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WO2025056330A1 - Compositions polymères stabilisées à résistance de couleur améliorée - Google Patents

Compositions polymères stabilisées à résistance de couleur améliorée Download PDF

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Publication number
WO2025056330A1
WO2025056330A1 PCT/EP2024/074153 EP2024074153W WO2025056330A1 WO 2025056330 A1 WO2025056330 A1 WO 2025056330A1 EP 2024074153 W EP2024074153 W EP 2024074153W WO 2025056330 A1 WO2025056330 A1 WO 2025056330A1
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Prior art keywords
hydroxy
bis
butyl
tert
benzoxazin
Prior art date
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PCT/EP2024/074153
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English (en)
Inventor
Ram. B GUPTA
Jerry Mon Hei ENG
Jian-Yang Cho
Samim Alam
Lei Zhang
Parker RENEAU
Andrea Landuzzi
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Cytec Industries Inc
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Cytec Industries Inc
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Publication of WO2025056330A1 publication Critical patent/WO2025056330A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • a variety of organic materials are known to undergo degradation by several mechanisms including exposure to electromagnetic radiation such as sunlight and other sources of ultraviolet (“UV”) radiation and heat.
  • electromagnetic radiation such as sunlight and other sources of ultraviolet (“UV”) radiation and heat.
  • polymeric materials such as plastics often discolor, lose gloss and mechanical properties and/or become brittle as a result of prolonged exposure to the sun.
  • UV radiation such as sunlight and other sources of ultraviolet (“UV”) radiation and heat.
  • polymeric materials such as plastics often discolor, lose gloss and mechanical properties and/or become brittle as a result of prolonged exposure to the sun.
  • a large body of art has been developed directed toward materials such as UV light absorbers and various other stabilizers, which are capable of inhibiting such degradation in these materials.
  • UV light absorbers such as benzotriazoles and benzophenones were initially used to stabilize polymeric materials, and to prevent the degradation of such materials from exposure to UV light. Later, it was discovered that hindered amine light stabilizers (“HALS”), which scavenge free radicals formed in the polymeric material when exposed to UV light, were more effective than UV light absorbers (“UVAs”). Accordingly, the use of HALS and UV light absorbers in combination are conventionally used to stabilize polymeric materials.
  • HALS hindered amine light stabilizers
  • UVAs UV light absorbers
  • UVAs by themselves or in combination with HALS to stabilize polymers such as coatings and plastics against weathering due to the direct or indirect impact of heat and ultraviolet light has remained an active area of research.
  • stabilizer compositions While it is the intent of most stabilizer compositions to reduce or prevent degradation caused by heat, such stabilizer compositions do not typically yield the desired result. Frequently, stabilizer compositions that are useful for reducing or preventing degradation caused by heat are hindered or completely relinquished due to the antagonistic effect when combined with compounds useful for absorption of ultraviolet light.
  • polymeric resins can be achieved by blending certain additives with the polymeric resins. For example, in certain instances it is desirable to modify the surface interface of polymeric materials to produce a variety of related surface effects such as improved slip or lubricity, reduced blocking, or to lubricate processing equipment. It may also be desirable in certain instances to modify polymeric surfaces to improve release of adhesives and promote demolding or adhesion of other materials from a polymeric composition surface. In other instances, polymer films having good clarity and optical properties, and which resist fogging, are desirous.
  • a variety of prior art additives classified as anti-block additives, slip aids, coefficient of frictions modifiers, anti-fog agents, anti-static agents, and release aids have been used in an attempt to provide these attributes to different types of organic materials.
  • These various prior art additives are generally described to be surface active compounds (i.e., surfactants).
  • embodiments disclosed herein relate to a stabilized polymer composition
  • a stabilized polymer composition comprising an organic polymeric material to be stabilized and a stabilizer composition comprising at least one UV absorber selected from o-hydroxyphenyl-triazine UV absorber class; a secondary hindered amine light stabilizer (sec. -HALS); at least one antioxidant selected from hindered phenol, phosphite, phosphonite, or any mixture thereof; a tertiary hindered amine light stabilizer (tert. -HALS); an alkoxylated alcohol; and optionally a hindered benzoate.
  • the stabilized polymer composition is more resistant to discoloration due to gas fading and thermal oxidation compared to the polymer composition wherein the aforementioned stabilizer composition does not include a tertiary HALS stabilizer and an alkoxylated alcohol.
  • embodiments disclosed herein relate to a process for making a stabilized article that includes adding the stabilized polymer composition to a device or process for performing industrial molding; industrial fiber making; industrial tape; and extruded sheets.
  • the stabilizer compositions according to the present disclosure are suitable for use in stabilizing various organic materials subject to mechanical stress, discoloration, or effects such as oxidation, chain scission, and uncontrolled recombination and cross- linking reactions that are caused by photo-oxidation and can be incorporated into such organic material to protect it from these deleterious effects, or it can be used as, or within, a UV filter layer for preventing UV radiation from reaching the organic material or an article of manufacture produced with the organic material.
