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WO2011089111A1 - Tétra-aminodisiloxanes et polyimides produits avec ceux-ci - Google Patents

Tétra-aminodisiloxanes et polyimides produits avec ceux-ci Download PDF

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Publication number
WO2011089111A1
WO2011089111A1 PCT/EP2011/050602 EP2011050602W WO2011089111A1 WO 2011089111 A1 WO2011089111 A1 WO 2011089111A1 EP 2011050602 W EP2011050602 W EP 2011050602W WO 2011089111 A1 WO2011089111 A1 WO 2011089111A1
Authority
WO
WIPO (PCT)
Prior art keywords
radicals
phenyl
group
linear
branched
Prior art date
Application number
PCT/EP2011/050602
Other languages
German (de)
English (en)
Inventor
Ricardo Chavez Medellin
Ralf Riedel
Andre Zimmermann
Emanuel Ionescu
Wilfried Aichele
Original Assignee
Robert Bosch Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Priority to EP11701067A priority Critical patent/EP2526108A1/fr
Publication of WO2011089111A1 publication Critical patent/WO2011089111A1/fr

Links

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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • 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
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety

Definitions

  • polyimides are known as special polymers for various applications which require very good temperature stability. They also have good mechanical properties and are chemically resistant and resistant to oxidation.
  • polyimides having high thermal resistance are prepared in two stages from an aromatic diamine and an aromatic dianhydride as a powder. In the first stage, the addition of the diamines with tetracarboxylic dianhydrides leads to polyamide-polycarboxylic acids which are soluble in dipolar aprotic solvents and in a second step cyclize with intramolecular dehydrogenation to give mostly insoluble polyimides.
  • thermoplastic processability of the polyimides depends strongly on two parameters: the structure of the polymer chains and the molecular weight.
  • polyimides especially homopolymeric polyimides
  • these polyimides have the disadvantage that they can not be processed as thermoplastics, because for polyimides with high molecular symmetry, the melting temperature is above its decomposition temperature. For this reason, thermoplastically processable materials are produced as copolymers.
  • the copolymer-based polyimides allow thermoplastic processing, but strict adherence to the stoichiometry of the starting materials is indispensable for a suitable property profile of the polymers. Therefore, the reaction conditions must be strictly controlled in order to reproducibly preserve the composition and the properties of the material. From a certain molecular weight, it is no longer possible, even in the case of the copolymers, to process these polyimides from the melt.
  • Item of the present invention is a tetraaminodisiloxane of the following formula (I)
  • R 1 R 2 identical or different, selected from the group of the linear, branched or cyclic alkyl radicals, alkenyl radicals, alkynyl radicals, aryl radicals, heteroaryl radicals,
  • R 3 , R 4 , R 5 , R 6, identically or differently, are selected from the group consisting of H, linear, branched or cyclic alkyl radicals, alkenyl radicals, alkynyl radicals, aryl radicals, heteroaryl radicals, halogens and pseudohalogens.
  • novel tetraaminodisiloxanes for the production of novel thermoplastic polyimide-based plastics with high thermal resistance, which can be processed by means of extrusion or injection molding.
  • the selection and provision of the new starting materials will influence the property profile of the Thermoplastics, in particular with respect to the mechanical and thermal properties allows.
  • thermoplastic polyimide-based plastics may have a melting temperature in the range of 300 ° C-400 ° C and a decomposition temperature above 400 ° C. Furthermore, these materials are resistant to solvents and oxidation.
  • the new tetraaminodisiloxanes and the polyimides obtainable from them fulfill the abovementioned property profile well. Furthermore, the tetraaminodisiloxanes have the advantage that they can synthesize polyimides as homopolymers with correspondingly preferred tetracarboxylic dianhydrides. Thus, the use of monofunctional end groups for thermoplastic processability of the polyimides is not needed. Deterioration of the mechanical properties due to remaining monofunctional monomers or oligomers occurring thereby is effectively prevented.
  • polyimides are prepared for the first time as so-called ladder polymers. In these are two linear molecular chains at defined intervals through
