GB2351732A - Unsaturated polyalkylpiperidine stabilizers - Google Patents

Unsaturated polyalkylpiperidine stabilizers Download PDF

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GB2351732A
GB2351732A GB0014735A GB0014735A GB2351732A GB 2351732 A GB2351732 A GB 2351732A GB 0014735 A GB0014735 A GB 0014735A GB 0014735 A GB0014735 A GB 0014735A GB 2351732 A GB2351732 A GB 2351732A
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tert
bis
phenyl
hydrogen
butyl
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GB0014735D0 (en
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Carl-Eric Magnus Wilen
Jan Anders Harry Naesman
Alfred Steinmann
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BASF Schweiz AG
Ciba SC Holding AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Priority claimed from GB9913587A external-priority patent/GB2338489B/en
Publication of GB0014735D0 publication Critical patent/GB0014735D0/en
Publication of GB2351732A publication Critical patent/GB2351732A/en
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    • 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
    • C07D211/08—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 hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/10—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 hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/12—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 hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with only hydrogen atoms attached to the ring nitrogen atom
    • 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
    • C07D211/48—Oxygen atoms attached in position 4 having an acyclic carbon atom attached in position 4
    • 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
    • C07D211/56—Nitrogen atoms
    • C07D211/58—Nitrogen atoms attached in position 4
    • 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
    • C07D211/68—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 one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—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 one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • C07D211/68—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 one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—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 one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D211/74—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • 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
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring

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

Abstract

Novel ethylenically unsaturated sterically hindered amines of the polyalkylpiperidine type (HALS) can be employed advantageously for stabilizing organic material against the damaging effect of light, oxygen and/or heat.

Description

2351732 Unsaturated polValkylpiperidines The invention relates to novel
ethylenically unsaturated sterically hindered amines of the polyalkylpiperidine type, to organic material stabilized by adding the monomers or polymers of the invention, and to the corresponding use of the novel compounds.
The stability of organic polymers to the damaging action of light, oxygen or heat is frequently improved by adding hindered amines as stabilizers. Also proposed are individual polymeric hindered amines or copolymers comprising certain units of hindered amines (HALS): (US-5541274; US4210612; US-4413096; US4294949; US-4499220; US-5047489), in which case the polymerization of the HALS monomers is initiated by adding azo compounds or peroxides as freeradical initiators, or the HALS units are attached to the polymer subsequently by reaction. The copolymerization of an unsaturated HALS with propylene in the presence of certain catalysts of the Ziegler-Nafta type is described by C.-E. Wilen et al., J. Polym. Sc. (A), Polym. Chem. 30, 1163 (1992); and G. Bertolini et al., J. Polym. Sc. (A), Polym. Chem. 32, 961 (1994).
US-A-5703149 describes the addition of a stabilizer from the class of the sterically hindered amines, for the polymerization of ethylene over a metallocene catalyst, shortly after the beginning of the polymerization reaction.
It has now been found that using metallocene catalysts it is also possible, surprisingly, to obtain polymers which contain the sterically hindered amine in bonded form and which are notable for particularly advantageous properties, especially when used as stabilizers for organic material against the damaging effects of light, oxygen and/or heat or as self-stabilized HALS-containing copolymers.
