US3505285A - Stabilised polyamides containing a copper salt and a phosphine - Google Patents

Stabilised polyamides containing a copper salt and a phosphine Download PDF

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Publication number
US3505285A
US3505285A US576831A US3505285DA US3505285A US 3505285 A US3505285 A US 3505285A US 576831 A US576831 A US 576831A US 3505285D A US3505285D A US 3505285DA US 3505285 A US3505285 A US 3505285A
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Prior art keywords
phosphine
polyamide
iodide
copper
weight
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US576831A
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English (en)
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Karl-Heinz Hermann
Hans Rudolph
Werner Daum
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Bayer AG
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Bayer AG
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only

Definitions

  • This invention relates to stabilised polyamides using copper compounds as stabilisers.
  • Mouldings of polyamdes obtained by polymerising diamines with dicarboxylic acids or from aminocarboxylic acids or their lactarns; for example filaments, bristles or films, are deteriorated by the action of air and oxygen, particularly at elevated temperatures, to such an extent that their relative viscosity decreases whilst their strength and elasticity deteriorate. At the same time, the polyamide becomes progressively browner in colour.
  • the known stabilisers have the disadvantage either that their stabilising action is too weak, as is the case, for example, with manganese salts, phosphorus compounds and phenols, or the disadvantage that they cause discolouration, particularly when they are added to the polyamide-forming starting mixture before polymerisation, as is the case for example with copper salts, or that they are sensitive to light and, over a period of time, discolour the polyamide, as is the case for example with aromatic amines and phenols.
  • polyamides can be stabilised without the aforementioned disadvantages by using, as the stabiliser, a combination of (a) a salt of monovalent or bivalent copper with an inorganic or organic acid, and (b) aphosphine.
  • a further object of this invention is to combine the stabilising mixture consisting of a copper salt and a phosphine with an inorganic or organic salt of hydriodic acid.
  • the more difficulty volatile compounds from the triaryl-, trialkylor tri-(aryl-alkyD-phosphine series are preferably used in accordance with the invention as the phosphines.
  • phosphines are triphenyl phosphine, tris-(dimethylaminophenyl)-phosphine, tritolyl phosphine, phenyldimethyl phosphine, dimethylarninophenyl-dimethyl phosphine, naphthyl diethyl phosphine, tributyl phosphine, tripentyl phosphine, trioctyl phosphine,
  • Preferred copper salts are the cupric and cuprous salts of hydrohalic acids and hydrocyanic acid, and the copper salts of aliphatic carboxylic acids.
  • Suitable copper salts are cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cupric chloride, cupric acetate and cupric stearate.
  • the copper salts are preferably added in such a quantity that the polyamide contains 0.0001 to 0.1% by weight, most preferably 0.001 to 0.02% by weight, of copper.
  • the phosphorus compounds are preferably added in such a quantity that the polyamide contains 0.001 to 0.1% by weight, most preferably 0.001 to 0.05% by weight, of phosphorus.
  • Ammonium iodide sodium iodide, potassium iodide, calcium iodide, magnesium iodide, zinc iodide or cadmium iodide.
  • Hydriodides of primary amines such as hexadecylamine hydriodide; hexamethylene diamine dihydriodide and cyclohexylamine hydriodide.
  • Hydriodides of secondary amines such as N-ethylbenzylamine hydriodide; piperidine hydriodide and N- methyloctadecylamine hydriodide.