  • the stabilizer compositions according to the disclosure can be readily combined with an organic material to be stabilized, or vice versa, by any suitable method known to those of skill in the art.
  • the term “combined” or “combining” in reference to the stabilizer composition and the organic material to be stabilized includes all manners and/or techniques known to those skilled in the art for intermixing, admixing, integrating, mixing, or blending two or more substances.
  • the components of the stabilizer compositions can be combined with the material to be stabilized by at least one technique chosen from extruding, pelletizing, grinding, and molding.
  • combining can be performed by at least one of melting, dissolution in a solvent, direct mixing, and dry mixing.
  • the incorporation of the stabilizer compositions according to the disclosure, and of optional further co-stabilizers and/or co-additives, into the organic materials to be stabilized can be carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions, or suspensions for example in an inert solvent, water, or oil.
  • Such stabilizer compositions are preferably non- aqueous.
  • co-active agent and UV stabilizers for the stabilizer composition, and optional further co-stabilizers and/or co-additives, into the organic material to be stabilized can be carried out by any suitable method known to those of skill in the art and include, for example, before or after molding, or also by applying the dissolved or dispersed stabilizer mixture to the organic material to be stabilized, with or without subsequent evaporation of the solvent or suspension/dispersion agent. They may be added directly into processing apparatus (e.g., extruders, internal mixers, kneaders etc.) as a dry mixture or powder, or as a solution or dispersion, or suspension or melt.
  • processing apparatus e.g., extruders, internal mixers, kneaders etc.
  • the stabilizer compositions according to the disclosure can also be combined into organic materials such as polymers at a time before, during, or just after, for example, polymerization of corresponding monomers, or before crosslinking.
  • the stabilizer compositions according to the disclosure can also be combined into the organic material to be stabilized in pure form (i.e., neat and directly to the resin) or encapsulated in waxes, oils or polymers.
  • additives can also be preblended (i.e., mixed together) for simple addition to an organic material to be stabilized.
  • Individual components of the stabilizer composition, and optional further co-stabilizers and/or co-additives, can also be sprayed onto the organic material to be stabilized. They are able to dilute other conventional additives or their melts so that they can also be sprayed together with these additives onto the materials to be stabilized.
  • Addition by spraying during the deactivation of any polymerization catalysts can be particularly advantageous as the steam evolved can be used for deactivation of the catalyst.
  • the disclosure provides stabilizer compositions having a stabilizing amount of an ultraviolet light absorber (UVA) selected from the group consisting of orthohydroxyphenyl triazine compounds; orthohydroxybenzophenone compounds; orthohydroxyphenyl benzotriazole compounds; benzoxazinone compounds; and mixtures thereof; and from 1 wt.% to 99 wt. % of a co-active agents based on the total weight of the stabilizer composition.
  • UVA ultraviolet light absorber
  • the stabilizer compositions also include a stabilizing amount of both a secondary and tertiary hindered amine light stabilizer (HALS); an alkoxylated alcohol; an antioxidant selected from hindered phenol, phosphite, phosphonite or any mixture thereof; and optionally a hindered benzoate.
  • HALS secondary and tertiary hindered amine light stabilizer
  • an alkoxylated alcohol an antioxidant selected from hindered phenol, phosphite, phosphonite or any mixture thereof
  • optionally a hindered benzoate optionally a hindered benzoate.
  • embodiments also include masterbatch concentrates having a stabilizer composition as described in any embodiment herein, and an organic material that is identical to or compatible with an organic material to be stabilized.
  • the organic material identical to or compatible with the organic material to be stabilized acts as a carrier vehicle of the stabilizer compositions described herein, which is then admixed with the organic material to be stabilized.
  • the amount of stabilizer composition present as a portion of the total masterbatch concentrate will vary based on, for example, the type of material to be stabilized and/or its end-use application, in some embodiments the stabilizer composition will be present in an amount from 10 wt. % to 90 wt. %, based on the total weight of the masterbatch concentrate. In other embodiments, the stabilizer composition can be present at from 30 wt. % to 80 wt. %; or from 40 wt. % to 75 wt. % of the total weight of masterbatch concentrate.
  • stabilizer compositions include an ultraviolet light absorber (UVA) selected from the group consisting of orthohydroxyphenyl triazine compounds, orthohydroxybenzophenone compounds, orthohydroxyphenyl benzotriazole compounds, benzoxazinone compounds, and mixtures thereof; secondary and tertiary hindered amine light stabilizers (HALS); an alkoxylated alcohol; an antioxidant selected from hindered phenol, phosphite, phosphonite or any mixture thereof; and optionally a hindered benzoate.
  • UVA ultraviolet light absorber
  • HALS secondary and tertiary hindered amine light stabilizers
  • HALS secondary and tertiary hindered amine light stabilizers
  • an alkoxylated alcohol an antioxidant selected from hindered phenol, phosphite, phosphonite or any mixture thereof
  • optionally a hindered benzoate optionally a hindered benzoate.
  • orthohydroxyphenyl triazines are an effective class of triazines for use in the stabilizer compositions.
