Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2150/00—Compositions for coatings

Definitions

• the present invention relates to a process for preparing polyorganosiloxanes which ensures that polar Si-O-C-bonded and silanol groups are reduced to a minimum and thus the polyorganosiloxanes have suitable dielectric properties for high-frequency applications.
• Polyphenylene ethers are currently used intensively as binders for this area of application, as they combine low dielectric loss factors with good mechanical and thermal properties and water repellency.
• other organic polymers are currently also being considered in the current development activities for this field of application, such as bismaleimide polymers, bismaleimide triazine copolymers and hydrocarbon resins, although this list could be supplemented by others.
• Polyorgansiloxanes basically have excellent heat resistance, weathering stability and hydrophobicity, are flame-resistant and have low dielectric loss factors.
• polyorganosiloxanes are preferably produced by a hydrolytic condensation process. Alcohols are optionally also used here. See for example:
• compositions of physical mixtures of polyphenylene ethers with polyorganosiloxanes to improve specific properties can be found in US 3737479 (improving impact strength), US 5834585 (mixtures of chemically curable polyphenylene ethers with improved processability), US 2004/0138355 (improving flame retardance through mixtures with closed and partially open silsesquioxane cage structures), US Pat. No. 3,960,985 (improving the thermal stability of mixtures of polyphenylene ethers with alkenyl aromatic polymers by adding small amounts of chain-side Si-H-functional polydimethylsiloxanes).
• US 2016/0244610 describes compositions made from mixtures of olefinically unsaturated MQ resins with unsaturated modified polyphenylene ethers, the dielectric and thermal properties of the polyphenylene ethers being said to be improved through the use of the MQ resin.
• the examples in US 2016/0244610 have very high dielectric loss factors of the compositions according to the invention.
• 5,548,053 represents an older but still superior prior art for reducing polar groups with regard to the synthesis of MQ resins
• the MQ resins according to US 2016/0244610 have poorer properties for use in high-frequency applications with regard to the number of silicon-bonded polar groups than those available under US 5548053.
• alkoxy groups would also remain in the resin in large quantities in addition to residual amounts of silanol groups.
• US 2018/0220530 also describes compositions made from mixtures of silicone resins, in this case of the MT, MDT, MDQ and MTQ type, which are claimed as a lump sum and as classes without further restrictions.
• the claimed silicone resins are all produced by a hydrolytic process.
• the dielectric loss factors sought in both inventions are ⁇ 0.007. This requirement is met with freshly produced test specimens from the materials according to the invention, although not significantly below it, so that the prior art according to US 2018/0215971 and US 2018/0220530 leaves clear room for improvement.
• alkali metal siliconates obtainable from the reaction of organosilanols or alkoxy-functional silane or siloxane precursors with alkali metal hydroxides, are reacted with chlorosilyl components in an anhydrous condensation process.
• the alkali metal siliconates reacted in the process according to the invention are produced in a separate upstream synthesis step.
• an auxiliary base is added to the during the reaction to bind the hydrogen chloride formed. Salt is filtered off or removed as an aqueous solution during work-up with water. In this way, silanol-free and alkoxy-free linear polyorganosiloxanes are obtained.
• the present invention is dedicated to the task of providing crosslinkable polyorganosiloxanes with dielectric properties suitable for use as binders for high-frequency applications in a water-free process in such a way that they can be produced economically, in particular without the detour via metal siliconates or other raw materials to be produced in a separate step, with a minimum to Si-O-C-bonded polar groups and in a structural variety sufficient for the application, in particular also with a three-dimensional structure.
• binders As pure binders, they have a dielectric loss factor of not more than 0.0040 at 10 GHz, wet any fillers that reduce the dielectric loss factor well, allow the production of tack-free prepregs and produce preparations that are compatible with organic polymers.
• the invention relates to a process for the production of
• radicals R can be identical or different radicals and can be either a hydrogen radical or a monovalent Si C-bonded, unsubstituted or heteroatom-substituted organic hydrocarbon radical having 1 to 18 carbon atoms, which can also be an unsaturated hydrocarbon radical,
• Y is a chemical bond, an oxygen atom or a di- to twelve-valent organic unsubstituted or heteroatom-substituted organic radical with 1 to 24 carbon atoms, which is bonded to the silicon atoms by Si-C linkage
• the radicals R 1 , R 2 and R 3 independently of one another is a hydrogen radical or a saturated or unsaturated Si-C bonded C1 - C18 hydrocarbon radical, which may be unsubstituted or substituted by heteroatoms, or a C1 - C12 hydrocarbon radical bonded via an oxygen atom, which may contain heteroatoms, or a silanol radical
• the radicals R 1 , R 2 and R 3 can each assume their meaning independently of one another, so that several radicals R 1 , R 2 or R 3 , which are bonded to the same silicon atom, can mean different radicals from the defined group R 4 radicals, independently of one another, are either a hydrogen radical, a silanol radical or a monovalent Si-C
• R 7 3-h R 4 h Si(SiR 5 2 ) i SiR 4 j R 7 3-j (IV) where R 7 is a hydrolyzable group as described above and R 4 , R 5 , h, i and j are the have the same meanings as mentioned above, and/or organyl-bridged silicones of the formula (V)
• the object is achieved by the process for preparing the polyorganosiloxanes of the formula (I), which consists of two steps, the first step being a hydrolytic condensation and the second step being an anhydrous condensation from the first Step existing silanol groups are reduced so that the polyorganosiloxane compositions are obtained without the use of metal siliconate intermediates and in a non-hydrolytic process.
• a feature of the polyorganosiloxanes of the formula (I) obtained by the process according to the invention is that they are largely free of silanol groups and silicon-bonded alkoxy groups.
• Alkoxy groups in particular with short alkyl groups and silanol groups, lead to higher dissipation factors and also contribute to increasing the dissipation factor by forming points of attack for moisture.
• polyorganosiloxanes of the formula (I) include both polymeric and oligomeric organosiloxanes.
• the Si-C bond Since the electronegativity difference between silicon and oxygen according to the Allred and Rochow electronegativity scale of 1.76 ⁇ m 1 is larger than the electronegativity difference between silicon and carbon according to the same table, the Si-C bond has a lower polarity than the Si- O bond. It is therefore to be expected that the replacement of Si-O bonds with Si-C bonds will make a further contribution to reducing the overall polarity of organopolysiloxanes and thus contribute to reducing the dissipation factor of corresponding components. This effect is all the more pronounced the more Si-O bonds can be replaced by Si-C or Si-Si bonds.
• An M-resin composed of different M units is understood from formula (Ia) assuming all a is 2 and Y is either a chemical bond or a Si-C bonded bridging group each silicon atom of the bridged unit is surrounded by only one oxygen atom, which maintains a bond to a neighboring silicon atom and can therefore be understood in terms of the general M, D, T, Q nomenclature as an M 2 building block in which two M Units bonded to one another or coupled to one another by a bridging radical.
• This structural peculiarity of chain-forming M units both from the organically bridged and the di,- oligo- or polysilane units must be taken into account in this case.
