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WO2009007265A1 - Compositions de stabilisateurs - Google Patents

Compositions de stabilisateurs Download PDF

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Publication number
WO2009007265A1
WO2009007265A1 PCT/EP2008/058358 EP2008058358W WO2009007265A1 WO 2009007265 A1 WO2009007265 A1 WO 2009007265A1 EP 2008058358 W EP2008058358 W EP 2008058358W WO 2009007265 A1 WO2009007265 A1 WO 2009007265A1
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WO
WIPO (PCT)
Prior art keywords
tert
butyl
bis
polypropylene
hydroxy
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Application number
PCT/EP2008/058358
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English (en)
Inventor
Karl-Heinz Hornbach
Philipp Walter
Original Assignee
Basf Se
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Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to EP08774512A priority Critical patent/EP2164892A1/fr
Publication of WO2009007265A1 publication Critical patent/WO2009007265A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic 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
    • C08K5/04—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
    • C08K5/1545—Six-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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • the present invention relates to novel stabilizers mixtures, to compositions comprising a polypropylene-based thermoplastic polymer, and to the novel stabilizer mixtures, as well as the use thereof for stabilizing polypropylene-based thermoplastic polymers against oxidative, thermal or light-induced degradation.
  • Polypropylene-based thermoplastic polymers for example polypropylene (PP), are prone to degradation due to their general structure and the method how these polypropylene-based thermoplastic polymers are being prepared.
  • Tertiary carbon atoms as well as catalyst residuals are making polypropylene-based thermoplastic polymers vulnerable to degradation by autoxidation during long-term exposure or polymer processing at high temperatures, for example higher than 230 0 C.
  • MFR low melt flow rate
  • phenol/phosphite blends IRGANOX 1010 and IRGAFOS 168 in combination with acid scavengers such as calcium stearate (CaSt) or hydrotalcites (Hycite 713) are used as stabilizer packages.
  • acid scavengers such as calcium stearate (CaSt) or hydrotalcites (Hycite 713) are used as stabilizer packages.
  • carbon-centered radical scavengers such as certain type of lactones and vitamin E improve the processing stability.
  • the present invention accordingly relates to a mixture for the stabilization of a polypropylene-based thermoplastic polymer comprising a) at least a compound of the formula I
  • component (c) is present in an amount of 0.0001 to 20%, based on the total weight of components (a), (b) and (c).
  • Component (c) is preferably present in an amount of 0.001 to 15%, for example 0.01 to 15%, typically 0.1 to 15%, based on the total weight of components (a), (b) and (c). In a preferred mixture, component (c) is present in an amount of 1 to 15%, for example 2 to 10%, typically 5 to 10%, based on the total weight of components (a), (b) and (c). In a very specifically preferred mixture, component (c) is present in an amount of 5 to 7%, for example 6%, based on the total weight of components (a), (b) and (c).
  • the weight ratio of component (a) to component (b) is from 2 : 1 to 1 : 4, for example 2 : 1 to 1 : 1.
  • Component (c) is preferably a compound of the formula
  • R 2 is C 7 -C 3 oalkyl
  • R 3 is Ci-C 3 oalkyl
  • Alkyl having from 1 to 30 carbon atoms is a branched or unbranched radical, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1 -methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1 -methylhexyl, n-heptyl, iso- heptyl, 1 ,1 ,3,3-tetramethylbutyl, 1 -methylheptyl, 3-methylheptyl, n-octyl, isooctyl, 2-ethyl- hexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, is
  • component (c) is a compound of the formula I, wherein R 1 is — (CH 2 )- CH- (CH 2 )- CH- (CH 2 )- CH-(CH 3 ) 2 .
  • This compound is vitamin E which is CH 3 CH 3 commercially available as Irganox E 201 (RTM) [Ciba Specialty Chemicals Inc.].
