WO2014149894A1 - Compositions de stabilisant métallique mixte - Google Patents

Compositions de stabilisant métallique mixte Download PDF

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Publication number
WO2014149894A1
WO2014149894A1 PCT/US2014/021393 US2014021393W WO2014149894A1 WO 2014149894 A1 WO2014149894 A1 WO 2014149894A1 US 2014021393 W US2014021393 W US 2014021393W WO 2014149894 A1 WO2014149894 A1 WO 2014149894A1
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Prior art keywords
alkyltin
zinc
compound
composition
octoate
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PCT/US2014/021393
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English (en)
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WO2014149894A8 (fr
Inventor
Michael Denoux
Garrett Mineo
Anthony Joseph DIMAIO
Peter Frenkel
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Galata Chemicals Llc
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Publication of WO2014149894A1 publication Critical patent/WO2014149894A1/fr
Publication of WO2014149894A8 publication Critical patent/WO2014149894A8/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
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin 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
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • C08K5/58—Organo-tin compounds containing sulfur

Definitions

  • the invention relates to liquid, storage-stable mixed metal heat stabilizer compositions for protecting halogen-containing polymers and co-polymers against color development under elevated temperature and shear conditions.
  • the blends comprise an alkyltin composition and an organozinc compound.
  • Alkyltin stabilizers are known to be particularly effective in preventing an early discoloration of halogen-containing polymers at elevated temperatures, for example, "PVC Degradation and Stabilization," Wypich, George; ChemTec, Toronto 2008, p.321-335. "Handbook of Vinyl Formulating", 2 nd edition; Grossman, Richard F.; Wiley & Sons, 2008, p. 92-107. "PVC Handbook”; Wilkes, Charles E., et al; Hanser, Cincinnati 2005, p.108-116.
  • various attempts have been made to partially replace the alkyltin compounds with other organometallic compounds while maintaining initial and mid-term heat stability.
  • JP 54,154,441 discloses the preparation of heat stabilizers for halogen-containing resins where the stabilizers comprise four components: a) a zinc salt of an organic acid, b) at least one salt of organic acid or alkylphenol and the metal selected from barium, calcium, tin, magnesium or strontium, c) dehydroacetic acid or its sodium salts, and d) an isocyanurate.
  • the high number of components differing in terms of mutual solubility prevents the formation of storage-stable liquid stabilizers, since the resultant combination would either precipitate, separate or appear cloudy.
  • Japanese Kokai No. 5237,956 discloses a stabilized halogen-containing resin composition containing an alkyltin compound and a specific metal salt.
  • US Patent No. 4,358,555 discloses heat stabilizing blends for halogen-containing polymers, where the blends comprise a) at least one alkyltin mercaptide, b) at least one zinc mercaptoester, and c) at least one basic alkali or alkaline-earth metal compound. Also disclosed are heat stabilizer blends comprising a) at least one alkyltin mercaptide, b) at least one alkyltin sulfide or oxide, c) at least one zinc mercaptoester, and d) at least one basic alkali or alkaline- earth metal compound.
  • the alkyltin sulfides or oxides are employed in the stabilizer compositions in amounts up to 50% of the combined weight of the alkyltin mercaptide and alkyltin sulfide or oxide present in the stabilizer compositions.
  • metals include calcium and magnesium.
  • zinc mercaptoesters include organozinc compounds having two mercaptoester groups, where each group was bonded to the zinc atom through the sulfur atom.
  • US Patent No. 8,198,352 describes high purity monoalkyltin stabilizers, such as mono- octyltin tris (2-ethylhexyl thioglycolate), where the mono-alkyltin compounds can be used in combination with metal salt co-stabilizers, including solid stearates of zinc, calcium or magnesium.
  • metal salt co-stabilizers including solid stearates of zinc, calcium or magnesium.
  • the invention relates to a stabilizer composition
  • a stabilizer composition comprising 75.0% to 99.9 % by weight of an alkyltin composition comprising at least 15.0 wt% of a di-alkyltin compound; and 0.1 % to 25.0% by weight of an organozinc compound selected from the group consisting of zinc salts of C1-C24 linear, branched, cycloaliphatic or aromatic organic acids, zinc diketonates, zinc alcoholates and mixtures thereof.
  • the stabilizer composition is a storage-stable liquid having a viscosity of less than 1,500 cP at 25°C.
