WO1999023154A1 - Resines thermoplastiques stabilisees par des melanges de dithiocarbamate et d'amines ou de phenols - Google Patents

Resines thermoplastiques stabilisees par des melanges de dithiocarbamate et d'amines ou de phenols Download PDF

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Publication number
WO1999023154A1
WO1999023154A1 PCT/US1998/020563 US9820563W WO9923154A1 WO 1999023154 A1 WO1999023154 A1 WO 1999023154A1 US 9820563 W US9820563 W US 9820563W WO 9923154 A1 WO9923154 A1 WO 9923154A1
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Prior art keywords
butyl
phenol
composition
stabilizer
phenylenediamine
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PCT/US1998/020563
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English (en)
Inventor
Robert S. Archibald
Leigh C. Allen
Christopher J. Fagouri
Sharon A. Roys
Tracy L. Coffin
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Uniroyal Chemical Company, Inc.
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Publication of WO1999023154A1 publication Critical patent/WO1999023154A1/fr

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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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/13—Phenols; Phenolates
    • 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

  • the present invention relates to the stabilization of thermoplastic resins against thermo-oxidative degradation.
  • U.S. Patent Number 3,322,802 discloses certain oxidized dithiocarbamates derived from divalent, trivalent, and tetravalent metals and methods for their preparation.
  • the compounds are said to be high in biocidal activity and useful as 5 industrial and agricultural bactericides and fungicides and as antifouling agents in paints. They are also said to be useful as vulcanization accelerators, as antioxidants in polymers, and as oxidation and wear inhibitors in lubricants.
  • thermoplastic polymer compositions that degrade relatively rapidly on exposure to the environment.
  • the compositions o comprise a thermoplastic vinyl polymer or copolymer and at least one nonionic organo-soluble complex of a metal selected from iron, manganese, silver, palladium, molybdenum, chromium, tungsten, or cerium, and a complexing agent, either or both of the complex and complexing agent being an antioxidant, the complex being activatable by light of wavelength less than 330 nm and optionally heat to give a more photo-oxidatively active form of the metal in an amount such as to cause degradation of the polymer composition at the end of its desired life.
  • a metal selected from iron, manganese, silver, palladium, molybdenum, chromium, tungsten, or cerium
  • a complexing agent either or both of the complex and complexing agent being an antioxidant
  • the complex being activatable by light of wavelength less than 330 nm and optionally heat to give a more photo-oxidatively
  • European Patent Publication Number 0 080 409 discloses rubber compounds that are useful in molding bags that resist oils at 140 degrees/skbar and contain epichlorohydrin polymers (100 parts), plasticizers (0.5 to 20 parts), reinforcing fillers (1 to 150 parts), metal stearates (0.5 to 7.5 parts), Pb 3 O 4 (0.5 to 7.5 parts), stabilizers (0.5 to 5.5 parts), and vulcanizing agents (0.5 to 5.5 parts).
  • U.S. Patent Number 4,797,511 discloses a composition stabilized against oxidative degradation comprising: a polyolefin, carbon black homogeneously incorporated in said polyolefin, a stabilizing amount of thiodiethylene bis(3,5-di-t- butyl-4-hydroxy)hydrocinnamate (Naugard 35 or EL50) first stabilizer component incorporated into said polyolefin and a second stabilizer component of at least one amine antioxidant selected from the group consisting of a para-substituted aralkyl- substituted diphenylamine; a para-phenylenediamine and a polymerized dihydroquinoline incorporated into said polyolefin.
  • U.S. Patent Number 4,837,259 discloses polypropylene stabilized against oxidative degradation by the presence therein of a stabilizing amount of an antioxidant composition that comprises:
  • European Patent Publication Number 0 328 788 discloses a composition comprising 100 parts by weight (pbw) of an aromatic vinyl compound-conjugated diene block copolymer and 1.0-5.0 pbw of a mixture of two or more compounds chosen from a dithiocarbamate derivative, a triazine derivative and a polyphenol compound, an adhesive composition containing it and a process for the preparation of said compositions by mixing the components in question.
  • JP 71037440 discloses the use of thiourea, Irganox RA-565, Soxinol PZ ⁇ (Me j NCS ⁇ Zn ⁇ , Irganox RA-1093, and Soxinol M (2-mercaptobenzothiazole) as discoloration stabilizers for polypropylene fibers and films containing a phenolic antioxidant.