The invention provides compounds of the formula V, VI, VII or VIII R2 R3 R4 R6-N K RS (V) H R, c _ R7 H2C R R3 2 Y--\ R6 N HC - NW9 (V1) (C H-C=CH2 / / _ j H W; Ri 0 R2 R3 (V]]) %-N -R E-C=CH 2 P, H W7 R, R3 R 17 R2 '3 ---- / R 18 -- N -0-Si-R 20 (V111) R. PDR R 21 \ R 19 in which IR,, R2 and R3 are Cl-C4alkyl; or R2 and R3 together are C4- Clialkylene; R, is hydrogen; R. is hydrogen, OH, Cl-Cl.alky], C37C, 2alkenyl, acryloyloxy, acryloylamido, or is a radical of the formula -X- (CO)i-R8, where i is 0 or 1; or R4 and R5 together are =Q % is hydrogen, C,-C18alkyl, C3-Qalkenyl, C7-Cl,phenylalkyl, or C7-C,,phenytalkyl substituted on the phenyl hng by Cl-C,2alkyl andlor OH; the index j is a number from the range 1-12, especially 4-12; T7'S Cl-C.alkylene; W7 iSC,-C,alkyl; or W7 together with R, is C,-C,,alkylene; R. is C,-C,,,alkyl, C3-C12aikenyl, C7-Cl.5phenylaiky], C,-Cl, phenylaikenyl, C7-Cl.phenytalkyl substituted in the phenyl moiety by C,- Calkyl or C,-C,aRoxy, or is phenyl orCl-C4alkylorCl-C4alkoxy- substituted phenyl; R. is C,-C12alkyl or CS-CUCYCloalkyl; R', is hydrogen, C,-C,2a]kyl orC5-C12cycloalkyLl R,8 and R,, independently of one another are C,-Calkyl, especially methyl; R2. is C3-C,.alkenyl, C7-Cl, cycloalkenylaikyi Or C7-Cl,,bicycloalkenylalky]; R17 and R21 are hydrogen, or R17 together with R21 is a chemical bond; R22 is C2-C,.alkylene, phenylene, phenylene- or cyclohexylene-interrupted C2-C,Oalkylene, or alkylene-phenylene of a total of 2-16 carbon atoms; especially straight- chain C2-C,.alkylene; X is -NH-, -NFR,- or -0-.
With particular preference, R,, R2, R3 and W7 are hydrogen.
Of these compounds, preference is given to compounds of the formula V or VI, in which R,-R, are as defined earlier above for the formula]a; the index j is a number from the range 1-12, especially 4-12; R'7 is C,-C. alkylene; W7'S C,-C.alkyl; or W7 together with R, 'S C4-C11alkylene; R', is hydrogen, C,-C,.alkyl or CS-C12CYcloalkyl.
In the compounds V-VII, R,-R, preferably have the following definitions:
IR,, R2 and R3 are Cl-C4alky]; or R2 and R3 together are C4-C11alkylene; R, is hydrogen; and R. is hydrogen or -X-(CO)i-R8, the index i being 0 or 1; R. is hydrogen, Cl-Cl.alky], or phenyl-substituted C,-C8alky]; where R, , is Cl-Clsaikyl, C7-C15phenylaikyi,C7-C15phenylaikyl substituted in the phenyl moiety by C,-CalkylOr Cl-C4alkoxy, or is phenyl orCl-C4alkyi- orClC4alkoxysubstituted phenyl; F is C,-C12alkyl or C5-Cl2CYcloalky]; and X is -NH-, -NIR,- or -0-.
The unit (CjH2,) in the formula V1 is preferably straight-chain corresponding to the formula (CH2)j.
Particular preference is given to compounds of the formula V, especially those of the formula Va R2 P'3 R4 R6-N > RS (Va) // C - (CH 2) m R, H 2 C in which m is a number from the range 1-8; R, is methyl or ethyl; R2 and R3 are as defined for R, or together are C4-C11alkylene; R4 is hydrogen and R. is hydrogen or a radical of the formula -X-(CO)i-Re; the index i being 0 or 1; or R4 and R. together are =Q F is hydrogen or C,-C,,,alky]; IR, is C,-Clalky], C,-C,.phenylalkyl, C7-C,5phenylalkyl substituted in the phenyl moiety by Cl-C4alkyl or C,-C4alkoxy, or is phenyl or C,-Qalkyl- or Cl-C4aikoxysubstituted phenyl; FR, is C,-CUalkyl or CS-CUCYcloalkyl; and X is -NH-, -NIR,, or -0-.
The novel compounds of the formula V are advantageously prepared by reacting a suitable saturated ketone, for example diacetoneamine, with a preferably terminally unsaturated ketone, for example 3-buten-2-one, 4penten-2-one, 5-hexen-2-one, 6-hepten-2-one, 7-octen-2-one, 8-nonen-2-one or g-decen-2-one, with or without the addition of solvent.
The reaction can otherwise be carded out in analogy to known preparation methods for sterically hindered amines; temperature, work-up and any subsequent reactions, such as hydrogenation, esterification, amidation, etc., can be carried out in analogy to known reactions.