  • the invention relates to a stabilized polymer composition
  • a stabilized polymer composition comprising a halogen-containing polymer and a liquid, storage-stable stabilizer composition comprising 75.0% to 99.9% by weight of a mixture of an alkyltin composition comprising at least 15.0 wt% of a di-alkyltin compound; and 0.1% to 25.0% by weight of an organozinc compound selected from the group consisting of zinc salts of Ci-C 2 4 linear, branched, cycloaliphatic or aromatic organic acids, zinc diketonates, zinc alcoholates and mixtures thereof.
  • the stabilizer composition is a storage-stable liquid having a viscosity of less than 1,500 cP at 25°C, and is present in an amount from 0.01 to 10 parts by weight per 100 parts by weight of the halogen-containing polymer.
  • the invention relates to a process comprising blending a stabilizer composition with a halogen-containing polymer, the stabilizer composition comprising 75.0% to 99.9% by weight of a mixture of an alkyltin composition comprising at least 15.0 wt% of a di-alkyltin compound; and 0.1 %> to 25.0% by weight of an organozinc compound selected from the group consisting of zinc salts of Ci-C 24 linear, branched, cycloaliphatic or aromatic organic acids, zinc diketonates, zinc alcoholates and mixtures thereof.
  • the stabilizer composition is a storage-stable liquid having a viscosity of less than 1,500 cP at 25°C.
  • the invention relates to a process comprising blending 75.0% to 99.9% by weight of an alkyltin composition comprising at least 15.0 wt% of a di-alkyltin compound, and 0.1 %> to 25.0% by weight of an organozinc compound selected from the group consisting of zinc salts of Ci-C 24 linear, branched, cycloaliphatic or aromatic organic acids, zinc diketonates, zinc alcoholates and mixtures thereof, thereby forming a stabilizer composition which is a storage-stable liquid having a viscosity of less than 1,500 cP at 25°C; and blending the stabilizer composition with a halogen-containing polymer.
  • an organozinc compound selected from the group consisting of zinc salts of Ci-C 24 linear, branched, cycloaliphatic or aromatic organic acids, zinc diketonates, zinc alcoholates and mixtures thereof, thereby forming a stabilizer composition which is a storage-stable liquid having a viscosity of less than
  • the invention relates to a stabilizer composition
  • a stabilizer composition comprising an alkyltin composition and an organozinc compound.
  • the alkyltin composition contains at least 15.0 wt% of a di-alkyltin compound based on the weight of the alkyltin composition.
  • the alkyltin composition contains at least 25.0 wt %, more preferably at least 50.0 wt% of a di-alkyltin compound.
  • the di- alkyltin compound is selected from the group consisting of di-alkyltin thioglycolate esters, di- alkyltin carboxylates, di-alkyltin maleates, di-alkyltin sulfides, di-alkyltin diketonates, di-alkyltin alcoholates, di-alkyltin reverse esters (mercaptoethylesters) and mixtures thereof.
  • the alkyl groups of the di-alkyltin compound are selected from linear, branched or cyclic Ci-C 2 o alkyls, preferably linear Ci-Cio alkyls.
  • the alkyl groups of the di-alkyltin compound are selected from methyl, n-butyl or n-octyl.
  • the di-alkytin compound is selected from the group consisting of di-n-butyltin bis(2-ethylhexylmercaptoacetate), dimethyltin bis(2-ethylhexylmercaptoacetate), di-n-octylltin bis(2-ethylhexylmercaptoacetate) and mixtures thereof.
  • the alkyltin composition can contain up to 100% of the di-alkyltin compound, however, the alkyltin composition may also optionally contain a mono-alkyltin compound.
  • a mono- alkyltin compound is present in the alkyltin composition, it is present in amounts of 0.1% up to 85.0%) by weight, preferably up to 75.0% by weight, and more preferably up to 50.0%> by weight of the alkyltin composition.
  • the mono-alkyltin compound is selected from the group consisting of mono-alkyltin thioglycolate esters, mono-alkyltin carboxylates, mono- alkyltin maleates, mono-alkyltin sulfides, mono-alkyltin diketonates, mono-alkyltin alcoholates, mono-alkyltin reverse esters and mixtures thereof.
  • the alkyl groups of the mono- alkyltin compound are selected from linear, branched or cyclic Ci-C 2 o alkyls, preferably linear Ci-Cio alkyls.
  • the alkyl groups of the mono-alkyltin compound are selected from methyl, n-butyl or n-octyl.