  • thiourea Irganox RA-565
  • Soxinol PZ ⁇ (Me j NCS ⁇ Zn ⁇ Irganox RA-1093
  • Soxinol M (2-mercaptobenzothiazole) 2-mercaptobenzothiazole
  • Hwahak Kwa Hwahak Kongop (1975), 18(6), 302-9 discloses the use of tetraethylthiuram disulfide (I) and tetramethylthiuram disulfide (II) as heat stabilizers for S-modified neoprene rubber.
  • the scorch time linearly increased with increasing I and II content, while Ni bis(N,N-dibutyl dithiocarbamate) (III), N-phenyl-2- naphthylamine (IV), thiophenylamine (V) and BHT accelerated the crosslinking.
  • Ill, IV, and V were good antioxidants and prevented dehydrochlorination.
  • the rubber containing 1 percent I had a storability (plasticity decrease by 70 percent) of 1.5 years.
  • the present invention is characterized by a polymeric material that includes a stabilizing mixture comprising two components.
  • the first component is a metal dithiocarbamate salt.
  • the second component is selected from the group consisting of an amine antioxidant and a sterically hindered phenol. s
  • the blends of amine or phenolic stabilizers with the metal dithiocarbamate salts of this invention have been unexpectedly found to protect thermoplastic resins against polymer breakdown, as shown by extended oxidative induction time (OIT) and percent retention of elongation and IZOD impact values.
  • OIT extended oxidative induction time
  • composition o comprising:
  • thermoplastic resin (A) a thermoplastic resin
  • a first stabilizer comprising at least one metal dithiocarbamate 5 salt of the structure
  • M is a divalent, trivalent, or tetravalent metal
  • X is an integer of from 2 to 4 that equals the valence of M, and the moiety
  • a second stabilizer selected from the group consisting of:
  • the present invention is directed to a method for stabilizing a composition comprising a thermoplastic resin and carbon black against oxidative degradation comprising adding to said composition a stabilizing amount of:
  • M is a divalent, trivalent, or tetravalent metal
  • X is an integer of from 2 to 4 that equals the valence of M, and the moiety
  • a second stabilizer selected from the group consisting of: (1) at least one amine antioxidant selected from the group consisting of:
  • composition comprising:
  • thermoplastic resin (A) a thermoplastic resin
  • a first stabilizer comprising at least one metal dithiocarbamate salt of the structure
  • M is a divalent, trivalent, or tetravalent metal
  • X is an integer of from 2 to 4 that equals the valence of M, and the moiety
  • a second stabilizer selected from the group consisting of:
  • At least one amine antioxidant selected from the group consisting of: (i) a hydrocarbon-substituted diarylamine,
  • thermoplastic resins that can be stabilized against oxidative degradation employing mixtures of the above-described metal dithiocarbamate salts and either the amines or hindered phenols include resins derived from ethylene including low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), or other ethylene derived resins that have densities from 0.85 to 1.4 gm/cm 3 ; homopolymers derived from mono- and di-ethylenically unsaturated hydrocarbon monomers of C 3 and above, such as, polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, polybutene-1 , polyisobutylene, and the like; copolymers derived from two or more monomers, such as, ethylene-propylene copolymers having at least a majority of propylene, propylene-butene
  • This invention specifically excludes resins that are nonthermoplastic and mixtures that do not contain carbon black.
  • R and R' are hydrocarbon groups, for example, aryl or alkyl, that can be the same or different, and they can be joined through a methylene group or through an oxygen or sulfur atom to form, with the nitrogen, a heterocyclic ring.
  • the hydrocarbon groups can be alkyl groups having from 1 to 12 carbon atoms, cycloalkyl groups, and hydrocarbon-substituted cycloalkyl groups having from 5 to 12 carbon atoms, or aryl, aralkyl, or alkaryl groups having from 6 to 12 carbon atoms.
  • the groups R and R' may form, with the nitrogen, heterocyclic rings containing four to five carbon atoms, zero to one oxygen atom, and zero to one sulfur atom.
  • the total number of carbon atoms in the groups R and R' (attached to the same nitrogen atom) is o preferably 24 or less.
  • Typical radicals in the amine groups include, but are not limited to, phenyl, naphthyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, benzyl, phenethyl, and the like.
  • the amine nitrogen can be included in, for example, morpholino, thiamorpholino, and piperidino groups.