  • Hydriodides of tertiary amines such as N,N- dimethylbenzene-amine hydriodide; N,N,N-triethanolaminehydriodide; pyridine hydriodide; trioctadecylaminehydriodide and N,N-dimethyldodecylamine hydriodide.
  • Iodides of quaternary ammonium compounds such as N-benzyl-N,N,N-trimethylammonium iodide; N-ethyl- N-benzyl-N,N-diethylammonium iodide; N-dodecyl-N,N, N-triethyl-ammonium iodide and N,N,N,N',N,N-hexamethyl-N,N-ethylene-bis-ammonium iodide.
  • Hydriodides of aminocarboxylic acid esters and amides such as N,N-dimethyl-6-aminocaproic acidmorpholide hydriodide; N,N dimethyl 6 aminocaproic acid dodecylamide hydriodide; N-methyl-N-cyclohexyl-6- aminocaproic acid ethyl ester hydriodide and N,N-dimethyl-1l-aminoundec-anic acid anilaide hydriodide.
  • Iodides of carbamylamrnonium compounds such as N- (N-dodecylcarbamylpentyl) N,N,N trimethylammonium iodide and N-(N'-3,4-dichlorophenylcarbamylpentyl) -N,N,N-trimethylammonium iodide.
  • the inorganic or organic salts of hydriodic acid are preferably added in such quantity that the polyamide contains 0.001 to 5% by weight, most preferably 0.01 to 1.0% by weight, of iodine.
  • the combinations according to the invention of copper salts and phosphorus compounds can be either mixtures of the components, or stable, crystallised addition compounds of phosphines and substances correspond ing to the formula CuX, in which X represents chlorine, bromine, iodine or cyanogen.
  • X represents chlorine, bromine, iodine or cyanogen.
  • Example of these addition compounds which can be obtained from the components, optionally at elevated temperature, are CuC1 2 triphenyl phosphine, CuBr 2 triphenyl phosphine, CuI tri-nbutylphosphine, CuI .tri-n-pentylphosphine, Cul X 2 triphenyl phosphine and CuCNXtriphenyl phosphine.
  • the stabiliser combinations according to the invention may be added to the polyamide-forming starting mixture before polymerisation, after which polymerisation may be carried out either continuously or in batches, as known per se, Without there being any discolouration of the polyamide melt.
  • the polyamides may also contain the usual additives such as pigments, dyes, light stabilisers, fillers such as glass fibres, lubricants, mould-release agents and crystallisation activators.
  • polyamides stabilised in accordance with the invention against, in particular, damage by oxidation at elevated temperatures are eminently suitable for the production of industrial silk for fishing nets, drive belts, conveyor belts, tyre cord and mouldings exposed to thermal stressing in the presence of air or oxygen.
  • the advantages set out below can be obtained by using copper compounds in combination with phosphines, optionally together with inorganic or organic salts of hydriodic acid. These advantages can be explained by the chemical resistance of the phosphines to hydrolysing or decomposing agents, and by the fact that secondary reactions involving the products of hydrolysis or decomposition are avoided.
  • EXAMPLE 1 A mixture of 1.1 kg. of caprolactam, 35 g. of aminocaproic acid and 0.79 g. of CuCI 2 triphenyl phosphine (corresponding to 0.008% by weight of copper and 0.008% by weight of phosphorus in the end product), is polycondensed in the usual way in an auto clave at a temperature of 270 C. The resulting polyamide is then spun into a filament, chapped into granular form, freed from monomeric components by boiling with water and then dried. The resulting product is completely colourless and has a relative viscosity of 3.12 (measured on a 1% by Weight solution in m-cresol). In order to test the stability of the product to atmospheric oxidation, it is stored at 150 C. in a drying cabinet to which air has free access. After 144 hours, its relative viscosity is 3.46, after 500 hours it is 3.16 and after 1000 hours it is 2.96.