• Simple M units as they correspond to the synthesis equivalents for the units of the formula (R 3 SiO 1/2 ) f and as used in US 20180220530 are not used in the first step of the synthesis, the hydrolytic reaction step. Although this is possible in principle, it does not bring about the same effect in reducing the silanol groups as using these groups in the second anhydrous synthesis step.
• the units of the formula (R 3 SiO 1/2 ) f are therefore used only in the second anhydrous reaction step to the To reduce the number of silanol groups and thereby achieve an improvement over the prior art according to US 20180220530. This is an essential distinguishing feature of the procedure according to the invention.
• R, R 1 , R 2 , R 3 , R 4 and radicals R 5 excluding the radicals R 5 which are radicals of the formula (II) are saturated or unsaturated hydrocarbon radicals which may contain aromatic or aliphatic double bonds, e.g. B.
• alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neo- Pentyl and tert-pentyl, hexyl, such as n-hexyl, heptyl, such as n-heptyl, octyl, such as n-octyl and iso-octyl, such as 2, 2, 4-trimethylpentyl and the 2-ethylhexyl 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, tetradecyl radicals, such as the n-tetradecyl radical, hexade
• Preferred heteroatoms which can be contained in the radicals R, R 1 , R 2 , R 3 , R 4 and R 5 are oxygen atoms.
• nitrogen atoms, phosphorus atoms, sulfur atoms and halogen atoms such as chlorine atoms and fluorine atoms are also possible but not preferred.
• preferred organic radicals R, R 1 , R 2 , R 3 , R 4 and R 5 containing heteroatoms are radicals which are acryloyloxy or Contain methacryloyloxy radicals of acrylic acid or methacrylic acid and acrylic acid esters or methacrylic acid esters of unbranched or branched alcohols having 1 to 15 carbon atoms.
• Preferred such radicals are those derived from methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate , 2-ethylhexyl acrylate and norbornyl acrylate.
• Methyl acrylate, methyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate and norbornyl acrylate are particularly preferred.
• These radicals are preferably not bonded directly to the silicon atom, but are bonded via a hydrocarbon spacer which can comprise 1 to 12 carbon atoms, preferably comprising 1 or 3 carbon atoms and, apart from the heteroatoms contained in the acryloyloxy or methacryloyloxy radical, none further heteroatoms included.
• the radicals R, R 1 , R 2 , R 3 , R 4 and R 5 are preferably selected from methyl, phenyl, vinyl, acryloyloxy and methacryloyloxy radicals and the acrylic acid esters or methacrylic acid esters of unbranched or branched alcohols with 1 to 15 carbon atoms.
• R3 are those of the formula (VII).
• R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently a hydrogen radical, a hydrocarbon group or a hydrocarbon group substituted with foreign atoms, where at least one of the radicals R 9 , R 10 , R 11 , R 12 , R 13 and R 14 represent a hydrocarbon group which is bonded to the silicon atom via a Si-C or a Si-OC bond, it being preferred that this hydrocarbon group via which the radical of formula (VII ) bonded to a silicon atom is a C3 hydrocarbyl group containing no heteroatoms.
• the radical R 9 , R 10 , R 11 , R 12 , R 13 and R 14 can also be a chemical bond, so that the radical of the formula (II) via this radical, which represents a chemical bond, via a Si-C bond is directly bonded to the silicon atom.
• radicals R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are the hydrogen radical, saturated hydrocarbon radicals such as methyl, ethyl, n-propyl, isopropyl, the primary, secondary and tertiary butyl radical, and the hydroxyethyl radical , aromatic residues such as the phenylethyl residue, the phenyl residue, the benzyl residue, the methylphenyl residue, the dimethylphenyl residue, the ethylphenyl residue, heteroatom-containing residues such as the hydroxymethyl residue, the carboxyethyl residue, the methoxycarbonylethyl residue and the cyanoethyl residue and acrylate and methacrylate residues such as methyl acrylate, methyl methacrylate, Ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate,
• adjacent radicals R 9 and R 11 and the adjacent radicals R 10 and R 12 can also combine with one another to form the same cyclic saturated or unsaturated radical be connected so that fused polycyclic structures arise.
• phenol residues of the formula (VII) 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 and 2-methyl-6-allylphenol residue, which may optionally be substituted on the oxygen atom.
• fluorine-containing radicals are the trifluoropropyl, nonafluorohexyl and heptadecafluorooctyl radicals.
• Y is preferably a linking organic moiety having 1 to 24 carbon atoms between two to twelve siloxanyl units.
• Y is preferably divalent, trivalent or tetravalent, in particular bivalent.
• Preferred bridging aromatic radicals Y are those of
• R 15 , R 16 , R 17 and R 18 can denote a hydrogen radical or an optionally substituted hydrocarbon radical or a group of the formula OR 19 where R 19 denotes a hydrocarbon radical.
• Adjacent radicals such as, for example, R 15 and R 17 or R 16 and R 18 in formula (VIIIa) can be present coupled to one another to form cyclic radicals, so that fused ring systems are formed.
• bridging aromatic radicals are the p-, m- or o-phenylene radical, the 2-methyl-1,4-phenylene radical, the 2-methoxy-1,4-phenylene radical, the p-phenylene radical being particularly preferred.
• radicals can be coupled to one another, so that, for example, two or more units of the formula (IIIa) are coupled to one another and this oligomeric bridging structural element is present by attachment of the corresponding carbon atoms of the terminal aromatic rings to the silicon atom.
• the aromatic units can be bonded directly to one another or they can be coupled to one another by a bridging group such as an alkanediyl unit, for example the methylene group, the 1,2-ethanediyl group, 1,1-ethanediyl group, the 2,2-dimethylpropyl group or a sulfone group .
• aromatic bridging moieties are those in which two optionally substituted phenolic rings are bridged via an alkanediyl or other moiety.
• Typical representatives are 2,2-bis(4-hydroxyphenyl)propane residues substituted on the phenol oxygen (substituted bisphenol A residues), 2,2-bis(4-hydroxyphenyl)methane residues (substituted bisphenol F residues), bis(4-hydroxyphenyl)sulfone residues ( Bisphenol S residues) where the Phenolic oxygens are typically substituted with groups of the type -(C 3 H 6 )-, where the groups -(C 3 H 6 )- are bonded to silicon atoms Si-C, thereby providing the bridging.
• Preferred radicals Y which are not bridged by an aromatic unit are alkanediyl, alkenediyl and alkynediyl radicals which may contain heteroatoms and which may contain aromatic groups as substituents which, however, do not assume or contribute to the task of bridging in these radicals.
• 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 and the 1,2-cyclohexylethanediyl group.
• each of these groups can have any other connectivity apart from alpha-omega connectivity, i.e. bridging through the first and last atom of a linear unit, i.e. the use other chain carbon atoms have a bridging effect.
• 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 carbon atoms of the hydrocarbon structure to silicon atoms.
• Examples of typical fluorine-substituted bridging radicals Y are the -C(CF 3 ) 2 -, the -C (H)FC (H)F- and the -C (F 2 )-C (F 2 )- radical.
• heteroatom-containing bridging radicals are, for example, the ethyleneoxypropylene radical and the ethyleneoxybutylene radical.
