DE102007013608A1 - Si-substituted quinones as co-catalysts in transition-metal-catalyzed hydrosilylation - Google Patents

Abstract

The invention relates to catalyst systems, te quinone compound as a co-catalyst, their preparation and their use in processes for the addition of silanes or siloxanes having SiH groups, to compounds having olefinic double bonds.

Description

The The invention relates to catalyst systems containing a transition metal and an Si-substituted quinone compound as a co-catalyst, their preparation and their use in addition processes of silanes or siloxanes having SiH groups on compounds with olefinic double bonds.

The Addition of Si-H-functional compounds to compounds with aliphatic unsaturated bonds, in particular C = C double bonds (Hydrosilylation) has been known for a long time.

about the hydrosilylation can be Si-containing organic compounds, Organosilanes and organopolysiloxanes are produced. she will especially in the addition-curing curing of Organopolysiloxanes used in the silicone industry, for example for the production of elastomers, impression compounds in the dental industry or of anti-adhesive coatings in paper and paper Film industry.

Suitable catalysts for the hydrosilylation reaction are particularly late transition metals and corresponding compounds, in particular platinum and its compounds, for example in the form of US 3,715,334 and US 3,775,452 known so-called Karstedt catalyst, a dimeric platinum-tetramethyl-divinyl-siloxane complex (divinyltetramethyl-disiloxane = DVTMS), describable by the formula [Pt ₂ (DVTMS) ₃ ]. The Karstedt catalyst is prepared from hexachloroplatinic acid H ₂ PtCl ₆ , which is also frequently used as an alcoholic solution as hydrosilylation catalyst.

at Many applications of the hydrosilylation reaction is one high reactivity of the catalyst systems used necessary, to achieve quantitative sales in this way. One The main problem is therefore the deactivation of the hydrosilylation catalyst during the hydrosilylation reaction, resulting in incomplete implementations. Such deactivation phenomena Although often by Katalysatornachdosierungen be remedied, however, lead specifically in siloxane chemistry to the fact that higher metal concentrations are present in the product and this in addition to toxicological concerns about increased color intensities leads. Also in the production of crosslinked silicone polymers sometimes very high throughput rates have to be achieved, for example in the production of anti-adhesive coatings in the paper and film industry. In this case, as a rule used Karstedt catalyst are therefore usually relatively high Pt concentrations of 100-200 ppm, based on the total mass, used to achieve sufficiently fast cure times, which represents a significant cost factor as the catalyst can not be recovered. Another disadvantage of this catalyst system is that after some time in the reaction medium metallic Pt colloids are formed, which are insoluble in the reaction medium and are almost inactive and discoloration of the crosslinked Lead polymer.

An improvement in the transition metal-catalyzed hydrosilylation could be achieved in many cases by the addition of promoters. Such promoters are already widely described for the Pt-catalyzed hydrosilylation reaction. Thus, for example, the compounds or compound groups listed below were used. Molecular oxygen in US 5,359,111 described, aldehydes in US 5,616,763 described, unsaturated ketones in US 5,424,470 described heterocycles such as lactones in WO 2003/037961 A2 described, carboxylic acids in US 6,166,238 or amines in WO 2003/044028 A1 described. However, these promoters are usually very substrate- or catalyst-specific or incompatible with silicone polymers and thus not applicable, for example, in the addition-curing of organopolysiloxanes.

Defined Pt complexes whose activity exceeds those of the Karstedt catalyst have also been described. The patent WO 1998/00463 discloses the synthesis of Pt (0) complexes obtainable, for example, by reacting the Karstedt catalyst with electron-deficient olefins or quinones as ligands. In the WO 1995/025734 Pt (0) -quinone complexes are described as photoactivatable hydrosilylation catalysts. A disadvantage of these systems is the sometimes expensive preparation of the Pt catalysts by the modification of the Karstedt catalyst, as well as the limited solubility of some representatives in the silicones to be crosslinked.

It thus set itself the task of providing a catalyst system, whose activity exceeds that of the common Pt catalyst systems and in the desired systems a good solubility having.

• (C) mindestens einen Metallkatalysator der 8. Nebengruppe, und
• (D) mindestens einer Si-substituierten Chinon-Verbindung der allgemeinen Formel (1) oder (2), oder ihren Mischungen, als Co-Katalysator
  
  wobei R ein- oder mehrwertige, substituierte oder nicht-substituierte Kohlenwasserstoffreste, Siloxyreste der allgemeinen Formel OSiR'₃, R' ein- oder mehrwertige, substituierte oder nicht-substituierte Kohlenwasserstoffreste, x 0–200, Y Sauerstoff, oder ein einwertiger C1-C20 Kohlenwasserstoffrest, Z¹, Z² unabhängig von einander Wasserstoff-, Halogen-, Hydroxy-, Alkyl-, Aryl, Alkoxy-, Aryloxy-, Siloxyrest, oder einen substituierten oder nicht substituierten aromatischen oder nicht aromatischen Ring bilden, Z³ unabhängig von einander Wasserstoff-, Halogen-, Hydroxy-, Alkyl-, Aryl, Alkoxy-, Aryloxy-, Siloxyrest

bedeuten.This object has been achieved by the catalyst system according to the invention containing

• (C) at least one metal catalyst of the 8th subgroup, and
• (D) at least one Si-substituted quinone compound of the general formula (1) or (2), or theirs Mixtures, as co-catalyst
  
  wherein R is mono- or polyhydric, substituted or unsubstituted hydrocarbon radicals, siloxy of the general formula OSiR ' ₃ , R' mono- or polyhydric, substituted or unsubstituted hydrocarbon radicals, x 0-200, Y oxygen, or a monovalent C1-C20 Hydrocarbon radical, Z ¹ , Z ² independently of one another hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy, aryloxy, siloxy, or form a substituted or unsubstituted aromatic or non-aromatic ring, Z ³ independently Hydrogen, halogen, hydroxy, alkyl, aryl, alkoxy, aryloxy, siloxy

mean.