  • morpholino morpholino
  • thiamorpholino and piperidino groups.
  • the foregoing terms should be understood to be generic in the sense of s including structural isomers where appropriate, for example, isopropyl, t-butyl, neopentyl, 2-ethylhexyl, and the like.
  • the metal, M is preferably selected from the group consisting of the divalent metals copper, zinc, manganese, nickel, lead, cadmium, cobalt, tin(II), barium, and mercury, the trivalent metals iron(III) and bismuth, and the tetravalent o metal tin(IV). It is preferred that M be a divalent metal, and more preferred that it be zinc.
  • the first stabilizer be zinc dibenzyldithiocarbamate or zinc dibutyldithiocarbamate.
  • the amine antioxidants can be hydrocarbon substituted diarylamines, such 5 as, aryl, alkyl, alkaryl, and aralkyl substituted diphenylamine antioxidant materials.
  • hydrocarbon substituted diphenylamines include substituted octylated, nonylated, and heptylated diphenylamines and para- substituted styrenated or ⁇ -methyl styrenated diphenylamines.
  • the sulfur-containing hydrocarbon substituted diphenylamines such as p-(p-toluenesulfonylamido)- diphenylamine, are also considered as part of this class.
  • Ar and Ar' are independently selected aryl radicals, at least one of which is preferably substituted with at least one alkyl radical.
  • the aryl radicals can be, for example, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, and the like.
  • the alkyl substituent(s) can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isomers thereof, and the like,
  • Preferred hydrocarbon-substituted diarylamines are those disclosed in U.S.
  • R is selected from the group consisting of phenyl and p-tolyl radicals
  • R 2 and R 3 are independently selected from the group consisting of methyl, phenyl, and p-tolyl radicals;
  • R is selected from the group consisting of methyl, phenyl, p-tolyl, and neopentyl radicals;
  • R 5 is selected from the group consisting of methyl, phenyl, p-tolyl, and 2-phenylisobutyl radicals;
  • Re is a methyl radical
  • R t through R 5 are independently selected from the radicals shown in
  • Formula I and R 7 is selected from the group consisting of methyl, phenyl, and p-tolyl radicals;
  • X is a radical selected from the group consisting of methyl, ethyl, C 3 -C 10 sec-alkyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -methylbenzyl, chlorine, bromine, carboxyl, and metal salts of the carboxylic acids where the metal is selected from the group consisting of zinc, cadmium, nickel, lead, tin, magnesium, and copper; and,
  • Y is a radical selected from the group consisting of hydrogen, methyl, ethyl,
  • R] is selected from the group consisting of phenyl or p-tolyl radicals
  • R 2 and R 3 are independently selected from the group consisting of methyl, phenyl, and p-tolyl radicals;
  • R 4 is a radical selected from the group consisting of hydrogen, C 3 -C, 0 primary, secondary, and tertiary alkyl, and C 3 -C, 0 alkoxyl, which may be straight chain or branched; and
  • X and Y are radicals selected from the group consisting hydrogen, methyl, ethyl, C 3 -C 10 sec-alkyl, chlorine, and bromine.
  • R is selected from the group consisting of phenyl and p-tolyl radicals
  • R I0 is a radical selected from the group consisting of methyl, phenyl, p-tolyl and 2-phenyl isobutyl;
  • R u is a radical selected from the group consisting methyl, phenyl, and p-tolyl.
  • R, 2 is selected from the group consisting of phenyl or p-tolyl radicals
  • R, 3 is selected from the group consisting of methyl, phenyl, and p-tolyl radicals
  • Ri 4 is selected from the group consisting of methyl, phenyl, p-tolyl, and 2- phenylisobutyl radicals;
  • Ru is selected from the group consisting of hydrogen, ⁇ ,c_-dimethylbenzyl, ⁇ -methylbenzhydryl, triphenylmethyl, and , p-trimethylbenzyl radicals.
  • Typical chemicals useful in the invention are as follows:
  • R is phenyl and R 10 and R n are methyl.
  • R ⁇ 6 and R 17 are methyl or phenyl are especially preferred.
  • the compound wherein R ⁇ 6 and R, 7 are both methyl is 4,4'-bis( ⁇ ,c_-dimethylbenzyl)diphenylamine) and the compound wherein R 16 and R17 are both phenyl is 4,4'-bis( ⁇ - methylbenzyl)diphenylamine.