• the viscosity of the organopolysiloxanes used according to the invention can vary over a wide range, depending on the average number of structural units per molecule forming them, or they can also be solids.
• liquid organopolysiloxanes which can be used according to the invention have viscosities at 25° C. of from 20 to 8,000,000 mPas, preferably from 20 to 5,000,000 mPas, in particular from 20 to 3,000,000 mPas.
• solid organopolysiloxanes which can be used according to the invention have glass transition temperatures in the range from 25.degree. C. to 250.degree. C., preferably from 30.degree. C. to 230.degree. C., in particular from 30.degree. C. to 200.degree.
• Those organopolysiloxanes that have proven to be particularly suitable have bridging phenylene units and an overall aromatic content of at least 20 mol %, based on all Si—C-bonded substituents as 100 mol %.
• Phenylene units are both monomeric and oligomeric and substituted as well as unsubstituted phenylene units understood as illustrated in the examples of the nature of the bridging substituents of this type are described.
• radicals R 5 of formula (II) are linear and cyclic structures of average composition
• Examples of preferred hydrolyzable radicals R 7 and R 8 are a halogen, acid or alkoxy group, particularly preferably a chlorine, acetate, formate, methoxy or ethoxy group.
• the compounds (VI) are according to methods according to the
• compounds (VI) are obtained, for example, from olefinically unsaturated organic precursors such as, for example, acetylene, diallyl or divinyl compounds and Si—H-functional silicone building blocks by hydrosilylation.
• olefinically unsaturated organic precursors such as, for example, acetylene, diallyl or divinyl compounds and Si—H-functional silicone building blocks by hydrosilylation.
• the first process step, the cohydrolysis is preferably carried out in such a way that a mixture of the compounds (III), (IV), (V) and (VI), where they are used, is metered into water or dilute acids with cooling.
• gaseous acids such as HCl
• dosing into a concentrated aqueous HCl solution also makes sense if the acid released is to be recovered as a gas.
• the hydrolysis is exothermic to a greater or lesser extent, so that cooling is necessary both in the interest of carrying out the reactions safely and also, if appropriate, to avoid side reactions in corresponding sequences of the syntheses. To complete the reactions, however, it can be advantageous and necessary to use elevated temperatures.
• reaction times are generally very short, so that the time required to carry out the process in batch mode depends mainly on the cooling capacity.
• the cohydrolysis of (III), (IV) and/or (V) can also be carried out continuously, for which both loop and column reactors and tubular reactors are suitable.
• the process can be carried out at atmospheric pressure. Depending on the objective, however, higher or lower pressure is also practicable. It is essential that, at the end of the first process step, the amount of water present is reduced to such an extent that there are at most residual amounts of water which, as unintentional contamination, cannot be further depleted using methods according to the prior art. Ideally, the remaining amount of residual water is reduced so that it is below the detection limit, so that an anhydrous medium can be assumed. This depletion of water is necessary for the successful implementation of the process according to the invention because water fundamentally entails the option of forming silanol groups if the conditions under which polyorganosiloxanes can react with water are present, ie usually acidic or basic conditions.
• silanol groups are to be depleted, the presence of water is detrimental in the next step.
• the water-depleted reaction mixture from the first step is referred to as anhydrous.
• the second process step is carried out with the dehydrated reaction mixture from the first step.
• the silanol groups on the polyorganosiloxane from the first step are reacted with silanes of the formula (VI) by metering them in, if appropriate dissolved in an inert solvent.
• An auxiliary base is advantageously used to start and accelerate the reaction.
• the radical R 8 is a halogen radical, in particular a chloride radical.
• Basic salts or nitrogen-containing compounds such as amines, ureas, imines, guanidines and amides are suitable as auxiliary bases for scavenging the hydrogen halide formed.
• Examples of basic salts are sodium hydride, sodium amide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate, calcium oxide, magnesium oxide, magnesium carbonate.
• nitrogen-containing compounds are ammonia, ethylamine, butylamine, triethylamine, trimethylamine, tributylamine, N,N-dimethyldecylamine, triisooctylamine, urea, tetramethylurea, guanidine, tetramethylguanidine, N-methylimidazole, N-ethylimidazole, piperidine, pyridine, picoline, N-methylmorpholine .
• Amine compounds in which the nitrogen atoms do not carry any hydrogen atoms are preferably used.
• the auxiliary base is preferably used in at least an equimolar amount with respect to the halosilane.
• Per mole equivalent of halosilane preferably at least 0.5, particularly preferably at least 1.0, in particular at least 2.0 base equivalents of auxiliary base are used. It is also possible to use larger additional amounts of auxiliary base, for example if this is to serve as a solvent at the same time. In most cases, however, this does not bring 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 appropriate, 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.
• halosilanes or halosilanes of the formula (VI) are preferably used in such a way that an equimolar amount of halide radicals is present in relation to the silanol radicals on the polyorganosiloxane species from the first reaction step.
• the reaction of the halosilanes of the formula (VI) with the silanol radicals of the polyorganosiloxane species from the first reaction step is preferably carried out at a temperature of at least -20.degree. C., particularly preferably at least 0.degree. C., in particular at least 10.degree.
• the maximum permissible temperature also results from the boiling point of the solvent used and of the halosilanes of the formula (VI), the reaction temperature preferably not exceeding 200.degree. C., particularly preferably 175.degree. C., in particular 150.degree.
• the reaction mixture can be cooled or heated, and individual reaction components can optionally be adjusted to temperature in advance before they are reacted with one another, for example in order to be able to use the heat of reaction.
• the process can be carried out either batchwise in stirred reactors or continuously in column, loop, fluidized bed or tubular reactors. Any low molecular weight siloxanes formed during the reaction can, if necessary, be removed from the reaction mixture by distillation.
• the halide salts formed during the reaction can be decanted off, filtered off or centrifuged off or dissolved in water and separated off.
• the amount of solvent already present can be adjusted as required, for example in order to facilitate phase separations by adjusting density differences, or other solvents can be added whose solubility or
• Miscibility with water is as low as possible, in particular at most 5% by weight at 25°C.
• Any excess halosilane of the formula (VI) present is preferably removed by distillation before the aqueous work-up. This prevents the presence of an aqueous acidic solution which could potentially lead to the formation of silanol groups again on the polyorganosiloxane.
• the second reaction step is preferably carried out with exclusion of moisture, ie in a dried atmosphere or under reduced pressure, particularly preferably under an inert gas such as argon, nitrogen, carbon dioxide or lean air, preferably at 900 to 1100 hPa.
• an inert gas such as argon, nitrogen, carbon dioxide or lean air
• Aromatic hydrocarbon solvents such as benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene or mixtures thereof are particularly suitable as aprotic solvents for both the first and the second step.
• the suitability of the solvent is determined by its ability to dissolve the resulting polyorganosiloxanes. The solvent must dissolve the resulting polyorganosiloxane sufficiently well, must be immiscible with water, ie it must itself not be able to dissolve more than 5% by weight of water and must not take part in the reaction.
• Aromatic solvents best meet the conditions mentioned and are therefore preferred.
• disiloxanes which are generally used as symmetrical disoloxanes, to reduce the number of silanol groups is ruled out as not being according to the invention.
