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US20170190874A1 - Stabilizer Compounds - Google Patents

Stabilizer Compounds Download PDF

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Publication number
US20170190874A1
US20170190874A1 US15/312,752 US201515312752A US2017190874A1 US 20170190874 A1 US20170190874 A1 US 20170190874A1 US 201515312752 A US201515312752 A US 201515312752A US 2017190874 A1 US2017190874 A1 US 2017190874A1
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groups
group
formula
aryl
polymer
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Joel Pollino
Gregory GOSCHY
Satchit Srinivasan
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Solvay Specialty Polymers USA LLC
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Solvay Specialty Polymers USA LLC
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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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen

Definitions

  • the present invention describes the use and synthesis of new piperidine-based stabilizer compounds (SC), which provide UV, thermal, and thermo-oxidative stability to polymers.
  • SC piperidine-based stabilizer compounds
  • Aromatic polysulfones and polyetherketones are, for example, widely used in applications where their strength, resistance to harsh chemicals and to high temperatures is necessary.
  • UV degradation is usually catalyzed in high heat environments in the presence of oxygen.
  • the UV degradation of polymers can affect a material's mechanical properties, produce discoloration and fading, roughen the surface, decrease tensile strength, and reduce their overall life time performance.
  • a wide range of light and heat stabilizers for polymers are known and have been used alone or in various combinations to prevent or retard the kinetics of polymer degradation that is initiated by exposure to light and heat.
  • the effectiveness of stabilizers to defend a material against UV radiation and heat depends on several factors including; the intrinsic efficacy of the stabilizer, its concentration, and its solubility in a particular polymer matrix, as well as how well it is distributed in the matrix. Intrinsic volatility of the stabilizer is also an important factor to consider when working with materials which are processed at high temperatures as it may lower the concentration of the stabilizer in a particular polymer matrix as a result of evaporation during processing and subsequent use.
  • Heat stabilizers have been used for many years in various polymer matrixes.
  • Common types of heat stabilization packages include organophosphites, used as a short-term antioxidant to protect the polymer from the high temperature and high shear, and/or phenolic antioxidants used for long-term protection.
  • UV absorbers UV absorbers
  • excited state quenchers radical scavengers
  • peroxide decomposers Certain derivatives of 2,2,6,6-tetramethyl piperidine, also known as hindered amine light stabilizers (HALS), have been known for a long time to improve the light stability, aging properties, and extended field life of polymeric compositions.
  • HALS hindered amine light stabilizers
  • U.S. Pat. No. 4,049,647 discloses their use in low melting temperature polymeric materials such as polyolefins, aliphatic polyamides and polystyrene.
  • the present invention relates to stabilizer compounds (SC) of formula (I) or formula (II):
  • R J is selected from the group consisting of —H, aliphatic groups and alkoxy groups, and wherein each of R K , equal to or different from each other and from R J , is selected from aliphatic groups, and wherein R L is a monovalent substituent selected from the group consisting of:
  • Ri and Rm are the same or different from each other and are independently selected from the group consisting of —H, —CF 3 , —CN, —C( ⁇ O)NH 2 , —NO 2 , alkyl groups, perfluorinated groups, aryl groups, aryl amine groups, aryl ether groups, aryl sulfone groups, aryl thioether groups, fused aryl ring systems, sulfonic acids, carboxylic acids, phosphonic acids, sulfonic acid salts, carboxylic acid salts, and phosphonic acid salts, and wherein Ri is either in an ortho, meta or para position, and wherein Rm is either in an ortho or meta position, and wherein Q is selected from the group consisting of a bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —NH—, —S—, —C(CF 3 ) 2 —, —C( ⁇ CCl 2 —
  • Ri and Rm are the same or different from each other and are independently selected from the group consisting of —H, —CF 3 , —C( ⁇ O)NH 2 , —NO 2 , alkyl groups, perfluorinated groups, aryl groups, aryl amine groups, aryl ether groups, aryl sulfone groups, aryl thioether groups, fused aryl ring systems, sulfonic acids, carboxylic acids, phosphonic acids, sulfonic acid salts, carboxylic acid salts, and phosphonic acid salts, wherein Ri and Rm are independently either in an ortho or meta position, and wherein Q is as above described and wherein G* is a divalent group selected from the group consisting of alkyl groups, perfluorinated groups, aryl groups, aryl amine groups, aryl ether groups, aryl sulfone groups, aryl thioether groups, and fused aryl ring systems.