Prefers x is 0-50. Y is preferably a C 1 -C 3 hydrocarbon radical.

For the catalyst (C), platinum or its compounds are preferably used. Particularly preferably in the form of H ₂ PtCl ₆ , preferably dissolved in an alcohol, for example isopropanol, or the Karstedt catalyst of the formula [Pt ₂ (DVTMS) ₃ ].

The Preparation of the Si-substituted quinones (D) takes place via the known from the prior art method of organic or silicon organic chemistry.

So For example, 2,5-bis (siloxy) -substituted 1,4-benzoquinones may be over an optionally base-assisted reaction of 2,5-dihydroxybenzoquinone with triorganochlorosilanes or hexaalkyldisilazane.

Examples for particularly preferred co-catalysts (D) are compounds of the formulas (3), (4) and (5).

• 1) Pt-katalysierte Hydrosilylierung mit SiH-funktioneller Verbindung
• 2) säureinduziertes Entschützen der OH-Funktion
• 3) Oxidation des Hydrochinons zum Si-substituierten Chinon (D).

The synthesis of co-catalysts (D), with Y = monovalent C ₁ -C ₂₀ hydrocarbons, can be carried out, for example, starting from the known compound 2-allyl-bis-1,4-trimethylsiloxy-benzene and in a reaction sequence from

• 1) Pt-catalyzed hydrosilylation with SiH-functional compound
• 2) acid-induced deprotection of the OH function
• 3) Oxidation of the hydroquinone to the Si-substituted quinone (D).

• (A) Verbindungen, die aliphatische Kohlenstoff-Kohlenstoff-Mehrfachbindungen aufweisen, mit
• (B) Organosiliciumverbindungen mit Si-gebundenen Wasserstoffatomen, in Anwesenheit von
• (C) mindestens einem Metallkatalysator der 8. Nebengruppe,

dadurch gekennzeichnet, dass von Beginn an oder während der Reaktion

• (D) mindestens eine Si-substituierte Chinon-Verbindung der allgemeinen Formel (1) oder (2), oder ihren Mischungen, als Co-Katalysator zugesetzt wird,
  
  
  wobei R ein- oder mehrwertige, substituierte oder nicht-substituierte Kohlenwasserstoffreste, Siloxyreste der allgemeinen Formel OSiR'₃, R' ein- oder mehrwertige, substituierte oder nicht-substituierte Kohlenwasserstoffreste, x 0–200, Y Sauerstoff, oder ein einwertiger C1-C20 Kohlenwasserstoffrest, Z¹, Z² unabhängig von einander Wasserstoff-, Halogen-, Hydroxy-, Alkyl-, Aryl, Alkoxy-, Aryloxy-, Siloxyrest, oder Z¹ und Z² bilden einen substituierten oder nicht substituierten, aromatischen oder nicht aromatischen Ring, Z³ unabhängig von einander Wasserstoff-, Halogen-, Hydroxy-, Alkyl-, Aryl, Alkoxy-, Aryloxy-, Siloxyrest bedeuten.

Another object of the invention is the use of the catalyst system of the invention in a process for the addition of Si-bonded hydrogen to aliphatic carbon-carbon multiple bond by reacting

• (A) Compounds having aliphatic carbon-carbon multiple bonds, with
• (B) organosilicon compounds having Si-bonded hydrogen atoms, in the presence of
• (C) at least one metal catalyst of the 8th subgroup,

characterized in that from the beginning or during the reaction

• (D) at least one Si-substituted quinone compound of the general formula (1) or (2), or mixtures thereof, is added as co-catalyst,
  
  
  wherein R is mono- or polyhydric, substituted or unsubstituted hydrocarbon radicals, siloxy of the general formula OSiR ' ₃ , R' mono- or polyhydric, substituted or unsubstituted hydrocarbon radicals, x 0-200, Y oxygen, or a monovalent C1-C20 Hydrocarbon radical, Z ¹ , Z ² independently of one another represent hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy, aryloxy, siloxy radical, or Z ¹ and Z ² form a substituted or unsubstituted, aromatic or nonaromatic ring , Z ³ independently of one another represent hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy, aryloxy, siloxy.

Prefers x is 0-50. Y is preferably a C 1 -C 3 hydrocarbon radical.

The Method is for both the synthesis of low molecular weight Compounds as well as for curing higher molecular weight Compounds applicable, in particular of polymers with unsaturated Groups, in particular with carbon-carbon double bonds.

at the compound (A) used according to the invention This may be silicon-free organic compounds with aliphatic unsaturated groups as well as organosilicon compounds to act with aliphatically unsaturated groups.

