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
  • 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
  • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
• • 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
  • C07F7/20—Purification, separation

Definitions

• the present invention relates to a novel process for an aqueous work-up of aminofunctional organosilane containing ammonium halides and / or organic amine hydrohalides, as obtained, for example, in the preparation of an amino-functional organosilane by reacting a halogen-functional organosilane with excess ammonia or an organic amine.
• Aminosilanes have a diverse range of applications. They are used for example for glass fiber sizes or used in the foundry industry as processing aids, they also serve as adhesion promoters for storage-stable resins.
• the process for preparing amino-functional organosilanes by reacting appropriate halogenated organofunctional silanes with ammonia or an amine has in common that the resulting salt-like compounds, in particular ammonium halides and / or organic Aminhydrochlohde as much as possible to separate completely from the desired product and the products still have an undesirable halide content.
• halide contents in the product of less than 100 ppm by weight can be achieved by this comparatively simple procedure.
• the present process is generally applicable to all amino-functional organosilanes.
• a comparatively simple and at the same time economical aqueous work-up of crude product from an aminosilane synthesis could thereby advantageously be made possible.
• an ammonium halide and / or organic aminofunctional organosilane containing aminhydrohalides the preparation of which is based on the reaction of a halogen-functional organoalkoxysilane with excess ammonia or organic amine, preferably under pressure and in the liquid phase, and subsequent separation and workup of crude product and resulting salt, can work up in a simple and economical manner by using the aminofunctional organosilane containing ammonium halides and / or organic amine hydrohalides (hereinafter referred to as raw product or product mixture)
• such an amniofunctional organosilane obtained by the process according to the invention advantageously has a content of hydrolyzable chloride of less than 100 ppm by weight up to the detection limit of 6 ppm by weight.
• hydrolyzable chloride examples include u. a. organic Aminhydrochlohde, ammonium chlorides, chlorosilanes, etc.
• the determination of hydrolyzable chloride can be done, for example potentiographically with silver nitrate.
• amino-functional organosilanes of the general formula (I) but also those of the general formula (II) and / or (III) or their respective crude products or corresponding product mixtures of organosilanes of the formulas (I), (II) and / or or (III) as used in u. a. work up during production, work up:
• R groups are the same or different and R is hydrogen (H) or is a linear or branched alkyl group having 1 to 4 carbon atoms, preferably H or n-butyl, groups R 'are identical or different and R' is hydrogen (H) or a linear or branched alkyl group having 1 to 8 C atoms or an aryl group, preferably methyl or ethyl, groups R "are identical or different and R" is a linear or branched alkyl group having 1 to 8 C
• Atoms such as methyl, ethyl, propyl, butyl, preferably methyl, or an aryl group
• Z is a bivalent alkyl group from the series -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) S-, - (CH 2 ) 4 - or - (CH 2 ) (CH) CH 3 (CH 2 ) -, preferably propyl
• n is 0, 1, 2 or 3, preferably 0, and z is 0, 1 or 2 is
• R is a hydrogen (H) or a linear or branched alkyl group having 1 to 4 C atoms, preferably H or n-butyl
• groups R ' are identical or different and R' is hydrogen (H) or a linear or branched alkyl group having 1 to 8 C atoms or an aryl group, preferably methyl or ethyl
• groups R "are identical or different and R" is a linear or branched alkyl group having 1 to 8 C atoms, such as Methyl, ethyl, propyl, butyl, preferably methyl, or an aryl group
• Zs are the same or different and Z is a bivalent alkyl group selected from the group - CH 2 -, - (CH 2 J 2 -, - ( CH 2 ) S-, - (CH 2 ) 4 - or - (CH 2 ) (CH) CH 3 (CH 2 ) -, preferably propyl
• n is independently 0, 1,
• Tris-amino-functional organosilanes ie tris-silylated amines, represented by the general formula (III):
• groups R ' are identical or different and R' is a hydrogen (H) or a linear or branched alkyl group having 1 to 8 C atoms or an aryl group, preferably methyl or ethyl, groups R "are identical or different and R "is a linear or branched alkyl group having 1 to 4 C atoms, such as methyl, ethyl, propyl, butyl, preferably methyl, or an aryl group