  • EXAMPLE 2 As in Example 1, a polyamide with a relative viscosity of 3.18 is prepared from 0.30 g. of Cu(II)Cl 2I-l O (corresponding to 0.011% by weight of copper in the end product) and 0.52 g. of tripheuyl phosphine (corresponding to 0.006% by weight of phosphorus in the end product). The product is completely colourless. After it has been stored at 150 C. in a drying cabinet to which air has free access, its relative viscosity is 3.48 after 144 hours, 3.09 after 500 hours and 2.94 after 1000 hours. A polyamide prepared under identical conditions, except that only 0.30 g. of Cu(II)Cl 2H O are added, is greenish in colour.
  • EXAMPLE 3 2 kg. of polycaprolactam with a relative viscosity of 3.15 are fused by means of a conventional screw extruder EXAMPLE 4 As in Example 3, a polyamide with a relative viscosity of 3.01 is prepared from 0.35 g. of Cu(II)-acetate H O (corresponding to 0.006% by weight of copper) and 0.44 g. of diphenyl ethyl phosphine (corresponding to 0.003% phosphorus). The product is completely colourless. After it has been stored at C in a drying cabinet to which air has free access, its relative viscosity is 3.24 after 144 hours, 3.05 after 500 hours and 2.92 after 1000 hours. A polyamide prepared under identical conditions, except that only 0.35 g. to Cu(-II)-acetate were added, is slightly greyish-green in colour.
  • a deep blue-grey coloured polyamide is obtained from 0.50 g. of Cu(I)-I- triisopropyl phosphite (corresponding to 0.008% by weight of copper and 0.004% by weight of phosphorus in the end product).
  • a deep-blue-grey coloured polyamide is obtained from 0.32 g. of Ou(II)- Cl .2H O (corresponding to 0.012% by weight of copper in the end product) and 1.24 g. of trinonylphenyl phos phite (corresponding to 0.006% by weight of phosphorus in the end product).
  • Triphenyl phosphine on its own does not have any stabilising effect on polyamides. This is demonstrated by the following comparison test:
  • EXAMPLE 5 1 kg. of a conventionally prepared colourless polycaprolactam with a relative viscosity of 3.12 (measured on a 1% by weight solution in m-cresol), is fused by means of a conventional screw extruder in which it is homogeneously mixed "with various stabilisers. The stabilised polycaprolactam is spun itno a filament of approx. 3 mm. diameter, chopped into granular form and dried. The granulate is then stored at 150 C. in a drying cabinet to which air has free access, and its relative viscosity measured after 144, 500 and 1000 hours.
  • ammonium iodide 9 "do 1. 57 0. 056 .do 1. 26 0. 011 0. 011 do 3. 05 3. 81 3. 48 3. 12 10 N-ethyl-N-benzyl-N,N- 1.28 0.056 bib(10 1.26 0.011 0.011 do 3.06 3.82 3.55 3,38
  • ammonium hydroiodide g N,N41imethyl-fi-amino-caproie 2.01 0.056 .d0 1.26 0.011 0,011 Do.
  • a thermally stabilised polyamide comprising a high molecular weight polyamide and as stabilising agents admixed therewith (a) a copper salt selected from the group consisting of a chloride, bromide, iodide, cyanide, and a salt of an aliphatic carboxylic acid of monovalent and bivalent copper, and (b) a tertiary phosphine, said copper salt being present in such a quantity that the polyamide contains 0.0001 to 0.1% by weight of copper, said phosphine being present in such a quantity that the polyamide contains 0.001 to 0.1% by weight of phosphorus.
  • a thermally stabilised polyamide comprising a high molecular weight polyamide and as stabilising agents admixed therewith (a) a copper salt selected from the group consisting of a chloride, bromide, iodide, cyanide, and a salt of an aliphatic carboxylic acid of monovalent and bivalent copper, (b) a phosphine, and (c) a salt of hydroiodic acid selected from the group consisting of ammonium iodide, sodium iodide, potassium iodide, calcium iodide, magnesium iodide, zinc iodide, cadmium iodide, 21 hydroiodide of a primary amine, a hydroiodide of a sec- 5 wherein said salt of hydriodic acid is potassium iodide.
  • a copper salt selected from the group consisting of a chloride, bromide, iodide, cyanide, and a salt of an
  • thermoly stabilised polyamide of claim 2 wherin said salt of hydriodic acid is N,N-dimethyldodecy1- amine hydroiodide.

