboratory paddle stirrer. The procedure is continued as described in Example 2 and the following result is obtained according to 29 Si NMR as percentage composition (in mol%):

[0353] [(CH3)SiO 3 / 2 ]6i,2[(CH3)(OH)2SiO 1 / 2 ]i,2[(CH3)(OH)SiO 2 / 2 ] 23 ,6

[0354] [(CH3)2(C 10 HI3O2)S10 1 / 2 ]6,3[(CH3)2(C7H 11 O2)SiO 1 / 2 ]7,7< and according to SEC a molecular weight of Mw = 4259 g / mol and Mn = 2028 g / mol. The number of hydroxyaryl functional groups relative to all Si-bonded groups is 4.1 mol-%.

[0355] The number of olefinically unsaturated groups is 5.0 mol-%. 3.2. Oxidative coupling of the polyorganosiloxane from 3.1. with phenols:

[0356] The procedure is the same as described in 1.2.

[0357] 178 g of brown, clear product is obtained, which is solid at room temperature and can be easily dissolved in both toluene and xylene at a concentration of 50 wt% to form a brown, clear, low-viscosity solution. 29 Si-NMR spectroscopy shows that the obtained copolymer has the percentage composition (mol-%):

[0358] [(CH3)SiO 3 / 2 ]63.7[(CH3)(OH)2Si0 1 / 2 ] 0,7 [(CH3)(OH)SiO 2 / 2] 21,6

[0359] [(CH3)2(C 10 H 13 O2)SiO 1 / 2 ] 0,3 [(CH3)2(poly-2,6-dimethylphenol)SiO 1 / 2 ] 5,9 [(CH3)2(C7H 11 O2)SiO 1 / 2 ]7,8• The molecular weight is determined to be Mw = 13394 g / mol, Mn = 5094 g / mol. The proportion of poly-2,6-dimethylphenol units in the polyorganosiloxane polyphenylene ether copolymer is 1 H-NMR 60 wt%.

[0360] This copolymer is referred to below as 3.2.

[0361] It contains more than 30 weight percent polyarylene ether units, more than 0.5 mol% olefinically unsaturated groups, and the proportion of three-dimensionally crosslinked silicone building blocks in the polyorganosiloxane framework is more than 40 mol%, in particular more than 50 mol%. Thus, all criteria for inventiveness are met.

[0362] Since there are no Si-H groups, curing can only occur radically.

[0363] Example 4: Inventive copolymer functionalized with chloropropionyl chloride

[0364] The copolymer 1.2.1. is further processed as follows: A 50 wt. % solution of the copolymer 1.2.1. is prepared by dissolving 100 g of this copolymer (5.8 mmol) in 100 g of toluene.

[0365] 34.4 g (0.27 mol) of 3-chloroprionyl chloride (126.97 g / mol) are added, and the mixture is stirred at 80°C for 2 h. The mixture is then cooled to 50°C, and 33.5 g (0.33 mol) of triethylamine (101.19 g / mol) are added. After the addition is complete, the mixture is stirred at 50°C for 60 minutes to complete the reaction.

[0366] The aqueous workup is carried out analogously to Example 1.

[0367] A brown, clear solid reaction product with a molecular weight of Mw = 19438 g / mol, Mn = 7020 g / mol is obtained. According to 29Si NMR spectroscopy, the resulting copolymer has the following percentage composition (mol%):

[0368] [(C6H5)SiO 3 / 2 ] 90,8 [(CH3)2(H)SiO 1 / 2 ] 1,2 [(CH3)2SiO 2 / 2 ] 2,2

[0369] [(CH3)2(CI3H 16 O4)SiO 1 / 2 ]0.4[(CH3)2(poly-2,6-dimethylphenol-0 (0=)C-CH=CH2)SiO 1 / 2 ] 5,4 .

[0370] The residue (poly-2,6-dimethylphenol-0 (0=)C-CH=CH2) represents a polyarylene ether residue bonded to the polyorganosiloxane framework via the eugenol group, which has been acrylate-functionalized at the terminal phenol-OH group by reaction with 3-chloropropionyl chloride.

[0371] The rest (C 13 H 16 O4) means an acrylate-functionalized eugenol residue.