  • Orthohydroxyphenyl triazines are well known in the art and in the field of stabilizer additive technology. They have been disclosed and treated in many references and patents including U.S. Patent Nos. 6,051,164; and 6,843,939, the orthohydroxyphenyl triazines compounds of which are incorporated herein by reference.
  • Particularly preferred orthohydroxyphenyl triazines include 2-(2’-hydroxyphenyl)-l,3,5-triazine compounds according to Formula (I): R 34 -4 wherein R 34 and R 35 are the same or different and are independently chosen from: a C 6 -C 10 aryl group, wherein the C 6 -C 10 aryl group is optionally substituted at from 1 to 3 substitutable positions with one or more group chosen from OH, halogen, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 - 12 alkoxyester, C 2 - 12 alkanoyl, or phenyl, wherein the phenyl is optionally substituted at from 1 to 3 substitutable positions with one or more group chosen from: hydroxyl, halogen, C 1 - 12 alkyl, C 1 - 12 alkoxy, C 1 - 12 alkoxyester, or C 2 - 12 alkanoyl; mono- or di-C 1 -C 12 hydrocar
  • orthohydroxyphenyl triazines include, but are not limited to, those under the trade names CYASORB® UV-1164 (available from Cytec Industries Inc., Woodland Park, NJ); TINUVIN® 1577FF or TINUVIN® 400 (available from BASF, Ludwigshafen, Germany).
  • the orthohydroxyphenyl triazine compound of the stabilizer composition includes, but is not limited to, one or more of the following compounds:
  • UVAs that are suitable for use in the compositions described herein include one or more of orthohydroxybenzophenones, orthohydroxyphenylbenzotriazoles, oxanilides, cyanoacrylates, or benzoxazinone compounds.
  • the UVA component of the stabilizer composition includes orthohydroxytriazines, orthohydroxybenzophenones, orthohydroxyphenyl benzotriazoles, or benzoxazinones individually.
  • the UVA component includes a combination of two or more of such UVA compounds. Orthohydroxybenzophenones, orthohydroxybenzotriazles, and benzoxazinones are also well known to those skilled in the art of stabilizer additive technology.
  • orthohydroxybenzophenones for use with the stabilizer compositions contemplated herein include any one or more of 2-hydroxy-4-methoxybenzophenone (commercially available from Cytec Industries Inc. as CYASORB® UV-9); 2,2’-dihydroxy-4- methoxybenzophenone (commercially available from Cytec Industries Inc. as CYASORB® UV-24); 2-hydroxy-4-octyloxybenzophenone (commercially available from Cytec Industries Inc.
  • orthohydroxyphenyl benzotriazoles useful in the UVA component of the stabilizer compositions described herein include any one or more of those commercially available from Cytec Industries Inc. (e.g., CYASORB® UV- 5411), or 2-(2'-hydroxy-5'- methylphenyl)-benzotriazole; 2-(2'-hydroxy-5'-tert- butylphenyl)benzotriazole; 2-(2'- hydroxy-3'-methyl-5'-tert-butylphenyl)-benzotriazole; 2-(2'-hydroxy-5'- cyclohexylphenyl)-benzotriazole; 2-(2'-hydroxy-3',5'-dimethylphenyl)- benzotriazole; 2- (2'-hydroxy-5'-tert-butylphenyl)-5-chloro-benzotriazole; 2-(2’ -hydroxy- 5-tert- octylphenyl)-2H-
  • Stabilizer compositions may further comprise an inorganic UV blocker.
  • Suitable inorganic UV blockers may be titanium oxide, zinc oxide, cerium oxide, barium sulfate, or any combinations thereof.
  • Inorganic UV blockers may be present in the stabilizer composition of the final polymeric article in an amount ranging from a lower limit of 0.01, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, or 1.0 wt. % to an upper limit of 1.0, 2.0, 3.0, 4.0 or 5.0 wt. %, where any lower limit may be used in combination with any suitable upper limit.
  • HALS Hindered Amine Light Stabilizer
  • HALS compounds scavenge free radicals formed in polymeric materials when exposed to UV light and are more effective as a combination of a secondary and a tertiary HALS than when UVAs are used with a lone HALS.
  • the benefits imparted by various HALS compounds in combination with UVAs have been demonstrated in at least U.S. Patent Nos. 6,051,164 and 6,843,939, which teachings are incorporated herein by reference.
