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  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/12—Organo silicon halides
  • C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
  • B01J31/0237—Amines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
  • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
  • B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2282—Unsaturated compounds used as ligands
  • B01J31/2291—Olefins
• • 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
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
  • B01J2231/32—Addition reactions to C=C or C-C triple bonds
  • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0202—Polynuclearity
  • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/828—Platinum

Definitions

• the present invention relates to a method for synthesizing at least one 3-halopropyltrihalosilane compound, a catalyst composition and its use in a hydrosilylation reaction as well as a reactive composition.
• Hydrosilylation reactions also called catalytic hydrosilation, are amongst the most important reactions to produce functional silanes. They describe the addition of Si-H bonds across unsaturated bonds.
• An important group of silanes produced by this reaction are 3-halopropyltrihalosilane compounds such as 3-chloropropyltrichlorosilane (also referred to as trichloro(3-chloropropyl)silane). They are conventionally prepared by hydrosilylation of an allyl halide such as allylchloride and a H- silane such as a trihalosilane (e.g. trichlorosilane) in the presence of platinum catalysts. This type of reactions generally suffers from moderate selectivity and yield.
• cocatalysts have been employed to improve yield and selectivity.
• cocatalysts are phosphines, oxygen, organic oxo-compounds like ketones and aldehydes, tertiary alcohols, alcoholates and nitrogenbased compounds to name but a few.
• US 4,292,434 publishes the synthesis of 3-chloropropyltrichlorosilane using amines as cocatalyst for chloroplatinic acid or platinum dihalide as main catalyst.
• the procedure requires the preparation of the catalyst in a step preceding the synthesis of the desired silane. This additional step is naturally unwanted as it increases the time required to preparing the desired silane, increasing unfavorably the cost and time needed for its preparation.
• Examples 3 and 4 of US 3,925,434 disclose the reaction of allyl chloride with trichlorosilane in the presence of a catalyst system consisting of chloroplatinic acid and phenothiazine.
• the selectivity of the reaction is moderate only (see table I in the cited document).
• Many by-products are formed and a large fraction in the crude mixture forms propyltrichlorosilane.
• the removal of the chlorine atom from the propyl group is undesired as the thus obtained alkylsilane cannot be further functionalized.
• DE 102 43 180 discloses the preparation of 3-chloropropyltrichlorosilane using a platinum catalyst and a ligand selected from aliphatic amides, nitriles and amines.
• Preferred amides are N,N-dime- thylacetamide and N,N-dimethylformamide
• preferred amines are N,N-dimethylbutylamine, tert-bu- tylamine or triethylamine.
• CN 108069996 reports the making of 3-chloropropyltrichlorosilane using chloroplatinic acid as platinum catalyst and formamide and N-alkyl derivatives thereof.
• CN 102 127 104 discloses the synthesis of 3-chloropropyltrichlorosilane in the presence of n-butyl- amine. However, the selectivity using this aliphatic amine as cocatalyst is poor.
• At least one H-silane selected from the group consisting of trihalosilane, methyldihalosilane and dimethylhalosilane; characterized in that the reaction of the at least one unsaturated compound and the at least one H- silane is carried out in the presence of:
• the method according to the invention allows for high yields of 3-halopropyltrihalosilane compounds to be obtained. Further, the selectivity of the inventive method is enhanced resulting in less undesired side-products such as propyltrihalosilanes and silicontetrahalides.
• selectivity means in particular the selectivity of 3-halopropyltrihalosilane compounds over propyltrihalosilane. An improved selectivity facilitates the purification of the desired 3- halopropyltrihalosilane compounds.
• the inventive method further is ecologically and environmentally benign and more atom-efficient than the prior art methods.
• alkyl according to the present invention comprises branched or unbranched alkyl groups comprising cyclic and/or non-cyclic structural elements, wherein cyclic structural elements of the alkyl groups naturally require at least three carbon atoms.
• C1-CX-alkyl in this specification and in the claims refers to alkyl groups having 1 to X carbon atoms (X being an integer).
• C1-C8-alkyl for example includes, among others, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, neo-pentyl, hexyl, heptyl and octyl.