  • a second class of amine antioxidants comprises the reaction products of a diarylamine and an aliphatic ketone.
  • the diarylamine aliphatic ketone reaction products that are useful herein are disclosed in U.S. Patent Nos. 1,906,935; 1,975,167; 2,002,642; and 2,562,802. Briefly described, these products are obtained by reacting a diarylamine, preferably a diphenylamine, which may, if desired, possess one or more substituents on either aryl group, with an aliphatic ketone, preferably acetone, in the presence of a suitable catalyst.
  • diarylamine reactants include dinaphthyl amines; p-nitrodiphenylamine; 2,4-dinitrodiphenylamine; p-aminodiphenylamine; p-hydroxydiphenylamine; and the like.
  • acetone other useful ketone reactants include methylethylketone, diethylketone, monochloroacetone, dichloroacetone, and the like.
  • a preferred diarylamine-aliphatic ketone reaction product is obtained from the condensation reaction of diphenylamine and acetone (NAUGARD A, Uniroyal Chemical), for example, in accordance with the conditions described in U.S. Patent
  • the commercial product is supplied as a light tan-green powder or as greenish brown flakes and has a melting range of 85° to 95 °C.
  • a third class of suitable amines comprises the N,N' hydrocarbon substituted p-phenylene diamines.
  • the hydrocarbon substituent may be alkyl or aryl groups, which can be substituted or unsubstituted.
  • alkyl unless specifically described otherwise, is intended to include cycloalkyl. Representative materials are:
  • N,N'-diphenyl-p-phenylenediamine N,N'-di-beta naphthyl-p-phenylenediamines; mixed diary l-p-N,N'-bis-(l-ethyl-3- methylpentyl)-p-phenylenediamine; and N,N'-bis-(l methylheptyl)-p-phenylenediamine.
  • a final class of amine antioxidants comprises materials based on quinoline, especially, polymerized l,2-dihydro-2,2,4-trimethylquinoline.
  • Representative materials include polymerized 2,2,4-trimethyl-l,2-dihydroquinoline; 6-dodecyl- 2,2,4-trimethyl-l,2-dihydroquinoline; 6-ethoxy-2,2,4-trimethyl-l-2- dihydroquinoline, and the like.
  • the hindered phenols that are useful in the practice of the present invention preferably have a molecular weight above 500 daltons.
  • Preferred examples include 2,4-dimethyl-6-octyl-phenol; 2,6-di-t-butyl-4-methyl phenol (i.e., butylated hydroxy toluene); 2,6-di-t-butyl-4-ethyl phenol; 2,6-di-t-butyl-4-n-butyl phenol; 2,2'- methylenebis(4-methyl-6-t-butyl phenol); 2,2'-methylenebis(4-ethyl-6-t-butyl- phenol); 2,4-dimethyl-6-t-butyl phenol; 4-hydroxymethyl-2,6-di-t-butyl phenol; n-octadecyl-beta(3,5-di-t-butyl-4-hydroxyphenyl)propionate; 2,6-dio
  • octadecyl-3,5-di-t-butyl-4-hydroxy hydrocinnamate NAUGARD 76, Uniroyal Chemical
  • IRGANOX 1076 Ciba-Geigy
  • tetrakis ⁇ methylene(3,5-di-t-butyl-4-hydroxy-hydrocinnamate) ⁇ methane IRGANOX 1010, Ciba-Geigy
  • 1 ,2-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamoyl)hydrazine IRGANOX MD 1024,Ciba-Geigy
  • l,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-s- triazine-2,4,6 (lH,3H,5H)trione IRGANOX 3114, Ciba-Geigy
  • hindered phenols having molecular weights above 700 especially polyphenols that contain three or more substituted phenol groups, such as tetrakis ⁇ methylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate) ⁇ methane s (IRGANOX 1010, Ciba-Geigy) and l,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4- hydroxybenzyl)benzene (ETHANOX 330, Ethyl Corp.).