  • the stabilizer compositions described herein include a stabilizing amount of at least one secondary and at least one tertiary HALS compound that includes a functional group according to Formula (II): wherein R 31 is chosen from: hydrogen (for secondary HALS); or (for tertiary HALS) OH; C 1 -C 20 hydrocarbyl; —CH 2 CN; C 1 -C 12 acyl; or C 1 -C 18 alkoxy; R 38 is chosen from: hydrogen; or C 1 -C 8 hydrocarbyl; and each of R 29 , R 30 , R 32 , and R 33 is independently chosen from C 1 -C 20 hydrocarbyl, or R 29 and R 30 and/or R 32 and R 33 taken together with the carbon to which they are attached form a C 5 - C 10 cycloalkyl; or a functional group according to Formula (IIa): wherein m is an integer from 1 to 2; R 39 is chosen from: hydrogen; OH; C 1 -C
  • Exemplary HALS compounds contemplated for use as a component of the stabilizer compositions described herein can include one or more of those commercially available from Cytec Industries Inc. such as mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6- tetramethylpiperidine (e.g., CYASORB® UV-3853), or bis(2,2,6,6-tetramethylpiperidin- 4-yl) sebacate; bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate; bis(l,2,2,6,6- pentamethylpiperidin-4-yl)sebacate; bis(l-octyloxy-2,2,6,6-tetramethylpiperidin-4- yl)sebacate; bis(l,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-butyl-4- hydroxybenzylmal onate; a condensate
  • CYASORB® UV-3346 a condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin- 4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-l,3,5-triazine, methylated (commercially available from Cytec Industries Inc.
  • Preferred secondary hindered amine light stabilizers may be selected from bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate; a mixture of
  • Secondary Hindered Amine Light Stabilizer may be present in the stabilizer composition of the final polymeric article in an amount ranging from a lower limit of 0.005 wt. %, 0.01 wt. %, 0.05 wt.%, or 0.1 wt. % to an upper limit of 2.5 wt. %, 5 wt. %, or 10 wt. % where any lower limit may be used in combination with any suitable upper limit.
  • Preferred tertiary hindered amine light stabilizers may be selected from bis(l,2,2,6,6-pentamethylpiperidin-4-yl)sebacate; bis(l, 2,2,6, 6-pentamethyl-4- piperidinyl); bis(l,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-butyl-4- hydroxybenzylmal onate; a condensate of 1 -(2 -hydroxy ethyl)-2, 2,6, 6-tetramethyl-4- hydroxypiperidine and succinic acid; a mixture of bis(l, 2,2,6, 6-pentamethylpiperidin-4- yl) sebacate and methyl l,2,2,6,6-pentamethylpiperidin-4-yl sebacate (TINUVINTM 292); bis(l,2,2,6,6-pentamethylpiperidin-4-yl) //-
  • Tertiary Hindered Amine Light Stabilizer may be present in the stabilizer composition of the final polymeric article in an amount ranging from a lower limit of 0.005 wt. %, 0.01 wt. %, 0.05 wt.%, or 0.1 wt. % to an upper limit of 2.5 wt. %, 5 wt. %, or 10 wt. % where any lower limit may be used in combination with any suitable upper limit.
  • the weight ratio of the sec. -HALS to tert. -HALS can vary depending on the components within the composition, the type of material to be stabilized, and/or the application of the stabilized material. In one or more embodiments, the ratio of the sec.- HALS to tert. -HALS can be present at a weight ratio from 10: 1 to 1 : 10, from 8: 1 to 1 :8, from 5: 1 to 1 :5, or from 2: 1 to 1 :2.
  • Stabilizer compositions comprise an alkoxylated alcohol.
  • the alkoxylated alcohol is according to Formula (III):
  • hydrocarbyl as used herein is a generic term encompassing aliphatic, alicyclic and aromatic groups having an all-carbon backbone and consisting of carbon and hydrogen atoms. In certain cases, as defined herein, one or more of the carbon atoms making up the carbon backbone may be optionally replaced or interrupted by a specified atom or group of atoms, such as by one or more heteroatom of N, O, and/or S.
  • hydrocarbyl groups include alkyl, cycloalkyl, cycloalkenyl, carbocyclic aryl, alkenyl, alkynyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkenylalkyl, and carbocyclic aralkyl, alkaryl, aralkenyl and aralkynyl groups.
  • Preferred non-aromatic hydrocarbyl groups are saturated groups such as alkyl and cycloalkyl groups.
  • the hydrocarbyl groups can have up to one hundred carbon atoms, unless the context requires otherwise.
  • Hydrocarbyl groups with from 1 to 60 carbon atoms are preferred, with 1 to 36 carbons more preferred.
  • particular examples are C12-60 hydrocarbyl groups, C12-30 hydrocarbyl groups, C12-22 hydrocarbyl groups, C1-10 hydrocarbyl groups, or C1-4 hydrocarbyl groups, although any individual value, range, or combination of values selected from Ci through Ceo hydrocarbyl groups is contemplated by the inventors as if specifically recited herein.
  • alkyl is intended to include linear, branched, or cyclic hydrocarbon structures and combinations thereof.
  • Lower alkyl refers to alkyl groups of from 1 to 6 carbon atoms. Examples of lower alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, s-and t-butyl, pentyl, hexyl, or cyclohexyl and the like.
  • Preferred alkyl groups include those of C36 or below.
  • R of Formula (III) can be an alkyl group having from 12 to 30 carbon atoms.
  • R can contain from 12 to 22 carbon atoms, and ideally from 12 to 18 carbons, or 12 to 15 carbons.