  • Another aspect of the present invention relates to two distinct methods for the manufacture of said stabilizer compounds (SC).
  • Still another aspect of the present invention relates to a polymer composition (P) comprising said at least one stabilizer compound (SC) and at least one polymer and to a method for stabilizing a polymer comprising the addition of at least one stabilizing compound (SC) to at least one polymer.
  • Yet another aspect of the present invention is directed to an article comprising said polymer composition (P).
  • R J , R K , R L and R N are as above described, imparts high performance aromatic polymers compositions with good heat and light resistance, while surprisingly maintaining their glass transition temperatures to a very high level.
  • R J can be a —H, or a branched, linear or cyclic aliphatic groups or alkoxy groups.
  • Non-limitive Examples of R J are notably —H, —CH 3 , —CH 2 CH 3 , —(CH 2 ) 5 CH 3 , —(CH 2 ) 7 CH 3 , —(CH 2 ) 2 OCH 3 , —OCH 3 , —O(CH 2 ) 5 CH 3 , —O(CH 2 ) 7 CH 3 ,
  • R J is preferably selected from the group consisting of —H, —CH 3 , —CH 2 CH 3 , —OCH 3 , and —OCH 2 CH 3 . Most preferably, R J is —CH 3 .
  • each of R K equal to or different from each other and from R J , can be any branched, linear or cyclic aliphatic groups.
  • R K are notably:
  • R K is preferably selected from the group consisting of —CH 3 , and —CH 2 CH 3 .
  • R L is a monovalent substituent selected from the group consisting of a group of general formula (Y-I) and (Y-II), as above defined.
  • Ri may be in an ortho, meta or para position, and Rm may be in an ortho or meta position. Ri is preferably in a para position. Ri and Rm are preferably —H.
  • Q is preferably —SO 2 —.
  • G is preferably —C( ⁇ O)NH 2 .
  • R N is a divalent substituent selected from the group consisting of a group of general formula (Z-I) and (Z-II), as above defined.
  • Non-Limiting examples of Ri and Rm are notably:
  • Alkyl Groups —CH 3 —CH 2 —O—CH 3 ,
  • Q is as above described for formula (Y-I). It is preferably a bond or —SO 2 —.
  • G* may be selected from the group consisting of alkyl groups, perfluorinated groups, aryl groups, aryl amine groups, aryl ether groups, aryl sulfone groups, aryl thioether groups, fused aryl ring systems.
  • the stabilizer compounds (SC) of formula (I) are preferably selected from the group consisting of structures (A-A) to (A-C) herein below:
  • the stabilizer compounds (SC) of formula (II) are preferably selected from the group consisting of structures (B-A) to (B-B) herein below:
  • another aspect of the present invention is directed to a method for the manufacture of the stabilizer compound of formula (I), comprising the step of reacting compounds of formulae (III) and (IV) together in the presence of a base,
  • X i is a halogen selected from the group consisting of chlorine, fluorine, bromine, and iodine, and wherein R J , R K , R L are as defined above for formula (I).
  • X i is preferably selected from the group consisting of chlorine and fluorine.
  • the compounds of formula (IV) possess preferably an electron withdrawing group para to the halogen Xi.
  • Still another aspect of the present invention is directed to a method for the manufacture of the stabilizer compound of formula (II), comprising the step of reacting compounds of formulae (III) and (IV) together in the presence of a base,
  • X i or X j are the same or independently selected halogens from the group consisting of chlorine, fluorine, bromine, and iodine, and wherein R J , R K , R N are as defined above for formula (II).
  • Xi is preferably selected from the group consisting of chlorine and fluorine.
  • the reaction is preferably carried out in a polar aprotic solvent.