[0372] Acrylate residues bound to the polyorganosiloxane framework are not present under the selected conditions, since the Si-acetyloxy bond is not stable under the hydrolytic conditions of the processing, is cleaved and [(C6H5)SiO 3 / 2] groups, which contribute to the polyorganosiloxane network. The acrylic acid amine adducts are removed during aqueous workup.

[0373] During processing, some of the Si-H groups are lost due to the elimination of the hydridic hydrogen, forming [(CH3)2SiO 2 / 2 ] groups.

[0374] This copolymer is referred to as 4.1.

[0375] Example 5: Inventive copolymer prepared from bisphenol A and phenol

[0376] The polyorganosiloxane according to Example 2.1 is subjected to oxidative coupling as follows:

[0377] The procedure corresponds to that described in Example 2.2, with the difference that 122 g (1 mol) of 2,6-xylenol (122.2 g / mol) and 18 g (0.06 mol) of 2,2'-diallylbisphenol A (308.41 g / mol) are dissolved in 200 ml of toluene and added.

[0378] A copolymer with the following percentage composition (mol-% according to 29 Si NMR)

[0379] [(C6H5)SiO3 / 2] 51,9 [(C6H5)(OH)SiO 2 / 2 ] 21,2 [(CH3)2(H)Si0 1 / 2 ] 10,9[ (CH3)2SiO 2 / 2 11,7 [(CH3)2(C 10 H 13 O2)SiO 1 / 2 ] 0,3 [(CH3)2(poly-2,6-dimethylphenol diallylbisphenol A copolymer)SiO 1 / 2 ] 6,2 [(CH3)2(C7H 11 O2)SiO 1 / 2 ] 7,8 , The molecular weight is determined to be Mw = 18443 g / mol, Mn = 6198 g / mol.

[0380] This copolymer is referred to as 5.1.

[0381] Example 6: Use of a compressed siloxane building block. 6.1. Preparation of a hydroxyaryl-functional

[0382] Polyorganosiloxane

[0383] From the polyorganosiloxane [(CH3)SiO 3 / 2 ] 13,1 [(CH3)(OH)SiO 2 / 2 ] 0,9 [(CH3)O 2 / 2 Si-CH2-CH2-Si(CH3)O 2 / 2 ]61,7 [(CH3)2(H)SiO 1 / 2 ] 24,3 , Mw = 1569 g / mol, Mn = 948 g / mol, a methacrylate- and hydroxyaryl-functional polyorganosiloxane is prepared analogously to the procedure in Example 2.1., whereby, in contrast to Example

[0384] 2.1. instead of eugenol 2,6-dimethyl-4-allylphenol (= 4-allyl-2,6-xylenol, C 11 H 14 O2, Mw = 162.2 g / mol) in an amount of 178 g (= 1.1 mol), with the following result:

[0385] Loud 29 Si-NMR gives a hydroxyaryl-functional polyorganosiloxane with the following percentage composition (mol-

[0386] [(CH3)SiO 3 / 2 ]I3[(CH3)(OH)SiO 2 / 2 ]11[(CH3)O 2 / 2 Si-CH2-CH2-

[0387] Si(CH3)O 2 / 2 ] 61,6 [(CH3)2(H)SiO 1 / 2 ] 0,1 [(CH3)2(C 11 H 15 O2)SiO 1 / 2 ]13,1[(CH3)2(C7H 11 O2)SiO 1 / 2]11.2, Mw = 2304 g / mol, Mn = 1399 g / mol. This polyorganosiloxane is referred to below as 6.1.

[0388] 6.2. Preparation of a copolymer of formula (I) according to the invention by oxidative coupling

[0389] Analogous to the procedure described in Example 2.2, a polyarylene ether polysiloxane copolymer according to the invention is prepared from 6.1 by oxidative coupling. The final product, referred to below as 6.2, has the following percentage composition (mol-% according to 29 Si NMR):

[0390] [(CH3)SiO 3 / 2 ] 13,3 [(CH3)(OH)SiO 2 / 2 ] 10,7 [(CH3)O 2 / 2 Si-CH2-CH2-Si(CH3)O 2 / 2 ] 61,6 [(CH3)2(H)SiO 1 / 2 ]0.1[(CH3)2(C 11 H15O2)SiO 1 / 2 ] 0,7 [(CH3)2(poly-2,6-dimethylphenol)SiO 1 / 2 ] 12,5 [(CH3)2(C7H 11 O2)SiO 1 / 2]11.1, Mw = 24678 g / mol, Mn = 8893 g / mol. This polyorganosiloxane is referred to below as 6.2.