  • alkoxy refers to groups of
  • T1 from 1 to 20 carbon atoms of a straight, branched, or cyclic configuration, or combinations thereof either attached to the parent structure through an oxygen atom, or incorporated into the backbone of a moiety via an oxygen atom.
  • Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, cyclopropyloxy, cyclohexyloxy and the like.
  • R’ can be methyl or ethyl. In still other embodiments, R’ can be H.
  • the stabilizer compositions according to the present disclosure can include a co-active agent that can be alkoxylated with one or more alkoxide.
  • the co-active agent according to Formula (III) can be ethoxylated.
  • the co-active agent according to Formula (III) can be propoxylated.
  • the co-active agent according to Formula (III) can include a mixture of ethoxylated alcohols and propoxylated alcohols, or can be an alcohol that is both ethoxylated and propoxylated.
  • the degree of alkoxylation i.e., the number of ethoxy and/or propoxy groups in the co-active agent
  • the degree of alkoxylation contemplated by the inventors for the co-active agents described herein ranges from 1 to 100.
  • the degree of alkoxylation given by “y” of the co-active agent according to Formula (III) can range from 1 to 75. In other embodiments, the degree of alkoxylation can range from 2 to 25, or from 2 to 12.
  • the co-active agent can be an alcohol, such as when R” is H.
  • alkoxylated alcohols according to Formula (III) can be made by known methods already available to those of ordinary skill in the art, there are also a host of such compounds presently commercially available.
  • Such commercially available alkoxylated compounds include, but are not limited to, any of the alkoxylated alcohols commercially available or known under the BRIJ® trade name (available from Sigma Aldrich, St.
  • the alkoxylated alcohol can be chosen from any one or more of diethylene glycol octadecyl ether (available as BRIJ® S2); triethylene glycol octadecyl ether (available as BRIJ® S3); polyoxyethylene (5) octadecyl ether (available as Steareth-5); polyoxyethylene (10) octadecyl ether (available as JEECOL® SA- 10); polyoxyethylene (2) oleyl ether (available as BRIJ® 93); polyoxyethylene docosyl ether (available as NOVEL® 22-4); polyoxyethylene (4) oleyl ether (available as HETOXOL® OL-4) or LEUNAPONTM F 1618-55 (C16-C18 alkyl alcohol ethoxylate).
  • BRIJ® S2 diethylene glycol octadecyl ether
  • BRIJ® S3 triethylene glycol octadecyl ether
  • Alkoxylated alcohol may be present in the stabilizer composition of the final polymeric article in an amount ranging from a lower limit of 0.001 wt. %, 0.01 wt. %, 0.05 wt.%, or 0.1 wt. % to an upper limit of 0.25 wt. %, 0.5 wt. %, or 1 wt. % where any lower limit may be used in combination with any suitable upper limit.
  • the weight ratio of the tert. -HALS to alkoxylated alcohol can vary depending on the components within the composition, the type of material to be stabilized, and/or the application of the stabilized material. In embodiments, the ratio of the tert. -HALS or sec - HALS to alkoxylated alcohol can be present at a weight ratio from 100: 1 to 1 : 1, from 50: 1 to 25: 1, or from 10: 1 to 5: 1.
  • Suitable co-additives may be nucleating agents, fillers, metallic stearates, reinforcing agents, plasticizers, lubricants, rheology agents, catalysts, leveling agents, optical brighteners, anti-static agents, blowing agents, flame retardants, dyes, pigments, hindered benzoates, thioesters, hydroxylamines, antioxidants, hindered phenols, phosphites, phosphonites, benzofuranones, nitrones, and mixtures thereof.
  • co- additives include but are not limited to any of those disclosed in U.S. Publication Nos. 2004/0152807; 2009/0085252; 2012/0146257; and 2013/0145962, which are expressly incorporated herein by reference, or known to those skilled in the art.
  • Co-additives may be present in the stabilizer composition of the final polymeric article in an amount ranging from a lower limit of 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, or 1 wt. % to an upper limit of 1, 2, 3, 4, 5, 10, or 20 wt. %, where any lower limit may be used in combination with any suitable upper limit.
  • Suitable hindered benzoates or benzamides for use with the UVA portion of the stabilizer composition include those according to Formula (VI): wherein each of R 21 and R 22 is independently chosen from a C1-12 alkyl;
  • T is chosen from O or NR 24 , where R 24 is H or a C1-30 hydrocarbyl; and R 23 is H or a C1-30 hydrocarbyl.
  • Preferred hindered benzoates can include any one or more of those commercially available from Cytec Industries Inc. such as hexadecyl-3, 5-di-tert-butyl-4- hydroxybenzoate (e.g., CYASORB® UV-2908), or 2,4-di-tert-butylphenyl-3,5-di-tert- butyl-4-hydroxybenzoate; octadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate; octyl-3,5-di- tert-butyl-4-hydroxybenzoate; decyl-3, 5-di-tert-butyl-4-hydroxybenzoate; dodecyl-3,5- di-tert-butyl-4-hydroxybenzoate; tetradecyl-3, 5 -di -tert-butyl-4-hydroxybenzoate; behenylyl-3,5-di-tert-buty
  • Hindered benzoates and/or benzamides may be present in the stabilizer composition of the final polymeric article in an amount ranging from a lower limit of 0.005 wt. %, 0.01 wt. %, 0.05 wt.%, or 0.1 wt. % to an upper limit of 0.25 wt. %, 0.5 wt. %, or 1 wt. % where any lower limit may be used in combination with any suitable upper limit.
