WO1993004109A1 - Compositions de copolymeres de polyetherimidesiloxane renfermant un homopolymere de polyetherimide a fort ecoulement a l'etat fondu - Google Patents

Compositions de copolymeres de polyetherimidesiloxane renfermant un homopolymere de polyetherimide a fort ecoulement a l'etat fondu Download PDF

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Publication number
WO1993004109A1
WO1993004109A1 PCT/US1991/006100 US9106100W WO9304109A1 WO 1993004109 A1 WO1993004109 A1 WO 1993004109A1 US 9106100 W US9106100 W US 9106100W WO 9304109 A1 WO9304109 A1 WO 9304109A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyetherimide
composition
melt flow
formula
radicals
Prior art date
Application number
PCT/US1991/006100
Other languages
English (en)
Inventor
Norman Eugene Durfee, Jr.
John Andrew Rock
Original Assignee
General Electric 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 General Electric Company filed Critical General Electric Company
Priority to JP91514765A priority Critical patent/JPH05506475A/ja
Priority to PCT/US1991/006100 priority patent/WO1993004109A1/fr
Priority to EP91915465A priority patent/EP0554263A1/fr
Publication of WO1993004109A1 publication Critical patent/WO1993004109A1/fr
Priority to KR1019930701240A priority patent/KR930702423A/ko