Compounds of the formula V] are judiciously obtained by condensing a compound of the formula X R 2 R 3 )L- %-N HC - NT9 (X) H W / R, - with a suitable unsaturated acid or acid derivative, for example of the formula X-CO-(C,H2j)-CH=CH2, in which the index j is as defined above for formula V1 and X is H or halogen, especially H or Cl. The reaction can be carded out in a manner known per se, for example in the presence of solvents andlor catalysts; also possible is a condensation without such additives, using for example the acid and removing the condensation product by heating. Examples of solvents which can be used include hydrocarbons and chlorinated hydrocarbons; examples of catalysts include, for example, bases, among which are tertiary amines.
Compounds of the formula VII are judiciously obtained in analogy to known methods, for example by addition of unsaturated halogens or Grignard compounds of the type X-R22-CH=CH2 onto the desired 4-oxopiperidine compound with subsequent elimination of water.
Compounds of the formula V] If are judiciously obtained in analogy to known methods, for example by reacting suitably substituted monochlorosilanes with the desired 4-oxopiperidine compound or 4hydroxypiperidine compound.
Work-up can, if desired, be carried out by the conventional methods: for example, by distillation. chromatography, crystallization or recrystallization from the solution.
Other compounds of the formulae la and Ib are known in the majority of cases or can be prepared in analogy to known compounds.
The novel compounds of the formulae V-VIII, especially V and V1, are particularly suitable for use as stabilizers for organic material against its damage by light, oxygen and/or heat. Monomers of the formulae V-VIll, especially V and V1, are able, furthermore, to bind reactively to the substrate into which they are incorporated. The monomeric compounds of the invention feature high substrate compatibility and good persistency in the substrate.
Examples of materials to be stabilized in accordance with the invention are- 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-l-ene, poly-4-methyl pent- 1 -ene, polyisoprene or polybutadien6, 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), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups lVb, Vb, Vlb or Vill 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 n- or a-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(Ill) 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 [a, 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).
2. Mixtures of the polymers mentioned under 1), 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).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-l-ene copolymers, propyleneAsobutylene copolymers, ethylenelbut-l-ene copolymers, ethylenelhexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethyleneloctene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as 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 in 1) above, for example polyp ropyle ne/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C.-C.) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).
6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethyfenelpropylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrenerlsoprene/styrene, styrene/ethylenelbutylene/styrene or styrene/ethylene/propylene/ styrene.
7. Graft copolymers of styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadieneacrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maieimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propyleneldiene terpolymers; styrene and acryfonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chlodde/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from a,p-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrilel alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, or precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from mxylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,tdmethylhexamethyleneterephthalamide or polym-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly- 1,4dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acryfates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVCIEVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPOMIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PAIPP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
The invention therefore further provides compositions comprising A) an organic material sensitive to oxidative, thermal and/or actinic degradation and B) at least one compound of the formula V, VI, VI I and/or VI I I, and provides for the use of the novel monomeric compounds for stabilizing organic material against oxidative, thermal or actinic degradation. The invention likewise embraces a method of stabilizing organic material against thermal, oxidative and/or actinic degradation, which comprises adding to this material at least one compound of the formula V, V1, VII and/or Vill.
Of particular interest is the use of the novel monomeric compounds as stabilizers in synthetic organic polymers, especially thermoplastic polymers, and corresponding compositions.
The organic materials to be protected are preferably natural, semisynthetic or, preferably, synthetic organic materials. Particular preference is given to synthetic organic polymers or mixtures of such polymers, especially thermoplastic polymers such as polyolefins or styrene copolymers, examples being those listed above under 1., 2., 3., 6. and 7., such as polyethylene, polypropylene or styrene and copolymers, especially polyethylene (PE) and polypropylene (PP).
In general, the novel monomeric compounds are added in amounts of from 0. 01 to 50%, preferably from 0.05 to 20% and, in particular, from 0.05 to 10% to the material that is to be stabilized (amounts based on the weight of the material to be stabilized).