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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)
  • Polyamides (AREA)
US576831A 1965-09-11 1966-09-02 Stabilised polyamides containing a copper salt and a phosphine Expired - Lifetime US3505285A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEF47169A DE1237309B (de) 1965-09-11 1965-09-11 Verfahren zur Herstellung waermestabilisierter Polyamide
DEF48224A DE1245591B (de) 1965-09-11 1966-01-21 Verfahren zur Herstellung stabilisierter Polyamide

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US (1) US3505285A (id)
AT (1) AT259873B (id)
BE (1) BE686692A (id)
CH (1) CH472458A (id)
DE (2) DE1237309B (id)
DK (1) DK116244B (id)
ES (1) ES331089A1 (id)
GB (1) GB1084699A (id)
NL (1) NL6612672A (id)
NO (1) NO115681B (id)
SE (1) SE301382B (id)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3666717A (en) * 1969-04-15 1972-05-30 Ici Ltd Polyamides stabilized with a phosphine
US4043972A (en) * 1975-10-06 1977-08-23 Phillips Fibers Corporation Stabilizing polyamide antistatic compositions
US4937276A (en) * 1987-05-22 1990-06-26 Bayer Aktiengesellschaft Glass-fiber-reinforced stabilized polyamide molding compositions
US5686513A (en) * 1996-09-09 1997-11-11 Zimmer Aktiengesellschaft Process for the production of stabilizer concentrate for polyamide
US6011099A (en) * 1996-04-19 2000-01-04 Basf Aktiengesellschaft Oxidation-stabilized polyamide molding materials
WO2017174949A1 (fr) 2016-04-08 2017-10-12 Arkema France Composition à base de polyamide pour des tuyaux contenant du pétrole ou du gaz
WO2017174948A1 (fr) 2016-04-08 2017-10-12 Arkema France Composition de polymère thermoplastique et stabilisant a base de cuivre, sa préparation et ses utilisations
WO2018220105A1 (fr) 2017-06-02 2018-12-06 Arkema France Composition à base de polyamide pour des tuyaux de liquide de refroidissement
WO2020249899A1 (fr) 2019-06-11 2020-12-17 Arkema France Compositions de polyamide presentant un module eleve et une faible constante dielectrique et leur utilisation
WO2021191547A1 (fr) 2020-03-24 2021-09-30 Arkema France Compositions a mouler renforcees avec des fibres de verre ayant des proprietes choc ameliorees
WO2021250352A1 (fr) 2020-06-10 2021-12-16 Arkema France Compositions de polyamide presentant un module eleve et une faible constante dielectrique et leur utilisation
WO2023275463A1 (fr) 2021-06-28 2023-01-05 Arkema France Compositions de soufflage moulage a base de polyamides branches et leurs utilisations
WO2023275464A1 (fr) 2021-06-28 2023-01-05 Arkema France Compositions de soufflage moulage a base de polyamides branches et leurs utilisations
WO2023049161A1 (en) * 2021-09-21 2023-03-30 Ascend Performance Materials Operations Llc Stabilizing component for polyamide resin composition

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3666675A (en) * 1970-01-21 1972-05-30 Univ Temple Method for producing luminescence using complex luminescent materials
US3806487A (en) * 1972-07-03 1974-04-23 Monsanto Co Stabilization of pigmented nylon against actinic radiation
DE3917294A1 (de) † 1989-05-27 1990-11-29 Huels Chemische Werke Ag Mit laserlicht beschriftbare hochpolymere materialien
DE4020447A1 (de) * 1990-06-27 1992-01-02 Bayer Ag Stabilisatorkombinationen und ihre verwendung zur herstellung von stabilisierten, schlagzaehmodifizierten polyamiden

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2510777A (en) * 1946-12-30 1950-06-06 Du Pont Polyamide treated with a hypophosphorous acid compound
US2705227A (en) * 1954-03-15 1955-03-29 Du Pont Heat stabilization of polyamides
GB839067A (en) * 1957-04-11 1960-06-29 Inventa Ag Improvements relating to the production of objects from synthetic linear polyamide
GB864701A (en) * 1958-07-18 1961-04-06 Ici Ltd Improved polyamide resins
US3428597A (en) * 1965-02-02 1969-02-18 Stamicarbon Stabilization of polyamides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1152816B (de) * 1962-01-27 1963-08-14 Basf Ag Verfahren zum Herstellen von stabilisierten Polyamiden