Examples of organic compounds which can be used as component (A) in the process according to the invention are all types of olefins, such as 1-alkenes, vinylcyclohexane, 2,3-dimethyl-1,3-butadiene, 7-methyl-3-methylene -1,6-octadiene, 2-methyl-1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, 4,7-methyl len-4,7,8,9-tetrahydroindene, methylcyclopentadiene, 5-vinyl-2-norbornene, bicyclo [2.2.1] hepta-2,5-diene, 1,3-diisopropenylbenzene, vinyl-containing polybutadiene, 1,4 Divinylcyclohexane, 1,3,5-triallylbenzene, 1,3,5-trivinylbenzene, 1,2,4-trivinylcyclohexane, 1,3,5-triisopropenylbenzene, 1,4-divinylbenzene, 3-methylheptadiene (1, 5), 3-phenyl-hexadiene (1,5), 3-vinyl-hexadiene (1,5) and 4,5-dimethyl-4,5-diethyl-octadiene (1,7), N, N -Methylene bis (acrylic acid amide), 1,1,1-tris (hydroxymethyl) propane triacrylate, 1,1,1-tris (hydroxymethyl) -propane trimethacrylate, tripropylene glycol diacrylate, diallyl ether, diallylamine, diallyl carbonate, N, N ' Diallyl urea, triallylamine, tris (2-methylallyl) amine, 2,4,6-triallyloxy-1,3,5-triazine, triallyl-s-triazine-2,4,6 (1H, 3H, 5H) -trione, Diallylmalonsäureester, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, poly (propylene glycol) methacrylate, allyl glycols, allyl glycidyl ether and Allylbernsteinsäureanhydrid.

In In a preferred embodiment, (A) is allyl glycidyl ether or allyl succinic anhydride used.

Of Further can in the inventive Process as component (A) aliphatically unsaturated Organosilicon compounds are used.

If component (A) organosilicon compounds are used which have SiC-bonded radicals having aliphatic carbon-carbon multiple bonds, these are preferably those of units of the formula (6) R ² _a R ¹ _b SiO _{(4-ab) / 2} (6) in which
R ^{2 may be the} same or different and represents a substituted or unsubstituted organic radical free of aliphatic carbon-carbon multiple bonds,
R ^{1 may be the} same or different and represents a monovalent, optionally substituted, SiC-bonded hydrocarbon radical having an aliphatic carbon-carbon multiple bond,
a is 0, 1, 2 or 3 and
b is 0, 1, 2 or 3
with the proviso that the sum is a + b ≤ 4.

The organosilicon compounds (A) used according to the invention may be both silanes, ie compounds of the formula (6) with a + b = 4, as well as siloxanes, ie compounds containing units of the formula (6) with a + b ≦ 3 On average (A) contains at least 2 radicals R ¹ per molecule.

R ² comprises the monovalent radicals -F, -Cl, -Br, -OR ⁶ , -CN, -SCN, -NCO and SiC-bonded, optionally substituted hydrocarbon radicals which are interrupted by oxygen atoms or the group -C (O) - can, as well as divalent, on both sides according to formula (6) Si-bonded radicals. R ⁶ is generally hydrogen or a monovalent, optionally substituted hydrocarbon radical having 1 to 20 carbon atoms, preferably hydrogen, alkyl radicals and aryl radicals, hydrogen, the methyl and the ethyl radical being particularly preferred.

Examples of radicals R ² are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl -, neo-pentyl, tert-pentyl, hexyl, such as the n-hexyl, heptyl, such as the n-heptyl, octyl, n-octyl again, and iso-octyl, such as the 2,2,4-trimethylpentyl, nonyl 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, cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, aryl radicals such as Phenyl, naphthyl, anthryl and phenanthryl radical, alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals, such as the benzyl radical, the .alpha.- and .beta.-phenylethyl radical and radicals of the formula --C ( R ¹ ) = CR ¹ ₂ , where R ^{1 has} the abovementioned meaning.

Examples of substituted radicals R ² are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, as well as haloaryl radicals, such as the o -, m- and p-chlorophenyl. Radical R ² is preferably a monovalent, aliphatic carbon-carbon multiple bond-free, SiC-bonded, optionally substituted hydrocarbon radical having 1 to 18 carbon atoms, more preferably a monovalent, free of aliphatic carbon-carbon multiple bonds, SiC -bonded hydrocarbon radical having 1 to 6 carbon atoms, in particular the methyl or phenyl radical.

If radical R ² is SiC-bonded, substituted hydrocarbon radicals, are as Substituents halogen atoms, phosphorus-containing radicals, cyano radicals, -OR ⁶ , -NR ⁶ -, -NR ⁶ ₂ , -NR ⁶ -C (O) -NR ⁶ ₂ , -C (O) -NR ⁶ ₂ , -C (O) R ⁶ , -C (O) OR ⁶ , -SO ₂ -Ph and -C ₆ F ₅ with R ^{6 is} as defined above and Ph is equal to phenyl radical.

The radical R ¹ can be any groups which are accessible to an addition reaction (hydrosilylation) with an SiH-functional compound.

If radical R ¹ is SiC-bonded, substituted hydrocarbon radicals, halogen atoms, cyano radicals, alkoxy groups and siloxy groups are preferred as substituents.

R ¹ is preferably alkenyl and alkynyl groups having 2 to 16 carbon atoms, such as vinyl, allyl, methallyl, 1-propenyl, 5-hexenyl, ethynyl, butadienyl, hexadienyl, cyclopentenyl Cyclopentadienyl, cyclohexenyl, vinylcyclohexylethyl, divinylcyclohexylethyl, norbornenyl, vinylphenyl and styryl radicals, vinyl, allyl and hexenyl radicals being particularly preferably used.