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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to polyetherimide homopolymer siloxane polyetherimide copolymer blends, and more particularly relates to siloxane polyetherimide compositions containing a small amount of high melt flow polyetherimide homopolymer.
  • U.S. patent application 092,940 filed September 4, 1987; and EP 266595 corresponding to U.S. patent application 925,916 filed November 3, 1986.
  • Male, et. al., U.S. patent application 092,940 discloses blends comprising (i) a polyetherimide (ii) a siloxane polyetherimide copolymer and a perfluorocarbon, and discloses that the siloxane polyetherimide copolymer is employed in an impact strength enhancing concentration; for example, from about 2% to about 90% by weight of the blend, and that the perfluorocarbon polymer is employed in a flammability-retarding amount, typically from about 0.2% by weight to 20% by weight of the polymer blend.
  • EP 266915 published May 11, 1988 and U.S. patent application 925,916 filed November 3, 1986, disclose blends comprising (i) a polyetherimide and ( ⁇ ) a siloxane polyetherimide copolymer in an impact strength enhancing concentration, for example from about 2% to about 90% by weight of the blend. While the foregoing discloses improving the impact strength of polyetherimide compositions, there is a need to improve the impact strength and tensile elongation of siloxane-polyetherimide copolymer compositions. Accordingly, one object of the present invention is to provide siloxane-polyetherimide compositions exhibiting improved levels of impact strength and tensile elongation.
  • the present invention involves polyetherimide- siloxane copolymer compositions containing small amounts of high melt flow polyetherimide homopolymer to improve the impact strength and tensile elongation of the composition.
  • the composition is useful as a molding resin for making molded articles, wire coatings and extruded parts.
  • the polyetherimide resin has a relatively high melt flow which is preferably at least 15 g/10 min., more preferably between 15 and
  • the siloxane polyetherimide copolymers employed in the blends of this invention may be prepared in a manner similar to that used for polyetherimides, except that a portion or all of the organic diamine reactant is replaced by an amine-ter inated organosiloxane of the formula: (I)
  • n and m independently are integers from 1 to about 10, preferably from 1 to about 5, most preferably about 3, and g is an integer from 1 to about 40, preferably from about 5 to about 25, and most preferably from 8 to 12.
  • siloxane polyetherimide copolymers employed in the compositions of the present invention are referred to as late addition siloxane polyetherimide copolymers which are made by first reacting the organic diamine of formula XII with excess bis(ether anhydride) and to form anhydride terminated oligo ers and then reacting the amine-terminated organosiloxane of formula I.
  • the diamine component of the siloxane polyetherimide copolymers generally contains from about 20 to 50 mole % of the amine-terminated organosiloxane of formula I and from about 50 to 80 mole % of the organic diamine of formula XII. In preferred copolymers, the diamine component contains from about 25 to about 40 mole %, most preferably about 35 to 40 mole % of the amine-terminated organosiloxane.
  • polyetherimides used for preparing the blends of this invention contain repeating groups of the formula: (II)
  • a is an integer greater than 1, e.g., from 10 to 10,000 or more; T is — 0 — or a group of the formula:
  • Z is a member of the class consisting of (A):
  • X is a member selected from the group consisting of divalent radicals of the formulas:
  • R is a divalent organic radical selected from the group consisting of (a) aromatic hydrocarbon radicals having from 6 to about 20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals having from 2 to about 20 carbon atoms, cycloalkylene radicals having from 3 to about 20 carbon atoms, and (c) divalent radicals of the general formula:
  • the polyetherimide may be a copolymer which, in addition to the etheri ide units described above, further contains polyimide repeating units of the formula:
  • R is as previously defined and M is selected from the group consisting of:
  • polyetherimides can be prepared by any of the methods well known to those skilled in the art, including the reaction of the aromatic bis(ether anhydride) of the formula:
  • T and R are defined as described above.
  • Bis(ether anhydride)s of formula XI include, for example, 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride; 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride; and 1,4-bis(3,4-d carboxyphenoxy)benzene dianhydride; 4,4'-bis(phthalic anhydride)ether.
  • a preferred class of aromatic bis (ether anhydride)s included by formula XI includes compounds of formula XIII, XIV, and XV, which follow:
  • Y is selected from the group consisting of — 0 —, — S —,
  • Aromatic bis(ether anhydride)s of formula XIII include, for example:
  • Aromatic bis(ether anhydride)s of formul a XIV i ncl ude for example: 2,2-bis(4-(2,3-dicarboxyphenoxy)phenyl)propane di nhydride;
  • aromatic bis(ether anhydride)s of formula XV may be, for example,
  • a dianhydride such as pyromellitic anhydride
  • bis(ether anhydride) is used in combination with the bis(ether anhydride).
  • the bis(ether anhydride)s of formula XI are shown in U.S. Patent No. 3,972,902 (Darrell Heath and Joseph Wirth).
  • the bis(ether anhydride)s can be prepared by the hydrolysis, followed by dehydration, of the reaction product of a nitrosubstituted pheny! dinitrile with a metal salt of dihydric phenol compound in the presence of a dipolar, aprotic solvent.
  • the organic diamines of formula XII include, for example: m-phenylenediamine (MPD), p-phenylenediamine, 4,4'-diaminodipheny1propane,
  • N-methyl-bis(3-aminopropyl )amine N-methyl-bis(3-aminopropyl )amine, hexamethylenediamine, heptamethylenediamine, nonamethylenediamine, decamethylenediamine, and mixtures of such diamines.
  • Both the polyetherimides and the siloxane polyetherimide copolymers used in the blends of this invention may be prepared by any of the procedures conventionally used for preparing polyetherimides. A presently preferred method of preparation is described in U.S. Patent No. 4,417,044, which is incorporated herein by reference.
  • Blending the polyetherimide resin with the polyetherimide-siloxane copolymer in the amounts of the present invention provides a blend which is primarily polyetherimide-siloxane copolymer but which exhibits certain improved properties over either the polyether-siloxane copolymer or polyetherimide resin alone.
  • the blends may contain other materials, such as fillers. additives, reinforcing agents, pigments and the like. These blends exhibit very low flammabilities.
  • the polyetherimide resin is employed in the present blends in small amounts which enhance the impact strength and tensile elongation of the composition.
  • concentration of the polyetherimide homopolymer can range from 1% to 10% by weight based on the total weight of the composition, more preferably from 2.5% to 7.5% by weight thereof, and most preferably from 5% to 7.5% by weight thereof; preferably the polyetherimide-siloxane copolymer is present at a level of from 99.0% to 90% by weight of the composition, more preferably from 97.5% to 92.5% by weight thereof, and most preferably from 92.5% to
  • Examples A, B, C, D and E are comparative examples.
  • Example A is 100% by weight of a polyetherimidesiloxane copolymer
  • Example B is 100% by weight of a polyetherimide.
  • Examples 1, 2, 3, 4, 5 and 6 illustrate the enhanced properties obtained by blending a small amount of a relatively high melt flow polyetherimide with a relatively large amount of a late addition polyetherimide- siloxane.
  • the amine terminated organosiloxane (ATO) was present at a level of about 40 mole percent based on the total moles of amine terminated organosiloxane and organic diamine.
  • the moles of BPADA employed was substantially equal to the combined moles of MPD and ATO.
  • PEI for examples for 1 to 4 is a polyetherimide made by reacting BPADA, MPD and having a melt flow value of 20 g/10 min.
  • TS Tensile strength in pounds per square inch as determined according to ASTM D638.
  • TE Tensile elongation in % as determined according to ASTM D638.
  • NI Notched Izod in ft-lb/in as determined according to ASTM D256.
  • MI Melt index in g/10 min as determined according to ASTM D1238 modified by using a weight of 6700 grams at a temperature of 343.3°C (650°F).
  • the above LA PEI/Si is a late addition polyetherimide siloxane made by first reacting excess BPA dianhydride with meta phenylene diamine to form anhydride terminated oligo ers and then reacting silicone diamine (wherein g is 9) therewith to form late addition polyetherimidesiloxanes.
  • the PEI is the reaction product of BPA dianhydride and metaphenylene diamine having an MI of 20 g/10 min.
  • Note example -3 provides the highest tensile elongation and notched Izod values.
  • the values set forth for example B (Melt Flow between 16 to 20 g/10 min) are not the actual values but are the typical values for the type of PEI employed in examples 1 to 4.
  • the PEI/Si was the late addition polyetherimide siloxane of Table 1.
  • the PEI's of examples C, 5 and 6 had different melt flow values.
  • the PEI's of C, 5 and 6 are made by reacting MPD with BPADA.
  • the PEI of E and B is the reaction product of BPADA and MPD.