  • Preferred hydroxylamines include, but are not limited to, any one or more of N,N- dihydrocarbylhydroxylamine chosen from: N,N-dibenzylhydroxylamine; N,N- diethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N- didodecylhydroxylamine; N,N-ditetradecylhydroxylaamine; N,N- dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine; N-hexadecyl-N- tetradecylhydroxylamine; N-hexadecyl-N-heptadecylhydroxylamine; N-hexadecyl-N- octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and N,N- di(
  • Hydroxylamines may be present in the stabilizer composition of the final polymeric article in an amount ranging from a lower limit of 0.005 wt. %, 0.01 wt. %, 0.05 wt.%, or 0.1 wt. % to an upper limit of 0.25 wt. %, 0.5 wt. %, or 1 wt. % where any lower limit may be used in combination with any suitable upper limit.
  • Preferred hindered phenols include, but are not limited to, any one or more of (l,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-l,3,5-triazine-2,4,6-(lH,3H,5H)- trione; l,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-l,3,5-triazine-2,4,6(lH,3H,5H)- trione; l,l,3-Tris(2’-methyl-4’-hydroxy-5’-t-butylphenyl)butane; Triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate]; 4,4’-Thiobis(2-t-butyl-5- methylphenol); 2,2’-Thiodiethylene bis[3-(3-/-butyl-4-hydroxyl-5-
  • Hindered phenol may be present in the stabilizer composition of the final polymeric article in an amount ranging from a lower limit of 0.005 wt. %, 0.01 wt. %, 0.05 wt.%, 0.1 wt. %, or 0.25 wt. % to an upper limit of 0.3 wt. %, 0.5 wt. %, 0.75 wt. %, or 1 wt. % where any lower limit may be used in combination with any suitable upper limit.
  • Preferred organic phosphites and phosphonites include, but are not limited to, any one or more of triphenyl phosphite; diphenyl alkyl phosphites; phenyl dialkyl phosphites; trilauryl phosphite; trioctadecyl phosphite; distearyl pentaerythritol phosphite; tris(2,4- di-tert-butylphenyl) phosphite; tris(nonylphenyl) phosphite; a compound of formulae (A), (B), (C), (D), (E), (F), (G), (H), (J), (K) and (L):
  • the nonliving organic material to be stabilized is a polyolefin.
  • Polyolefins suitable for use with the stabilizer composition according to embodiments include, but are not limited to:
  • (A) Polymers of monoolefms for example polyethylene, polypropylene, polyisobutylene, polybut-l-ene, and poly-4-methylpent-l-ene, polymers of di olefins such as polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), or ultralow density polyethylene (ULDPE);
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium.
  • the catalysts can be used by themselves in the polymerization 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 la, Ila and/or Illa 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);
  • (C) Mixtures of the polymers mentioned under (A), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE); and
  • (D) Copolymers of monoolefms and diolefins with each other or with other vinyl monomers for example ethyl ene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1- ene copolymers, propylene/isobutylene copolymers, ethylene/but-l-ene copolymers, ethyl ene/hexene copolymers, ethylene/methylpentene copolymers, ethyl ene/heptene copolymers, ethyl ene/octene copolymers, propyl ene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl a
  • Particularly preferred organic materials for stabilizing and providing articles of manufacture include polyolefin polymers such as i) polymers of monoolefms chosen from polyethylene, polypropylene, polyisobutylene, polybut-l-ene, or poly-4-methylpent-l- ene; ii) polymers of diolefins chosen from polyisoprene or polybutadiene; iii) polymers of cycloolefins chosen from cyclopentene or norbornene; iv) polyethylene chosen from optionally crosslinked polyethylene, high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), or ultralow density polyethylene (ULDPE); v) thermoplastic olefins (TPO
  • the stabilizer composition can be present in the stabilized organic material as a stabilized polymer composition (e.g., in an article of manufacture) from 0.005 wt. % to 10.0 wt. % (i.e., any value from 0.01 wt. % to 10.0 wt. %, including any value therebetween).
  • the stabilizer composition may be present in an amount ranging from a lower limit of 0.005 wt. %, 0.01 wt. %; 0.02 wt. %; 0.03 wt. %; 0.04 wt. %; 0.05 wt. %; 0.075 wt. %; 0.10 wt. %; 0.15 wt.