• Z are the same or different and Z is a bivalent alkyl group from the series -CH 2 -, - (CH 2 J 2 -, - (CH 2 ) 3 -, - (CH 2 ) 4 - or - (CH 2 ) (CH) CH 3 (CH 2 ) -, preferably propyl, n is independently 0, 1, 2 or 3, preferably 0, and x is independently 0, 1 or 2,
• the present invention thus relates to a process for working up an amine amalgium id eu nd / or organ isch e
• Amino-functional organosilane containing hydrohalides [also abbreviated to "aqueous work-up"], wherein the ammonium halides and / or organic amine hydrohalides containing amino-functional organosilane
• X is Cl, Br or J
• Z is a bivalent alkyl group selected from the group -CH 2 -, - (CH 2 J 2 -, - (CH 2 ) S -, - (CH 2 ) 4 - or - (CH 2 ) (CH) CH 3 (CH 2 ) -, preferably propyl
• groups R ' are identical or different and R' is a hydrogen (H) or a linear or branched alkyl group having 1 to 8
• R is identical or different and R" is a linear or branched alkyl group having 1 to 8 C atoms, such as methyl, ethyl, propyl, butyl, preferably methyl, or an aryl group, and n is 0, 1, 2 or 3, preferably 0,
• R groups are identical or different and R is hydrogen (H) or a linear or branched alkyl group having 1 to 4 C atoms, preferably H or n-butyl and z is 0, 1 or 2,
• groups R are the same or different and R is hydrogen (H) or a linear or branched alkyl group having 1 to 4 C atoms, preferably H or n-butyl, groups R 'are identical or different and R' is hydrogen (H) or a linear or branched alkyl group having 1 to 8 carbon atoms or an aryl group, preferably methyl or
• Butyl, preferably methyl, or an aryl group, Z is a bivalent alkyl group from the series -CH 2 -, - (CH 2 J 2 -, - (CH 2 ) 3 -, - (CH 2 ) 4 - or - (CH 2 ) (CH) CH 3 (CH 2 ) -, preferably propyl, n is 0, 1, 2 or 3, preferably 0, and z is 0, 1 or 2,
• the crude product or product mixture is obtainable when - A) a halogen-functional organosilane of the general formula (IV)
• R groups are identical or different and R is hydrogen (H) or a linear or branched alkyl group having 1 to 4 C atoms, preferably H or n-butyl and z is 0, 1 or 2,
• the liquid phase thus obtained is converted into a crystallizer, it being possible optionally to add at least one nonpolar organic solvent, preferably toluene, and the crystallizer at a lower pressure stage than the preceding reaction stage or at Operating ambient pressure, ammonium halide or organic amine hydrohalide and crude product separates.
• at least one nonpolar organic solvent preferably toluene
• step - D) it is advantageously possible in a further step - D) to add to the resulting crude product or product mixture, optionally at least one nonpolar organic solvent, preferably toluene, to add an aqueous lye, to react, then to separate the aqueous from the organic phase, from remove any organic solvent present, preferably by distillation, and
• at least one nonpolar organic solvent preferably toluene
• halogen-functional organoalkoxysilane of the general formula (IV) it is possible, but not exclusively, to use 3-chloropropylmethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane or 3-chloropropylmethyldimethoxysilane.
• chloroalkylalkoxysilanes for example 3-chloropropyldiethylmethoxysilane or 3-chloropropylmethylpropylethoxysilane.
• an organic amine of the general formula (V) may be used, for example but not exclusively, methylamine, dimethylamine, ethylamine, diethylamine or propylamine.
• the residue from the salt separation of the aminosilane production process can be solid or liquid and preferably precipitates in a crystallization unit.
• the aminofunctional organosilane containing ammonium halides and / or amine hydrohalides, in particular a corresponding crude product or product mixture may advantageously be initially mixed, preferably with a substantially non-polar organic solvent, preferably selected from the series hexane, heptane, octane, cyclohexane, in particular toluene, and / or other non-polar solvents are added.
• the mixture with an aqueous liquor preferably a strong liquor having a pH of at least 12, more preferably 13 to 14, treated.
• the pH can be determined in a manner known to those skilled in the art, for. B. by means of pH paper.
• the lye used is preferably a NaOH or KOH liquor.
• the concentration of the aqueous liquor can be selected so that the aqueous phase reaches a pH of 12 after work-up. pH values above 12 are preferable.
• the volume of the aqueous phase can be determined by the amount of NaCl formed during the work-up, and usually depends on the free chloride content of the raw material.
• the mixture thus obtained is allowed to react with stirring for up to 30 minutes, preferably 10 seconds to 10 minutes, more preferably 15 seconds to 5 minutes, most preferably 20 seconds to 3 minutes, in particular 25 seconds to 1 minute.
• a heatable / coolable stirred tank with a conically tapered bottom including a bottom drain and viewing window.
• Boiler and stirrer are preferably made of a non-rusting material, such as stainless steel or enamelled steel.