  • a polar aprotic solvent that is capable of dissolving the two starting materials (i.e. compounds of formulae (III) and (IV) or (III) and (V)) can be used in the disclosed methods.
  • the polar aprotic solvent is preferably selected from tetrahydrofuran (THF) or N-methylpyrrolidone (NMP).
  • the reaction temperature can be any temperature up to the boiling point of the solvent, while the lower temperatures usually lead to slower kinetic rates of the reaction(s).
  • the solvent used is THF
  • the reaction is preferably carried out at a temperature of between 25° C. and 66° C. at atmospheric pressure, more preferably between 40 and 66° C. and most preferably between 55 and 66° C.
  • the solvent used is N-methylpyrrolidone
  • the reaction is preferably carried out at a temperature of between 25° C. and 204° C. at atmospheric pressure, more preferably between 50 and 150° C. and most preferably between 80 and 120° C. Excellent results were obtained when the reaction was carried out at a temperature of 66° C. at atmospheric pressure when the solvent used was THF, and 100° C. at atmospheric pressure when the solvent used was NMP.
  • the steps of reacting compounds of formulae (III) and (IV) or compounds of formulae (III) and (V) in the above dislcosed methods for the manufacture of the stabilizer compounds of formula (I) or (II), are preferably carried out in the presence of a base capable of deprotonating a secondary alcohol, and preferably having a pKa of at least 16.
  • the base can be added to compound of formula (III) alone or to a mixture of compounds of formulae (III) and (IV).
  • the base is most preferably the potassium tert-butoxide.
  • the first general procedure was utilized when para-substitution with an electron withdrawing group, R L , as given above (i.e. SO 2 , CF 3 , CN, etc) allowed for the reaction to proceed toward completion and produce high yields aided by utilizing reflux with THF as the polar aprotic solvent.
  • R L an electron withdrawing group
  • the second general procedure was preferably used when there was an absence of an electron withdrawing group, where the use of a higher boiling and more polar aprotic solvent lead to higher yields and/or lower reaction times.
  • a polymer composition (P) comprising at least one of the above disclosed stabilizer compounds (SC) and at least one polymer.
  • the polymers of the polymer composition (P) are high performance aromatic polymers comprising advantageously more than 35 mol %, preferably more than 45 mol %, more preferably more than 55 mol %, still more preferably more than 65 mol % and most preferably more than 75 mol % of recurring units which are aromatic recurring units.
  • aromatic recurring unit is intended to denote any recurring unit that comprises at least one aromatic group in the main polymer backbone.
  • the polymer of the polymer composition (P) may be a semi-crystalline polymer or an amorphous polymer.
  • Semi-crystalline polymers may typically have glass transition temperatures of at least 120° C., preferably at least 140° C. and melting temperatures generally greater than 250° C., preferably greater than 300° C.
  • Amorphous polymers typically have a glass transition temperature of at least 140° C., more typically of at least 150° C. and up to 200° C.
  • Glass transition temperature (Tg) and melting temperature (Tm) are generally determined by DSC, according to ASTM D3418.
  • the polymer of the polymer composition (P) may be selected from the group consisting of polyolefins, polyesters, polyethers, polyketones, poly(etherketone)s, poly(ethersulfone)s, polyamides, polyurethanes, polystyrenes, polyacrylates, polymethacrylates, polyacetals, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitriles, polybutadienes, acrylonitrile butadiene styrene, styrene acrylonitrile, acrylate styrene acrylonitrile, cellulosic acetate butyrate, cellulosic polymers, polyimides, polyamideimides, polyetherimides, polyphenylsulfides, polyphenylene oxides, polyvinylchlorides, polyvinylbutyrates, polycarbonates, epoxy resins, polysiloxanes, and polyketimines.
  • aromatic poly(sulfone)s aromatic poly(ether ketone)s such as poly(ether ether ketone)s (PEEK), aromatic poly(amide)s, aromatic poly(imide)s, poly(phenylene)s, and aromatic liquid crystalline polymers.
