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WO1993006171A1 - Melanges polymeres de dicarboxymides de norbornene - Google Patents

Melanges polymeres de dicarboxymides de norbornene Download PDF

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Publication number
WO1993006171A1
WO1993006171A1 PCT/US1992/007953 US9207953W WO9306171A1 WO 1993006171 A1 WO1993006171 A1 WO 1993006171A1 US 9207953 W US9207953 W US 9207953W WO 9306171 A1 WO9306171 A1 WO 9306171A1
Authority
WO
WIPO (PCT)
Prior art keywords
norbornene
polymer
monomer units
polymer blend
acid
Prior art date
Application number
PCT/US1992/007953
Other languages
English (en)
Inventor
Jawed Asrar
Peter Malcom Goman
Original Assignee
Monsanto Company
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 Monsanto Company filed Critical Monsanto Company
Publication of WO1993006171A1 publication Critical patent/WO1993006171A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • thermoplastics 15 typically characterized as semicrystalline thermoplastics and are widely used in a wide range of applications. Due to high strength polyamides are commonly and advantageously used as tire cord, carpet fiber, tough fabrics, etc. However, due to other
  • polyamides have limited use in other engineering thermoplastic applications. For instance, due to low impact strength, polyamides often require toughening, e.g. with rubber impact modifier, to provide sufficient impact strength required of many
  • Polyamides also typically have unsatisfactory load bearing properties at moderate to high temperatures due to the low glass transition temperature of the polyamide. Heat distortion temperature determined under the force of a load
  • HDTUL High-modified polyamides, having high impact strengths that commend their use for many engineering thermoplastic
  • Metathesis ring-opening polymers of norbornene * dicarboximides especially the N-methyl, N-ethyl, N-propyl and N-phenyl i ides, exhibit high glass transition temperatures, e.g. about 200 °C, and high HDTUL, e.g. about 150 to 180 °C.
  • high glass transition temperatures e.g. about 200 °C
  • high HDTUL e.g. about 150 to 180 °C.
  • metathesis ring-opening polymers of norbornene dicarboximides can be effectively blended with polyamides to provide blends having the attendant advantageous properties of polyamides but with an exceptionally high heat distortion temperature. Even more advantageous blends - are achieved when the metathesis ring-opened unsaturated polymer of norbornene dicarboximide includes a small amount of an acid containing species.
  • this invention provides . polymer blends comprising a metathesis ring-opening polymerized unsaturated polymer of norbornene dicarboximide and a polyamide or other polymer having acid-reactive functionality.
  • this invention provides polymer blends comprising a metathesis ring-opening polymerized unsaturated copolymer of monomer units of norbornene dicarboximide and a norbornene carboxylic acid.
  • Such copolymer can be used alone in blends with acid-reactive polymers or, alternatively, as a compatibilizer in blends of norbornene dicarboximide polymer and acid-reactive polymers.
  • the polymer blends of this invention comprise polymers having acid-reactive functionality such as polyamides and metathesis ring-opening polymerized unsaturated polymers of a norbornene dicarboximide, e.g. about 10 to 90 parts by weight of polymer having acid-reactive functionality and, conversely, about 90 to 10 parts by weight of metathesis ring-opening polymerized unsaturated polymer. More preferred blends, depending on the desired properties, can comprise at least about 30 parts by weight of each polymer.
  • Preferred polymers having acid-reactive functionality include polyamides having amine end groups such as nylon-6 or nylon-6,6 and, optionally, toughened polyamides, e.g. having 5 rubber toughening agents.
  • Other useful acid-reactive functional polymers include polyesters having hydroxyl end groups.
  • the norbornene dicarboximide of the metathesis ring-opening polymerized polymers can be
  • alkyl, cycloalkyl or aromatic i ides 10. alkyl, cycloalkyl or aromatic i ides.
  • Polymers having advantageously high glass transition temperatures, e.g. above 150 °C, and preferably above 200 ⁇ C, include polymers and copolymers comprising monomer units of N-methyl, N-ethyl, N-propyl, N-isopropyl,
  • Such polymers can be prepared by known methods for metathesis ring-opening polymerization of norbornene derivative monomers which provide unsaturated polymer. Especially preferred methods are disclosed by Hardiman 0 in WIPO International Publication Number WO 91/18938.
  • the metathesis ring- opening polymerized polymer comprises a copolymer of a norbornene derivative monomer having acid functionality that allows reactive interaction with . 5 polymers having acid-reactive functionality.
  • Preferred metathesis ring-opening polymerized unsaturated copolymers comprise monomer units of norbornene dicarboximide and a norbornene carboxylic acid or ester.
  • the 0 norbornene carboxylic acid will comprise a dicarboxylic acid or the acid anhydride, mono ester or diester thereof.
  • copolymer will generally 5 comprise less than about 10 mole percent of the acid monomer units, e.g. about 0.5 to 3 mole percent of acid monomer units.
  • compatibilizer copolymers can readily be prepared from mixtures of monomer using metathesis ring-opening polymerization methods generally useful for norbornene derivative monomers.
  • the acid-functional copolymers of this invention can be used by themselves in blends with polymers having acid-reactive functionality, e.g. to provide blends of copolymer and polyamide.
  • the acid-functional copolymers of this - invention can be used as additives to compatibilize blends of norbornene dicarboximide polymer and polymers having acid-reactive functionality, e.g. blends of poly(N-methyl norbornene dicarboximide) and nylon-6.
  • the compatibilization of such blends is facilitated in that the.low level of acid functiorrality provides reactive compatibilization with the polyamide and the structural similarity provides miscibility compatibilization with the norbornene dicarboximide polymer.
  • a polymer of N-methyl norbornene dicarboximide monomer units was prepared by dissolving 4.5 kilograms of N-methyl norbornene dicarboximide in 9.9 kilograms of toluene at 65 °C. After adding 38.5 ml of hexene-1, a molecular weight controlling agent, to the agitated solution, polymerization was effected by adding 114.5 ml of a catalyst solution (0.5 M tungsten hexachloride and 1.5 M diethylacetal of formaldehyde in toluene) and 214 ml of diethyl aluminum chloride. The exothermic metathesis ring- opening polymerization raised the solution temperature to 105 °C in about 20 minutes.
  • a catalyst solution 0.5 M tungsten hexachloride and 1.5 M diethylacetal of formaldehyde in toluene
  • the homopolymer was intimately blended with an equal parts by weight of an EPDM rubber-modified nylon-6,6 (Zytel ST-801 from DuPont) in a Braybender twin screw extruder having barrel and nozzle tempera ⁇ tures of about 300 °C and screw speed of 80-90 rpm. Samples for analysis were extruded through an Arburg molder at about 300 ⁇ C and 6900 kPa into molds at about 130 "C. Analytical results of the properties of each of the blend are reported in Table 1.
  • the polymers and blends were injection molded into specimen bars (127 X 12.7 X 3.2 mm) which were conditioned for at least 24 hours at 23 "C and 50% relative humidity.
  • HDTUL was measured according to ASTM D-648; tensile strength, tensile modulus and elongation were measured according to ASTM D-638; flexural strength and flexural modulus were measured according to ASTM D- 790; and notched Izod impact strength was measured according to ASTM D-256.
  • EXAMPLE 3 The polymerization of N-methyl norbornene dicarboximide was repeated essentially in the manner of Example 1 except that monomer solution contained about 2 percent norbornene dicarboxylic acid anhydride, providing an acid functionalized copoly(N- methyl norbornene dicarboximide/norbornene dicarboxylic anhydride) comprising about 1 percent monomer with acid functionality and having an inherent viscosity of 0.47, an HDTUL of 160 °C, Flexural strength of 140 MPa and flexural modulus of 3 GPa.
  • Equal parts of acid anhydride-modified copolymer were blended with equal parts of each of the following polymers: (a) nylon-6,6 (Vydyne 21 from