  • wt. % 0.20 wt. %; 0.25 wt. %; 0.30 wt. %; 0.35 wt.%; 0.50 wt. %; 0.75 wt. %; 1.0 wt. %; 1.5 wt. % to an upper limit of 2.0 wt. %; 2.5 wt. %; 3.0 wt. %; 3.5 wt.%; 4.0 wt. %; 4.5 wt. %; 5.0 wt. %; 7.5 wt. %; or 10.0 wt. %, where any lower limit may be used in combination with any suitable upper limit, based on the total weight of the stabilized organic material, and in some cases based on the number and type of stabilizing additives being added and/or the characteristics of the material to be stabilized.
  • Stabilized polymer compositions according to embodiments are more resistant to discoloration due to gas fading and thermal oxidation compared to a comparative polymer composition wherein the comparative stabilizer composition does not include a combination of a secondary and a tertiary HALS stabilizer and an alkoxylated alcohol.
  • Stabilized polymer compositions according to embodiments may have an improved thermal aging resistance demonstrated by measurement of the yellow index (YI) and gas fade resistance demonstrated by measurement of the gas fade as delta E.
  • Delta YI and delta E are the difference between samples measured before and after exposure.
  • Yellowness Index (YI) and Delta E data were obtained using a Macbeth Color Eye Colorimeter as per the ASTM D2244-79 with 1” view and D65/10 0 observer.
  • YI yellow index
  • Delta E data were obtained using a Macbeth Color Eye Colorimeter as per the ASTM D2244-79 with 1” view and D65/10 0 observer.
  • thermal aging test plaques were placed inside a circulating air oven at a temperature of 80 °C and the yellowness index was measured at various time intervals.
  • samples plaques have been placed inside a rotary platform inside a Gas Fade instrument at a temperature of 57 °C developed by Syensqo.
  • Stabilized polymer compositions according to embodiments may have a thermal aging resistance delta YI of less than or equal to 3 at 250 hrs, or 20 at 500 hrs, or 65 at 850 hrs, or 75 at 1000 hrs; and/or a delta E of less than or equal to 3 at 250 hrs, or 10 at 500 hrs, or 30 at 850 hrs, or 35 at 1000 hrs.
  • Stabilized polymer compositions according to embodiments may have a gas fade resistance delta YI of less than or equal to 3.5 at 24 hrs, or 4.5 at 48 hrs, or 5 at 72 hrs; and/or a delta E of less than or equal to 1.5 at 24 hrs, or 2.1 at 48 hrs, or 2.3 at 72 hrs.
  • embodiments herein relate to processes for stabilizing an organic material subject to degradation and/or discoloration due to effects from light, oxygen, and/or heat, as well as the articles of manufacture thereby obtained. These processes are each achieved by adding before, during, or after processing a stabilizing amount of a stabilizer composition according to embodiments as described throughout the specification and claims to the organic material to be stabilized.
  • the stabilizer composition can be added to the organic material to be stabilized as a neat composition.
  • a masterbatch concentrate as described herein can be added to the organic material to be stabilized.
  • embodiments described herein also provide processes for forming a stabilized article of manufacture, or for protecting an organic material from degradation due to the effects of light and/or heat from UV irradiation, by combining an organic material with a stabilizer composition as herein described.
  • the process can further include shaping the organic material into an article of manufacture by industrial molding, extruding, molding, blowing, casting, thermoforming, or compacting the organic material into an article of manufacture, thereby forming a stabilized article of manufacture.
  • the organic material may be used in industrial fiber or tape making.
  • the process can include combining the organic material with a masterbatch concentrate as herein described.
  • stabilizer compositions and processes are suitable for use with, and readily adapted to, any industrial polymeric molding process including, but not limited to, injection molding, rotomolding, blow molding, reel-to-reel molding, metal injection molding, compression molding, transfer molding, dip molding, gas assist molding, insert injection molding, micro molding, reaction injection molding, two shot injection molding, as well as any variations or combinations thereof.
  • the industrial molding process is rotomolding comprising the steps of: a) filling a mold with the stabilized polymer composition as defined above, b) rotating the mold around at least one axis while heating the mold in an oven, thereby fusing the composition and spreading it to the walls of the mold; c) cooling the mold; d) opening the mold; and e) removing the hollow article from the mold.
  • Yellowness Index (YI) data was obtained using a Macbeth Color Eye Colorimeter as per the ASTM D2244-79 with 1” view and D65/10 0 observer and Color, delta E, was calculated from L*a*b* values obtained from before and after exposure.
  • YI Yellowness Index
  • thermal aging test plaques were placed inside a circulating air oven at a temperature of 80 °C and the Yellowness Index was measured at various time intervals.
  • samples plaques have been placed inside a rotary platform inside a Gas Fade instrument at a temperature of 57 °C developed by Syensqo.
  • sample plaques were placed inside a QUV-B 313 accelerated weathering tester by Q-Lab.
  • the delta YI is the difference between Yellowness Indexes of sample measured before and after exposure. Lower Delta E and Delta YI indicates the lower color and lower yellowness development after the exposure.
  • Results obtained from Table 4 demonstrated that when L-55 and tertiary HALS were added to the stabilizer system containing secondary HALS, triazine UV absorber and antioxidant, the color (Delta E) further reduced after exposing to air oxidative aging at a temperature of 80 °C.