  • Si-O-Si "sprouts" are highly resistant due to their structure: if a chain strand breaks, the chain will still be held together by the second strand, especially with regard to high thermal stability in ladder polymers The reason for this is that chain-breaking occurs in normal thermoplastics, for example as a result of heat, which rapidly leads to a considerable deterioration of the mechanical properties linked chain strands are cleaved in one and the same place before it comes to a chain scission and thus to a molecular weight degradation, which leads to the deterioration of the mechanical properties.
  • each radical R 3 , R 4 , R 5 , R 6 also more than one Substituents of the corresponding phenyl ring selected from the group mentioned, represents.
  • the radicals R 1 and R 2 can be selected from the group of the linear or branched C 1 -C 20 -alkyl radicals, the C 1 -C 20 -aryl radicals and the C 1 -C 20 -heteroaryl radicals.
  • the amino groups can each be arranged in para or meta position to the disiloxane group.
  • R 1 and R 2 may be selected from the group of the phenyl and naphthyl radicals and the amino groups may be arranged in para and / or meta position to the disiloxane group.
  • tetraaminodislioxanes of the general formulas (I I) or (I I I) are preferably used for the preparation of polyimides with outstanding properties because of their structure:
  • the tetracarboxylic acid component b) can be selected from the group of benzene-1, 2,4,5-tetracarboxylic acid-1,2,2,5-dianhydride, 3,3 ', 4,4'-benzophenone tetracarbon - Acid dianhydride and 4,4'-oxybis (phthalic anhydride).
  • the tetraaminosiloxane component a) may furthermore preferably be selected from the group of para- and / or meta-tretraaminophenyl disiloxanes having the radicals R 1 , R 2 , identical or different, selected from the group of the linear or branched alkyl radicals, the aryl radicals and the heteroaryl radicals.
  • the radicals R 1 and R 2 are phenyl radicals.
  • a polyimide according to the invention may preferably be used for producing an injection-molded part, as a component in the engine compartment of a motor vehicle, as a bearing component or as an insulation material in the printing or electronics industry.
  • the polymers produced according to the invention can be used in particular as building materials for the manufacture of highly stressed thermal components in the engine compartment of motor vehicles such as seals or piston rings, and as a replacement for the commercial polymer "Vespe from DuPont, the used as sintered material for bearings.
  • 1 .4 Hydrolysis of chlorophenyl bis (4- (tert-butylcarbamate-N-yl) phenyl) silane and of chlorophenyl bis (3-firt-butylcarbamate-N-yl) phenyl) silane
  • Chlorophenyl bis (4- (ieri-butylcarbamate-N-yl) phenyl) silane and chlorophenyl bis (3- (ieri-butylcarbamate-N-yl) phenyl) silane were reacted with water at RT. Hydrolysis produces silanols which are converted into disiloxanes in a condensation step. Subsequently, the powder was washed three times with water and dried at 80 ° C.
  • v (crrf 1 ) 3600 (m, -NH 2 ); 3385 (s, -NH 2 ); 1430 (s, Si-C phenyl); 1 130 (s, Si-C phenyl); 1068 (see Si-O); 700 (s, Si-C phenyl).
  • the polyamic acid solution obtained under point 2.1 was heated at 150.degree. C. for 12 hours. Depending on the polyamic acid used, the polyimide precipitates out of solution or remains in the solution. When the polyimide precipitates out of solution, the resulting suspension was filtered, the solid product washed with water and then dried at 80 ° C. If the pro- If the product remains in the solution, it was precipitated by the addition of water and then subjected to a work-up as described above.
  • Decomposition temperature (° C) 443 (determined by TGA under Ar atmosphere)
  • Decomposition temperature (° C) 380 (determined by TGA under Ar atmosphere).
  • Decomposition temperature (° C) 350 (determined by TGA under Ar atmosphere).
  • Decomposition temperature (° C) 352 (determined by TGA under Ar atmosphere).
  • Decomposition temperature (° C) 347 (determined by TGA under Ar atmosphere).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne le tétra-aminodisiloxane de la formule (I) suivante dans laquelle R1 et R2 sont identiques ou différents et sont choisis dans le groupe des restes alkyle, restes alcényle, restes alcinyle, restes aryle, restes hétéroaryle linéaires, ramifiés ou cycliques, et R3, R4, R5 et R6 sont identiques ou différents et sont choisis dans le groupe H, des restes alkyle, restes alcényle, restes alcinyle, restes aryle, restes hétéroaryle, halogène et pseudohalogène linéaires, ramifiés ou cycliques, ainsi que des polyimides produits par utilisation dudit tétra-amino-disiloxane.
PCT/EP2011/050602 2010-01-21 2011-01-18 Tétra-aminodisiloxanes et polyimides produits avec ceux-ci WO2011089111A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11701067A EP2526108A1 (fr) 2010-01-21 2011-01-18 Tétra-aminodisiloxanes et polyimides produits avec ceux-ci