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2510777A (en) * 1946-12-30 1950-06-06 Du Pont Polyamide treated with a hypophosphorous acid compound
US2705227A (en) * 1954-03-15 1955-03-29 Du Pont Heat stabilization of polyamides
GB839067A (en) * 1957-04-11 1960-06-29 Inventa Ag Improvements relating to the production of objects from synthetic linear polyamide
GB864701A (en) * 1958-07-18 1961-04-06 Ici Ltd Improved polyamide resins
US3428597A (en) * 1965-02-02 1969-02-18 Stamicarbon Stabilization of polyamides

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3666717A (en) * 1969-04-15 1972-05-30 Ici Ltd Polyamides stabilized with a phosphine
US4043972A (en) * 1975-10-06 1977-08-23 Phillips Fibers Corporation Stabilizing polyamide antistatic compositions
US4937276A (en) * 1987-05-22 1990-06-26 Bayer Aktiengesellschaft Glass-fiber-reinforced stabilized polyamide molding compositions
US6011099A (en) * 1996-04-19 2000-01-04 Basf Aktiengesellschaft Oxidation-stabilized polyamide molding materials
US5686513A (en) * 1996-09-09 1997-11-11 Zimmer Aktiengesellschaft Process for the production of stabilizer concentrate for polyamide
WO2017174949A1 (fr) 2016-04-08 2017-10-12 Arkema France Composition à base de polyamide pour des tuyaux contenant du pétrole ou du gaz
WO2017174948A1 (fr) 2016-04-08 2017-10-12 Arkema France Composition de polymère thermoplastique et stabilisant a base de cuivre, sa préparation et ses utilisations
WO2018220105A1 (fr) 2017-06-02 2018-12-06 Arkema France Composition à base de polyamide pour des tuyaux de liquide de refroidissement
WO2020249899A1 (fr) 2019-06-11 2020-12-17 Arkema France Compositions de polyamide presentant un module eleve et une faible constante dielectrique et leur utilisation
FR3097226A1 (fr) 2019-06-11 2020-12-18 Arkema France Compositions de polyamide presentant un module eleve et une faible constante dielectrique et leur utilisation
WO2021191547A1 (fr) 2020-03-24 2021-09-30 Arkema France Compositions a mouler renforcees avec des fibres de verre ayant des proprietes choc ameliorees
FR3108615A1 (fr) 2020-03-24 2021-10-01 Arkema France Compositions a mouler renforcees avec des fibres de verre ayant des proprietes choc ameliorees
WO2021250352A1 (fr) 2020-06-10 2021-12-16 Arkema France Compositions de polyamide presentant un module eleve et une faible constante dielectrique et leur utilisation
FR3111351A1 (fr) 2020-06-10 2021-12-17 Arkema France Compositions de polyamide presentant un module eleve et une faible constante dielectrique et leur utilisation
WO2023275463A1 (fr) 2021-06-28 2023-01-05 Arkema France Compositions de soufflage moulage a base de polyamides branches et leurs utilisations
WO2023275464A1 (fr) 2021-06-28 2023-01-05 Arkema France Compositions de soufflage moulage a base de polyamides branches et leurs utilisations
WO2023049161A1 (en) * 2021-09-21 2023-03-30 Ascend Performance Materials Operations Llc Stabilizing component for polyamide resin composition

Also Published As

Publication number Publication date
DE1245591B (de) 1967-07-27
BE686692A (id) 1967-02-15
NO115681B (id) 1968-11-11
CH472458A (de) 1969-05-15
ES331089A1 (es) 1967-09-16
GB1084699A (en) 1967-09-27
NL6612672A (id) 1967-03-13
SE301382B (id) 1968-06-04
AT259873B (de) 1968-02-12
DK116244B (da) 1969-12-22
DE1237309B (de) 1967-03-23

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