[0391] Example 7: Comparative example: Oil copolymer from prior art US 8017697

[0392] Example 1 from US 8017697 was reproduced as described therein. The required eugenol-terminated polydimethylsiloxane with a chain length of 45 was, in contrast to US 8017697, not purchased from Momentive Performance Materials but prepared according to the hydrosilylation procedure for eugenol in Example 1 from US 5357022. The identity of the product, in particular that the correct chain length of the polydimethylsiloxane was present and that the hydrosilylation reaction was successful, was confirmed by 29 Si NMR spectroscopy confirmed.

[0393] The reaction conditions and the relative amounts of the raw materials used were adjusted according to Table 2 in US 8017697 .

[0394] The following properties were determined for the copolymer obtained:

[0395] Mw = 49900 g / mol, Mn = 18500 g / mol, Mw / Mn = 2.7 Weight fraction of dimethylsiloxane in the copolymer: 5.0% No indications of siloxane not incorporated into the copolymer were found, so a siloxane incorporation efficiency of close to 100% can be assumed. With this result, the reproduction of Example 1 according to US 8017697 can be considered successful and the product obtained corresponds to the invention according to US 8017697. It contains neither olefinically unsaturated groups nor network-forming siloxane building blocks, as corresponds to this prior art. This copolymer is referred to below as 7.1. Example 8: Use of the inventive and non-inventive organopolysiloxanes according to Examples 1 - 7 for the production of metal-clad laminates.

[0396] The inventive and non-inventive polyorganosiloxanes obtained according to Synthesis Examples 1 to 7 were used as binders to produce copper-clad laminates with a glass fiber-reinforced composite layer. The following starting materials were used:

[0397] Copper foil: 35 pm thick copper foil (285 ± 10 g / m 2 ) from Jiangtong-yates Copper Foil Co Ltd, with a surface roughness of Rz ≤ 8 pm and a mean surface roughness of Ra d 0.4 pm, purity > 99.8%.

[0398] Glass fiber: E-glass fiber Type 1080 E manufactured by Changzhou Xingao Insulation Materials Co. Ltd. Thickness 0.055 ± 0.012 mm, 47.5 ± 2.5 g / m 2 .

[0399] All organopolysiloxane polyarylene ether copolymers were used as solutions in xylene. The solutions contained 35 weight percent copolymer and initiator and 65 weight percent xylene.

[0400] To initiate the curing of the olefinically unsaturated copolymers 1.2.2., 2.2., 3.2., 4.1., 5.1. and 6.2., the organopolysiloxanes were each mixed with 1 weight percent of dicumyl peroxide, based on the amount of polyorganosiloxane used, which was then evenly distributed in the resin matrix by stirring. The non-inventive copolymer 7.1. was treated analogously once for comparison purposes, even though it is chemically not possible to cure and crosslink it in this way. Furthermore, a chemically curable binder preparation was produced using 7.1. by preparing a chemically curable mixture following the instructions in Example 1 in EP0592145. The weight percentages given below refer to 100% of the finished formulation.

[0401] According to Example 1 of EP0592145, 21.7 wt% of 7.1 was dissolved in 65.1 wt% toluene and mixed with 8.9 wt% EPON 828 (Hexion Inc.), 3.3 wt% N,N'-1,3-phenylenebismaleimide and 1.1 wt% aluminum triacetylacetonate (= Al(acac)3), maintaining the temperatures and sequence as specified in Example 1 in EP0592145.

[0402] The laminates for testing were prepared from the resulting mixture as further described below.

[0403] Laminates of 1.2.2., 2.2., 3.2., 4.1., 5.1., and 6.2. were produced by impregnating 30 x 30 cm glass fiber layers layer by layer with the respective copolymer as a xylene solution using a deaerator roller, ensuring that no bubbles were formed. The procedure for 7.1. was analogous, but in this case, the solution prepared specifically for this purpose according to the state of the art, as described in this example above, was used. To ensure comparability, the copolymers 1.2.2., 2.2., 3.2., 4.1., 5.1., and 6.2. were also adjusted to approximately 35% by weight solids, including the initiator, as a xylene solution, as stated above.