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Mélanges polymères comprenant: (a) un polymère insaturé polymérisé ouvrant un cycle de métathèse d'ensembles monomères de dicarboxymides de norbornène et/ou un copolymère insaturé ouvert au cycle de métathèse d'un ensemble monomère de dicarboxymides de norbornène et d'un ensemble monomère d'acides carboxiliques de norbornène et (b) un polymère possédant une fonctionnalité acido-réactive, par exemple un polyamide, tel que nylon-6 ou nylon-6,6. Les monomères de dicarboxymides de norbornène peuvent être des imides aromatiques ou des imides d'alkyle ou de cycloalkyle, de préférence des imides de méthyle, d'éthyle, de propyle, d'isopropyle, de cyclohéxyle ou de phényle. Les ensembles monomères préférés d'acides carboxyliques de norbornène sont des acides dicarboxyliques de norbornène, des anhydrides d'acide, des monoesters ou des diesters.
PCT/US1992/007953 1991-09-25 1992-09-22 Melanges polymeres de dicarboxymides de norbornene WO1993006171A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76529291A 1991-09-25 1991-09-25
US765,292 1991-09-25

Publications (1)

Publication Number Publication Date
WO1993006171A1 true WO1993006171A1 (fr) 1993-04-01

Family

ID=25073151

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/007953 WO1993006171A1 (fr) 1991-09-25 1992-09-22 Melanges polymeres de dicarboxymides de norbornene

Country Status (1)

Country Link
WO (1) WO1993006171A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395851B1 (en) 2000-06-09 2002-05-28 Eastman Chemical Company Copolymerization of norbornene and functional norbornene monomers
EP1553131A1 (fr) * 2004-01-09 2005-07-13 E.I. du Pont de Nemours and Company Compositions de polymères pour des matériaux perfectionnés
JP2009209324A (ja) * 2008-03-06 2009-09-17 Kuraray Co Ltd 酸素吸収性樹脂組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2249913A1 (fr) * 1973-11-05 1975-05-30 Showa Denko Kk
JPS5213548A (en) * 1975-07-22 1977-02-01 Showa Denko Kk Heat-resistant resin composition
EP0409291A2 (fr) * 1987-11-17 1991-01-23 Japan Synthetic Rubber Co., Ltd. Composition de résine thermoplastique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2249913A1 (fr) * 1973-11-05 1975-05-30 Showa Denko Kk
JPS5213548A (en) * 1975-07-22 1977-02-01 Showa Denko Kk Heat-resistant resin composition
EP0409291A2 (fr) * 1987-11-17 1991-01-23 Japan Synthetic Rubber Co., Ltd. Composition de résine thermoplastique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1, no. 54 (C-014)25 May 1977 & JP,A,52 013 548 ( SHOWA DENKO ) 2 January 1977 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395851B1 (en) 2000-06-09 2002-05-28 Eastman Chemical Company Copolymerization of norbornene and functional norbornene monomers
US6512065B2 (en) 2000-06-09 2003-01-28 Eastman Chemical Company Copolymers of norbornene and functional norbornene monomers
EP1553131A1 (fr) * 2004-01-09 2005-07-13 E.I. du Pont de Nemours and Company Compositions de polymères pour des matériaux perfectionnés
JP2009209324A (ja) * 2008-03-06 2009-09-17 Kuraray Co Ltd 酸素吸収性樹脂組成物

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