• disiloxanes cleave in the presence of acids by breaking the Si-O-Si bond, the acids are usually used as an aqueous preparation, which intentionally introduces water in the second step of the synthesis, which does not rule out the tendency to reproduce silanol groups and the second step would no longer be anhydrous and would be reduced in efficiency.
• the polyorganosiloxanes of the formula (I) are chemically curable, ie they can be cured by a chemical reaction to form a crosslinked, insoluble network. Curing takes place via the olefinically unsaturated groups, which are described above. Typically, either a free radical polymerization reaction is used for curing, or if olefinic or acetylenic unsaturated functional groups and silicon-bonded hydrogen as a radical is present, a hydrosilylation cure.
• the polyorganosiloxanes of the formula (I) all have olefinic functional groups via which they can be chemically crosslinked.
• Possible chemical crosslinking reactions include the known reactions according to the prior art, in particular free-radical crosslinking, which can be initiated both using suitable radiation sources such as UV light and by unstable chemical compounds that decompose into free radicals, and addition crosslinking, for example by hydrosilylation of the olefinically unsaturated ones Group is carried out with a Si-H function in the presence of a suitable hydrosilylation catalyst.
• a sufficient amount of functional groups must be present. At least an average of 1.0 functional groups must be present per polyorganosiloxane molecule used according to the invention in order to achieve adequate curing, preferably an average of at least 1.1, in particular an average of at least 1.2, functional groups are present per polyorganosiloxane molecule according to the invention.
• the functional groups can be different, so that for example part of the functional groups is an Si—H group and another part of the functional groups is an olefinically unsaturated group which is free-radically curable or hydrosilylatable.
• Other combinations of complementary functional groups are also conceivable, where complementary means that the selected combinations of functional groups can react with one another.
• Suitable initiators to start the radical polymerization 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-di-tert-butylperoxycyclohexane, 2,2-di(tert-butylperoxy )butane, bis(4- tert -butylcyclohexan
• initiator or initiator mixture for free-radical reactions can also be used.
• the suitability of a The initiator or initiator mixture for free-radical reactions depends on its decomposition kinetics and the requirement conditions to be met. If these framework conditions are adequately observed, the person skilled in the art will be able to select a suitable initiator.
• catalysts are compounds or complexes from the group of noble metals containing platinum, ruthenium, iridium, rhodium and palladium, preferably metal catalysts from the group of platinum metals or compounds and complexes from the group of platinum metals.
• metal catalysts from the group of platinum metals or compounds and complexes from the group of platinum metals.
• 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.
• PtCl 4 H 2 PtCl 6 x6H 2 O, Na 2 PtCl 4 x4H 2 O , platinum olefin complexes, platinum alcohol complexes, platinum alcoholate complexes, platinum ether complexes, platinum aldehyde complexes, platinum ketone complexes, including reaction products from H 2 PtCl 4 x6H 2 O and cyclohexanone, Platinum-vinyl siloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane containing or not containing detectable inorganically bound halogen, bis-(gamma-picoline)platinum chloride, trimethylenedipyridineplatinum chloride, dicyclopentadieneplatinum dichloride, dimethylsulfoxyethenylplatinum( II) dichloride, cyclooctadiene platinum dichloride, norbornadiene platinum dichloride, gam
• hydrosilylation catalysts This list is only illustrative and not limiting.
• the development of hydrosilylation catalysts is a dynamic field of research that constantly produces new active species that can of course also be used here.
• the hydrosilylation catalyst is preferably a platinum compound or complex, preferably platinum chlorides and platinum complexes, in particular platinum-olefin complexes and particularly preferably platinum-divinyltetramethyldisiloxane complexes.
• the hydrosilylation catalyst is used in amounts of 2 to 250 ppm by weight, preferably in amounts of 3 to 150 ppm, in particular in amounts of 3 to 50 ppm.
• the polyorganosiloxanes of the formula (I) are bonded to a metal substrate in a third step.
• the polyorganosiloxanes of formula (I) are particularly suitable for use as binders and / or as adhesion promoters for the production of metal-clad laminates, in particular for electronic applications, in particular for metal-clad laminates and in particular for use in high-frequency applications, especially those at frequencies operate at 1 GHz and above.
• metal-clad electrical laminates such as are used to produce printed circuit boards in electronic devices, in particular for high-frequency applications.
• Said metal-clad electrical laminates can, but do not have to, contain reinforcing materials. That is, they may contain, for example, reinforcing fabrics such as woven or nonwoven fabrics, or they may be free of such. If a reinforcing material is included, it is preferably arranged in layers.
• a reinforcing layer can be made up of a large number of different fibers.
• Such reinforcing layers help control shrinkage and provide increased mechanical strength.
• the fibers forming this layer can be selected from a large number of different possibilities.
• Non-limiting examples of such fibers are glass fibers such as E-glass fibers, S-glass fibers and D-glass fibers, silica fibers, polymer fibers such as polyetherimide fibers, polysulfone fibers, polyetherketone fibers, polyester fibers, polycarbonate fibers, aromatic polyamide fibers or liquid crystalline fibers.
• the fibers can have a diameter of 10 nm to 10 ⁇ m.
• the reinforcement layer has a thickness of at most 200 ⁇ m, preferably at most 150 ⁇ m.
• a preferred application is the use of the polyorganosiloxanes of the formula (I) as a binder or co-binder 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.
• the polyorganosiloxanes of the formula (I) can be used as the sole binder. They can also be used mixed with organic monomers, oligomers and polymers. Typically used organic monomers, oligomers and polymers include polyphenylene ethers, bismaleimides, bismaleimide triazine copolymers, hydrocarbon resins, both aliphatic such as polybutadiene and aromatic such as polystyrene, and hybrid systems having both aliphatic and aromatic character such as styrene polyolefin copolymers , wherein the form of the copolymers is in principle not limited, epoxy resins, cyanate ester resins and optionally others, the selection being understood to be illustrative and not restrictive.
• 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 mixed with one another.
• the proportion of organic monomers, oligomers and polymers in the preparations containing the polyorganosiloxanes of the formula (I), if the organic components are also used, is between 10 and 90%, based on the mixture of the polyorganosiloxanes of the formula (I) and the organic monomers , oligomers and polymers 100%, preferably 20-90%, in particular 30-80%.
• Monomers, oligomers or polymers are optionally dissolved in other organic monomers with olefinically or acetylenically unsaturated groups as reactive diluents, such as styrene, alpha-methyl styrene, para-methyl styrene and vinyl styrene, chloro- and bromostyrene.
• reactive diluents such as styrene, alpha-methyl styrene, para-methyl styrene and vinyl styrene, chloro- and bromostyrene.
• typical non-reactive solvents for solving the polyorganosiloxanes of formula (I) and optionally mixtures thereof with organic monomers, oligomers and Polymers are used, such as 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, methyl propionate, ethyl propionate , Good solubility, in particular of mixtures of polyorganosiloxanes of the formula (I) with organic monomers, oligomers and polymers, being most likely achieved in aromatic solvents such as toluene, xylene, ethylbenzene and mixtures thereof.
