[go: up one dir, main page]

WO1992014780A1 - Copolymers stabilises de monoxyde de carbone et d'olefine - Google Patents

Copolymers stabilises de monoxyde de carbone et d'olefine Download PDF

Info

Publication number
WO1992014780A1
WO1992014780A1 PCT/US1992/001308 US9201308W WO9214780A1 WO 1992014780 A1 WO1992014780 A1 WO 1992014780A1 US 9201308 W US9201308 W US 9201308W WO 9214780 A1 WO9214780 A1 WO 9214780A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyketone
epoxy
polyketone composition
stabilizing
composition
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.)
Ceased
Application number
PCT/US1992/001308
Other languages
English (en)
Inventor
Andrzej M. Piotrowski
Norbert A. Langwald
Theodore A. Marolewski
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.)
Akzo NV
Original Assignee
Akzo NV
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 Akzo NV filed Critical Akzo NV
Publication of WO1992014780A1 publication Critical patent/WO1992014780A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups

Definitions

  • Copoly ers of carbon monoxide and an olefin commonly termed a "polyketone",' are a well-recognized class of copolymers synthesized through copoly erization of carbon monoxide with one or more olefins in the presence of a suitable catalyst.
  • the present invention resides in the use of a blend of an amine compound and an epoxy compound as the stabilizing agent for the aforementioned class of polyketone.
  • such polymers will have a molecular weight of anywhere from about 1,000 to about 1,000,000, preferably about 50,000 to about 250,000. They can be formed by polymerizing the appropriate monomers (i.e. carbon monoxide and the selected olefin or olefins) in the presence of a catalytic amount of a catalyst formed from a compound of a Group VIII metal, an anion of a non- hydrohalogenic acid, and a bidentate ligand of phosphorus, arsenic or antimony.
  • the appropriate monomers i.e. carbon monoxide and the selected olefin or olefins
  • the above- referenced polymers have intimately mixed therewith a suitable stabilizing quantity of a blend of an amine compound and an epoxy compound.
  • the amine compound which can be used herein needs to have at least one amine functionality (i.e., organic compounds derived from ammonia by replacement of one or more hydrogen atoms by alkyl, aryl, etc., groups as described in greater detail below) which will not react with the polyketone, e.g., by forming a Schiff base with the polyketone.
  • Monoa ines and polyamines are contemplated for use herein. If a polyamine is chosen, the chosen polyamine needs to be one in which the multiple amine functionalities do not cause crosslinking of the polyketone.
  • Aromatic amines which can be used in accordance with the present invention may contain from one, or two, or three aromatic structures, from about 6 to about 50 carbon atoms inclusive, and at least one a ino group.
  • HN(Ar-R) 2 where Ar is selected from phenyl and naphthyl and R is hydrogen or alkyl are .'preferred.
  • Representative amines of this type include VANLUBE 848 mixed octylated diphenylamine and diphenylamine and VANLUBE 81 p,p'-dioctyldiphenylamine, both available from R.. T. Vanderbilt Company Inc. Also included is IRGANOX LQ6, an alkylated phenyl naphthylamine from Ciba-Geigy.
  • Aliphatic amines which can be used include the primary and secondary amines containing bulky hindering substituents (such as branched groups, including t-butyl) , and the tertiary amines.
  • the epoxy compound stabilizer component which can be used with the aforementioned aromatic amine compound include the type of epoxy compounds described in U.S. Patent No. 3,948,832 at Col. 2, lines 20 to 47 inclusive, which is incorporated herein by reference.