• Substituted alkyl groups may theoretically be obtained by replacing at least one hydrogen by a functional group.
• alkyl groups are preferably selected from substituted or unsubstituted C1-C8-alkyl, more preferably from substituted or unsubstituted C1-C4-alkyl because of their improved water-solubility.
• aryl refers to ring-shaped aromatic hydrocarbon residues, for example phenyl or naphthyl where individual ring carbon atoms are optionally replaced by N, O and/or S, for example benzothiazolyl. Preferably, none of said carbon atoms is replaced by other elements such as those described hereinbefore. Furthermore, aryl groups are optionally substituted by replacing a hydrogen atom in each case by a functional group.
• C5-CX-aryl refers to aryl groups having 5 to X carbon atoms (optionally replaced by N, O and/or S) in the ring-shaped aromatic group (X naturally being an integer). C5-C6-aryl is preferred, C6-aryl is even more preferred, unless stated otherwise.
• each of the residues is selected independently from each other unless stated otherwise hereinafter, meaning they can be selected to be the same members or different members of said group.
• Methods described herein comprise the named method steps. The named method steps are preferably carried out in the given order unless stated otherwise. The methods optionally comprise further method steps to be carried out before, after and/or between said method steps. Preferences and details described for one aspect of the present invention apply mutatis mutandis to the other aspects thereof unless stated otherwise or technically unfeasible.
• 3-halopropyltrihalosilane compounds in the context of the present invention include inter alia 3-halopropyltrihalosilane, 3-halopropylmethyldihalosilane, or 3-halopropyldimethylhalosilane and those compounds described in the following.
• Preferred 3-halopropyltrihalosilane compounds are selected from the group consisting of 3-chloropropyltrichlorosilane, 3-bromopropyltri- chlorosilane, 3-chloro-2-methyl-propyltrichlorosilane and 3-bromo-2-methyl-propyltrichlorosilane.
• 3-chloropropyltrichlorosilane and 3-chloro-2-methyl-propyltri- chlorosilane as the at least one 3-halopropyltrihalosilane compound, 3-chloropropyltrichlorosilane is most preferred in this context.
• the at least one unsaturated compound is selected from the group consisting of allyl halide such as allyl chloride (also referred to as 3-Chloroprop-1-ene, CAS no. 107-05-1) and methallyl halide such as methallyl chloride (also referred to as 3-Chloro-2-methylprop-1-ene, CAS 563-47-3).
• allyl halide such as allyl chloride (also referred to as 3-Chloroprop-1-ene, CAS no. 107-05-1)
• methallyl halide such as methallyl chloride (also referred to as 3-Chloro-2-methylprop-1-ene, CAS 563-47-3).
• the halide is preferably chloride. Preference is given to allyl halide. It is even more preferred that the at least one unsaturated compound is allyl chloride.
• the at least one H-silane is selected from the group consisting of trihalosilane, methyldihalosilane and dimethylhalosilane.
• a H-silane comprises at least one hydrogen atom bound to the silicon atom via a single bond.
• the at least one H-silane is preferably selected from the group consisting of trihalosilane and methyldihalosilane. Even more preferred is trihalosilane.
• the halogen atoms present in the at least one H-silane are preferably independently selected from the group consisting of chlorine and bromine, more preferably the halogen atoms are chlorine atoms.
• the at least one H-silane is trichlorosilane (H-SiCh).
• the molar ratio of the at least one unsaturated compound to the at least one H-silane preferably ranges from 2:1 to 0.2:1 , more preferably from 1 .5:1 to 0.5:1 and even more preferably from 1 .2:1 to 0.8:1
• the Karstedt catalyst is known in the art.
• a Karstedt catalyst is a platinum complex of 1 ,1 ,3,3-tetra- methyl-1 ,3-divinyldisiloxane (CAS no. 68478-92-2).
• the Karstedt catalyst is typically employed as alcoholic solution.
• the alcohol in this context is preferably selected from the group consisting of methanol, ethanol, n-propanol, /so-propanol and mixtures of the aforementioned with particular preference given to /so-propanol.