  • Aromatic poly(sulfone)s include notably polyphenylsulfone, polysulfone, polyethersulfone, and polyetherethersulfone, the structural repeat units of which are listed below:
  • Aromatic poly(ether ketone)s include notably poly(etherketone), poly(etheretherketone) and poly(etherketoneketone), the structural repeat units of which are listed below:
  • the polymer composition (P) may also further comprises at least another ingredient selected from the group consisting of dyes, pigments, fillers, UV stabilizers, light stabilizers, optical brighteners.
  • the polymer composition (P) comprises advantageously at least 0.01 wt. %, preferably at least 1.0 wt. %, more preferably at least 1.5 wt. %, still more preferably at least 2.0 wt. % and most preferably at least 2.5 wt. % of the stabilizer compounds (SC). Also, the polymer composition (P) comprises advantageously at most 10 wt. %, preferably at most 9 wt. %, more preferably at most 8 wt. %, still more preferably at most 6 wt. % and most preferably at most 5 wt. % of the stabilizer compounds (SC).
  • the polymer composition (P) comprises advantageously at least 20 wt. %, preferably at least 30 wt. %, more preferably at least 40 wt. %, still more preferably at least 50 wt. % and most preferably at least 60 wt. % of the at least one polymer. Also, the polymer composition (P) comprises advantageously at most 99.99 wt. %, preferably at most 99.95 wt. %, more preferably at most 99.90 wt. %, still more preferably at most 99.5 wt. % and most preferably at most 99 wt. % of the at least one polymer.
  • the polymer composition (P) may further comprise at least one additional stabilizer selected from the group consisting of 2-(2′-hydroxyphenyl) benzotriazoles, oxamides, 2-(2-hydroxyphenyl)1,3,5-triazines, 2-hydroxybenzophenones, cyanoacrylates, benzo-oxazolines, and hindered phenolic antioxidants.
  • at least one additional stabilizer selected from the group consisting of 2-(2′-hydroxyphenyl) benzotriazoles, oxamides, 2-(2-hydroxyphenyl)1,3,5-triazines, 2-hydroxybenzophenones, cyanoacrylates, benzo-oxazolines, and hindered phenolic antioxidants.
  • HALS hindered amine light stabilizers
  • HALS are (2,2,6,6-tetramethylpiperidyl) sebacate, (2,2,6,6-tetramethylpiperidyl-) succinate, condensate of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensate of N,N′-bis(2,2,6,6-tetramethyl-1-4-piperidyl)hexamethylene diamine and 4-tert-octylamino-2,6-dichloro-1,3,-5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4 butanetetraoate, 1,1′-(1,2-ethanediyl)-bis(
  • the HALS may be incorporated in the polymer composition (C) in conventional amounts, generally higher than 0.05 wt. % and preferably higher than 0.1 wt. %; further, these amounts are generally lower than 5 wt. % and preferably lower than 1 wt. %.
  • the polymer composition (P) may also contain a variety of other polymer additives in addition to the stabilizer compounds of the present disclosure.
  • additives may include fillers in spherical, spheroidal or polyhedral form, collectively known as “ingredients” herein.
  • these other fillers calcium carbonate, calcium sulfate, barium sulfate, glass beads, ceramic beads, antimony trioxide, zinc borate, and other metal salts and oxides, can be utilized.
  • nucleating agents such as silica, adhesion promoters, compatibilizers, curing agents, lubricants, mold release agents, dyes and colorants, smoke-suppressing agents, heat stabilizers, antioxidants, UV absorbers, tougheners such as rubbers, plasticizers, anti-static agents, melt viscosity depressants such as liquid crystalline polymers, and compounds of similar structures.
  • nucleating agents such as silica, adhesion promoters, compatibilizers, curing agents, lubricants, mold release agents, dyes and colorants, smoke-suppressing agents, heat stabilizers, antioxidants, UV absorbers, tougheners such as rubbers, plasticizers, anti-static agents, melt viscosity depressants such as liquid crystalline polymers, and compounds of similar structures.
  • fillers and other ingredients in the final polymer composition (C) including the stabilizer compounds of the present disclosure will depend primarily on the intended use for the articles of manufacture.
  • the components of the polymer composition (P) along with the optional additional ingredients may be incorporated into the polymer compositions (P) by a variety of different methods and procedural steps which aim to provide their collective improvement in stability properties throughout the mixture.
