EP0595850A1 - Alliage polymere de polyetherimides et de copolyesters a cristaux liquides - Google Patents

Alliage polymere de polyetherimides et de copolyesters a cristaux liquides

Info

Publication number
EP0595850A1
EP0595850A1 EP92914523A EP92914523A EP0595850A1 EP 0595850 A1 EP0595850 A1 EP 0595850A1 EP 92914523 A EP92914523 A EP 92914523A EP 92914523 A EP92914523 A EP 92914523A EP 0595850 A1 EP0595850 A1 EP 0595850A1
Authority
EP
European Patent Office
Prior art keywords
structural units
polymer alloy
polyetherimide
alloy according
carbon atoms
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP92914523A
Other languages
German (de)
English (en)
Inventor
Michael Römer
Andreas Schleicher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Publication of EP0595850A1 publication Critical patent/EP0595850A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3823—Polymers with mesogenic groups in the main chain containing heterocycles having at least one nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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

  • LCP liquid crystalline copolyesters
  • PEI polyetherimides
  • EP-A-209 391 discloses polymer alloys containing 5 to 60% by weight of a fibrous liquid-crystalline polyester obtained by melt spinning and 40 to 95% by weight of a thermoplastic, which can also be a polyetherimide.
  • the liquid crystalline copolyesters used in the only example of an LCP-PEI polymer alloy contain structural units derived from p-hydroxybenzoic acid, terephthalic and isophthalic acid and from dihydroxydiphenyl.
  • the LCP: PEI ratio is 30:70% by weight. If the proportion of the copolyester is more than 60% by weight, the processing of the products is unsatisfactory.
  • EP-A-278 066 describes polymer alloys made from polyetherimides and liquid-crystalline copolyesters, which structural units are derived from dihydroxyphenyl or diphenyl and dicarboxyphenyl or diphenyl and, if appropriate, from hydroxyphenyl or hydroxydiphenylmonocarboxylic acid or structural units are derived from 2-hydroxynaphthyl-6-carboxylic acid and 4-hydroxybenzoic acid contain.
  • Polymer alloys whose LCP content is more than 50% by weight could not be used to produce injection molded articles suitable for physical tests.
  • Polymer alloys with an LCP content of 5 to 50% by weight are characterized by higher tensile modulus of elasticity than pure PEI, however the mechanical properties such as elongation at break and impact resistance are still in need of improvement.
  • EP-A-291 323 describes polymer alloys composed of polyetherimides and liquid-crystalline copolyesters which contain 6-oxy-2-naphthoyl and 4-oxybenzoyl structural units.
  • the LCP content can be 35 to 95% by weight or the PEI content 65 to 5% by weight.
  • the physical properties are improved compared to LCP-PEI polymer alloys according to the prior art; The elongations at break achieved are unsatisfactory and therefore still in need of improvement.
  • the object of the invention is therefore to provide polymer alloys made from liquid-crystalline copolyesters or copolyesteramides and polyetherimides with improved mechanical properties with respect to elongation at break and impact strength and improved heat resistance.
  • the invention relates to polymer alloys containing at least one fully aromatic, liquid-crystalline copolyester (A) and at least one polyetherimide (B), characterized in that the liquid-crystalline copolyester (A) has structural units of the formula I.
  • T is selected from hydrogen, an alkyl radical with 1 to 4 C atoms, an alkoxy radical with 1 to 4 C atoms or a halogen
  • M is selected from hydrogen, an alkyl radical with 1 to 4 carbon atoms, an aryl radical with 6 to 10 C atoms, an alkylaryl radical with 6 to 10 C atoms or a halogen
  • the structural units can independently of one another contain identical or different radicals T or M
  • the proportion of copolyester (A) in the polymer alloy 50 to 98 wt .-% and the proportion of polyetherimide (B) is 2 to 50 wt .-%, so that the proportions of (A) and (
  • the liquid-crystalline copolyesters (A) have anisotropic melts and have average molar masses (weight average) of 2,000 to 20,000, preferably from 3,500 to 50,000, in particular from 4,000 to 30,000 g / mol.
  • the proportion of structural units of the formula I or of the formulas I and II in the copolyester (A) is 30 to 90 mol% and the sum of the structural units of the formulas III to VI is 10 to 70 mol%, the proportions totaling 100 Add mol%.
  • copolyesters (A) which are composed of structural units of the formulas I, II, III and V, the proportion of structural units of the formula I 15 to 1 mol% and that of the formula II 50 to 79 Mol%, the formula III is 20 to 10 mol% and the formula V 20 to 10 mol%.