Particular preference is given to the use of the compounds of the invention in amounts in which the HALS monomer or comonomer is present in amounts of from 0.05 to 1.5%, in particular from 0. 1 to 0.5%.
Incorporation into the materials can take place, for example, by mixing in or applying the stabilizers of the invention, with or without further additives, by the methods customary in the art. Where polymers are concerned, especially synthetic polymers, incorporation can take place prior to or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as lattices. A further possibility for incorporation of the stabilizers of the invention into polymers is to add them before, during or directly after the polymerization of the corresponding monomers and/or prior to crosslinking. In this case the novel polymeric or monomeric compounds can be added per se or else in encapsulated form (in waxes, oils or polymers, for example).
The stabilizers of the invention can also be added in the form of a masterbatch which comprises the compound(s), for example, in a concentration of from 2.5 to 25% by weight, to the polymers that are to be stabilized.
The stabilizers of the invention can judiciously be incorporated by the following methods: - as an emulsion or dispersion (e.g. to lattices or emulsion polymers), - as a dry mix during the mixing of additive components or polymer mixtures, - by direct addition to the processing apparatus (e.g. extruders, intemal mixers, etc.), or - as a solution or melt.
With particular advantage, the stabilizer of the invention is added to a thermoplastic polymer prior to its processing at elevated temperature, as is often performed, for example, by means of an extruder.
In addition to the stabilizers of the invention, the compositions of the invention may include, as additional component C, one or more conventional additives, such as those indicated below, for example.
The conventional additives are judiciously employed in amounts of 0.01 10, for example 0.01-3% by weight, based on the material to be stabilized.
1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyi-4-methylphenoi, 2-tert-butyi-4,6-dimethylphenol, 2,6-di-tert-butyi-4-ethyl phenol, 2,6-di- tert-butyi-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6- dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyi)-4,6-dimethyiphenol, 2,6-dioctadecyi-4-methylphenol, 2,4,6-tricyclohexyl phenol, 2,6-di-tert- butyi-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyi-4-methylphenol, 2,4-dimethyi-6- (1'-methylundec-l'-yl)phenol, 2,4-dimethyi-6-(1'methylheptadec-l'- yi)phenol, 2,44 methyl-6-(1'-methyitridec- V-y1) phenol and mixtures thereof.
1.2. Alkyithiomethylphenois, for example 2,4-dioctyithiomethyl-6-tertbutylphenol, 2,4-dioctyithiomethyi-6-methylphenol, 2,4-dioctyithiomethyi6-ethylphenol, 2,6-di-dodecyithiomethyi-4nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tertbuty]-4-methoxyphenol, 2,5A i-te rt-butyl hyd roq u i none, 2,5-di-tertamyihydroquinone, 2,6-diphenyi-4-octadecyloxyphenol, 2,6-di-tertbutyihydroquinone, 2,5-di-tert-butyi-4-hydroxyanisole, 3,5-di-tert-butyl4-hydroxyanisole, 3,5-di-tert-butyi-4-hydroxyphenyI stearate, bis-(3,5-ditert-butyi-4-hydroxypheryl) adipate.
1.4. Tocopherols, for example cL-tocopherol, P-tocopherol, y-tocopherol, 5-tocopherol and mixtures thereof (Vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tertbutyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tertbutyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2methylphenol), 4,4thiobis-(3,6-d i-sec-a myl phenol), 4,4'-bis(2,6-dimethyl-4hydroxyphenyl)disulfide.