• aromatic solvents such as
• polyorganosiloxanes of formula (I) are used in combination with an organic oligomer or polymer or mixtures thereof, it is essential that polyorganosiloxanes of formula (I) are used which are compatible with the organic components of choice and not lead to phase separations. In these cases, polyorganosiloxanes of the formula (I) which are richer in phenyl should generally be used, since phenyl groups increase compatibility with the organic components.
• polyorganosiloxanes of the formula (I) richer in aromatics are to be used, with both the bridging aromatic groups and aromatic substituents terminally bonded to silyl units contributing to the adjustment of compatibility.
• the exact amount of aromatic groups that is necessary to make the polyorganosiloxanes of the formula (I) compatible with a specific selection of organic binders must be determined as a function of the selection of organic binders.
• the compatibility of one or more polyorganosiloxanes of the formula (I) with one or more organic oligomers or polymers can be easily determined by mixing the organic binder(s) with the polyorganosiloxane(s) of the formula (I), advantageously in a solvent that dissolves and mixes all selected components, then removes the solvent by methods according to the prior art, for example by distillation or spray drying, and evaluates the residue obtained visually or with the aid of microscopic, if appropriate, electron microscopic methods.
• Compatible mixtures can be recognized by the fact that no silicone domains separate from the organic components and are recognizable as a separate phase.
• formulation components such as additives, which may also include silanes, such as antifoams and deaerators, wetting and dispersing agents, leveling agents, compatibilizers, adhesion promoters, curing initiators, catalysts, stabilizers, fillers including pigments, Dyes, inhibitors, flame retardants and crosslinking auxiliaries is in accordance with the invention and the selection of such components is not limited in principle.
• compatibility tests in terms of suitable miscibility behavior, compatibility tests with regard to reactivity may also be necessary to prevent premature gelation and to ensure that during curing a sufficiently rapid polymerization or copolymerization of all components is achieved with one another, as well as Tests for sufficient wetting and, if necessary, other properties. This must be observed and taken into account when creating the formulation.
• fillers examples include 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 also be functionally and optionally reactively equipped 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, hollow ceramic spheres, aluminum nitride, silicon carbide, beryllium oxide, magnesium oxide, magnesium hydroxide, solid glass spheres, hollow glass spheres and boron nitride.
• ceramic fillers such as silicas, for example precipitated silicas or pyrogenic silicas, which can be both hydrophil
• Core-shell particles made of various materials can be used as further fillers, such as silicone resin beads coated on the surface with silica and elastomer particles coated with polymer, it also being possible for the elastomer particles to be silicone elastomers, and one typical example for a surface coating of such an elastomer particle is a polymethyl methacrylate shell.
• the ceramic fillers preferably have particle sizes, expressed as the D 90 value, of from 0.1 ⁇ m to 10 ⁇ m. 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 or binders, reactive monomers, additives, and fillers as 100 %. This means that the amount of any non-reactive solvent used is not counted.
• thermally conductive those that are thermally conductive should be particularly emphasized. These are aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllia, zinc oxide, zirconium silicate, magnesia, silica and alumina.
• the binder preparations can contain flame-retardant additives in an amount of usually 5 to 25 percent by weight.
• flame-retardant additives in an amount of usually 5 to 25 percent by weight.
• polyorganosiloxanes of the formula (I) it is a special feature of the polyorganosiloxanes of the formula (I) that they reduce the need for flame-retardant additives, since the polyorganosiloxanes of the formula (I) themselves already show flame-retardant properties.
• Polysilsesquioxanes and siloxanes are known to exhibit flame retardant properties and it is well known in the art that they themselves are used as flame retardant additives. It is therefore a particular advantage of the present invention that it is possible here to combine the function of the binder with the function of flame retardancy.
• the amount of flame-retardant additives can therefore be reduced.
• the amount of flame retardant additives preferably only 0 to 10 percent by weight, particularly preferably 0 to 8 percent by weight, in particular 0 to 5 percent by weight, ie it is possible when using the polyorganosiloxanes of the formula (I) depending on the selection of the organopolysiloxane and the amount used to use a flame retardant avoid additives.
• 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, and they can optionally have 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.
• flame-retardant additives examples include melamine cyanurate, phosphorus-containing components such as phosphinates, diphosphinates, phosphazenes, vinylphosphazenes, phosphonates, phosphaphenantrene oxides, fine-grain melamine polyphosphates.
• bromine-containing flame-retardant additives are bispentabromophenylethane, ethylenebistetrabromophthalimide, tetradecabromodiphenoxybenzene, decabromodiphenyl oxide or brominated polysilsesquioxanes.
• Some flame retardant additives increase their effect synergistically. This is the case, for example, for the combination of halogenated flame retardant additives with antimony trioxide.
• the polyorganosiloxanes of the formula (I) are preferably crosslinked in a fourth step.
• Crosslinking auxiliaries used are, in particular, polyunsaturated, free-radically curable or hydrosilylatable monomers and oligomers, as illustrated in the following non-limiting examples. These include, for example, diolefinically unsaturated components such as 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, for example diallyl-, divinyl-, diacryloyl- or dimethacryloyl-substituted organic monomers or oligomers such as conjugated and non-conjugated dienes such as 1,9-decadiene, 1,3-butadiene.
• diolefinically unsaturated components such as symmetrically olef
• This also includes tri-olefinically unsaturated monomers or oligomers such as 1,2,4-trivinylcyclohexane, triallyl cyanurates or triallyl isocyanurates, tri(meth)acrylates such as, for example, trimethylolpropane trimethacrylate.
• monomers or oligomers such as 1,2,4-trivinylcyclohexane, triallyl cyanurates or triallyl isocyanurates, tri(meth)acrylates such as, for example, trimethylolpropane trimethacrylate.
• tetraunsaturated substituted monomers and oligomers such as 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetraphenyl-2,4,6,8-tetravinylcyclotetrasiloxane , 2,2-bis[[(2-methyl-l-oxoallyl)oxy]methyl]-1,3-propanediylbismethacrylate (pentaerythritol tetramethacrylate), tetraallyl orthosilicate, tetraallyl-cia,cis,cis,cis-1,2,3,4 -cyclopentanetetracarboxylate, tetraallylsilanes, glyoxalbis(diallylacetal).
• 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane 2,4,6,8-tetraphenyl
• components with multiple Si-H functions 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 multiple chain and/or terminal Si-H functional oligo- and polyorganosiloxanes.
• crosslinkers such as 1,1,3,3-tetramethyl-1,3-disiloxane, 2,4,6,8- Tetramethylcyclotetrasiloxane, 1,4-bis(dimethylsilyl)benzene or multiple chain and/or terminal Si-H functional oligo- and polyorganosiloxanes.
• Suitable catalysts or initiators for the free-radical curing of the binder preparations of polyorganosiloxanes of the formula (I) and organic monomers, oligomers and polymers are the same as those already mentioned above, ie in particular peroxides.
• other free-radical initiators are suitable for initiating the free-radical curing both of the polyorganosiloxanes of the formula (I) alone and of the binder preparations described, such as azo components such as ⁇ , ⁇ 'azobis(isobutyronitrile), redox initiators such as combinations of peroxides such as hydrogen peroxide and iron salts or azides such as acetyl azide.