  • the compound of the formula I is Irganox 1010 (RTM) and the compound of the formula Il is lrgafos 168 (RTM). Both are commercially available from Ciba Specialty Chemicals Incorporation. - A -
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylunde
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydroquinones and alkylated hvdroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-ter
  • Hydroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl- 2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
  • 2,2'-thiobis(6-tert-butyl-4-methylphenol 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl- 2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-d
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate di-octadecyl-2-(3-tert-butyl-4-
  • Aromatic hydroxybenzyl compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzy
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl- ⁇ -tert-butyM-hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • 1.1 Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxy- methyl-1-phospha-2,6,7-triox
  • esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-triox
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[
  • Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec- butyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1- ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2- naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3- dimethylbutyl)-N'-phenyl-
  • 2-(2'-Hvdroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(3'
  • benzotriazol-2-ylphenyl 2-[2'-hydroxy-3'-( ⁇ ! ⁇ -dimethylbenzyl)-5'-(1 ! 1 ! 3,3-tetramethylbutyl)- phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-( ⁇ , ⁇ -dimethylbenzyl)- phenyl]benzotriazole.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphe- nylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinna- mate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, methyl ⁇ -carbomethoxy-p-methoxycin- namate, N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline, neopentyl tetra( ⁇ -cyano- ⁇ , ⁇ -di- phenylacrylate.
  • Nickel compounds for example nickel complexes of 2,2'-thio-bis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldi
  • Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 , 2,2,6, 6-pentamethyl-4- piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2- hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert- oct
  • Sanduvor (Clariant; CAS Reg. No. 106917-31-1], 5-(2-ethylhexanoyl)oxymethyl-3,3,5- trimethyl-2-morpholinone, the reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine- 4-yl)butylamino]-6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine), 1 ,3,5- tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4-yl)amino)-s-triazine, 1 ,3,5-tris(N- cyclohexyl-N-(1 ,2,2,6,6-pentamethylpiperazine-3-one-4-yl)amino)-s-triazine.
  • Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxani- lide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy- disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di- tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphit
  • Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N, N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N, N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N- octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl- alpha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N
  • Thiosynergists for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ - dodecyl
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. 10.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • Preferred further additives are for example light-stabilizers, acid scavengers and/or antistatic agents.
  • the mixture of components (a), (b) and (c) and optionally further additives is suitable for stabilizing polypropylene-based thermoplastic polymers against oxidative, thermal or light-indu- ced degradation. Special attention is drawn to their excellent action as antioxidant in the stabilization of polypropylene-based thermoplastic polymers with a melt flow rate lower than 20 after multiple pass extrusion.
  • Polypropylene-based thermoplastic polymers an be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Na and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
  • These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
  • polypropylene-based thermoplastic polymers are:
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, propylene/but-1-ene copolymers, propylene/isobu- tylene copolymers; propylene/butadiene copolymers, terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned above, for example polypropylene/ethylene-propylene copolymers.
  • a further object of the invention is therefore a composition
  • a composition comprising i) a polypropylene- based thermoplastic polymer which is susceptible to oxidative, thermal or light-induced degradation, and ii) at least a mixture of components (a), (b) and (c).
  • the mixture of components (a), (b) and (c) and optionally further additives will preferably be added to the polypropylene-based thermoplastic polymer to be stabilized in concentrations of 0.001 to 5 %, preferably 0.01 to 5 %, typically 0.01 to 1 %, based on the weight of said material.
  • the mixture of components (a), (b) and (c) and optionally further additives will preferably be added to the polypropylene-based thermoplastic polymer to be stabilized in concentrations of 0.05 to 0.5%, for example 0.1 %, based on the weight of said material.
  • the co-stabilizers are added, for example, in concentrations of from 0.01 to 10 %, based on the total weight of the polypropylene-based thermoplastic polymer to be stabilized.
  • compositions also comprise, besides components (i) and (ii), further additives selected from the group consisting of light-stabilizers and/or acid scavengers.
  • light-stabilizers and/or acid scavengers are for example salts of carboxyl acids like for example calcium stearate, zinc stearate or zinc octoate; or metal oxides.
  • alkaline earth metal salts of higher fatty acids or lactic acid such as, for example, calcium stearate, calcium lactate or calcium stearoyl-2-lactylate.
  • the terms calcium lactate and calcium stearoyl-2-lactylate are to be understood as meaning those compounds as disclosed in U.S. 4,366,280.