The molecular weight of the component (A) can vary within wide limits, preferably between 10 ² and 10 ⁶ g / mol. The component (A) may be, for example, a relatively low molecular weight alkenyl-functional silane or oligosiloxane, such as vinyltrimethylsilane or 1,3-divinyl-tetra methyldisiloxane, but also a high polymer polydimethylsiloxane having chain or terminal Si-bonded vinyl groups, for example having a molecular weight of 10 ⁵ g / mol (number average determined by NMR).

Also, the structure of the component (A) -forming molecules is not limited. It may be, for example, the structure of a high molecular weight, ie oligomeric or polymeric siloxane linear, cyclic, branched or resinous, network-like. Linear and cyclic polysiloxanes are preferably composed of units of the formula R ² ₃ SiO _1/2 , R ¹ R ² ₂ SiO _1/2 , R ¹ R ² SiO _2/2 and R ² ₂ SiO _2/2 , wherein R ² and R ^{1 have} the meaning given above. Branched and network-like polysiloxanes additionally contain trifunctional and / or tetrafunctional units, preference being given to those of the formulas R ² SiO _3/2 , R ¹ SiO _3/2 and SiO _4/2 . Of course, mixtures of different, the criteria of the component (A) sufficient siloxanes can be used.

Prefers as component (A) are all terminal olefins and all allyl-containing, vinyl-containing and alkyne-containing systems, allyl-containing Systems are particularly preferred.

When Organosilicon compound (B) can all be hydrogen functional Organosilicon compounds are used, which also so far at Hydrosilylation reactions have been used.

As organosilicon compounds (B) having Si-bonded hydrogen atoms, those containing units of the formula (7) are preferably used. R ² _c H _d SiO _{(4-cd) / 2} (7) in which
R ^{2 may be the} same or different and has the meaning given above, wherein
c is 0, 1, 2, or 3 and
d is 0, 1, 2 or 3,
with the proviso that the sum of c + d ≤ 4 and preferably at least two Si-bonded hydrogen atoms per molecule.

The organosilicon compounds (B) used in accordance with the invention may be both silanes, ie compounds of the formula (7) where c + d = 4,
as well as siloxanes, ie compounds containing units of formula (7) with c + d ≤ 3.

HSi be mentioned as concrete examples of SiH-functional organosilanes called (OR _'3) wherein R''is an alkyl radical, HSi (Me) _3-p Cl _p, where p is a number from 1 to 3 and HSiR ''' ₃ , wherein R''' is an alkyl or aryl radical.

Preferably these are the ones used according to the invention Organosilicon compounds to organopolysiloxanes, in particular to those which consist of units of the formula (7).

Preferably contains the inventively used Organosilicon compound (B) Si-bonded hydrogen in the range from 0.02 to 1.7 weight percent, based on the total weight the organosilicon compound (B).

The molecular weight of the component (B) in the case of siloxane can also vary within wide limits, for example between 10 ² and 10 ⁶ g / mol. For example, component (B) may be, for example, a relatively low molecular weight SiH-functional oligosiloxane, such as tetramethyldisiloxane, but also a high-polymer polydimethylsiloxane possessing chain or terminal SiH groups, or a silicone resin having SiH groups. Also, the structure of the component (B) forming molecules is not fixed; In particular, the structure of a relatively high molecular weight, that is to say oligomeric or polymeric SiH-containing siloxane can be linear, cyclic, branched or even resinous, network-like.

at the process according to the invention becomes an ingredient (B) preferably used in an amount such that the molar ratio of aliphatically unsaturated groups of the constituent (A) to SiH groups of component (B) between 0.1 and 20, especially preferably between 1.0 and 5.0.

The Components used according to the invention (A) and (B) are commercial products or according to in the chemistry conventional methods to produce.

The Invention also relates to silicone elastomers available by crosslinking the hydrosilylatable compositions described above (A) and (B), in particular the polyorganosiloxane compositions described.

The Invention also relates to the invention Processed polysiloxane or organosilane compositions, for example for the production of dental impressions, Adhesives, release liners, flat gaskets, sealants and Coatings are usable.

In the process according to the invention, all catalysts which have hitherto been used for the addition of Si-bonded hydrogen to aliphatically unsaturated compounds can be used as component (C). Examples of such catalysts are metallic and finely divided platinum, ruthenium, rhodium and palladium, which can each be supported, such as silica, alumina or activated carbon, compounds or complexes of said metals, such as hexachloroplatinic acid, platinum halides, platinum-olefin complexes, platinum Alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H ₂ PtCl ₆ .6H ₂ O and cyclohexanone, platinum-vinylsiloxane complexes, especially platinum Divinyltetramethyldisiloxane complexes with or without detectable inorganic halogenated content, bis (γ-picoline) platinum dichloride, trimethyldipyridine platinum dichloride, dicyclopentadiene platinum dichloride, dimethylsulfoxide-ethylene-platinum (II) dichloride, and reaction products of platinum tetrachloride with olefin and primary amine or secondary amine or primary and secondary amine as the reaction product au s Platinum tetrachloride dissolved in 1-octene with sec-butylamine.