  • copolyesters (A) are those with structural units of the formulas I and VI, the proportion of structural units of the formula I being 40 to 80 mol% and of structural units of the formula VI being 60 to 20 mol%.
  • copolyesters (A) are prepared by polycondensation according to known methods, which are described, for example, in US Pat. Nos. 4,161,470 and 3,637,595.
  • Polyetherimides (B) suitable for the polymer alloys according to the invention have structural units of the formula VII
  • _ is an integer multiple of 1, especially 10 - 10,000, the group -O-A for
  • R 'equal to hydrogen, halogen, C. -C ⁇ alkyl or alkoxy, -Z- is a double-bonded structural unit selected from
  • -R 1 is C 1 -C 4 alkyl, preferably methyl, CC 4 alkoxy, preferably methoxy, or halogen, preferably bromine
  • r is zero or an integer 1, 2, 3 or 4 and the radicals are -R 1 and the indices r can be the same or different
  • -D- a group selected from -C n H 2n -, preferably - C (CH 3 ) 2 - or -CH 2 -, -SO-, -S0 2 -, - CO-, -O-, -S-, -C (CF 3 ) 2 - and n is an integer from 1 to 5 and -B- is a double-bonded structural unit selected from one unsubstituted or substituted by CC 4 alkyl, C.-C ⁇ alkoxy or halogen Cs-Ca j -aryl radical, C 2 -C 20 -alkylene or cycloalkylene, C 2 -C 8
  • Polyetherimides (B) with structural units of the following formula are preferably used:
  • bonds of the -O-Z-O structural units can be in the 3,3'-, 3,4'-, 4,3'- or 4,4'-position.
  • Z is preferably Z3, in particular
  • B is preferably selected from m-phenylene is particularly preferred.
  • Particularly preferred polyetherimides (B) are those with structural units of the formula:
  • Such polyetherimides are commercially available, for example from the General Electric Company in unreinforced and glass and mineral reinforced form as ® Ultem.
  • polyetherimides are prepared by known methods, for example by reaction of aromatic bis (ether anhydrides) and organic diamines, which are described in detail in US Pat. Nos. 3,847,867, 3,847,869, 3,850,885, US -A-3 852 242, US-A-3 855 178, US-A-4 417 044 and EP-A-0 330 739.
  • Polyimides (B) with structural units of the following formulas are also suitable for the polymer alloys according to the invention:
  • R 2 is C 1 -C 6 -alkyl, such as methyl, ethyl, the various isomers of propyl, butyl, pentyl or hexyl, or halogen
  • R 3 is 0, S, CO, SO, S0 2 , alkylene each having 1 to 9 carbon atoms, for example methylene, ethylene, propylene or butylene, alkylidene each having 1 to 6 carbon atoms, for example ethylidene, isopropylidene, propylidene or isobutylidene, cycloalkylene or cycloaikylidene each having 4 to 9 carbon atoms and the Index h denotes integers zero, 1, 2, 3 or 4, or ( ⁇ ) a radical of the general formula
  • R 4 has the meaning of a substituted or unsubstituted aromatic radical of the formulas mentioned in (a) and (ß) and the index h has the meaning given above, "E" for
  • R 5 is independently hydrogen, alkyl having 1 to 6 carbon atoms, such as methyl, ethyl, the various isomers of propyl, butyl, pentyls or hexyls or alkoxy having 1 to 6 carbon atoms, for example methoxy, ethoxy or butoxy, and the index i stands for integers zero, 1, 2 or 3 and the index j stands for integers zero, 1 or 2.
  • Preferred polyimides of the invention are those with the following structural units:
  • Particularly preferred polyimides (B) are those with the following structural units:
  • polyimides can also be synthesized by known methods, which are described, for example, in “Polyimides - Materials, Chemistry and Characterization” (Elsevier, 1989) and in “Polyimides” (Consultants Bureau, 1987).
  • polyetherimides includes homopolymers and copolymers, such as multipolymers or block polymers.
  • the Staudinger indices of the polyetherimides used are 0.1-3 dl / g, preferably 0.3-1.5 dl / g, and particularly preferably 0.3-1 dl / g, measured at 25 ° C., for example in N-methylpyrrolidone or Methyl chloride.
  • the proportion of liquid-crystalline copolyesters (A) is preferably 55 to 95% by weight, in particular 75 to 95% by weight, and the proportion of polyetherimides (B) is preferably 45 to 5% by weight, in particular 25 to 5% by weight.
  • the polymer alloys according to the invention are produced and processed by known methods for thermoplastics at temperatures optimized for the respective material, such as. B. by extrusion or injection molding.
  • the polymer alloys according to the invention can contain additives, for example plasticizers, thermal stabilizers, UV stabilizers, impact modifiers or reinforcing additives such as glass, carbon, ceramic, mineral or high-modulus fibers.
  • additives for example plasticizers, thermal stabilizers, UV stabilizers, impact modifiers or reinforcing additives such as glass, carbon, ceramic, mineral or high-modulus fibers.