  • a further description of calcium lactate may be found, for example, in The Merck Index, Eleventh Edition, 1683, page 254 (1989).
  • a useful description of calcium stearoyl-2-lactylate may be found, for example, in The Merck Index, Eleventh Edition, 1711 , page 257 (1989).
  • Especially preferred co-additives are phenolic antioxidants (point 1.1 to 1.16 of the list), UV absorbers and light-stabilizers (point 2 of the list), for example sterically hindered amines (HALS, point 2.6 of the list).
  • phenolic antioxidants point 1.1 to 1.16 of the list
  • UV absorbers and light-stabilizers point 2 of the list
  • HALS sterically hindered amines
  • a conventional stabilizer combination for the processing of polymeric organic materials such as, for example, polyolefins
  • a phenolic antioxidant with a secondary antioxidant based on an organic phosphite or phos- phonite is recommended.
  • many poly- olefin processors are obliged to operate processes in the high-temperature range above approx. 280 0 C.
  • the inclusion of a processing stabilizer of component (c) [tocopherol compound] is particularly suitable for high-temperature applications, especially in the temperature range above 300 0 C.
  • a further advantage of the stabilizer mixture of components (a), (b) and (c) is also that they can be used in a very small amount, which results in a reduction in the overall antioxidant concentration compared with conventional stabilizer mixtures.
  • a low concentration of component (c) [most preferably 6%, based on the total weight of components (a), (b) and (c)] allows the overall stabilizer concentration to be reduced by approximately a third in, for example, polypropylene-based thermoplastic polymers, which at the same time represents an economic advantage.
  • Components (a), (b) and (c), and also where applicable further additives are incorporated into the polypropylene-based thermoplastic polymer according to known methods, for example before or during the shaping, or alternatively by applying a solution or dispersion of the stabilizer mixture to the polypropylene-based thermoplastic polymer, if necessary with subsequent evaporation of the solvent.
  • the stabilizer mixture of components (a), (b) and (c), and where applicable further additives, may also be added to the polypropylene-based thermoplastic polymer to be stabilized in the form of a masterbatch.
  • the present invention relates therefore also to a masterbatch composition
  • a masterbatch composition comprising a stabilizer mixture comprising components (a), (b) and (c) and optionally further additives as outlined above and a thermoplastic material which is identical or compatible with the polypropylene-based thermoplastic polymer to be stabilized.
  • the masterbatch composition comprises 10 to 80% by weight of said thermoplastic material.
  • the stabilizer mixture of components (a), (b) and (c), and where applicable further additives, may also be added before or during polymerization or before crosslinking.
  • the stabilizer mixture of components (a), (b) and (c), and where applicable further additives, may be incorporated into the polypropylene-based thermoplastic polymers to be stabilized in pure form or encapsulated in waxes, oils or polymers.
  • the stabilizer mixture of components (a), (b) and (c), and where applicable further additives, may also be sprayed onto the polypropylene-based thermoplastic polymers to be stabilized.
  • the mixture can be used to dilute other additives (e.g. the above-mentioned conventional additives) or melts thereof, so that it is also possible for the mixture to be sprayed together with those additives onto polypropylene-based thermoplastic polymers to be stabilized.
  • Addition by spraying during the deactivation of the polymerisation catalysts is especially advantageous, it being possible, for example, for the vapour used for the deactivation to be utilised for the spraying.
  • polypropylene-based thermoplastic polymers are polymerized in the form of beads
  • the stabilizer mixture of components (a), (b) and (c), and where applicable other additives, may be applied by spraying.
  • the polypropylene-based thermoplastic polymers stabilized in that manner may be used in an extremely wide variety of forms, e.g. in the form of films, fibres, tapes, moulding compounds or profiles, or as binders for surface-coatings, especially powder coatings, adhesives or cements.
  • polypropylene-based thermoplastic polymers stabilized in that manner may likewise be used in an extremely wide variety of forms, especially in the form of thick-layer polypropylene moulded articles that are in lasting contact with extracting media, such as, for example, pipes for liquids or gases, films, fibres, geomembranes, tapes, profiles or tanks.