  • Representative compounds are organic compounds (e.g., aliphatic, including cycloaliphatic, or aromatic which contain one or more epoxy groups.
  • One particularly preferred epoxy is an epoxy cycloaliphatic carboxylate, such as (3' ,4'-epoxycyclohexylmethyl) 3,4- epoxycyclohexanecarboxylate.
  • both the amine and epoxy compounds chosen have a relatively low vapor pressure so that they will be retained in the po ⁇ yketone during high temperature processing or use of such compositions.
  • the amounts of the stabilizer blend that are used in accordance with the present invention can range anywhere from about 1%, by weight, up to about 25%, by weight of the polyketone. Preferable amounts range from about 5% to about 15%, by weight, of the polyketone. Generally, it is advisable to choose an amount of .stabilizer at the lower portions of the above given ranges in order to avoid adversely affecting the mechanical properties of the resulting polyketone.
  • the weight ratio of aromatic amine compound to epoxy compound in the stabilizer blend can range anywhere from about 1:5 to about 5:1.
  • the stabilizer blend of this invention is preferably added to the polyketone by blending when the polyketone is in the form of a powder or dissolved in a solvent.
  • the method of incorporation is not believed to be critical although it is preferred that a homogeneous mixture of polyketone and stabilizer blend be achieved.
  • Other additives such as fillers, extenders, plasticizers, coloring agents, other polymeric materials, etc. , can be added to the polyketone being stabilized.
  • the resulting stabilized polyketone compositions exhibit improved thermal stability and can be processed for extended periods of time at elevated temperatures with an enhanced degree of stability.
  • Typical methods of processing include injection molding, pressure forming, thermoforming and sheet extrusion.
  • the materials can be used in applications where such polyketones are likely to encounter elevated temperatures including the thermoforming of food or drink containers, the production of shaped automotive parts by injection molding, or the production of wire and cable coatings by extrusion.
  • a CO/C 2 H 4 polyketone copolymer or CO/C 2 H 4 /C 3 H 6 polyketone terpolymer was suspended in hot acetylacetone. The suspension was stirred for fifteen minutes at 120°C and was quickly filtered without cooling. The polymer was then washed with cold acetylacetone followed by washing with acetone and vacuum drying.
  • the CO/C 2 H 4 copolymer or CO/C 2 H 4 /C 3 H 6 terpolymer after catalyst residue removal was then added to an acetone solution of a modifier or modifier blend described hereinafter and was dried with constant stirring to achieve good sample uniformity. Samples were then pressed into pellets which were then placed in the preheated testing chamber of a RHEOMETRICS RMS 800 rheometer.
  • the rheometer is capable of measuring both components of complex viscosity (eta*) , namely, the real (or loss) component (eta'), which can be correlated to the contribution of the viscous behavior of the material, and the imaginary (or storage)' component (eta”) , which can be correlated to the contribution of the elastic behavior.
  • ERL - ERL4221 stabilizer: (3' ,4'-Epoxycyclohexylmethyl)3,4- epoxycyclohexanecarboxylate.
  • VL848 - VANLUBE 848 stabilizer: Mixed octylated diphenylamine and diphenylamine ( ⁇ 7%) .
  • VL81 - VANLUBE 81 stabilizer: p,p'-dioctyldiphenylamine.
  • ERL - ERL4221 stabilizer: (3' , 4'-EpoxycyclohexyImethy1) 3 ; 4- epoxycyclohexanecarboxylate.
  • VL848 - VANLUBE 848 stabilizer: Mixed octylated diphenylamine and diphenylamine ( ⁇ 7%) .
  • L06 - Irganox L06 stabilizer An alkylated phenyl naphthylamine.
  • ERL - ERL4221 stabilizer: (3',4'-Epoxycyclohexylmethyl)3,4- epoxycyclohexanecarboxylate.
  • VLSI - VANLUBE 81 stabilizer: p,p'-dioctyldiphenylamine.