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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)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Compositions de copolymères de polyetherimide siloxane contenant des quantités d'un homopolymère de polyetherimide à fort écoulement à l'état fondu. Ces compositions présentent des indices améliorés de résistance à la flexion par choc et d'allongement à la traction. Ces compositions sont utiles pour fabriquer des articles moulés.
PCT/US1991/006100 1991-08-27 1991-08-27 Compositions de copolymeres de polyetherimidesiloxane renfermant un homopolymere de polyetherimide a fort ecoulement a l'etat fondu WO1993004109A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP91514765A JPH05506475A (ja) 1991-08-27 1991-08-27 高メルトフローのポリエーテルイミドホモポリマーを含むポリエーテルイミドシロキサン共重合体組成物
PCT/US1991/006100 WO1993004109A1 (fr) 1991-08-27 1991-08-27 Compositions de copolymeres de polyetherimidesiloxane renfermant un homopolymere de polyetherimide a fort ecoulement a l'etat fondu
EP91915465A EP0554263A1 (fr) 1991-08-27 1991-08-27 Compositions de copolymeres de polyetherimidesiloxane renfermant un homopolymere de polyetherimide a fort ecoulement a l'etat fondu
KR1019930701240A KR930702423A (ko) 1991-08-27 1993-04-26 고용융 유동 폴리에테르이미드 단독중합체를 함유한 폴리에테르이미드실록산 공중합체 조성물

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1991/006100 WO1993004109A1 (fr) 1991-08-27 1991-08-27 Compositions de copolymeres de polyetherimidesiloxane renfermant un homopolymere de polyetherimide a fort ecoulement a l'etat fondu

Publications (1)

Publication Number Publication Date
WO1993004109A1 true WO1993004109A1 (fr) 1993-03-04