  • the alkyltin composition is selected from the group consisting of mixtures of mono-n-butyltin tris(2- ethylhexylmercaptoacetate and di-n-butyltin bis(2-ethylhexylmercaptoacetate, mixtures of mono- methyltin tris(2-ethylhexylmercaptoacetate) and dimethyltin bis(2-ethylhexylmercaptoacetate), and mixtures of mono-n-octylltin tris(2-ethylhexylmercaptoacetate) and di-n-octylltin bis(2- ethylhexylmercaptoacetate) .
  • the alkyltin composition is blended with an organozinc compound.
  • the amount of the alkyltin composition in the stabilizer composition ranges from 75.0 to 99.9%, preferably from 90.0 to 95.0% by weight.
  • the organozinc compound is selected from the group consisting of zinc salts of Ci-C 24 linear, branched, cycloaliphatic or aromatic organic acids, zinc diketonates, zinc alcoholates, their solutions in solvents, such as organic acids, esters, alcohols, ketones and mixtures thereof.
  • the organozinc compound is selected from zinc n-octoate, zinc iso-octoate, zinc 2- ethylhexanoate, zinc neodecanoate and zinc laurate, including the overbased modifications of the salts, as shown in "Metal Carboxylates"; Mehrota, Ram C, et al., Academic Press, 1983. Peterangelo, S.C; Hart, R.
  • the organozinc compound is selected from zinc n-octoate, zinc 2-ethylhexanoate or zinc iso-octoate.
  • the organozinc compound is blended with the alkyltin composition to form the stabilizer composition.
  • the amount of the organozinc compound in the stabilizer composition ranges from 0.1 to 25.0%, preferably from 5.0 to 10.0% by weight. Blending is carried out at 15-80°C, preferably at ambient temperature for 0.5-10 hours, preferably 1 hour.
  • surfactants, diluents, antioxidants, lubricants and co-stabilizers can also be present in the stabilizer composition.
  • the stabilizer composition is a storage-stable liquid.
  • storage-stable means that the composition possesses no visible precipitation, cloudiness or phase separation when measured fifteen days after preparation, while being kept at each of 10, 25 and 80°C.
  • Storage-stable also means that the stabilizer composition has a viscosity, measured at 25°C (Spindle 34 at 100 rpm) fifteen days after preparation, of lower than 1,500 cP. Preferably, the measured viscosity is below 1,000 cP.
  • Storage stability is an important property in the subject heat stabilizer compositions. Inferior storage stability, as evidenced by visible precipitation, cloudiness or phase separation in the stabilizer composition causes mal-distribution of the stabilizer in PVC and loss of stabilizer efficiency. Inferior storage stability, as evidenced by a viscosity higher than 1,500 cP causes higher motor loads and difficulties in metering such liquids via standard pumps.
  • the invention relates to a stabilized polymer composition
  • a stabilized polymer composition comprising a halogen-containing polymer and a liquid, storage-stable stabilizer composition comprising 75.0% to 99.9% by weight of an alkyltin composition comprising at least 15.0% by weight of a di-alkyltin compound; and 0.1 %> to 25.0%> by weight of an organozinc compound selected from the group consisting of zinc salts of Ci-C 2 4 linear, branched, cycloaliphatic or aromatic organic acids, zinc diketonates, zinc alcoholates and mixtures thereof.
  • the stabilizer composition is a storage-stable liquid having a viscosity of less than 1,500 cP at 25°C.
  • the subject composition is useful as a stabilizer for halogen-containing polymers, including homopolymers and copolymers of vinyl halogens, post-halogenated polymers and copolymers of vinyl halogens, and halogenated polymers of olefins, such as ethylene, propylene, and 1-butene.
  • the halogen of such polymers can be fluorine, chlorine, bromine, iodine, or mixtures thereof.
  • the polymer that is stabilized by the stabilizer compositions is poly(vinyl chloride) ("PVC").
  • PVC poly(vinyl chloride)
  • the PVC used can be obtained via polymerization in bulk or in suspension, in emulsion, in micro suspension, or in suspended emulsion.
  • PVC is intended to include both homopolymers and copolymers of vinyl chloride, i.e., vinyl resins containing vinyl chloride units in their structure, e.g., copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate; copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile; copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or anhydrides thereof, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride; post-chlorinated polymers and copolymers of vinyl chloride; copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl
  • PVC as employed herein is also intended to include graft polymers of PVC with ethyl-vinyl acetate (“EVA”), acrylonitrile/butadiene-styrene (“ABS”), and meth-acrylate- butadiene (“MBS").