  • a certain method comprises dry mixing the essential components and optional ingredients in powder or granular form, in appropriate proportions, using e.g. a mechanical blender, such as a drum blender and compounds of similar structures. The mixture is then melted batch-wise or in a continuous device, e.g.
  • extruders and compounds of similar structures extruding the mixture into strands and chopping the strands into pellets.
  • the mixture to be melted may also be prepared by well-known master-batch methods.
  • the continuous melting device may also be fed with the components and ingredients of the polymer composition (P) added separately without dry premixing.
  • a certain other method comprises dissolving the polymer(s) in one or more organic solvents then causing the dissolved polymer(s) to precipitate by the addition of a non-solvent, and finally molding the recovered dried cake.
  • polymer compositions (P) developed according to this disclosure is the manufacture of shaped articles by either extrusion or molding techniques. Therefore, another aspect of the present invention relates to an article comprising the polymer composition (P).
  • polymer compositions (C) of the present invention in connection with their high glass transition temperature, thermal stability, flame resistance, chemical resistance and melt processability, makes them particularly suitable for the manufacture, by any known processing method, of various articles.
  • the article of the present invention may be produced by extrusion or molding techniques.
  • Various molding techniques may be used to form shaped articles or parts of shaped articles from the polymer composition (P). Powders, pellets, beads, flakes, reground material or other forms of the polymer composition (P) may be molded, with or without liquid or other additives, pre mixed or fed separately.
  • the polymer composition (P) may notably be molded into a film, a sheet, or any molded article suitable for indoor and outdoor applications.
  • a last aspect of the present invention relates to a method for stabilizing a polymer comprising adding at least one stabilizing compound (SC) to at least one polymer.
  • SC stabilizing compound
  • the at least one stabilizing compound (SC) may act as an acid scavenger for the at least one polymer.
  • Stabilizer compound (A-A) 1,2,2,6,6-pentamethyl-4-(4-(phenylsulfonyl)phenoxy) piperidine was prepared using general synthetic method 1, more specifically; potassium tert-butoxide (50 mL of a 1M solution in THF, ⁇ 0.05 mol) was combined with a stirred solution of 1,2,2,6,6-pentamethylpiperidin-4-ol (10 g, 0.0495 mol) in THF (40 mL) at 25° C. and allowed to stir for 15 min.
  • Stabilizer compound (A-B) 4-(1,1′-biphenyl]-4-yloxy)-1,2,2,6,6-pentamethylpiperidine was prepared instead by general procedure 2.
  • the 1,2,2,6,6-pentamethylpiperidin-4-ol (15.91 g, 0.0929 mol) was added to a solution of potassium tert-butoxide (10.4 g, 0.0929 mol) dissolved in NMP (100 mL) at 25° C. (the resultant solution was red in color).
  • 4-fluorobiphenyl (8.0 g, 0.0465 mol) was also dissolved in NMP (200 mL), added to the stirred reaction mixture at 25° C., heated to 100° C.
  • Stabilizer compound (A-C) 4-((1,2,2,6,6-pentamethylpiperidin-4-yl)oxy) benzamide was prepared according to general procedure 2.
  • a solution of 1,2,2,6,6-pentamethylpiperidin-4-ol (37.33 g, 0.217 mol) in NMP (200 mL) was slowly added to a the stirred solution of KOtBu (24.35 g, 0.260 mol) in NMP (200 mL) resulting in a reaction that caused a color change to purple and the resultant mixture was allowed to stir at room temperature for 15 minutes to generate the potassium salt nucleophile.
  • the second fraction distilled at 85° C. and 0.8 torr (oil bath set to 160° C.) resulting in a colorless oil.
  • Stabilizer compound (B-A) 4,4′-((sulfonylbis(4,1-phenylene))bis(oxy))bis(1,2,2,6,6-pentamethylpiperidine) was prepared according to general procedure 1.