Preferably is the catalyst (C) platinum catalysts, particularly preferably platinum chlorides and platinum complexes, in particular hexachloroplatinic acid and platinum divinyltetramethyldisiloxane complex.

at The process according to the invention becomes the catalyst (C) in amounts of preferably 1 to 500 ppm by weight (parts by weight per million parts by weight), in particular 1 to 100 ppm by weight, each calculated as elemental platinum and based on the total weight the component (A) and (B) present in the compositions.

wobei
R³ Alkyl, Aryl oder Siloxy-Rest der Formel (OSiR⁴ ₃) mit R⁴ gleich Alkyl- oder Aryl-Rest
x 0–200
bedeuten.The cocatalysts (D) used according to the invention are preferably compounds of the formula (8)

in which
R ^{3 is} alkyl, aryl or siloxy radical of the formula (OSiR ⁴ ₃ ) where R ⁴ is alkyl or aryl radical
x 0-200
mean.

Especially preferably x = 0.

wobei R³ die oben genannte Bedeutung trägt, und z = 0–200 bedeutet.In a further preferred embodiment, the co-catalysts (D) used according to the invention are compounds of the formula (9)

where R ^{3 has} the abovementioned meaning, and z = 0-200.

Especially preferably z = 0-15.

at the process of the invention is the co-catalyst (D) in amounts of preferably 50-10000 ppm by weight, based on the total weight of the component present in the masses (A) and (B) used. For a faster and better Homogenization of the co-catalysts (D), in particular the representative with short silyl or siloxy groups, the mixture be treated by ultrasound.

The inventive method can in presence or absence of organic solvent (E) become.

Examples for suitable organic solvents (E) all solvents that have been used in hydrosilylation reactions could be used, such as toluene, xylene, isopropanol, acetone, Isophorone and glycols.

If organic solvents (E) are used is it is preferably toluene, isopropanol and glycols and especially preferably toluene.

If organic solvents in the process according to the invention (E) are amounts of preferably 5 to 60% by weight, more preferably 5 to 40% by weight, respectively based on the total weight of the reaction mixture.

at the method of the invention can in addition to components (A) to (E), all other substances which have also been used in hydrosilylation reactions were used.

Other components (F) which can be used in the process according to the invention are reinforcing fillers, for example fumed or precipitated silicas having BET surface areas of at least 50 m ² / g and carbon blacks and activated carbons such as furnace carbon black and acetylene black, wherein pyrogenic and precipitated silicas having BET surface areas of at least 50 m ² / g are preferred.

The mentioned silica fillers can have hydrophilic nature or rendered hydrophobic by known methods be. When incorporating hydrophilic fillers, the addition is a water repellent required.

Of the Content of active reinforcing filler (F) is in the range of 0 to 70% by weight, preferably 0 to 50% by weight.

In the process according to the invention optionally as constituent (G) further additives may contain up to a proportion of up to 70 wt .-%, preferably 0.0001 to 40 wt .-%. These additives may include, for example, inactive fillers, resinous polyorganosiloxanes other than siloxanes (A) and (B), dispersants, solvents, primers, pigments, dyes, plasticizers, organic polymers, Heat stabilizers and so on. These include additives such as quartz powder, diatomaceous earth, clays, chalks, lithopones, carbon blacks, graphite, metal oxides, metal carbonates, metal sulfates, metal salts of carboxylic acids, metal dusts, fibers such as glass fibers, plastic fibers, plastic powders, dyes, pigments, and others known in the art ,

In addition, additives (H) can be included which serve for the targeted adjustment of the processing time, light-off temperature and crosslinking speed. These inhibitors and stabilizers are very well known in the field of addition-crosslinking compositions. Examples of common inhibitors are acetylenic alcohols, such as 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol and 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-dodecin 3-ol, polymethylvinylcyclosiloxanes, such as 1,3,5,7-tetravinyltetramethyltetracyclosiloxane, low molecular weight silicone oils having methylvinylSiO _2/2 groups and / or R ₂ vinylSiO _{1/2 end} groups, such as divinyltetramethyldisiloxane, tetravinyldimethyldisiloxane, trialkylcyanurates, alkylmaleates, such as diallylmaleate, Dimethyl maleate and diethyl maleate, alkyl fumarates such as diallyl fumarate and diethyl fumarate, organic hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide and pinane hydroperoxide, organic peroxides, organic sulfoxides, organic amines, diamines and amides, phosphines and phosphites, nitriles, triazoles, diaziridines and oximes. The effect of these inhibitor additives (H) depends on their chemical structure so that it must be determined individually.

Of the Inhibitor content is preferably 0 to 50,000 ppm, particularly preferably 20 to 2000 ppm, in particular 100 to 1000 ppm.

at the components (A) used according to the invention Up to (H) can each be a single type of such Component, as well as a mixture of at least two different Types of such a component act.

at the method of the invention can the components used according to any and known methods be mixed together. Preferably, in the inventive Process either all reagents except catalyst (C) and cocatalyst (D) and then the reaction by addition of catalyst started or it will all reagents except for the Si-H-containing compounds (B) and then the Si-H-containing compounds added. The inventive method can be carried out continuously or discontinuously.

The Si-substituted quinone used according to the invention (D) can be from the beginning or during the ongoing reaction be added. Preferably, the Si-substituted quinone (D) not added at once, but continuously, preferably at the beginning of the reaction, fed to the reaction system.

at the process of the invention, the addition of Si-bonded hydrogen to aliphatic multiple bond below the same conditions as in the previously known hydrosilylation reactions. Preferably, these are temperatures of 20 to 200 ° C, more preferably from 60 to 140 ° C, and a pressure of 900 to 1100 hPa. But it can also higher or lower temperatures and pressures are applied.