• the polyorganosiloxanes of the formula (I) or the preparations containing them can be used either in a solvent-free form or as a solvent-containing preparation.
• they are used as a solvent-containing preparation in order to facilitate the homogeneous distribution of all the components of the formulation in one another and the wetting and impregnation of any reinforcing layer that may be used.
• a reinforcement layer is usually used. It is preferably a glass fiber fabric.
• the reinforcement layer can be saturated by impregnating application of the preparation, with various technical solutions being available for this, optionally also continuous processes, and the selection of which for producing the metal-clad laminates according to the invention is in no way restricted.
• Non-limiting examples of application techniques are dipping, if necessary webs of reinforcement material via roller systems in continuous processes, spraying, flow coating, doctor blade, etc. It is an advantage of the present invention that all available technologies can be used without restriction and modification and no special new process is required for the use of the polyorganosiloxanes of formula (I). In this respect, the present invention in the production of the metal-clad laminates is fully within the available prior art. What is new is the use of the polyorganosiloxanes of the formula (I) for the production of the relevant metal-clad laminates, which has hitherto been unknown.
• the 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 a vacuum.
• storable composite materials are obtained after this step under suitable conditions, such as cooling, which can optionally be further processed at a later point in time.
• the binder preparation is polymerized, again using methods according to the prior art. Any initiators used for the free-radical polymerization are heated above their decomposition temperature, so that they decompose to form free radicals and initiate the free-radical polymerization of the binder preparation. In principle, methods of radiation curing can also be used.
• hydrosilylation curing is used instead of free-radical polymerization
• a temperature suitable for the inhibitor used for the hydrosilylation catalyst used should be used in this step deactivate and release the catalytic activity of the hydrosilylation catalyst.
• This step is usually carried out at an elevated temperature of preferably 100 to 390° C., particularly preferably 100 to 250° C., in particular 130 to 200° C., the temperature being effective for a time of preferably 5 to 180 min, particularly preferably 5 to 150 minutes, in particular 10 to 120 minutes.
• elevated pressure is common to use in this step.
• Customary pressures are in the range from 1 to 10 MPa, particularly preferably from 1 to 5 MPa, in particular from 1 to 3 MPa.
• the lamination of the composite material with a conductive metal layer is carried out in this second step by applying a layer of at least one selected metal on one or both sides of the composite material made of reinforcement layer and binder composition before curing takes place.
• 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 particularly limited.
• the conductive metal layer preferably has a thickness of 3 to 300 ⁇ m, particularly preferably 3 to 250 ⁇ m, in particular 3 to 200 ⁇ m.
• 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 that in the case of two conductive ones Layers of conductive metal are used, both layers are copper.
• the conductive metal is preferably used in the form of a foil of the metal in question.
• the mean roughness value Ra of the metal foil used is preferably at most 2 ⁇ m, particularly preferably at most 1 ⁇ m, in particular at most 0.7 ⁇ m.
• various methods according to the prior art can be used, such as the use of an adhesion-promoting layer, electroplating deposition 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 connected to it by an adhesion-promoting layer.
• a layer of the binder preparation containing the polyorganosiloxanes of the formula (I) is produced by depositing a layer of binder preparation on a carrier, such as a separating film or separating plate, with any material being suitable for the carrier in principle which the dried or cured binder preparation can later be removed again, such as polytetrafluoroethylene, polyester and the like.
• a carrier such as a separating film or separating plate
• any material being suitable for the carrier in principle which the dried or cured binder preparation can later be removed again such as polytetrafluoroethylene, polyester and the like.
• the detachability and the film-forming properties on the respective carrier material must be determined individually depending on the composition of the binder. The statements made about Procedures remain valid for this amplification-free variant in the same way.
• Multi-layer structures can be created from the reinforced or non-reinforced composite materials from the first step and the laminated composite materials from the second step by stacking several layers of the composite materials from the first step alternately with the laminates from the second step and not yet hardened composite materials from the first step are then hardened in a process that essentially corresponds to the procedure for producing the metal-clad laminates.
• several layers of the reinforced or unreinforced composites from the first step can also be stacked one on top of the other in direct succession.
• the polyorganosiloxanes of the formula (I) can also be used in anti-corrosion preparations, in particular for use for the purpose of anti-corrosion at high temperature.
• the polyorganosiloxanes of the formula (I) and preparations containing them can also be used to protect reinforcing steel in reinforced concrete against corrosion. Corrosion-inhibiting effects in reinforced concrete are achieved both when the polyorganosiloxanes of the formula (I) and preparations containing them are introduced into the concrete mixture before they are shaped and cured, and when the polyorganosiloxanes of the formula (I) or preparations containing them, to the surface of the concrete after the concrete has hardened.
• the polyorganosiloxanes of the formula (I) can also be used to manipulate other properties of preparations which contain the organopolysiloxanes according to the invention or of solid bodies or films which are obtained from preparations which contain the polyorganosiloxanes of the formula (I).
• a preparation serve as, for example: - control of electrical conductivity and electrical resistance - control of the leveling properties of a preparation - control of the gloss of a moist or hardened film or an object - increase in weather resistance - increase in chemical resistance - increase in color stability - reduction in chalking tendency - reduction or increase in static and sliding friction on solid bodies or films obtained from preparations containing the polyorganosiloxanes of the formula (I) - stabilization or destabilization of foam in the preparation that contains the preparation - improvement in the adhesion of the preparation that contains the polyorganosiloxanes of the formula (I ) contains to substrates - control of the filler and pigment wetting and - dispersing behavior, - control of the rheological properties of the preparation containing the organopolysiloxanes according to the invention, - control of the mechanical properties, such as flexibility, scratch resistance, elasticity, extensibility, bendability, tear behavior, Rebound behavior, hardness, density, tear resistance, compression set, behavior at
• Examples of applications in which the polyorganosiloxanes of the formula (I) can be used to manipulate the properties described above are the production of coating materials and impregnations and coatings and coatings to be obtained therefrom on substrates such as metal, glass, wood, mineral Substrate, synthetic and natural fibers for the production of textiles, carpets, floor coverings or other goods that can be made from fibers, leather, plastics such as foils and molded parts.
• substrates such as metal, glass, wood, mineral Substrate, synthetic and natural fibers for the production of textiles, carpets, floor coverings or other goods that can be made from fibers, leather, plastics such as foils and molded parts.
• the polyorganosiloxanes of the formula (I) can also be used in preparations, with appropriate selection of the preparation components, as an additive for the purpose of defoaming, flow promotion, hydrophobicization, hydrophilicization, filler and pigment dispersion, filler and pigment wetting, substrate wetting, promotion of surface smoothness, reduction of adhesion and slip resistance on the surface of the cured mass obtainable from the additive preparation.
• the Polyorganosiloxanes of the formula (I) can be incorporated into elastomer compositions in liquid form or in hardened solid form. They can be used here for the purpose of reinforcing or improving other performance properties, such as controlling transparency, heat resistance, yellowing tendency, or weathering resistance.
• the apparatuses are commercially available laboratory devices such as are commercially available from numerous device manufacturers.