  • the stirred solution of 1,2,2,6,6-pentamethylpiperidin-4-ol (26.24 g, 0.153 mol) in THF (200 mL) was prepared and within fifteen minutes a solution of 4,4′-dichloro diphenyl sulfone (20 g, 0.0696 mol) was added to the stirred reaction vessel, which was heated, refluxed under N 2 for 72 hours, and followed by recrystallization from a mixture of EtOH/H 2 O 90:10 yielding compound VII (31.71 g, 81.8%) as a white fluffy solid.
  • Stabilizer compound (B-C) 4,4′-bis((1,2,2,6,6-pentamethylpiperidin-4-yl)oxy)-1,1′-biphenyl, was prepared according to general procedure 2.
  • the 1,2,2,6,6-pentamethylpiperidin-4-ol (19.81 g, 0.1157 mol) solution was followed by addition of the 4-4′-difluorobiphenyl (10.0 g, 0.0526 mol) solution as before and heated to 100° C. for 72 hours, cooled, and the resultant solid isolated.
  • the solid was purified according to the same procedure used for examples 3,4, and 6, ultimately providing compound (B-C) (9.80 g, 37%) which appeared as a fluffy, pearlescent white powder that was >95% pure as determined by GC-MS
  • Stabilizer compound (C-A),(4-((1,2,2,6,6-pentamethylpiperidin-4-yl)oxy)phenyl)(phenyl) methanone also was prepared according to general procedure 1, with the exception that the potassium tert-butoxide stirred solution of 1,2,2,6,6-pentamethylpiperidin-4-ol was slowly added to a stirred solution of 4-fluorobenzophenone and refluxed as above.
  • the crude mixture was isolated in the same manner as well, and the pure compound A-B (12.53 g, 72% yield) also appeared as pure (>99%) white crystals.
  • Stabilizer compound (C-B) 1,2,2,6,6-pentamethyl-4-phenoxypiperidine was identically prepared according to general procedure 2 with the exception that in this case, 4-fluorobenzene (12.49 g, 0.130 mol) was added dropwise to the stirred solution of 1,2,2,6,6-pentamethylpiperidin-4-ol (44.56 g, 0.260 mol) and upon complete addition, the reaction mixture was heated to 85° C. for 72 hours.
  • Stabilizer compound (C-C) bis(4-((1,2,2,6,6-pentamethylpiperidin-4-yl)oxy)phenyl)methanone, was also prepared according to general procedure 1 using a stirred solution of 1,2,2,6,6-pentamethylpiperidin-4-ol (34.55 g, 0.20 mol) in THF (200 mL). Fifteen minutes later, a solution of difluorobenzophenone (20 g, 0.0917 mol) was added during stirring, refluxed, and recrystallized from a mixture of EtOH/H 2 O 90:10 resulting in compound B-B (41.64 g, 87.1%) appearing as a white fluffy solid.
  • Stabilizer compound (C-D) 1,2,2,6,6-pentamethyl-4-((4trifluoromethyl)phenoxy)piperidine, was synthesized according to general procedure 1 using 2,2,6,6-pentamethylpiperidin-4-ol (12.52 g, 0.073 mol) and Potassium tert-butoxide (73 mL of a 1M solution in THF, 0.073 mol) in THF (40 mL) and 4-fluorobenzotrifluoride (10 g, 0.061 mol) in THF (50 mL). The final product was purified via multiple vacuum distillations (100-110° C.
  • Table 1 below provides a summary of the nine stabilizer compounds prepared including a listing of the general synthesis methods utilized in making them.
  • the aromatic polymer polysulfone manufactured by Solvay Specialty Polymers USA, L.L.C. under the tradename UDEL® polysulfone P1800 was solution blended with stabilizer compounds E1, E2 and E4 (as summarized in Table 2) at 5 mol % loading. This was accomplished by first dissolving the stabilizer compound and polymer in dimethyl formamide (DMF) to prepare a 23 wt. % solution (percent total solids) followed by film casting onto a glass plate pre-heated to 70 C using a 15 mil side of a square applicator (BYK Gardener).
  • DMF dimethyl formamide
  • the resulting 4′′ ⁇ 4′′ ⁇ 50 micron thick film was dried (on a glass plate) using a vacuum oven (120 C, ⁇ 25 mmHg) for 48 h, at which point the film was removed from the glass substrate using a razor blade.