  • the polymer alloys according to the invention can be used particularly advantageously as matrix materials for composite materials. They are also suitable for the production of moldings by the injection molding or extrusion process, for example in the form of fibers, films, lacquers and hoses.
  • the polymer alloys according to the invention have a variety of uses, for example as plug connections, electrical insulation in transformers, capacitors, cable and wire jackets, including glass fiber jackets in the electronics industry, the automotive and aerospace industries.
  • liquid-crystalline copolyesteramide (LCP) A1 contains structural units of the formula
  • LCP A1 is available, for example, as Vectra B950 from Hoechst Celanese Corporation.
  • liquid-crystalline copolyester (LCP) A2 contains structural units of the formula
  • the proportion of the oxynaphthoyl structural units is 4 mol%
  • the proportion of the oxybenzoyl structural units is 60 mol%
  • the proportion of the bisoxydiphenylene structural units is 18 mol%
  • the proportion of the terephthaloyl structural units is 18 mol%.
  • LCP A2 is available, for example, as Vectra E950 from Hoechst Celanese Corporation.
  • the polyetherimide (PEI) B1 contains structural units of the formula
  • PEI B1 is available as Ultem from General Electric.
  • the polymers used for the alloys were first dried at 150 ° C. for 2-4 hours and after mixing in an LSM 30.34 GL extruder from Leistritz, Nuremberg, under protective gas (nitrogen) at temperatures of 310-330 ° C. (LCPA1 / PEIB1) or 330 - 360 ° C (LCPA2 / PEIB1) extruded and then granulated.
  • the temperatures given here refer to the temperature profile from the feed to the extruder nozzle.
  • the granules obtained were dried for 4 hours at 150 ° C. and injection molded into molded parts such as shoulder sticks, plates, etc. and examined for physical properties.
  • a machine from Zwick, Ulm was used for tensile and strain tests to determine the tensile strength, elongation at break according to DIN 53455 and the tensile modulus of elasticity according to DIN 53457.
  • the bending stresses, the edge fiber elongation according to DIN 53452 and the bending modulus of elasticity according to DIN 53457 were determined with a bending stretching machine from Zwick, Ulm. Furthermore, the heat resistance (HDT) was determined according to DIN 53 461 method A.
  • samples of pure polyetherimide or pure copolyester were produced under the optimal conditions for the respective polymer.
  • Table 1 gives an overview of the mechanical and thermal properties of the polymer alloys and their individual components.
  • the LCP A2 / PEI B1 blends show an excellent elongation at break, which is comparable to the elongation at break of pure LCP A2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Un alliage polymère renferme 2 à 50 % en poids d'au moins un poly-étherimide et 50 à 98 % en poids d'au moins un copolyester à cristaux liquides, entièrement aromatique, dérivé de l'acide 2-hydroxy-6-naphtoïque ou de l'acide p-hydroxybenzoïque, et présente en outre des motifs structuraux d'un acide hydroxybenzoïque ou hydroxydiphénylcarboxylique, d'un acide aminocarboxylique aromatique et/ou d'un composé bishydroxy aromatique conjointement avec un acide dicarboxylique aromatique.
EP92914523A 1991-07-25 1992-07-08 Alliage polymere de polyetherimides et de copolyesters a cristaux liquides Withdrawn EP0595850A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4124602 1991-07-25
DE4124602 1991-07-25
PCT/EP1992/001539 WO1993002144A1 (fr) 1991-07-25 1992-07-08 Alliage polymere de polyetherimides et de copolyesters a cristaux liquides

Publications (1)

Publication Number Publication Date
EP0595850A1 true EP0595850A1 (fr) 1994-05-11

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Country Status (3)

Country Link
EP (1) EP0595850A1 (fr)
JP (1) JPH06504315A (fr)
WO (1) WO1993002144A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5633319A (en) * 1996-01-16 1997-05-27 General Electric Company Compatibilized blends of polyetherimides and liquid crystalline polyesters
CN101508897B (zh) * 2009-03-11 2011-11-09 中山大学 新型可纺性热致液晶聚酯酰亚胺及其合成方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4871817A (en) * 1986-12-31 1989-10-03 General Electric Company Polyetherimide-liquid crystal polymer blends
JPS6474259A (en) * 1987-09-12 1989-03-20 Mitsui Petrochemical Ind Wholly aromatic polyester composition
JPH0788027B2 (ja) * 1989-10-26 1995-09-27 ポリプラスチックス株式会社 回路形成用２色成形品
JP2535666B2 (ja) * 1989-11-30 1996-09-18 三井東圧化学株式会社 ポリイミド系樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9302144A1 *

Also Published As

Publication number Publication date
JPH06504315A (ja) 1994-05-19
WO1993002144A1 (fr) 1993-02-04

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