  • Results obtained from Table 6 demonstrated that when L-55 and tertiary HALS were added to the stabilizer system containing secondary HALS, triazine UV absorber, hindered benzoate and antioxidant, the color (delta E) further reduced after exposing to air oxidative aging at a temperature of 80 °C.
  • Results obtained from Table 8 demonstrated that when L-55 and tertiary HALS were added to the stabilizer system containing secondary HALS, triazine UV absorber and antioxidant, the color (delta E) further reduced after exposing to gas fade at a temperature of 57 °C.
  • Results obtained from Table 10 demonstrated that when L-55 and tertiary HALS were added to the stabilizer system containing secondary HALS, triazine UV absorber, hindered benzoate and antioxidant, the color (delta E) further reduced after exposing to gas fade at a temperature of 57 °C.
  • a linear medium density polyethylene resin (NOVAPOL® TF-0338-E) and additives were dry blended as per the Formulation Table 15 and extruded using a single screw extruder from Davis- Standard Corp (Model DS-15-HM) at a melt temperature of 370 °F and extruded polymer strands were pelletized. The extruded pellets were then grinded using a grinder from the Power King and sieved through a pack of mesh containing various porosity. The grinded polymers, which have a particle size from 150 micron to 425 micron, were collected for further evaluation.
  • the set up was design in a fashion that the surface of the polymer powder does not come in direct contact with the heated top platen of the compression mold. As the polymer powder melts, it fuses together without any external shear to produce a uniform article mimicking the rotational molding process. After 10 minutes of heating, the aluminum plate containing the melt cell with molten polymer was taken out of the heated platen and cooled down to room temperature using a cooling fan and the melt cell was removed. The resulting polymer article has a thickness in between 5.3 mm to 5.5 mm. When the polymer article was cooled down to room temperature, the color of the article was taken using the Color Eye Colorimeter as per the ASTM D2244-79.
  • Yellowness Index values of the article produced after a simulated rotational molding process is listed in Table 16.
  • the mold side refers to the side where the polymer comes in direct contact with the hot platen of the compression mold and the air side refers to the side where the polymer comes contact with the hot air produced by the heated top platen of the compression mold. It was found that the addition of L-55, the color of article reduces. The color is further reduced when a combination of a secondary HALS and tertiary HALS are used in the formulation with L-55.

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Abstract

La présente invention concerne une composition polymère stabilisée comprenant un matériau polymère organique à stabiliser et une composition stabilisante comprenant au moins un absorbeur d'UV choisi parmi une classe d'absorbeurs d'UV de type o-hydroxyphényl-triazine ; un stabilisant vis-à-vis de lumière consistant en une amine encombrée secondaire (sec .-HALS) ; au moins un antioxydant choisi parmi un phénol encombré, un phosphite, un phosphonite, ou tout mélange de ceux-ci ; un stabilisant vis-à-vis de la lumière consistant en une amine encombrée tertiaire (tert.-HALS) ; un alcool alcoxylé ; et facultativement un benzoate encombré qui est plus résistant à une décoloration due à une dégradation par un gaz et à l'oxydation thermique par comparaison avec la composition polymère où la composition stabilisante ne comprend pas de stabilisant HALS tertiaire et d'alcool alcoxylé. En outre, l'invention concerne un procédé de fabrication d'un article stabilisé qui comprend l'addition de la composition polymère stabilisée à un dispositif ou à un procédé pour effectuer un moulage industriel ; la fabrication de fibres industrielles; une bande industrielle; et des feuilles extrudées.
PCT/EP2024/074153 2023-09-13 2024-08-29 Compositions polymères stabilisées à résistance de couleur améliorée Pending WO2025056330A1 (fr)

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US2976259A (en) 1956-09-05 1961-03-21 American Cyanamid Co 2, 2'-dihydroxy-4-alkoxybenzophenones as ultraviolet light absorbers for resins
US3049443A (en) 1959-01-07 1962-08-14 American Cyanamid Co Process of dyeing synthetic fibers with o-hydroxybenzophenones
US3399169A (en) 1966-05-05 1968-08-27 American Cyanamid Co 2-hydroxy-4-alkoxy-4'-alkylbenzophenones and polymers stabilized therewith
US4322455A (en) 1980-09-15 1982-03-30 General Electric Company Process for producing an ultraviolet radiation stabilized polymeric article
US4446262A (en) 1981-06-19 1984-05-01 Teijin Limited Protection from ultraviolet light by use of novel ultraviolet absorber
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US6843939B2 (en) 2001-12-27 2005-01-18 Cytec Technology Corp. UV stabilizing additive composition
US20060052491A1 (en) 2002-10-02 2006-03-09 Adalbert Braig Synergistic uv absorber combination
US20090085252A1 (en) 2006-02-01 2009-04-02 Ernst Minder Use of Secondary Sterically Hindered Amines as Processing Additives in Rotomolding Processes
US20120146257A1 (en) 2010-12-13 2012-06-14 Cytec Technology Corp. Processing additives and uses of same in rotational molding
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