• Me 2 means two methyl radicals.
• PPE means polyphenylene ether
• HCl means hydrogen chloride
• 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 normal pressure of 1013 mbar.
• the refractive indices are determined in the wavelength range of visible light at 589 nm at 25°C and normal pressure of 1013 mbar in accordance with standard DIN 51423.
• the transmission is determined by UV VIS spectroscopy.
• a suitable device is, for example, the Analytik Jena Specord 200.
• the measurement parameters used are: Range: 190 - 1100 nm Step size: 0.2 nm Integration time: 0.04 s Measurement mode: step mode.
• the first step is the reference measurement (background).
• a quartz plate attached to a sample holder (dimensions of the quartz plates: HxW approx. 6 x 7 cm, thickness approx. 2.3 mm) is placed in the sample beam path and measured against air.
• a quartz plate attached to the sample holder with a sample applied - layer thickness applied sample approx. 1 mm - is placed in the sample beam path and measured against air.
• the internal settlement against the background spectrum provides the transmission spectrum of the sample.
• the molecular compositions are determined by means of nuclear magnetic resonance spectroscopy (for terminology, see ASTM E 386: High-resolution nuclear magnetic resonance spectroscopy (NMR): terms and symbols), the 1 H nucleus and the 29 Si nucleus being measured.
• Spectrometer Bruker Avance I 500 or Bruker Avance HD 500
• Probe head 5 mm BBO probe head or SMART probe head (from
• Pulprog zg30
• NS 64 or 128 (depending on probe sensitivity)
• Probehead 10mm 1H/13C/15N/29Si glass-free QNP probehead
• Pulprog zgig60
• Molecular weight distributions are determined as weight average Mw and as number average Mn using the gel permeation chromatography method (GPC or size exclusion chromatography (SEC)) with a polystyrene standard and refractive index detector (RI detector). Unless stated otherwise, THF is used as eluent and DIN 55672-1 is applied. The polydispersity is the quotient Mw/Mn.
• the glass transition temperature is determined by dynamic differential calorimetry (Differential Scanning Calorimetry, DSC) to DIN 53765, perforated crucible, heating rate 10 K/min.
• the particle sizes were measured using the Dynamic Light Scattering (DLS) method, determining the zeta potential.
• DLS Dynamic Light Scattering
• the following tools and reagents were used for the determination: polystyrene cuvettes 10 x 10 x 45 mm, single-use Pasteur pipettes, ultrapure water.
• the sample to be measured is homogenized and filled into the measuring cell without bubbles.
• the measurement takes place at 25°C after an equilibration time of 300s with high resolution and automatic measurement time setting.
• D(50) is to be understood as the volume-average particle diameter at which 50% of all measured particles have a have a volume average diameter smaller than the declared value D(50).
• the dielectric properties are determined according to
• micro/nanostructure was characterized by light microscopy or by means of transmission electron microscopy.
• Sample preparation 1 drop of sample (undiluted) on slide; covered with coverslip
• LEICA DMRXA2 with CCD camera LEICA DFC420 (2592x1944 pixels)
• 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 RT
• Reinforcement material was laminated metal layers determined according to the method IPC-TM 6502.4.8 "Peel Strength of Metalle Clad Laminates" in the version "as received", ie without thermal stress or exposure.
• Synthesis Example 1 Preparation of an organopolysiloxane by the process according to the invention:
• a mixture of 1267.8 g (6 mol) of phenyltrichlorosilane, 372.6 g (1.5 mol) of 3-(trimethoxysilyl)propyl methacrylate and 780 g of xylene is metered into a template of 3600 g of water over the course of 4 hours.
• the reaction of the chlorosilane in water is exothermic and produces hydrochloric acid, which dissolves in the water provided. Care is taken to ensure that the temperature does not exceed 50°C due to the exothermic temperature increase, and the dosing speed is reduced if necessary in order not to exceed this temperature limit.
• reaction mixture separates into a hydrochloric acidic aqueous phase, which sits at the bottom of the reaction vessel, and an organic silicone phase, which sits at the top.
• the aqueous phase is drained.
• the organic phase is then distilled from the water separator at ambient pressure until no more water separates out, i.e. the organic phase is technically anhydrous.
• the residual water content of the organic preparation is determined by Karl Fischer titration and is 856 ppm.
• the reaction mixture is allowed to cool to 40° C. and first 318 g (3.2 mol) of dimethyldichlorosilane and then 261 g (3.3 mol) of pyridine are metered in.
• the first dose lasts 30 minutes, the second 45 minutes.
• An exothermic rise in temperature is observed.
• the temperature is limited to 50°C by adjusting the dosing speed.
• stirring is continued for 60 minutes in order to complete the reaction.
• reaction After the reaction has ended, it is washed three times with one liter of deionized water each time and the aqueous phase is separated off in each case as described above.
• the residual HCl content in the organic phase is ⁇ 20 ppm.
• the solvent content is reduced by distillation, using a Solid content of 80% resin, ie the final resin solution consists of 20% xylene and 80% polyorganosiloxane.
• Methoxy groups cannot be detected in NMR.
• the residual silanol content is 0.05 percent by weight determined by 1 H-NMR spectroscopy.
• the molar composition of the silicon-containing portion of the preparation is:
• This product is hereinafter referred to as 1.1.
• Synthesis Example 2 Preparation of a silphenylene-bridged organopolysiloxane by the process according to the invention and comparison with a procedure which is hydrolytic in both steps and not according to the invention.
• 1,4-Bis(dimethoxyphenylsilyl)benzene is obtained by, according to the specified literature procedure according to “2.2. Synthesis of the 1,4-Bis(Dimethoxyphenylsilyl)Benzene (BDMPD)"
• 1,4-dibromobenzene is reacted.
• the structure was confirmed by 1 H-NMR spectroscopy and comparison with the cited literature.
• the dosing time is 4 hours.
• the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1/2 : 26.54%
• This product is hereinafter referred to as 2.1.
• Dosing speed adjusts so that the reaction temperature (internal temperature in the reaction vessel) remains limited to below 50°C.
• the mixture is stirred for a further 60 minutes, with neither heating nor cooling, in order to completely complete the reaction of the silanol groups with the vinyldimethylchlorosilane or the tetramethyldivinyldisiloxane that has formed therefrom.
• the water phase is separated off as described above and then washed three times with one liter of water as already described above. If necessary, the phase separation can be improved by heating to a heating jacket temperature of 60° C. with the stirrer switched off. After the washes, the HCl content in the xylene solution is less than 20 ppm.
• the amount of toluene is reduced by distillation in vacuo (20 mbar) at 110° C. to such an extent that a solution of 80% resin in 20% xylene is obtained.
• Methoxy groups can no longer be detected in the product obtained by 1 H-NMR. This means that the methacrylate-functional trimethoxysilane is also completely condensed in here, and the resulting methanol was removed during work-up. However, the proportion of silanol groups could only be reduced to 0.9 percent by weight (determined by 1 H-NMR) as a result of the post-treatment.