  • substituted phenol groups such as tetrakis ⁇ methylene (3,5-di-t-butyl-4-hydroxy-hydrocinnamate) ⁇ methane s (IRGANOX 1010, Ciba-Geigy) and l,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4- hydroxybenzyl)benzene (ETHANOX 330, E
  • the combined amounts of metal dithiocarbamate salts and either the amine derivative(s) or hindered phenol(s) incorporated into the thermoplastic resins of the present invention will, at a minimum, be that required to impart a significant level o of stability against oxidative degradation. In general, such amounts can vary from about 0.01 to about 5.0, and preferably from about 0.3 to about 1.2, weight percent of the thermoplastic resin. Although combined amounts of the antioxidants in excess of about 5 weight percent can be employed, such amounts may have a deleterious effect on the physical and mechanical properties of the polymeric 5 substrate, in which case they should ordinarily be avoided.
  • the relative proportions of metal dithiocarbamate salts to either the amine derivative(s) or hindered phenol (s) can vary widely.
  • the ratios of metal dithiocarbamate salts and either the amine derivative(s) or hindered phenol(s) can vary from about 20:1 to about 1:20 and, preferably, from about 10:1 to about 1:10, although ratios somewhat above and below the broader of these ranges can also be used with advantageous results.
  • thermoplastic resins are not critical and, in general, follow any of the known procedures for incorporating additives into such resins.
  • these materials can be introduced into the thermoplastic resin as a pre ix or they can be maintained separately and added to the resin simultaneously or sequentially and then homogeneously distributed throughout the polymer by milling, extrusion blending, or some other mechanical working procedure.
  • Either the first stabilizer or the second stabilizer or both can be added to the thermoplastic resin by way of a preconcentrate or in a carrier system, for example, in a suitable solvent or co-solvent.
  • additives can be introduced into the resin prior to, during, and/or following addition of the antioxidants.
  • additives include other stabilizers, colorants, reinforcements, fillers, antistatic agents, lubricants, plasticizers, and the like, present in the customary amounts.
  • Circular discs are cut from 0.25 mm films of the material to be tested and placed in aluminum pans for use in a Perkin-Elmer DSC-2C type differential scanning calorimeter (DSC).
  • the test chamber of the DSC calorimeter is purged with nitrogen during conditioning to an isocratic temperature of, for example, 10 200 °C followed by an immediate change to oxygen at a flow rate of 20 cc's per minute to induce thermaloxidative degradation.
  • Oxidative Induction Time is the time span in minutes between reaching the isocratic temperature when the oxygen environment is introduced and the time at which the DSC detects the onset of oxidation.
  • antioxidants/antioxidant compositions were incorporated into the resin in a roll mill by mastication.
  • the plastic mass removed from the roll mill was pressed into a plastic patty.
  • One section of the plastic patty was removed and
  • Arazate is zinc dibenzyldithiocarbamate.
  • Butazate is zinc dibutyldithiocarbamate.
  • Durazone 37F is 2,4,6-tris-(N-l,4-dimethyl-pentyl-p-phenylenediamino)-l,3,5- triazine.
  • Hexamine is a blend of diarylamine-ketone reaction product (65 percent) and N,N'- diphenyl-p-phenylenediamine (35 percent).
  • Flexzone 7L is N-l,3-dimethylbutyl-N'-phenyl-p-phenylenediamine.
  • Naugard 76 is octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinnamate.
  • Naugard A is a low temperature reaction product of diphenylamine and acetone.
  • Naugard EL50 is thiodiethylene bis(3,5-di-t-butyl-4-hydroxy)hydrocinnamate.
  • Naugard SA is N-phenyl-N'-(p-toluenesulfonyl)-p-phenylenediamine.
  • Naugard 445 is 4,4'-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine.
  • Naugard XL-1 is 2,2'-oxamidobis ⁇ ethyl-3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate ⁇ .
  • Naugard 10 is tetrakis ⁇ methylene(3,5-di-t-butyl-4-hydroxy-hydrocinna ⁇ ate) ⁇ methane.
  • Naugard Super Q is polymerized l,2-dihydro-2,2,4-tri ⁇ _ethylquinoline.
  • Octamine is octylated diphenylamine.
  • both hindered phenolic and amine antioxidants show great synergy with metal dithiocarbamate salts.
  • Examples 16-19 especially show great enhancement in OIT as compared to stabilizers used alone at the same total concentration.
  • the phenyl substituted Arazate shows some synergistic enhancement
  • the butyl substituted Butazate shows the greatest synergistic enhancement.
  • antioxidants/antioxidant compositions were incorporated into the resin in a C.W. Brabender mixing head operating at 30 rpm and at a temperature of 180°C under nitrogen.