• the aqueous phase usually contains the salt formed in the reaction in dissolved form, so the aqueous phase contains, for example, when using sodium hydroxide solution dissolved NaCl.
• the separated aqueous phase should additionally have a pH of at least 12.
• the organic phase can now be transferred into a further separation unit, for example into a distillation, or passed over a thin-film evaporator or via a short-path evaporator.
• the organic solvent preferably toluene, is removed, suitably by separation under reduced pressure.
• the organic phase obtainable by the process according to the invention can also be subjected to fine distillation so as to obtain the respective individual constituents of the organic phase obtained according to the invention.
• the liquid phase thus obtained can now be converted into a crystallizer, wherein in the crystal I isator an organic or organosilicon liquid or a mixture of said liquids, preferably toluene or hexane, heptane, octane, cyclohexane or a mixture thereof, presents and the crystal isator operates at a lower pressure level than the previous reaction stage.
• an organic or organosilicon liquid or a mixture of said liquids preferably toluene or hexane, heptane, octane, cyclohexane or a mixture thereof.
• the crystal isator operates at a lower pressure level than the previous reaction stage.
• the residual quantities of ammonia or organic amine are distilled off, if appropriate additionally by temperature-controlled energy supply.
• the crystallizer can also be cooled.
• the resulting here in the crystallizer ammonium halide or organic amine hydrohalide salt containing can now be separated from the crude product, for example by filtration, and the pure aminofunctional organosilane from the crude product advantageously win by aqueous workup.
• the pure product one can additionally one optionally carry out fractional distillation, which can be operated under atmospheric pressure or under reduced pressure.
• fractional distillation which can be operated under atmospheric pressure or under reduced pressure.
• you can work up the resulting residue also and thus to obtain a bis- and tris-amino-functional composition in a simple and economical way by adding said residue to a substantially non-polar organic solvent and a strong, aqueous alkali, mixes and reacts.
• the aqueous, salt-containing phase can be separated off from the organic phase and the solvent removed from the organic phase, preferably under reduced pressure.
• it is also possible to filter the organic phase remaining in the bottoms cf German patent application 10 2008 002 183.0 "Process for working up saline-containing residues from the preparation of amino-functional organosilanes").
• Such in a simple and economical manner worked up aminosilane can advantageously as a primer, as a component in coating systems, as a component in paints and coatings, as a drilling aid, as an agent or as an additive in the extraction and extraction of petroleum, as for example from WO 05/124100 WO 05/1 24099, US Pat. No. 4,498,538, US Pat. No.
• the present invention also provides the use of an aminosilane according to the invention for the aforementioned applications.
• Silver nitrate 0.01 mol / l or 0.005 mol / l, calibration solution, prepared by diluting the solution of 6.4,
• sample is placed in a 150 ml beaker and mixed with 20 ml of ethanol and 80 ml of acetic acid. Then it is titrated potentiographically with silver nitrate solution.
• the Titroprocessor is programmed so that the mass fraction of chloride in mg / kg is printed directly after the titration.
• V ⁇ consumption of AgNO 3 solution in ml
• V BI determined reactive consumption of AgNO 3 solution in ml
• the organic phase was freed of toluene at 89 to 95 mbar and 57 to 65 0 C on a rotary evaporator. Subsequently, the product was distilled at 3 mbar and 126 0 C.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=40791459

Family Applications (1)

Country Status (8)

Families Citing this family (10)

Citations (2)

Family Cites Families (24)

• 2008
  • 2008-06-03 DE DE102008002181A patent/DE102008002181A1/de not_active Withdrawn
• 2009
  • 2009-04-09 EP EP09757352.1A patent/EP2291385B1/de not_active Not-in-force
  • 2009-04-09 JP JP2011512043A patent/JP5627572B2/ja not_active Expired - Fee Related
  • 2009-04-09 KR KR1020107027075A patent/KR101588913B1/ko not_active Expired - Fee Related
  • 2009-04-09 ES ES09757352.1T patent/ES2524313T3/es active Active
  • 2009-04-09 US US12/988,637 patent/US20110046405A1/en not_active Abandoned
  • 2009-04-09 WO PCT/EP2009/054282 patent/WO2009146969A1/de not_active Ceased
  • 2009-06-02 CN CN200910141345.8A patent/CN101597300B/zh not_active Expired - Fee Related

Patent Citations (2)

Also Published As

Similar Documents

Legal Events