• the weight ratio of the at least one alcohol to the Karstedt catalyst preferably ranges from 20:1 to 1 :10, preferably from 10:1 to 1 :5, more preferably from 5:1 to 1 :2.
• the molar ratio of the Karstedt catalyst and the at least one unsaturated compound preferably ranges from 1 :10 to 1 :10,000,000, more preferably from 1 :100 to 1 :1 ,000,000, even more preferably from 1 :1 ,000 to 1 :100,000.
• the at least one cocatalyst is in accordance with formula (A): wherein
• R 1 is an aryl group; each R 2 is independently an alkyl group; and n is selected from 0 and 1 .
• R 1 is preferably an unsubstituted aryl group, more preferably an unsubstituted C5-C12-aryl, even more preferably an unsubstituted C5-C6-aryl, most preferably a (unsubstituted) phenyl group.
• R 2 is preferably a C1-C4-alkyl group, more preferably a methyl group, n is preferably 1.
• the at least one cocatalyst is selected from the group consisting of A/,/V-dimethyl- aniline and /V,/V-dimethylbenzamide.
• the molar ratio of the at least one cocatalyst according to formula (A) to the Karstedt catalyst preferably ranges from 1 : 1 to 100 : 1 , more preferably from 2 : 1 to 50 : 1 , even more preferably from 5 : 1 to 25 : 1 .
• the reaction of the at least one unsaturated compound and the at least one H-silane is carried out in at least one solvent, the solvent being preferably the at least one 3-halopropyltrihalo- silane compound applying the preferences outlined hereinbefore.
• Other solvents can be selected based on routine experiments by the person skilled in the art.
• the at least one 3-halo- propyltrihalosilane compound as the at least one solvent surprisingly increases the yield and selectivity of the reaction.
• the reaction of the at least one unsaturated compound and the at least one H-silane is carried out at a temperature ranging from 30 to 250°C, preferably from 50 to 220°C, more preferably from 80 to 200°C.
• the duration of the reaction of the at least one unsaturated compound and the at least one H- silane is not particularly limited.
• the reaction can be carried out until the at least one unsaturated compound and/or the at least one H-silane are consumed.
• the reaction of the at least one unsaturated compound and the at least one H-silane is carried out for 1 min to 24 h, preferably for 1 to 12 h, more preferably for 2 to 6 h.
• the reaction of the at least one unsaturated compound and the at least one H-silane is carried out in an inert atmosphere.
• an inert atmosphere such as nitrogen, argon, or a mixture of the aforementioned.
• the at least one unsaturated compound is allyl chloride
• the at least one H-silane is trichlorosilane
• the at least one cocatalyst according to formula (A) is selected from the group consisting of A/,/V-dimethylaniline and /V,/V-dimethylbenzamide.
• the method according to the invention preferably comprises the following method steps to be carried out in the given order:
• the 3-halopropyltrihalosilane compound is obtained. It is preferred that the at least one unsaturated compound is added continuously in method step A2.
• a continuous addition in the context of the present invention is to be understood that the at least one unsaturated compound is added for a certain period of time rather than in one step.
• a certain period of time means 1 to 25% of the total duration of the reaction, preferably 2 to 10%.
• the method for synthesizing at least one 3-halopropyltrihalosilane compound according to the invention is succeeded by a method step A3:
• the mixture obtained is purified by at least one method selected from the group consisting of distillation, filtration, precipitation or a combination of the aforementioned with distillation being the most preferred purification method.
• the present invention further concerns a catalyst composition suitable for mediating a hydrosilylation reaction, preferably the hydrosilylation reaction of at least one unsaturated compound selected from the group consisting of allyl halide and methallyl halide and at least one H-silane selected from the group consisting of trihalosilane, methyldihalosilane and dimethylhalosilane to give the 3-halopropyltrihalosilane compound, comprising a) a Karstedt catalyst; and
• R 1 is an aryl group; each R 2 is independently an alkyl group; and n is selected from 0 and 1 .