The inventive method has the advantage that the catalyst component (C) during the hydrosilylation reaction is activated or reactivated. Furthermore, that has inventive method has the advantage that a significant catalyst reduction can be achieved as the catalytic Activity of the original catalyst clearly can be extended. Furthermore, the inventive Method has the advantage that by reducing the catalyst also secondary effects can be achieved, such as improved color qualities and low percentage of toxic Heavy metals.

Of further, the inventive method has the Advantage that when adding the co-catalyst (D) from the beginning can be increased to the activity of the catalyst, which leads to a shortening of the reaction time.

In the examples below describe all information parts and percentages unless otherwise stated on the weight. Unless otherwise stated, the following are Examples at a pressure of the surrounding atmosphere, ie at about 1000 hPa, and at room temperature, ie at about 20 ° C, or at a temperature that occurs when merging the reactants at room temperature without additional heating or cooling, performed.

in the Below, all viscosity data refer to one Temperature of 25 ° C.

Konz

Konzentration

Kat

Katalysator

Co-Kat

Co-Katalysator

Ums

Umsatz

Selek

Selektivität

Ausb

Ausbeute

The following abbreviations are used below:

Konz

concentration

Kat

catalyst

Co-Kat

Co-catalyst

Ums

sales

Selek

selectivity

ausb

yield

Examples

Example 1: General reaction instructions for the preparation of 2,5-bis-siloxy-substituted benzoquinones:

A Solution of 2,5-dihydroxy-p-benzoquinone in THF is combined with 2.5 equivalents of a mono-chloro-functional silane or Siloxane and 2.5 equivalents of triethylamine are added and Heated under reflux for 8 h. It is about Celite filtered off and the filtrate evaporated in vacuo. The residue is recrystallized from n-heptane.

2,5- (Me ₃ SiO) ₂ -p-benzoquinone

• (will also be at MT Reetz et al., Tetrahedron Lett. 1975, 15, 1295-1296 described)

Analytical characterization:

• ¹ H-NMR (CDCl ₃ ): 5.94 ppm (s, 2H, C = CH), 0.31 ppm (s, 18H, SiMe ₃ )
• ¹³ C-NMR (CDCl _3): 184.2 ppm (C = O), 156.7 ppm (C = C), 112.5 ppm (C = C), 0.6 ppm (SiMe _3).
• ²⁹ Si-NMR _(CDCl3): 25.61 ppm (s)
• M.p. 95 ° C (DTA)

2,5- (tBuMe ₂ SiO) ₂ -p-benzoquinone:

Analytical characterization:

• ¹ H-NMR (CDCl ₃ ): 5.93 ppm (s, 2H, C = CH), 0.95 ppm (s, 18H, tBu), 0.25 ppm (s, 12H, SiMe ₂ )
• ¹³ C-NMR (CDCl ₃ ): 184.3 ppm (C = O), 157.2 ppm (C = C), 113.0 ppm (C = C), 25.4 ppm ( C H ₃ ) ₃ -C, 18.6 ppm (CH ₃ ) ₃ - C , -4.6 ppm (SiMe ₂ )
• ²⁹ Si-NMR _(CDCl3): 27.01 ppm (s)
• M.p. 130 ° C (DTA)

2,5- (tBuPh ₂ SiO) ₂ -p-benzoquinone:

Analytical characterization:

• ¹ H-NMR (CDCl ₃ ): 7.62 ppm (m, 8H, Ph), 7.39 ppm (m, 12H, Ph), 5.60 ppm (s, 2H, C = CH), 1.06 ppm (s, 18H, tBu)
• ¹³ C-NMR (CDCl _3): 183.3 ppm (C = O), 156.0 ppm (C = C), 135.2 ppm (Ph), 131.0 ppm (Ph), 130.4 ppm (Ph), 128.0 ppm (Ph), 113.8 ppm (C = C), 26.3 ppm (C H _{3) 3} -C, 19.8 ppm (CH _{3) 3} - C
• ²⁹ Si-NMR _(CDCl3): -0.36 ppm (s)
• Mp 148 ° C (DTA)

Example 2

Synthesis of 2- [3- (1,1,1,3,5,5,5-heptamethyltrisiloxy) propyl] -1,4-benzoquinone (4) Reaction Scheme 1:

Reaction Scheme 1 shows the reaction of the starting material 1 via the intermediates 2 and 3 to product 4. The procedure was as follows:
7.30 g (24.8 mmol) of 1 are dissolved in 10 ml of toluene under an inert gas atmosphere of argon, heated to 60 ° C. and treated with 0.10 ml of a 0.1 M solution of platinum (1,3-divinyl). -1,1,3,3-tetramethyldisiloxane in xylene. After dropwise addition of 5.60 g (25.2 mmol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane and heating to 80 ° C over 4 h, the volatiles are removed in vacuo. The crude product 2 is thus accessible in the form of 12.2 g (23.6 mmol, 95%) of a brown oil.