  • extracting media such as, for example, pipes for liquids or gases, films, fibres, geomembranes, tapes, profiles or tanks.
  • polypropylene-based thermoplastic polymer compositions according to the present invention can be advantageously used for the preparation of various shaped articles. Examples are:
  • Floating devices Floating devices, marine applications, pontoons, buoys, plastic lumber for decks, piers, boats, kayaks, oars, and beach reinforcements.
  • I-2) Automotive applications in particular bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter / filler, fuel pumps, fuel tank, body side mouldings, convertible tops, exterior mirrors, exterior trim, fasteners / fixings, front end module, glass, hinges, lock systems, luggage / roof racks, pressed/stamped parts, seals, side impact protection, sound deadener / insulator and sunroof.
  • Road traffic devices in particular sign postings, posts for road marking, car accessories, warning triangles, medical cases, helmets, tires.
  • I-6) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters.
  • Appliances, cases and coverings in general and electric/electronic devices personal computer, telephone, portable phone, printer, television-sets, audio and video devices), flower pots, satellite TV bowl, and panel devices.
  • Electric appliances in particular washing machines, tumblers, ovens (microwave oven), dish-washers, mixers, and irons.
  • shutters e.g. roller shutters
  • Pipes (cross-linked or not) for water, waste water and chemicals, pipes for wire and cable protection, pipes for gas, oil and sewage, guttering, down pipes, and drainage systems.
  • Glass substitutes in particular extruded plates, glazing for buildings (monolithic, twin or multiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles, and greenhouse.
  • Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.
  • IV-1 Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.
  • V) Films (packaging, dump, laminating, agriculture and horticulture, greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries, and connectors.
  • VI-2) Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs, and cans.
  • Vl 1-1 Extrusion coating (photo paper, tetrapack, pipe coating), household articles of any kind (e.g. appliances, thermos bottle / clothes hanger), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap-closures.
  • Support devices articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.
  • sports and fitness devices gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.
  • Vl 1-6 Boxes for CD's, cassettes and video tapes; DVD electronic articles, office supplies of any kind (ball-point pens, stamps and ink-pads, mouse, shelves, tracks), bottles of any volume and content (drinks, detergents, cosmetics including perfumes), and adhesive tapes.
  • Footwear (shoes / shoe-soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, artificial joints (human), printing plates (flexographic), printed circuit boards, and display technologies.
  • Vl 1-8) Devices of filled polymers talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO 2 , mica, nanocomposites, dolomite, silicates, glass, asbestos).
  • a further embodiment of the present invention relates to a shaped article, in particular a film, pipe, profile, bottle, tank or container, fiber containing a composition as described above.
  • a film is preferred.
  • the film can be prepared as a blown film cast film or via extrusion coating. Especially preferred is a multilayer film.
  • a further embodiment of the present invention relates to a molded article containing a composition as described above.
  • the molding is in particular effected by injection, blow, compression, roto-molding or slush-molding or extrusion.
  • the present invention relates also to a process for stabilizing a polypropylene-based thermoplastic polymer against oxidative, thermal or light-induced degradation, which comprises incorporating therein or applying thereto at least a mixture of components (a), (b) and (c).
  • a preferred embodiment of the present invention is likewise the use of a mixture of components (a), (b) and (c) as stabilizers, especially processing stabilizers (thermostabilizers), for polypropylene-based thermoplastic polymers against oxidative, thermal or light-induced degradation.
  • compositions comprising a polypropylene-based thermoplastic polymer comprising a polypropylene-based thermoplastic polymer.
  • Example 1 Stabilization of multiple-extruded polypropylene (PP).
  • melt flow index (MFI) [determined according to ISO 1 133] and Yellowness Index (Yl) [determined according to ASTM D 1925] is measured.
  • MFI melt flow index
  • Yl Yellowness Index

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un mélange pour la stabilisation d'un polymère thermoplastique à base polypropylène comprenant a) au moins un composé de formule (I), b) au moins un composé de formule (II), c) au moins un composé de tocophérol, le composant (c) étant présent en une quantité allant de 0,0001 à 20 %, en se basant sur le poids total des composants (a), (b) et (c).
