Classifications

• • C—CHEMISTRY; METALLURGY
  • 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
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
• • C—CHEMISTRY; METALLURGY
  • 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
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
• • C—CHEMISTRY; METALLURGY
  • 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

Definitions

• This invention relates to the preparation of ⁇ -[N-(2-aminoethyl)] aminoal ylalkoxysilanes " . More specifically, this invention relates to the preparation of such silanes by reaction of co-chloroalkylal oxysilane with excess emylenediamine utilizing a recycled emylenediamine hydrochloride salt phase stream.
• ⁇ -[N-(2- _u ⁇ oethyl)]aminoalkylalkoxysilanes have the general formula, 1 R 2 NCH l CH 2 NR ⁇ R 4 ' in which R 1 , R ⁇ , and R 3 independently are a member selected from the group consisting of a hydrogen atom or an alkoxysilane of the formula: R 5 Si(R 6 ) 3 . 8 (OR 7 ) a in which R 5 , R 6 , and R 7 are each independently C 1-8 al yl (including straight chain or branched alkyls) and a is 1, 2, or 3.
• R 4 is a said alkoxysilane.
• ⁇ -[N-(2-ammoe yl)]an ⁇ inoalkylalkoxysilanes are widely used as silane coupling agents and are effective for various polymer property modification purposes, for example, improving adhesion at an organic- inorganic interface.
• R 5 is any alkyl group and each of R 6 and R 7 is an alkyl radical having 1 to 8 carbon atoms and a is equal to 1, 2, or 3.
• the end product ⁇ -[N-(2- ammoemyl)]aminoalkylalkoxy- silane further reacts with the starting reactants ⁇ -chloroalkylalkoxysilane and emylenediamine to form poly- alkylated products as shown below.
• a present method for preparing ⁇ -[N-(2- arninoethyl)] am oalkyl-alkoxysilanes in a continuous flow process is as follows.
• An emylenediamine stream is co-fed to a reactor with an ⁇ - chloroalkylalkoxysilane stream of the formula: ClR 5 Si(R 6 OR 7 ) a
• the alcohol mentioned above is generated in a side reaction between extraneous water impurity that enters with both the emylenediamine and the alkoxysilane feeds.
• the side reaction is shown below, where b is equal to or less than a and a is equal to 1, 2, or 3.
• phase separator gravity, mechanical, electrical, etc.
• the lighter silane phase effluent stream from the phase separator which is mainly a mixture of emylenediamine, alcohol, and 3-[N- (2-ammoemyl)]arrrmoalkylalkoxysilane, is passed to a second distillation column where the ammoemylaminoalkylalkoxysilane is purified.
• the emylenediamine and alcohol are removed from the top of the column and recycled to an emylenediamine purification column that may also treat incoming emylenediamine.
• the arn oe ylaminoalkoxy silane stream is sometimes further purified in a stripping, distillation, or flash system to reduce the level of poly-alkylated emylenediamine.
• the emylenediamine overhead stream and new emylenediamine are also directed to the ethylene purification distillation column where alcohol is removed.
• the prior process requires, as described above, that the contents of the reactor, the reaction mixture, be passed through a distillation column for removal of a substantial amount of emylenediamine. The distillation operation was required before the residual reaction mixture could be separated into a product rich phase for product isolation and purification. It would be more efficient and economical to have a process in which the reaction mixture comprises two phases so that the product rich phase could be obtained without a preliminary distillation step and use of distillation equipment for that purpose. It is an object of this invention to provide such a process.
• the two liquid phase effluent from the reactor is a mixture of ⁇ - [ -(2-am oemyl)]ammoalkylalkoxysilane, emylenediamine, emylenediamine hydrochloride, and extraneous alcohol.
• the stream is first conducted to a phase separation vessel rather than to a distillation column.
• the top bulk phase contains predominantly silane and emylenediamine.
• the heavier bulk phase contains predominantly emylenediamine hydrochloride and emylenediamine.
• the heavier phase is recycled to the reactor in sufficient quantity to maintain the two phase system in the reactor and used to control the degree of polyalkylation. The balance of the heavier phase is removed from the process.
• the lighter phase is transferred to a purification system consisting of a distillation and/or a flash system where ⁇ -P ⁇ -(2-aminoemyl)]an ⁇ ino- alkylalkoxysilane(s) is purified by removal of the lower boiling species.
• the silane product is recovered in good yield and quality while the ethylenediamine is further purified by a second distillation and returned to the two phase system reactor.
• the reaction is preferably conducted at a temperature in the range of about 60° to 200°C.