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EP (1) EP0554263A1 (fr)
JP (1) JPH05506475A (fr)
KR (1) KR930702423A (fr)
WO (1) WO1993004109A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0955339A1 (fr) * 1998-05-06 1999-11-10 Eilentropp Kg Composition extrudable non-halogénée à partir de polymère de polyétherimide
US9243118B2 (en) 2012-06-07 2016-01-26 Sabic Global Technologies B.V. High modulus high strength high flow OSU compliant polyetherimide-carbon fiber composites for metal replacement
WO2016089583A1 (fr) * 2014-12-02 2016-06-09 Sabic Global Technologies B.V. Compositions de polyétherimide-siloxane à indice de fluidité à l'état fondu élevé, leur procédé de production, et articles fabriqués à partir de celles-ci
US10240030B2 (en) 2014-12-02 2019-03-26 Sabic Global Technologies B.V. Article comprising a high flow polyetherimide composition
EP3663367A1 (fr) * 2018-12-05 2020-06-10 SABIC Global Technologies B.V. Filament de type c ur-écorce, procédé de formation d'un filament de type c ur-écorce, procédé de formation d'un article par fabrication de filaments fusionnés et article ainsi formé

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4120780B2 (ja) * 2002-07-19 2008-07-16 信越化学工業株式会社 フェノール性水酸基を有するポリイミド樹脂の製造方法
JP4737447B2 (ja) * 2007-06-01 2011-08-03 信越化学工業株式会社 フェノール性水酸基を有するポリイミド樹脂及びポリイミド樹脂組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0266595A2 (fr) * 1986-11-03 1988-05-11 General Electric Company Compositions de résines de polyétherimide résistantes au feu
EP0307670A1 (fr) * 1987-09-04 1989-03-22 General Electric Company Mélanges ignifugés de polyétherimide et de copolymère siloxane-polyétherimide
EP0417513A1 (fr) * 1989-09-11 1991-03-20 General Electric Company Mélanges résistant à la flamme de polyéthérimide et de copolymères de siloxane-polyéthérimide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011279A (en) * 1975-09-23 1977-03-08 General Electric Company Process for making polyimide-polydiorganosiloxane block polymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0266595A2 (fr) * 1986-11-03 1988-05-11 General Electric Company Compositions de résines de polyétherimide résistantes au feu
EP0307670A1 (fr) * 1987-09-04 1989-03-22 General Electric Company Mélanges ignifugés de polyétherimide et de copolymère siloxane-polyétherimide
EP0417513A1 (fr) * 1989-09-11 1991-03-20 General Electric Company Mélanges résistant à la flamme de polyéthérimide et de copolymères de siloxane-polyéthérimide

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0955339A1 (fr) * 1998-05-06 1999-11-10 Eilentropp Kg Composition extrudable non-halogénée à partir de polymère de polyétherimide
US9243118B2 (en) 2012-06-07 2016-01-26 Sabic Global Technologies B.V. High modulus high strength high flow OSU compliant polyetherimide-carbon fiber composites for metal replacement
WO2016089583A1 (fr) * 2014-12-02 2016-06-09 Sabic Global Technologies B.V. Compositions de polyétherimide-siloxane à indice de fluidité à l'état fondu élevé, leur procédé de production, et articles fabriqués à partir de celles-ci
US10240030B2 (en) 2014-12-02 2019-03-26 Sabic Global Technologies B.V. Article comprising a high flow polyetherimide composition
EP3663367A1 (fr) * 2018-12-05 2020-06-10 SABIC Global Technologies B.V. Filament de type c ur-écorce, procédé de formation d'un filament de type c ur-écorce, procédé de formation d'un article par fabrication de filaments fusionnés et article ainsi formé
KR20200069229A (ko) * 2018-12-05 2020-06-16 사빅 글로벌 테크놀러지스 비.브이. 코어-쉘 필라멘트, 코어-쉘 필라멘트의 형성방법, 융합 필라멘트 제조에 의한 물품 제조방법 및 그에 의해 형성된 물품
KR102166965B1 (ko) 2018-12-05 2020-10-19 사빅 글로벌 테크놀러지스 비.브이. 코어-쉘 필라멘트, 코어-쉘 필라멘트의 형성방법, 융합 필라멘트 제조에 의한 물품 제조방법 및 그에 의해 형성된 물품

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Publication number Publication date
EP0554263A1 (fr) 1993-08-11
KR930702423A (ko) 1993-09-09
JPH05506475A (ja) 1993-09-22

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