[0404] The glass fiber layers were placed on a dimensionally stable, flat stainless steel base, onto which a layer of copper foil was applied before the first layer of glass fiber was laid down. A total of three layers of glass fiber fabric were impregnated one after the other. To remove any solvent, the impregnated fabrics were dried to constant weight at 60°C in a vacuum drying cabinet at 10 mbar. A second layer of copper foil was then applied on top of the impregnated glass fiber layer, and another dimensionally stable stainless steel plate was placed on top. The laminate was baked in a heatable press at 2 MPa pressure, 120 min at 200°C and 30 mbar vacuum. This produced copper-clad laminates with a total thickness of 260 ± 20 pm.

[0405] The dielectric properties were determined according to IPC TM 650 2.5.5.13 using a Keysight / Agilent E8361A network analyzer using the split-cylinder resonator method at 10 GHz. The following values ​​were obtained:

[0406] The D f - and the D k -values ​​of the copper-clad laminates made from the copolymers according to the invention are significantly lower than the D f -and D k Values ​​achieved with the copolymer using the prior art procedure. Since the lowest possible dielectric loss factors and dielectric constants are desired for high-frequency applications, the effect of the invention is clearly evident.

Claims

Patent claims 1. Polyarylene ethers containing olefinic unsaturated groups, polysiloxane copolymers of formula (I) [O 3-a / 2 R a Si-Y 1 (SiR a O 3-a / 2 ) b ] c (R 1 SiO 3 / 2 ) d (R 2 2SiO 2 / 2 ) e (R 3 3SiO 1 / 2 ) f (SiO 4 / 2 ) g (I) where Y 1 a chemical bond or a two- to twelve-coordinate organic unsubstituted or heteroatom-substituted aliphatic, cycloaliphatic or aromatic organic residue with 1 to 24 C atoms bonded to the silicon atoms by a Si-C bond means R, R 1 , R 2 and R 3are independent of each other, either the same or different, and represent either a hydrogen residue, a hydroxy residue, or a Si-C-bonded or Si-O-bonded monovalent, unsubstituted or heteroatom-substituted and optionally organofunctional organic hydrocarbon residue with 1 to 18 C atoms, or a Si-C-bonded polyarylene ether residue, wherein the proportion of hydroxy residues and Si-O-bonded residues relative to the sum of all residues R, R 1 , R 2 and R 3 than 100 wt% is at most 5 wt%, where the proportion of Si-C-bound polyarylene ether residues is based on the sum of all residues R, R 1 , R 2 and R 3 as 100% by weight is at least 10% by weight, wherein the proportion of olefinically or acetylenically unsaturated residues is based on all residues R, R 1 , R 2 and R 3 than 100 mol-% is at least 0.5 mol-%, where the polyarylene ether residue is selected from a Remainder of formula (II) or (III) R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 independently of one another a hydrogen radical, a monovalent hydrocarbon group, a hydrocarbon group substituted with heteroatoms, an organofunctional residue or a silyl group of the form (R 40 3Si-) are, where R 40 the meanings of R 3 has and the remains R 4 to R 12 They can also be bound to the aromatic ring via a heteroatom, with the R groups 4 , R 5 and R 6may also mean a chemical bond or a divalent aliphatic, cycloaliphatic or aromatic hydrocarbon residue with 1 to 12 carbon atoms, through which the bonding of the residues of formula (II) to the polyorganosiloxane skeleton is established, wherein at least one residue R 4 , R 5 or R 6 such a residue is one that forms a bond to the polyorganosiloxane backbone, wherein, as far as chemically possible, neighboring residues from the group of residues R 4 to R 12 They can also be linked together to form the same cyclic saturated or unsaturated residue, resulting in annelated polycyclic structures that include both cycloaliphatic and cycloaromatic structures or mixtures thereof. R 14 a chemical bond or a divalent, possibly substituted, arylene residue of the form (-C6R 15 / -) means, where R 15regardless of these, the same meaning as the remainders R 9 , R 10 , R 11 or R 12 may have or an alkylene residue of the form -CR 16 2 _ means, where R 16 independent of R 15 the same meanings as R 15 may have a divalent glycol residue of the form - [(OCH2)2O]1- or - [(OCH2CH (CH3)2)0] m -, where 1 and m each independently represent integers with values ​​from 1 to 50 inclusive, a divalent silyloxy residue of the form -Si(R 17 )2O 2 / 2 “, a divalent siloxane residue of the form - [(CH2)3Si-[O-Si(R) 18 )2] n O-Si(CH2)3-, a divalent silyl residue of the form -Si(R 19 )2 _ , where R 17 , R 18 and R 19 independently of each other and independent of R 15 which can have the same meanings as R 15and n means an integer with a value from 0 to 500 inclusive, a means an integer with a value of 0, 1 or 2, where the indices a on either side of the group ¥ can take on their meaning independently of each other, so that different a can independently mean different values ​​within the specified range of values, h has a value from 0 to 1000, b means an integer with a value from 1 to 11, c means a value from 0 to 0.9, d means a value from 0 to 1, e means a value from 0 to 0.5, f means a value from 0 to 0.6, and g means a value from 0 to 0.2, where c+d+e+f+g = 1 and at least c or d has a value other than 0 and the sum c+d represents at least 40% of the sum c+d+e+f+g, i means an integer with a value from 0 to 50 inclusive, j means an integer with a value from 0 to 10 inclusive, and k means an integer with a value from 0 to 50 inclusive, provided that at least one polyarylene ether residue of formula (II) or (III) is present for each polyarylene ether polysiloxane copolymer of formula (I).