Analytical characterization of 2:

• ¹ H-NMR (300 MHz, RT, CDCl ₃ ): δ = -0.01 (s, 3H, Si-CH ₃ ), 0.08 (s, 18H, Si-O-Si (CH ₃ ) ₃ ), 0.21, 0.23 (2 × s, 2 × 9H, CO-Si (CH ₃ ) ₃ ), 0.49 (t, 2H, Si-CH ₂ ), 1.57 (m, 2H, CH ₂ -CH ₂ -CH ₂ ), 2.49 (t, 2H, C-CH ₂ ), 6.55 (pq, 2H, CH _arom ), 6.59 (s, 1H, CH _arom ).

A Solution of 11.6 g (22.4 mmol) of crude product 2 in 60 mL THF is added at room temperature with 60 mL 10% aqueous Acetic acid and heated to reflux for 4 h. After cooling the reaction mixture to room temperature extracted with 50 mL dichloromethane. The organic phase becomes washed with saturated NaCl solution and with water. After removal of the volatiles in vacuo 8.30 g (22.3 mmol, 99%) of the hydroquinone 3 as a brown oil accessible.

Analytical characterization of 3:

• ¹ H-NMR (300 MHz, RT, CDCl ₃ ): δ = -0.05 (s, 3H, Si-CH ₃ ), 0.03 (s, 18H, Si-O-Si (CH ₃ ) ₃ ), 0.47 ( t, 2H, Si-CH ₂ ), 1.58 (m, 2H, CH ₂ -CH ₂ -CH ₂ ), 2.50 (t, 2H, C-CH ₂ ), 6.50 (pq, 2H, CH _arom ), 6.56 ( s, 1H, CH _arom ).

To a solution consisting of 4.10 g (11.0 mmol) of 3, 20 mL Isopropanol, 20 mL water and 0.13 g (2.16 mmol) glacial acetic acid At room temperature, 8.00 mg (0.04 mmol) of vanadium pentoxide and 0.66 g (6.16 mmol) of sodium chlorate. After 18 h stirring at room temperature, the volatiles are in a vacuum away. The residue is taken up in diethyl ether and Washes several times with water. After removal of the organic Solvent in vacuo, the benzoquinone 4 in the form of 3.05 g (8.23 mmol, 75%) of a brown oil.

Analytical characterization:

• ¹ H-NMR (300 MHz, RT, CDCl ₃ ): δ = -0.02 (s, 3H, Si-CH ₃ ), 0.05 (s, 18H, Si-O-Si (CH ₃ ) ₃ ), 0.48 ( t, 2H, Si-CH ₂ ), 1.51 (m, 2H, CH ₂ -CH ₂ -CH ₂ ), 2.40 (t, 2H, C-CH ₂ ), 6.53 (s, 1H, CH _arom ), 6.70 ( pq, 2H, CH _aroma ).

Catalyst testing:

Examples 3-13 (= B3-B13)

And Comparative Example 1 (= V1):

A mixture of 3.0 g of a SiH-functional siloxane having the composition Me ₃ Si [OSiMe ₂ ] - [OSiMe (H)] - OSiMe ₃ (x: y = 15: 1, x + y = 70, content of Si -found hydrogen 0.083%), 321 mg (2.20 mmol) of allyl glycidyl ether and 10 μl of a 0.1% H ₂ PtCl ₆ solution in isopropanol (resulting in a total Pt concentration of 3 ppm) is mixed with the added in Table 1 amount of an Si-substituted quinone compound as a co-catalyst and heated for 1.5 h at 80 ° C with stirring. After cooling, the mixture is analyzed by ¹ H NMR spectroscopy (conversion, selectivity, yield). In the comparative experiment, no co-catalyst is added. The yield in comparative experiment 1 is significantly worse than in the inventive examples. Table 1 Co-Kat Co-Kat conc [ppm] Ums [%] Selek [%] Yield [%] B3 2,5-bis-trimethylsiloxy-p-benzoquinone 2409 73 95 69 B4 2,5-bis-trimethylsiloxy-p-benzoquinone 1205 22 98 22 B5 2- [3- (1,1,1,3,5,5,5-heptamethyltrisiloxy) propyl] -1,4-benzoquinone 3136 83 94 78 B6 2- [3- (1,1,1,3,5,5,5-heptamethyltrisiloxy) propyl] -1,4-benzoquinone 1570 70 97 68 B7 2- [3- (1,1,1,3,5,5,5-heptamethyltrisiloxy) propyl] -1,4-benzoquinone 314 67 95 64 B8 2,5-bis (dimethyl-t-butyl-siloxy) -p-benzoquinone 3119 47 95 45 B9 2,5-bis (dimethyl-t-butyl-siloxy) -p-benzoquinone 1560 47 94 44 B10 2,5-bis (dimethyl-t-butyl-siloxy) -p-benzoquinone 312 33 97 32 B11 2,5-bis (diphenyl-t-butyl-siloxy) -p-benzoquinone 5220 48 96 46 B12 2,5-bis (diphenyl-t-butyl-siloxy) -p-benzoquinone 2610 38 98 37 B13 2,5-bis (diphenyl-t-butyl-siloxy) -p-benzoquinone 522 22 99 22 V1 - - 15 98 15

Examples 14-15 (= B14-B15)

And Comparative Example 2 (= V2)

In a three-necked flask with thermometer and reflux condenser, the amount of the cocatalyst indicated in Table 2 is dissolved in 10 ml of toluene, with 4.9 g (42 mmol) of triethylsilane, 4.3 g (43 mmol) of vinyltrimethylsilane and 9 μl of a 2% solution of a divinyl-tetramethyldisiloxane-platinum complex. The reaction mixture is stirred for 1 h at 55.degree. After cooling, the mixture is analyzed by ¹ H NMR spectroscopy and by GC analysis (conversion, selectivity, yield).