  • EVA ethyl-vinyl acetate
  • ABS acrylonitrile/butadiene-styrene
  • MFS meth-acrylate- butadiene
  • Preferred substrates are also mixtures of the above-mentioned homopolymers and copolymers, preferably vinyl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, more preferably blends with ABS, MBS, acrylonitrile butadiene (“NBR”), styrene-acrylonitrile (“SAN”), EVA, chlorinated polyethylene (“CPE”), poly(methyl methylacrylate), ethylene propylene diene monomer (“EPDM”), and polylactones.
  • vinyl chloride homopolymers preferably vinyl chloride homopolymers
  • other thermoplastic and/or elastomeric polymers more preferably blends with ABS, MBS, acrylonitrile butadiene (“NBR”), styrene-acrylonitrile (“SAN”), EVA, chlorinated polyethylene (“CPE”), poly(methyl methylacrylate), ethylene propylene diene monomer (“EPDM”), and polylactones.
  • vinyl acetate, vinylidene dichloride, acrylonitrile, chlorofluoroethylene and/or the esters of acrylic, fumaric, maleic and/or itaconic acids are monomers that are copolymerizable with vinyl chloride.
  • the halogen-containing polymer is selected from polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride or mixtures thereof. More preferably, the halogen-containing polymer is polyvinyl chloride.
  • the content of the subject stabilizer composition within the stabilized polymer composition is typically between 0.01 parts and 10 parts by weight, preferably between 0.1 and 7.0, and more preferably between 0.25 and 5.0 parts by weight for 100 parts by weight of the halogen-containing polymer.
  • the subject stabilized polymer compositions have improved dynamic heat stability, as measured by the yellowness index test ("YI") as defined in ASTM method E313.
  • YI yellowness index test
  • the stabilized polymer compositions have improved initial and mid-term dynamic heat stability.
  • Initial and mid-term dynamic heat stability is an important consideration for halogenated polymers because it significantly affects post-processing whiteness of PVC articles.
  • initial and mid-term stability is measured by the yellowness index within the first 15 minutes of the test.
  • polymer compositions stabilized with the subject mixed metal stabilizers demonstrate improved UV light stability.
  • the invention relates to blending a halogen-containing polymer and the stabilizer composition.
  • the stabilizer composition comprises 75.0% to 99.9% by weight of a mixture of an alkyltin composition comprising at least 15.0% by weight of a di-alkyltin compound; and 0.1 % to 25.0% by weight of an organozinc compound selected from the group consisting of zinc salts of C1-C24 linear, branched, cycloaliphatic or aromatic organic acids, zinc diketonates, zinc alcoholates and mixtures thereof.
  • the stabilizer composition is a storage-stable liquid having a viscosity of less than 1,500 cP at 25°C. In this way, both the alkyltin composition and the organozinc compound are added to the halogen-containing polymer together at the same time, thereby providing initial and mid-term heat stability.
  • an alkyltin composition comprising at least 15.0% by weight of a di-alkyltin compound
  • an organozinc compound selected from the group consisting of zinc salts of C1-C24 linear, branched, cycloaliphatic or aromatic organic acids, zinc diketonates, zinc alcoholates and mixtures thereof, thereby forming a stabilizer composition.
  • the stabilizer composition is a storage-stable liquid having a viscosity of less than 1,500 cP at 25°C.
  • the stabilizer composition is then blended with a halogen-containing polymer. In this way, both the alkyltin composition and the organozinc compound are added to the halogen-containing polymer together at the same time, thereby providing initial and mid-term heat stability.
  • the components of the stabilizer composition can be blended by a variety of processes well known to those skilled in the art, for example, by melt blending, dry blending, extrusion, and combinations thereof.
  • the halogen-containing polymer and the stabilizer composition can also be blended by those well-known processes.
  • Control example 1 is a mixture of mono-methyltin tris(2-ethylhexylmercaptoacetate) and dimethyltin bis(2-ethylhexylmercaptoacetate), having a content of the dimethyltin compound of greater than 70%, and is commercially available from Galata Chemicals as Mark 1900.
  • mixtures of Control example 1 and zinc 2-ethylhexanoate, commercially available from Galata Chemicals as Mark 552G were blended for 1 hour at ambient temperature. The blends were then tested for storage stability.
  • Control example 7 is a mixture of mono-n-octylltin tris(2-ethylhexylmercaptoacetate) and di-n-octyltin bis(2-ethylhexylmercaptoacetate), having a content of the di-n-octyltin compound of greater than 50%, and is commercially available from Galata Chemicals as Mark 17MOK.