• the vinyldimethylsilane used to reduce the silanol groups partially forms the symmetrical disiloxane, which is removed by distillation during work-up and by the reaction of the chlorosilane with water
• the HCl formed catalyzes the reaction of the silanol groups, which leads to a reduction in the same, but through condensation to a significantly higher molecular weight and thus a significant increase in the risk that the polyorganosiloxane obtained from the first step will polymerize to an insoluble product and thus become unusable. This effect is efficiently avoided by the procedure according to the invention.
• the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1/2 : 11.54%
• the silanol groups are found attached to the PhSiO 3/2 units.
• This product is hereinafter referred to as 2.2.
• Synthesis Example 3 Preparation of an organopolysiloxane with an alkylene bridge by the process according to the invention and comparison to an aqueous procedure not according to the invention.
• the synthesis according to synthesis example 1 is repeated, in contrast to synthesis example 1 the following amounts are used:
• the dosing time is 4 hours.
• Methoxy groups cannot be detected in NMR.
• the proportion of silanol groups could be reduced to approx. 0.05 percent by weight (determined by 1 H-NMR) as a result of the post-treatment.
• the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1/2 : 44.29%
• This product is hereinafter referred to as 3.1.
• Methoxy groups can no longer be detected in the product obtained by 1 H-NMR. However, the proportion of silanol groups could only be reduced to 1.0 percent by weight (determined by 1 H-NMR) as a result of the post-treatment.
• the molar composition of the silicon-containing portion of the preparation is:
• the silanol groups are found attached to the PhSiO 3/2 units.
• This product is hereinafter referred to as 3.2.
• Synthesis Example 4 Preparation of an organopolysiloxane with a Si-Si bond by the process according to the invention compared to an aqueous procedure not according to the invention.
• Methoxy groups cannot be detected in NMR.
• the proportion of silanol groups could be reduced to approx. 0.05 percent by weight (determined by 1 H-NMR) as a result of the post-treatment.
• the molar composition of the silicon-containing portion of the preparation is: Me 2 Si(Vi)O 1/2 : 40.34%
• This product is hereinafter referred to as 4.1.
• the following hydrolytic procedure for reducing the silanol groups is carried out, which is not mentioned in US 2018022053, but could in principle fall within the scope of the invention since the number of stages of the hydrolytic process is not restricted there.
• Methoxy groups can no longer be detected in the product obtained by 1 H-NMR. However, the proportion of silanol groups could only be reduced to 1.1 percent by weight (determined by 1 H-NMR) as a result of the post-treatment.
• the molar composition of the silicon-containing portion of the preparation is:
• the silanol groups are found attached to the PhSiO 3/2 units. This product is hereinafter referred to as 4.2.
• organopolysiloxanes prepared according to synthesis examples 1 to 4 and according to the comparative examples contained therein were used as binders in order to produce copper-clad laminates with a glass fiber-reinforced composite layer.
• the following ingredients were used:
• Copper foil 35 ⁇ m thick copper foil (285 ⁇ 10 g/m 2 ) from Jiangtong-yates Copper Foil Co Ltd, with a peak-to-valley height of Rz
• 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 .
• organopolysiloxanes were used as a solution in xylene.
• the solutions each contained 80% organopolysiloxane and 20% xylene.
• the organopolysiloxanes were each treated with 1 weight percent dicumyl peroxide based on the amount added polyorganosiloxane used, which was evenly distributed in the resin matrix by stirring.
• Laminates were produced by impregnating glass fiber layers measuring 30 ⁇ 30 cm in layers with the respective organopolysiloxane, optionally as a xylene solution, using a deaerating roller, without bubbles.
• the glass fiber layers were placed on a dimensionally stable, flat base made of stainless steel, to which a layer of copper foil was applied before the first layer of glass fiber was laid.
• a total of 3 layers of glass fiber fabric were impregnated one after the other.
• the impregnated fabrics were dried at 60° C. in a vacuum drying cabinet at 10 mbar to constant weight.
• a second layer of copper foil was applied to the impregnated glass fiber layer on top and another dimensionally stable stainless steel plate was placed.
• the laminate was heated in a heatable press at a pressure of 2 MPa, 120 min at 200° C. and a vacuum of 30 mbar. Copper-clad laminates with a total thickness of 260 ⁇ 20 ⁇ m are obtained.
• the dielectric properties were determined in accordance with 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:
• the Df and Dk values of the copper-clad laminates made from the organopolysiloxanes according to the invention are significantly lower than the Df and Dk values which are achieved with the organopolysiloxanes from the prior art procedure. Since the aim is for the lowest possible dielectric loss factors and dielectric constants for high-frequency applications, the effect according to the invention can be clearly seen.
• Use Example 2 Use of the organopolysiloxanes produced according to the invention and those not produced according to the invention according to synthesis examples 1-4 for the production of metal-clad laminates over prepregs.
• the organopolysiloxanes from Synthesis Examples 1-4 were used in both the inventive and noninventive procedures as a solution in xylene, preparations of 20% xylene and 80% polyorganosiloxane being used in each case.
• this time prepregs were produced by impregnating the glass fiber layers as individual layers on a polytetrafluoroethylene film with the resin preparation and then drying them to constant weight in a vacuum drying cabinet.
• three layers of impregnated glass fiber fabric produced in this way were then placed one on top of the other on a copper foil and the stack was closed off with a layer of copper foil.
• this multi-layer structure was pressed between two dimensionally stable stainless steel plates in a vacuum press under the conditions specified in example 1 and cured.
• the laminates obtained had thicknesses of 290 ⁇ 20 ⁇ m.
• the D k and D f values achieved for the copper-clad laminates from the organopolysiloxanes produced according to the invention are significantly lower than the D f and D k values achieved with the organopolysiloxanes from the comparative examples. Since the aim is for the lowest possible dielectric loss factors and dielectric constants for high-frequency applications, the effect according to the invention can be clearly seen.
• Use Example 3 Use of the organopolysiloxanes produced according to the invention and those not produced according to the invention according to synthesis examples 1-4 for the production of metal-clad laminates in a mixture with organic polymers for the production of metal-clad laminates.
• the procedure essentially corresponds to that described in application example 2, except that this time organic polymers were mixed with the organopolysiloxanes.
• the final solvent-free mixtures always contained 30 percent by weight organopolysiloxane and 70 percent by weight organic polymers.
• the polymers were always used in the same proportions. They were dissolved or dispersed in xylene, with 30 parts by weight of SA 9000, 25 parts by weight of B 3000 and 15 parts by weight of triallyl isocyanurate being dispersed with 100 parts by weight of xylene.
• the preparation obtained in this way was mixed with the xylene solutions of the organopolysiloxanes according to application example 2 in such a way that the specified mixing ratio in each case 30% organopolysiloxane and 70% organic components were present in the solution obtained. These solutions were then used to prepare copper clad laminates over prepregs as described in Application Example 2.
• the laminates obtained had thicknesses of 290 ⁇ 20 ⁇ m.
• the Dk and Df values achieved for the copper-clad laminates using the organopolysiloxanes produced according to the invention are significantly lower than the Df and Dk values which were achieved with the organopolysiloxanes from the comparative examples. Since the aim is for the lowest possible dielectric loss factors and dielectric constants for high-frequency applications, the effect according to the invention can be clearly seen.

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• 2021
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