In the comparative experiment, no co-catalyst is added. The yield in the comparative experiment is significantly worse than in the inventive examples. Table 2 Co-Kat Amount Co-Kat [mg] Ums [%] Selek [%] Yield [%] B14 2,5-bis-trimethylsiloxy-p-benzoquinone 21 mg 80 94 75 B15 2- [3- (1,1,1,3,5,5,5-heptamethyltrisiloxy) propyl] -1,4-benzoquinone 25 mg 97 94 91 V2 - - 66 91 60

Examples 16-23 (= B16-B23)

And Comparative Examples 3-4 (= V3-V4)

A mixture of 10 g of an α, ω-divinyldimethylpolysiloxane (viscosity η = 500 mPas), which is mixed with the hydrosilylation inhibitor 1-ethynylcyclohexanol and 250 mg of a SiH-functional polysiloxane of composition Me ₃ SiO- [Si (H) Me-O ] ₄₈ -SiMe ₃ , is added to a Pt-divinyl-tetramethyldisiloxane complex ("Karstedt catalyst"), and the amount of a cocatalyst indicated in Table 3. The mixture is after intensive homogenization with the aid of a doctor blade (60 microns) mounted on a glass slide and treated on a heat bench at a given temperature until no more lubricating shares can be found in a "Strichtest".

In the comparative experiments no co-catalyst is added. The crosslinking times in the comparative experiments are significantly longer than in the inventive examples. Table 3 Kat Conc Co-Kat Quantity co-cat Networking time B16 50 ppm Bis-trimethylsiloxy-p-benzoquinone 10 mg 7 s B17 50 ppm Bis (dimethyl-t-butyl-siloxy) -p-benzoquinone 10 mg 7 s B18 50 ppm Bis (diphenyl-t-butyl-siloxy) -p-benzoquinone 11 mg 8 s B19 50 ppm 2- [3- (1,1,1,3,5,5,5-heptamethyltrisiloxy) -propyl] -1,4-benzoquinone 11 mg 6 s V3 50 ppm - - 10 s B20 25 ppm Bis-trimethylsiloxy-p-benzoquinone 10 mg 11 s B21 25 ppm Bis (dimethyl-t-butyl-siloxy) -p-benzoquinone 30 mg 13 s B22 25 ppm Bis (diphenyl-t-butyl-siloxy) -p-benzoquinone 30 mg 15 s B23 25 ppm 2- [3- (1,1,1,3,5,5,5-heptamethyltrisiloxy) -propyl] -1,4-benzoquinone 11 mg 11 s V4 25 ppm - - 17 s

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• US 3715334 [0004]
• US 3775452 [0004]
• US 5359111 [0006]
• US 5616763 [0006]
• - US 5424470 [0006]
• WO 2003/037961 A2 [0006]
• US 6166238 [0006]
• WO 2003/044028 A1 [0006]
• WO 1998/00463 [0007]
• WO 1995/025734 [0007]

Cited non-patent literature

• MT Reetz et al., Tetrahedron Lett. 1975, 15, 1295-1296 [0074]

Claims (4)

Catalyst system comprising (C) at least one metal catalyst of the 8th transition group, and (D) at least one Si-substituted quinone compound of the general formula (1) or (2), or their mixtures, as cocatalyst

wherein R is mono- or polyhydric, substituted or unsubstituted hydrocarbon radicals, siloxy of the general formula OSiR ' ₃ , R' mono- or polyhydric, substituted or unsubstituted hydrocarbon radicals, x 0-200, Y oxygen, or a monovalent C1-C20 Hydrocarbon radical, Z ¹ , Z ² independently of one another represent hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy, aryloxy, siloxy radical, or Z ¹ and Z ² form a substituted or unsubstituted, aromatic or nonaromatic ring , Z ³ independently of one another represent hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy, aryloxy, siloxy. Catalyst system according to claim 1, characterized in that the catalyst (C) is a platinum catalyst is. A method for attaching Si-bonded hydrogen to aliphatic carbon-carbon multiple bond by reacting (A) compounds having aliphatic carbon-carbon multiple bonds with (B) organosilicon compounds having Si-bonded hydrogen atoms in the presence of (C) at least a metal catalyst of the 8th subgroup, characterized in that from the beginning or during the reaction (D) at least one Si-substituted quinone compound of the general formula (1) or (2), or their mixtures, is added as co-catalyst .

wherein R is mono- or polyhydric, substituted or unsubstituted hydrocarbon radicals, siloxy of the general formula OSiR ' ₃ , R' mono- or polyhydric, substituted or unsubstituted hydrocarbon radicals, x 0-200, Y oxygen, or a monovalent C1-C20 Hydrocarbon radical, Z ¹ , Z ² independently of one another represent hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy, aryloxy, siloxy radical, or Z ¹ and Z ² form a substituted or unsubstituted, aromatic or nonaromatic ring , Z ³ independently of one another represent hydrogen, halogen, hydroxyl, alkyl, aryl, alkoxy, aryloxy, siloxy. A method according to claim 3, characterized in that as compound (A) allyl glycidyl ether or allyl succinic anhydride is used.