  • Examples 8-12 mixtures of Control example 7 and zinc 2-ethylhexanoate, commercially available from Galata Chemicals as Mark 552G, were prepared as in Examples 2- 6. Control example 7 and Examples 8-12 were then tested for storage stability as with Control example 1 and Examples 2-6.
  • Table 2 summarizes the relative percentages of Control example 7 and zinc 2- ethylhexanoate for Examples 8-12, and the corresponding test results. Table 2.
  • Control example 13 is a mixture of di-n-butyltin bis(2-ethylhexylmercaptoacetate) and mono-n-butyltin tris(2-ethylhexylmercaptoacetate), having a content of the di-n-butyltin compound of greater than 90%, and is commercially available from Galata Chemicals as Mark 292.
  • Examples 14-18 mixtures of Control example 13 and zinc 2-ethylhexanoate, commercially available from Galata Chemicals as Mark 552G, were prepared as with Examples 2-6. Control example 13 and Examples 14-18 were then tested for storage stability as with Examples 2-6.
  • Table 3 summarizes the relative percentages of Control Example 13 and Examples 14-18, and the corresponding test results.
  • Example 19-28 mixtures of Control example 1 and organozinc compounds at various concentrations were blended and then tested for storage stability as with Examples 2-6. Table 4 summarizes the relative percentages of Examples 19-28, and the corresponding test results.
  • Rigid PVC formulations were prepared using the stabilizer formulations of Control example 1 and Examples 2-4.
  • the stabilizers were loaded at the same weight level of 1.5 parts per hundred ("phr") of PVC.
  • Each PVC compound test sample (prepared according to the formulation described in table 8) was placed into a Brabender mixer operated at 190°C and 65 RPM. Sample chips were taken every three minutes. Fusion time was approximately the same for each test series.
  • Color stability of the PVC was determined using a Hunter Lab colorimeter measuring Yellowness Index (YI) of the sample chips. Lower YI signifies lower discoloration as a result of thermal decomposition, and therefore, superior thermal stabilization. Results of the dynamic heat stability are shown in Table 5.
  • Blend samples of the subject stabilizers and a PVC compound were prepared for accelerated UV stability test by compounding a dry blend of the components in a two-roll testing mill, type W 150EP for 5 minutes at 177°C and 30 rpm roll speed. After 5 minutes, the milled rigid PVC sheets were taken off the instrument and flattened while still warm with a Ferro plate, to obtain a smooth, flat surface. Ten individual rigid sheet specimens were then cut to fit a standard 3"xl2" panel and secured by snap-in rings. The samples were then placed in a QUV Solar Eye accelerated weathering tester (manufactured by Q-Lab Corporation, Westlake, OH) and exposed to conditions under ASTM G-154 using a 340 nm UVA lamp.
  • QUV Solar Eye accelerated weathering tester manufactured by Q-Lab Corporation, Westlake, OH
  • the programmed QUV consisted of 8 Hours of UV-light exposure 60°C, followed by 4 Hours of condensation at 50°C. Individual samples were taken at 500 hour intervals and measured for color development (Yellowness Index - YI) using a Hunter ColorQuest II Colorimeter (manufactured by Hunterlab, Reston, VA).

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Abstract

L'invention concerne une composition de stabilisant comprenant 75,0 % à 99,9 % en poids d'une composition d'alkylétain comprenant au moins 15,0 % en poids d'un composé di-alkylétain ; et 0,1 % à 25,0 % en poids d'un composé organozinc choisi dans le groupe consistant en sels de zinc d'acides organiques cycloaliphatiques ou aromatiques, ramifiés, linéaires en C1-C24, dicétonates de zinc, alcoolates de zinc et leurs mélanges, la composition de stabilisant étant un liquide stable au stockage ayant une viscosité de moins de 1 500 cP à 25°C.
PCT/US2014/021393 2013-03-15 2014-03-06 Compositions de stabilisant métallique mixte WO2014149894A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105968411A (zh) * 2016-06-27 2016-09-28 浙江海普顿新材料股份有限公司 一锅法制备甲基锡复合热稳定剂的方法
WO2024072728A1 (fr) * 2022-09-27 2024-04-04 Galata Chemicals Llc Compositions de stabilisant thermique à base de métaux mixtes

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CN105968411A (zh) * 2016-06-27 2016-09-28 浙江海普顿新材料股份有限公司 一锅法制备甲基锡复合热稳定剂的方法
WO2024072728A1 (fr) * 2022-09-27 2024-04-04 Galata Chemicals Llc Compositions de stabilisant thermique à base de métaux mixtes

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