  • the free-standing film was then cut into 10 mm ⁇ 100 mm ⁇ 50 micron strips using a precision trammel cutter and mounted onto an aluminum frame designed for use in an Atlas ci4000 Xenon weather-o-meter. All films were checked for removal of residual solvent using FT-IR (the carbonyl band for DMF at 1680 cm-1 prior to UV exposure).
  • Table 2 summarizes the changes in transmission after UV ageing (exposure) in the same weather-o-meter for the mono-substituted piperidin-ol stabilizer compounds (A-A), (A-B), and (A-C) as well as for the comparative examples CE1 (C-A), and piperidine-based commercial compounds CE3 and CE4 (HALS).
  • Tg glass transition temperatures
  • DSC Differential scanning calorimetry
  • the temperature program provided two sequential heating and cooling cycles that were carried out between 25° C. and 225° C. at a rate of 20° C./min. All glass transition temperatures were determined using TA Thermal Advantage and Universal Analysis software and were made using the second heat cycle.
  • Table 4 summarizes the change in transmission after UV ageing (exposure) in the same weather-o-meter for the bis-substituted stabilizer compounds (B-A) (E4), and (B-B) (E5) as well as for the comparative examples CE5 (compound (C-C)).
  • Compound (C-D) of CE6 presented a very low thermal stability.
  • the temperature at which 10% wt. loss was observed by thermal gravimetric analysis (TGA) for compound (A-C) was 132° C. and would therefore not be suitable to be used at the processing temperatures of commodity polymers, let alone the high processing temperatures of high performance aromatic polymers.

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  • Compositions Of Macromolecular Compounds (AREA)
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US5976417A (en) * 1909-01-07 1999-11-02 Clariant Finance (Bvi) Limited Mixtures of HALS compounds
GB9100257D0 (en) * 1991-01-07 1991-02-20 Sandoz Ltd Improvements in or relating to organic compounds
US4049647A (en) * 1971-11-30 1977-09-20 Ciba-Geigy Corporation Bis piperidyl carboxylates
BE792043A (fr) * 1971-11-30 1973-05-29 Ciba Geigy Derives de la piperidine utilisables pour stabiliser des matieres organiques
JPS557861B2 (fr) * 1972-10-04 1980-02-28
US5030243A (en) 1989-01-05 1991-07-09 Ciba-Geigy Corporation Process for the photochemical stabilization of undyed and dyeable artificial leather with a sterically hindered amine
DE4000551A1 (de) 1989-01-13 1990-07-19 Ciba Geigy Ag Verfahren zum fotochemischen stabilisieren von gefaerbter wolle
DE4141661A1 (de) 1990-12-20 1992-07-02 Ciba Geigy Ag Stabilisierte chlorhaltige polymere
JP3560243B2 (ja) * 1992-02-03 2004-09-02 ヘキスト・セラニーズ・コーポレーション 紫外線安定剤，酸化防止剤および着色剤である４´−ヒドロキシアセトフェノン，４−ヒドロキシスチレン，１，１，１−トリス（４´−ヒドロキシフェニル）エタン，および１，３，５−トリス（４´−ヒドロキシフェニル）ベンゼンの誘導体
EP1449872A1 (fr) * 2003-02-21 2004-08-25 Clariant International Ltd. Stabilisation de matériaux polymériques
WO2004076419A1 (fr) * 2003-02-26 2004-09-10 Ciba Specialty Chemicals Holding Inc. Alcoxyamines steriquement encombrees et alcoxyamines hydroxy substituees hydrocompatibles
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US11111358B2 (en) 2021-09-07
CN106459489B (zh) 2019-07-12
US20200157312A1 (en) 2020-05-21
EP3145911A1 (fr) 2017-03-29
JP2017518285A (ja) 2017-07-06
EP3145911B1 (fr) 2020-07-08
WO2015177193A1 (fr) 2015-11-26
KR20170007748A (ko) 2017-01-20
CN106459489A (zh) 2017-02-22
JP6667458B2 (ja) 2020-03-18

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