2. Copolymers according to claim 1, wherein the unsubstituted residues R, R 1 , R 2 , R 3 selected from methyl, ethyl, n-propyl and phenyl residues.

3. Copolymers according to any one of the preceding claims, wherein the olefinically or acetylenically unsaturated residues R, R 1 , R 2 and R 3 selected from acrylate, methyl acrylate, methyl methacrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate, vinyl, allyl, propenyl, butenyl, 1,3-butadienyl and isoprenyl residues.

4. Copolymers according to any of the preceding claims, wherein the proportion of Si-C-bonded polyarylene ether residues relative to the sum of all residues R, R 1 , R 2 and R 3 where at least 30 percent by weight is less than 100 percent by weight.

5. Copolymers according to any of the preceding claims, which are solid at 25°C and have a glass transition temperature of 25°C to 350°C.

6. Copolymers according to any of the preceding claims, which do not contain units of the formula (R 2 2SiO 2 / 2 ) e contain.

7. Process for the preparation of the polyorganosiloxane polyarylene ether copolymers of formula (I) according to any one of the preceding claims by oxidative coupling of the arylhydroxy residues of the polyorganosiloxane compounds of formula (VII) [O 3-a / 2 R 31 a Si-Y 2 (SiR 31 aO 3-a / 2 )b] c (R 32 SiO 3 / 2 )d(R 33 2SiO 2 / 2 ) e (R 34 3SiO 1 / 2 ) f (SiO 4 / 2 )G (VII), wherein R 31 a remainder R, R 32 a remainder R 1 , R 33 a remainder R 2 , R 34 a remainder R 3 and Y 2 a remainder Y 1 This means, with the difference that if R 31 , R 32 , R 33 or R 34 a remainder of formula (II) or if Y 2includes such a remainder of formula (II), in which the index h is always 0 and the remainder R 13 always a hydrogen residue and that R 31 R 32 , R 33 and R 34 cannot mean a polyarylene ether residue of formula (III), and that Y 2 cannot contain a residue of formula (III), provided that at least 1 mol-% of all Si-bonded residues contain a residue of formula (II) with h = 0 and R 13 = hydrogen are, with phenols of formula (Villa) or (VIIIb) or a mixture of (Villa) and (VIIIb) where the remainders R 9 , R 10 , R 11 , R 12 and R 14and j having the meanings specified in the preceding claims. Use of the copolymers according to any one of claims 1 to 6 in the production of coating materials and impregnations and coatings and coverings obtained therefrom on substrates, as binders or as additives in preparations. Use of the copolymers according to any one of claims 1 to 6 for the production of metal-laminated materials. Use according to claim 9, wherein the metal is selected from copper, stainless steel, gold, aluminum, silver, zinc, tin, lead and transition metals.

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