Landscapes

  • 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

Des compositions de polycétone peuvent être stabilisées par l'addition, en une quantité propice à la stabilisation, d'un mélange d'un composé d'amine aromatique, tel qu'une amine aromatique (par exemple, une diphénylamine alkylée ou une naphtylamine de phényle alkylée) et, un composé époxy (tel qu'un carboxylate cycloaliphatique époxy).
PCT/US1992/001308 1991-02-19 1992-02-18 Copolymers stabilises de monoxyde de carbone et d'olefine Ceased WO1992014780A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US65759091A 1991-02-19 1991-02-19
US657,590 1991-02-19

Publications (1)

Publication Number Publication Date
WO1992014780A1 true WO1992014780A1 (fr) 1992-09-03

Family

ID=24637841

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/001308 Ceased WO1992014780A1 (fr) 1991-02-19 1992-02-18 Copolymers stabilises de monoxyde de carbone et d'olefine

Country Status (1)

Country Link
WO (1) WO1992014780A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997030112A1 (fr) * 1996-02-15 1997-08-21 Ciba Specialty Chemicals Holding Inc. Stabilisation de produits de recyclage de polyolefines
WO1999048980A1 (fr) * 1998-03-24 1999-09-30 Shell Internationale Research Maatschappij B.V. Compositions liantes a base de resines thermodurcissables, leur preparation et leur utilisation comme materiaux de revetement
GB2348430A (en) * 1999-03-29 2000-10-04 Bp Chem Int Ltd Process for drying polyketones
US6235750B1 (en) 1996-12-06 2001-05-22 Pfizer Inc 6-phenylpyridyl-2-amine derivatives useful as NOS inhibitors

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948832A (en) * 1974-09-25 1976-04-06 Atlantic Richfield Company Stabilized ethylene-carbon monoxide copolymers containing an epoxy compound
US4795774A (en) * 1987-10-05 1989-01-03 Shell Oil Company Polyketone stabilization
US4954548A (en) * 1989-04-27 1990-09-04 Shell Oil Company Ethylene-carbon monoxide copolymer stabilization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948832A (en) * 1974-09-25 1976-04-06 Atlantic Richfield Company Stabilized ethylene-carbon monoxide copolymers containing an epoxy compound
US4795774A (en) * 1987-10-05 1989-01-03 Shell Oil Company Polyketone stabilization
US4954548A (en) * 1989-04-27 1990-09-04 Shell Oil Company Ethylene-carbon monoxide copolymer stabilization

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997030112A1 (fr) * 1996-02-15 1997-08-21 Ciba Specialty Chemicals Holding Inc. Stabilisation de produits de recyclage de polyolefines
US6235750B1 (en) 1996-12-06 2001-05-22 Pfizer Inc 6-phenylpyridyl-2-amine derivatives useful as NOS inhibitors
WO1999048980A1 (fr) * 1998-03-24 1999-09-30 Shell Internationale Research Maatschappij B.V. Compositions liantes a base de resines thermodurcissables, leur preparation et leur utilisation comme materiaux de revetement
US6309527B1 (en) 1998-03-24 2001-10-30 Antonius Augustinus Broekhuis Thermosetting resinous binder compositions, their preparation and use as coating materials
GB2348430A (en) * 1999-03-29 2000-10-04 Bp Chem Int Ltd Process for drying polyketones

Similar Documents

Publication Publication Date Title
JP5325792B2 (ja) 静電気拡散性ポリアセタール組成物
KR0122076B1 (ko) 힌더 페놀 및 아민 산화방지제 혼합물을 포함하는 폴리에틸렌의 안정화 조성물
EP1129133A1 (fr) Resines thermoplastiques stabilisees par des melanges de phenols, d'amines secondaires et de thioethers steriquement entraves
US4795774A (en) Polyketone stabilization
EP3593363A1 (fr) Composition de gaine de fil et de câble de résine de base copolymère pa6/66 pour une aptitude au traitement et des propriétés améliorées
WO1992014780A1 (fr) Copolymers stabilises de monoxyde de carbone et d'olefine
JPH0762095B2 (ja) 少なくとも５００，０００ｇ／モルの平均分子量を有するポリエチレンを基体とする成形用組成物
WO2000059993A1 (fr) Resines polyacetaliques presentant une odeur de formaldehyde reduite
AU606258B2 (en) Copolymer composition
US5021496A (en) Filled polyketone blend
US5371127A (en) Stabilized carbon monoxide-olefin copolymers
US4954548A (en) Ethylene-carbon monoxide copolymer stabilization
US5266629A (en) Polyketone containing graphite nucleating agent
EP0328714B1 (fr) Composition à base de copolymère oxyméthylène stabilisé
US20250051562A1 (en) Polyoxymethylene compositions
EP4006093A1 (fr) Composition de gel de silicone durcissable de type à emballage unique et gel de silicone durci
EP0125888B1 (fr) Masses à mouler à base de téréphtalate de polybutylène
US4992499A (en) Stabilized ethylene monoxide copolymers
US5115009A (en) Polyketone polymer compositions containing a polar ester or amine lubricating compound
JPS6020408B2 (ja) 安定化したプロピレン系重合体組成物
US5508329A (en) Stabilized polyketone composition
US5115003A (en) Stabilized polyketone compositions containing a mixture of a hydroxyapatite and a mercaptobenzimidazole
US5079285A (en) Stabilized compositions
EP0395183B1 (fr) Compositions de polymères de polycétones
FI96037B (fi) Dispergoitu hiukkasmainen koostumus

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

NENP Non-entry into the national phase

Ref country code: CA