• the molar ratio of total emylenediamine to the alkoxysilane in the reactor, including the emylenediamine hydrochloride recycle, is at least 3 to 1 and no greater man 40 to 1.
• the process of this invention is particularly useful in the manufacture of 3-IN-(2-ammoemyl)]an ⁇ inopropylalkoxysilanes and 3-[N-(2- ammoemyl)]aminoisobutylalkylalkoxysilanes.
• 3-[N-(2- a ⁇ nmoemyl)]anm opropyltrimethoxysilane ( or -triethoxysilane) or 3-[N-(2- anm ⁇ oe yl)]ammoisobutylmemyldimethoxysilane (or -methyldietfaoxysilane) can be made in high yield and quality.
• these silanes can be made substantially as the mono-alkylated e ylenedia ines or as mixtures of predominately the mono-alkylated product with some amounts of the di-and tri-alkylated products.
• Figure 1 is a flow diagram of the process of this invention for producing ⁇ -[N-(2-ammoemyl)]ammoalkylalkoxysilanes .
• This invention provides a novel and improved method of producing ro-[N-(2-anunoemyl)3ammoalkylalkoxysilanes such that the number of required processing steps is reduced.
• the method is suitable for preparing an ⁇ -[N-(2-ammoemyl)]aminoalkylalkoxysilane of the general formula: in which R ⁇ R 2 and R 3 independently are a member selected from the group consisting of a hydrogen atom or an alkylalkoxysilane of the formula:
• R 4 is a said alkylalkoxysilane.
• the process comprises the establishment of a two-phase reaction system.
• Ethylenediamine is fed to a reactor with a chloroalkylalkoxysilane of the formula, ClR 5 Si(R 6 ) 3 . a (OR 7 ) a , as defined above.
• a suitable temperature of, for example, 60° to 200°C the dia ine and chloroalkyl- alkoxysilane react to form a desired silane product and emylenediamine monohydrochloride salt.
• this byproduct salt is recycled to the reaction mixture in sufficient amount to cause the formation of a salt rich phase that is separable from the silane product containing phase.
• the emylenediamine salt recycle allows the control of the formation of poly-alkylated emylenediamine.
• a reaction mixture for producing 3-jN(2-ammoemyl)]ammopropyltrimethoxysilane for example, about 1 to 15 moles of emylenediamine salt in the recycled salt phase reactor effluent per mole of silane product is suitable for forming the two phase mixture in the reactor.
• a product rich phase can be gravity, mechanically, or electrically separated from the emylenediamine hydrochloride phase without an mtervening distillation operation.
• the molar feed ratio of emylenediamine to emylenediamine hydrochloride be in the range of about 1 to 20, the optimum depending on the alkoxysilane used, when the desired product is predominately a mono-alkylated ethylene diamine.
• the two liquid phase effluent (flow stream 18) from the reactor which is predominantly a mixture of emylenediamine ⁇ -[N-(2- ammoemyl)]a ⁇ nmoalkylalkoxysilane, and emylenediamine mono- hydrochloride, is passed to a phase separator vessel 20 where the bottom phase (stream 22) is split into a relatively small purge stream (stream 24) and a recycle stream 14 that is fed back to the reactor 10.
• Recycle stream 14 ' typically contains both emylenediamine and its hydrochloride salt. The proportions depend upon the combination required for separation from the silane product containing phase. The amount of recycle is determined experimentally to produce the two-phase reactor system and effluent and to control the degree of polyalkylation.
• Predominantly emylenediamine (stream 32) is removed from the silane via the top of column 28 and recycled back to a emylenediarnine purification column 34.
• the silane product is removed from the bottom of the column, stream 30.
• a fresh emylenediamine stream (stream 36) is fed to the system, preferentially through the emylenediamine purification column 34 where low boiling impurities/byproducts (stream 38) are removed as the overhead stream.
• the purified emylenediamine (stream 12) is then fed to the two-phase system reactor 10.
• a preferred application for the process of this invention is in the production of H 2 NCH 2 CH 2 NHR 1 SiR 3 (3 . a) (OR 2 ) a where R 1 is a propyl or isobutyl group, R 2 and R 3 are each independently methyl or ethyl groups, and a is 1 , 2, or 3.
• R 1 is a propyl or isobutyl group
• R 2 and R 3 are each independently methyl or ethyl groups
• a is 1 , 2, or 3.
• recycle stream 14 provided the recycled emylenediamine monohydrochloride at the above stated rate of 1.9 moles per mole of 3-chloropropyltrimethoxysilane fed to the reactor.
• recycle stream 14 also contained about sixty percent of the ethylenediamine supplied to reactor 10.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2002
  • 2002-02-11 US US10/073,444 patent/US6452033B1/en not_active Expired - Lifetime
• 2003
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