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010001071A DE102010001071A1 (de) 2010-01-21 2010-01-21 Tetraaminodisiloxane und damit hergestellte Polyamide
DE102010001071.5 2010-01-21

Publications (1)

Publication Number Publication Date
WO2011089111A1 true WO2011089111A1 (fr) 2011-07-28

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/050602 WO2011089111A1 (fr) 2010-01-21 2011-01-18 Tétra-aminodisiloxanes et polyimides produits avec ceux-ci

Country Status (3)

Country Link
EP (1) EP2526108A1 (fr)
DE (1) DE102010001071A1 (fr)
WO (1) WO2011089111A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9672989B2 (en) 2015-05-29 2017-06-06 Avx Corporation Solid electrolytic capacitor assembly for use in a humid atmosphere

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054426A2 (fr) * 1980-12-15 1982-06-23 M & T Chemicals, Inc. Siloxanes
US20050085612A1 (en) * 2002-02-14 2005-04-21 Oliver Schafer Aminomethylene-functional siloxanes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56111833A (en) * 1980-02-08 1981-09-03 Sharp Corp Liquid-crystal display element
US4520075A (en) * 1983-09-02 1985-05-28 Nitto Electric Industrial Co., Ltd. Siloxane-modified polyimide precursor and polyimide
CA1299801C (fr) * 1987-03-31 1992-04-28 Chung J. Lee Polyimidesiloxanes solubles; methode de preparation et utilisation
US5286890A (en) * 1992-04-16 1994-02-15 Hughes Aircraft Company Aromatic amine terminated silicone monomers, oligomers, and polymers therefrom
JPH073018A (ja) * 1993-06-14 1995-01-06 Toshiba Chem Corp ポリイミド樹脂
JP4192451B2 (ja) * 2001-09-14 2008-12-10 宇部興産株式会社 発泡ポリイミドおよびその製法
MY142246A (en) * 2003-06-10 2010-11-15 Hitachi Chemical Co Ltd Adhesive film and process for preparing the same as well as adhesive sheet and semiconductor device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054426A2 (fr) * 1980-12-15 1982-06-23 M & T Chemicals, Inc. Siloxanes
US20050085612A1 (en) * 2002-02-14 2005-04-21 Oliver Schafer Aminomethylene-functional siloxanes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
POLICASTRO P P ET AL: "CHAPTER 12: Siloxane Polyimides for Interlayer Dielectric Applications", ACS SYMPOSIUM SERIES, AMERICAN CHEMICAL SOCIETY/OXFORD UNIVERSITY PRESS, US, vol. 407, 5 September 1989 (1989-09-05), pages 140 - 151, XP009145445, ISSN: 0097-6156, DOI: DOI:10.1021/BK-1989-0407.CH012 *
YASUHARU YAMADA: "Siloxane Modified Polyimides for Microelectronics Coating Applications", HIGH PERFORMANCE POLYMERS, INSTITUTE OF PHYSICS PUBLISHING, BRISTOL, GB, vol. 10, 1 March 1998 (1998-03-01), pages 69 - 80, XP001525451, ISSN: 0954-0083 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9672989B2 (en) 2015-05-29 2017-06-06 Avx Corporation Solid electrolytic capacitor assembly for use in a humid atmosphere

Also Published As

Publication number Publication date
EP2526108A1 (fr) 2012-11-28
DE102010001071A1 (de) 2011-07-28

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