  • the plastic mass was pressed into a film. Small sections of the film were removed and the OIT measurements were collected on a Mettler DSC at both 225°C and 250°C.
  • the OIT results are described in Table 2.
  • A is the ratio of Naugard 10 to Ultranox 626 (Total Weight Percent).
  • B is the ratio of Naugard 445 to Butazate (Total Weight Percent).
  • Ultranox 626 is bis(2,4-di-t-butyl)pentaerythritol diphosphite.
  • amine antioxidants provide greatly improved performance with metal dithiocarbamate salts as compared to a state-of-the-art hindered phenol and phosphite combination.
  • Examples 28-36 especially show great enhancement in OIT as compared to state-of-the-art additives at the same total concentration.
  • the metal dithiocarbamate salts and Naugard 445 mixtures clearly o exceed the state-of-the-art formulations at any loading and/or mixture ratio.
  • the formulations show greater enhancement at either equal ratios of antioxidants or slightly higher ratios of the Butazate to Naugard 445.

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Abstract

Une composition comprend: (A) une résine thermoplastique; (B) du noir de carbone; et (C) une quantité stabilisante de: (1) un premier stabilisant comprenant au moins un sel dithiocarbamate métallique de la structure (1) dans laquelle M représente un métal divalent, trivalent ou tétravalent, X représente un nombre entier compris entre 2 et 4 égal à la valence de M, et la fraction (2) représente le reste de n'importe quelle amine secondaire réagissant avec du disulfure de carbone pour former un dithiocarbamate; et (2) un second stabilisant choisi dans le groupe comprenant: (a) au moins un antioxydant aminé choisi dans le groupe renfermant: (i) une diarylamine à substitution hydrocarbure, (ii) un produit de réaction d'une diarylamine et d'une cétone aliphatique, (iii) une paraphénylènediamine à substitution N, N'-hydrocarbure, et (iv) une dihydroquinoline polymérisée, et (b) au moins un phénol entravé stériquement.
PCT/US1998/020563 1997-10-30 1998-09-30 Resines thermoplastiques stabilisees par des melanges de dithiocarbamate et d'amines ou de phenols WO1999023154A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002031038A1 (fr) * 2000-10-06 2002-04-18 Uniroyal Chemical Company, Inc. Resines thermoplastiques stabilisees par des melanges de phenols a encombrement sterique, des amines secondaires et des lactones
WO2002092685A1 (fr) * 2001-05-16 2002-11-21 Crompton Corporation Resines thermoplastiques en contact avec des metaux ou des sels metalliques stabilises au moyen de melange de dithiocarbamates et de desactivateurs de metaux
EP1260549A1 (fr) * 2001-05-22 2002-11-27 Microflex Corporation Gants médicaux souples à base de nitrile ne contenant pas d'oxide de zinc
US8287765B2 (en) 2008-06-17 2012-10-16 R.T. Vanderbilt Company, Inc. Systems and compositions for color stabilization of polymer

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002031038A1 (fr) * 2000-10-06 2002-04-18 Uniroyal Chemical Company, Inc. Resines thermoplastiques stabilisees par des melanges de phenols a encombrement sterique, des amines secondaires et des lactones
US6569927B1 (en) 2000-10-06 2003-05-27 Uniroyal Chemical Company, Inc. Thermoplastic resins stabilized by blends of sterically hindered phenols, secondary amines, and lactones
WO2002092685A1 (fr) * 2001-05-16 2002-11-21 Crompton Corporation Resines thermoplastiques en contact avec des metaux ou des sels metalliques stabilises au moyen de melange de dithiocarbamates et de desactivateurs de metaux
US6790888B2 (en) * 2001-05-16 2004-09-14 Crompton Corporation Thermoplastic resins in contact with metals or metal salts stabilized by blends of dithiocarbamates and metal deactivators
KR100838009B1 (ko) * 2001-05-16 2008-06-12 켐트라 코포레이션 디티오카바메이트와 금속 비활성제의 블렌드물에 의해안정화된 금속 또는 금속 염과 접촉하는 열가소성 수지
EP1260549A1 (fr) * 2001-05-22 2002-11-27 Microflex Corporation Gants médicaux souples à base de nitrile ne contenant pas d'oxide de zinc
US8287765B2 (en) 2008-06-17 2012-10-16 R.T. Vanderbilt Company, Inc. Systems and compositions for color stabilization of polymer

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