PCT/EP2008/058358 2007-07-10 2008-06-30 Compositions de stabilisateurs WO2009007265A1 (fr)

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WO2014140383A1 (fr) * 2013-03-15 2014-09-18 Baerlocher Gmbh Compositions de polymère stabilisées et leurs procédés de fabrication
WO2015200586A1 (fr) * 2014-06-25 2015-12-30 Exxonmobil Chemcal Patents Inc. Polypropylène à haute résistance à l'état fondu et procédé extrusion permettant de préserver la résistance à l'état fondu
US9453093B2 (en) 2012-10-31 2016-09-27 Exxonmobil Chemical Patents Inc. Broad molecular weight distribution polypropylene resins
US9464178B2 (en) 2012-10-31 2016-10-11 Exxonmobil Chemical Patents Inc. Articles comprising broad molecular weight distribution polypropylene resins
WO2017138981A1 (fr) 2016-02-12 2017-08-17 Exxonmobil Chemical Patents Inc. Copolymères d'oléfine cyclique et leurs procédés de fabrication
WO2018069540A1 (fr) * 2016-10-14 2018-04-19 Sabic Global Technologies B.V. Matériau d'emballage stérilisable
WO2018069488A1 (fr) * 2016-10-14 2018-04-19 Sabic Global Technologies B.V. Matériau d'emballage
WO2018106388A1 (fr) 2016-12-05 2018-06-14 Exxonmobil Chemical Patents Inc. Polyéthylènes métallocènes à large distribution orthogonale pour films
WO2018226345A1 (fr) 2017-06-07 2018-12-13 Exxonmobil Chemical Patents Inc. Polypropylènes à vaste distribution de poids moléculaire ayant des indices de fluidité élevés et un module de flexion élevé
WO2019013872A1 (fr) 2017-07-13 2019-01-17 Exxonmobil Chemical Patents Inc. Procédé de production de polypropylène durci sous contrainte
WO2019125526A1 (fr) 2017-12-19 2019-06-27 Exxonmobil Chemical Patents Inc. Polypropylènes et leurs procédés de fabrication
US20190322853A1 (en) * 2016-12-23 2019-10-24 Sabic Global Technologies B.V. Automotive part
CN110446748A (zh) * 2017-04-28 2019-11-12 Sabic环球技术有限责任公司 用于bopp应用的聚丙烯组合物、用于制备bopp膜的方法和所述bopp膜
CN110862613A (zh) * 2019-12-03 2020-03-06 江苏林辉塑料制品有限公司 一种抗老化垃圾桶及其制备工艺
WO2020231526A1 (fr) 2019-05-15 2020-11-19 Exxonmobil Chemical Patents Inc. Compositions à base de polypropylènes
WO2021126448A1 (fr) 2019-12-17 2021-06-24 Exxonmobil Chemical Patents Inc. Polyéthylènes à large distribution orthogonale pour films
WO2021126449A1 (fr) 2019-12-17 2021-06-24 Exxonmobil Chemical Patents Inc. Polyéthylènes à large distribution orthogonale pour films
US11267951B2 (en) 2010-12-13 2022-03-08 Cytec Technology Corp. Stabilizer compositions containing substituted chroman compounds and methods of use
US11312043B2 (en) 2010-12-13 2022-04-26 Cytec Technology Corp. Processing additives and uses of same in rotational molding
WO2023036716A1 (fr) 2021-09-09 2023-03-16 Totalenergies Onetech Compositions à base de polypropylène dotées de propriétés de transparence et d'allongement

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US11267951B2 (en) 2010-12-13 2022-03-08 Cytec Technology Corp. Stabilizer compositions containing substituted chroman compounds and methods of use
US11312043B2 (en) 2010-12-13 2022-04-26 Cytec Technology Corp. Processing additives and uses of same in rotational molding
US9453093B2 (en) 2012-10-31 2016-09-27 Exxonmobil Chemical Patents Inc. Broad molecular weight distribution polypropylene resins