• the catalyst composition according to the invention can mediate (or catalyze) a hydrosilylation reaction, especially the aforementioned reaction, i.e. in the latter case it allows the at least one unsaturated compound and the at least one H-silane to be converted into the 3-halopropyltrihalo- silane compound, without necessarily undergoing permanent change itself.
• Another aspect of the present invention is directed at the use of the catalyst composition according to the invention in a hydrosilylation reaction, preferably in the hydrosilylation reaction of at least one unsaturated compound selected from the group consisting of allyl halide and methallyl halide and at least one H-silane selected from the group consisting of trihalosilane, methyldihalo- silane and dimethylhalosilane to give the 3-halopropyltrihalosilane, compound.
• a reactive composition comprising a) at least one unsaturated compound selected from the group consisting of allyl halide and methallyl halide; b) at least one H-silane selected from the group consisting of trihalosilane, methyldihalosilane and dimethylhalosilane; c) a Karstedt catalyst; and d) the at least one cocatalyst according to formula (A): wherein
• R 1 is an aryl group; each R 2 is independently an alkyl group; and n is selected from 0 and 1 .
• the reactive composition can be used for synthesizing the at least one 3-halopropyltrihalosilane compound.
• the amount of the at least one unsaturated compound preferably ranges from 5 weight-% to 80 weight-%, more preferably from 10 weight-% to 60 weight-%, even more preferably from 15 weight- % to 50 weight-%, based on the total amount of the reactive composition.
• the amount of the at least one H-silane preferably ranges from 10 weight-% to 90 weight-%, more preferably from 20 weight-% to 85 weight-%, even more preferably from 30% to 80%, based on the total amount of the reactive composition.
• the amount of the Karstedt catalyst preferably ranges from 0.1 ppm to 10 weight-%, more preferably from 0.5 ppm to 1 weight-%, even more preferably from 1 ppm to 0.1 weight-%, based on the total amount of the reactive composition.
• the amount of the at least one cocatalyst according to formula (A) preferably ranges from 0.1 ppm to 10 weight-%, more preferably from 0.5 ppm to 5 weight-%, even more preferably from 1 ppm to 1%, based on the total amount of the reactive composition.
• the reactive composition preferably comprises at least one solvent, the solvent being preferably selected from those described hereinbefore.
• the amount of the at least one solvent in the reactive composition preferably ranges from 10 weight-% to 90 weight-%, more preferably from 20 weight- % to 80 weight-%, even more preferably from 30 weight-% to 70 weight-%, based on the total amount of the reactive composition.
• the amounts of the aforementioned components can optionally be reduced by the amount of the solvent.
• a 100 ml four-necked flask equipped with a Liebig condenser was placed in an oil bath and was then charged under a nitrogen atmosphere with 36.5 g 3-chloropropyltrichlorosilane, 15.0 g trichlorosilane, Karstedt catalyst (20 weight-% platinum in iso-propanol, 64 mg platinum per kg of the reactive composition) and a cocatalyst, if any, in the amount given in table 1 .
• the Liebig condenser itself was connected to a cooling trap (iso-propanol I dry ice). Via syringe pump, 8.5 g allyl chloride was added to the mixture (1 mL/min). After complete addition of the allyl chloride, the oil bath was heated to 180 °C until the bottoms temperature reached said temperature but at least for 3 h. The results are listed in table 1 .
• GC analysis Chromatograms were obtained using an Agilent 6890 N gas chromatograph equipped with a Restek RTX 200 column (L: 60 m, ID: 0.53 mm, dt: 3 pm) and applying the following temperature program: Temp: 40°C; Init Time: 7.00 min; Rate: 15 °C/min; Final Temp: 240°C; Final Time: 10.00 min; Inj. Temp: 250°C; Det. Temp: 280°C.
• the selectivity was calculated by dividing the GC area of 3-chloropropyltrichlorosilane by the GC area of silicon tetrachloride. As for every molecule of silicon tetrachloride a molecule of highly undesired propyltrichlorosilane is produced in the hydrosilylation reaction, the amount of silicon tetrachloride is a convenient method of assessing the selectivity of 3-chloropropyltrichlorosilane over propyltrichlorosilane.

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