US9464178B2 (en) 2012-10-31 2016-10-11 Exxonmobil Chemical Patents Inc. Articles comprising broad molecular weight distribution polypropylene resins
WO2014140383A1 (fr) * 2013-03-15 2014-09-18 Baerlocher Gmbh Compositions de polymère stabilisées et leurs procédés de fabrication
US10119010B2 (en) 2013-03-15 2018-11-06 Baerlocher Gmbh Stabilized polymer compositions and methods of making same
WO2015200586A1 (fr) * 2014-06-25 2015-12-30 Exxonmobil Chemcal Patents Inc. Polypropylène à haute résistance à l'état fondu et procédé extrusion permettant de préserver la résistance à l'état fondu
US20170210859A1 (en) * 2014-06-25 2017-07-27 Exxonmobil Chemical Patents Inc. High melt strength polypropylene and extrusion process for preserving melt strength
JP2017524042A (ja) * 2014-06-25 2017-08-24 エクソンモービル ケミカル パテンツ インコーポレイテッド 高溶融強度ポリプロピレンおよび溶融強度を保持するための押出方法
US11414526B2 (en) 2014-06-25 2022-08-16 Exxonmobil Chemical Patents Inc. High melt strength polypropylene and extrusion process for preserving melt strength
RU2692720C2 (ru) * 2014-06-25 2019-06-26 Эксонмобил Кемикэл Пейтентс Инк. Полипропилен с высокой прочностью расплава и способ экструзии для сохранения прочности расплава
WO2017138981A1 (fr) 2016-02-12 2017-08-17 Exxonmobil Chemical Patents Inc. Copolymères d'oléfine cyclique et leurs procédés de fabrication
EP3578581A1 (fr) 2016-02-12 2019-12-11 ExxonMobil Chemical Patents Inc. Compositions de polyéthylène comprenant des copolymères d'oléfines cycliques
WO2018069488A1 (fr) * 2016-10-14 2018-04-19 Sabic Global Technologies B.V. Matériau d'emballage
WO2018069540A1 (fr) * 2016-10-14 2018-04-19 Sabic Global Technologies B.V. Matériau d'emballage stérilisable
WO2018106388A1 (fr) 2016-12-05 2018-06-14 Exxonmobil Chemical Patents Inc. Polyéthylènes métallocènes à large distribution orthogonale pour films
US12195615B2 (en) * 2016-12-23 2025-01-14 Sabic Global Technologies B.V. Automotive part
US20190322853A1 (en) * 2016-12-23 2019-10-24 Sabic Global Technologies B.V. Automotive part
CN110446748A (zh) * 2017-04-28 2019-11-12 Sabic环球技术有限责任公司 用于bopp应用的聚丙烯组合物、用于制备bopp膜的方法和所述bopp膜
WO2018226345A1 (fr) 2017-06-07 2018-12-13 Exxonmobil Chemical Patents Inc. Polypropylènes à vaste distribution de poids moléculaire ayant des indices de fluidité élevés et un module de flexion élevé
WO2019013872A1 (fr) 2017-07-13 2019-01-17 Exxonmobil Chemical Patents Inc. Procédé de production de polypropylène durci sous contrainte
WO2019125526A1 (fr) 2017-12-19 2019-06-27 Exxonmobil Chemical Patents Inc. Polypropylènes et leurs procédés de fabrication
WO2020231526A1 (fr) 2019-05-15 2020-11-19 Exxonmobil Chemical Patents Inc. Compositions à base de polypropylènes
CN110862613A (zh) * 2019-12-03 2020-03-06 江苏林辉塑料制品有限公司 一种抗老化垃圾桶及其制备工艺
WO2021126449A1 (fr) 2019-12-17 2021-06-24 Exxonmobil Chemical Patents Inc. Polyéthylènes à large distribution orthogonale pour films
WO2021126448A1 (fr) 2019-12-17 2021-06-24 Exxonmobil Chemical Patents Inc. Polyéthylènes à large distribution orthogonale pour films
WO2023036716A1 (fr) 2021-09-09 2023-03-16 Totalenergies Onetech Compositions à base de polypropylène dotées de propriétés de transparence et d'allongement

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