1.6. Alkylidenebisphenols, for example 2,2'-methylene b is(6-te rt-b utyl4-methyl phenol), 2,2'methylenebis(6-tert-butyl-4-ethylphenol), 2,2'methylenebis[4-methyl-6-(a-methylcyclohexyl)phenol], 2,2'-methylenebis(4methyl-6-cyclohexyi phenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2, 2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tertbutylphenol), 2,2-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'methylenebis[6-(oL-methylbenzyl)-4nonylphenot], 2,2'-methylenebis[6-(a,adimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tertbutylphenol), 4,4'-methylenebis(6-tert-butyl-2-methyI phenol), 1,1-bis(5tert-butyl4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl2-hydroxybenzyi)-4-methylphenol, 1,1,3-tds(5-tert-butyi-4-hydroxy-2methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-ndodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl4'hydroxyphenyf)butyratel, bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis(3,5-dimethyl-2hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyt)-4-n-dodecyimercaptobutane, 1,1,5,5-tetra-(5tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. 0-, N- and S-benzyl compound, for example 3,5,3',5'-tetra-tert-butyl4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy3,5-di-tertbutylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-ditert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4hydroxy-5-methylbenzyl)-malonate, didodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis(4-(1,1,3,3-tetramethylbutyl)phenyq-2,2-bis(3,5-di-tert-butyl-4hydroxy benzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tds-(3,5-di-tertbutyl-4-hydroxybe nzyl)-2,4,6-tri methyl benzene, 1,4-bis(3,5-di-tertbutyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tertbutyl-4-hydroxybenzyl)phenol.
1.10. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-ditert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5di-tert-butyl-4-hydroxyanilino)-1,3,5-tdazine, 2-octylmercapt6-4,6-bis(3, 5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-tdazine, 2,4,6-tris(3,5-di-tertbutyl-4-hydroxyphenoxy)-1,2,3-tdazine, 1,3,5-tris-(3,5-di-tert-butyl-4hydroxybenzyl)isocyanurate, 1,3,5-tds(4-tert-butyl-3-hydroxy-2,6dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4hydroxyphenylethyl)-1,3,5-tdazine, 1,3,5-tris(3,5-di-tert-butyl-4hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tds(3,5dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3methylbenzy[phosphonate, the calcium salt of the monoethyl ester of 3,5di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4hydroxystearanilide, octyl N(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of ft-(3,5-di-tert-b utyl-4-hyd royphenyl) prop ionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4hydroxymethyl-l-phospha-2,6,7-tdoxabicyclo(2.2.2]octane.
1.14. Esters of B-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanedi- ol, 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-thia pentad eca no 1, trimethylhexanediol, trimethyl- olpropane,4-hydroxymethyl-l-p hosp ha-2,6,7-trioxab icyclo[2.2.2] octane.
1.15. Esters of_ Jroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hyd roxyethyl)isocyanu rate, N,N'bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-th ia pentad ecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-I -phospha-2,6,7-tdoxabicyclo[2.2. 2]octane.
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyI acetic acid with monoor 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, tds(hydroxyethyl)isocyanurate, N,Nbis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane, 4-hydroxymethyl-1 -phospha-2,6, 7-trioxabicyclo[2.2.2]octane.
1.17. Amides iydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tertbuty1-4-hydroxy- phenylpropionyl)trimethyienediamide, N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenyipropionyl)- hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4hydroxyphenyl]propionyloxy)ethyl]oxamid e (Nau- gardeXL-1 supplied by Uniroyal).
1. 18. Ascorbic acid (vitamin C) 1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p- phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3methylpentyl)-pphenylenediamine, N,N'-bis(l-methylheptyl)-p-phenylenediamine, N,N'dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'bis(2-naphthyl)-pphenylenediamine, N-isopropyl-N'-phenyl-pphenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N(l-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'phenyl-p-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'dimethyl-N,N'-di-secbutyl-p-phenylenediamine, diphenylamine, Nallyidiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1 -naphthylamine, N-(4-tert-octylphenyl)-l -naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylemine, for example p,p'-di-tert-ocMdiphenylamine, 4-nbutylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4dodecanoyla mi no phenol, 4-octadecanoylaminophenol, bis(4methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'd iaminod iphenyl methane, 4,4'-diaminodiphenylmethane, N,N,N,Ntetramethyl4,4'-diaminodiphenylmethane, 1,2-bis[(2methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (otolyl)biguanide, bis[4-(l',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl1-naphthylamine, a mixture of mono- and dialkylated tertbutylltert-octyidiphenylamines, a mixture of mono- and dialkylated nonyld iphenyla mines, a mixture of mono- and dialkylated cloclecyld i phenyla mines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylated tertbutyidiphenylamines, 2,3-dihydro-3,3-di-' methyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- und dialkylated tert-butylltertoctylphenothiazines, a mixture of mono- und dialkylated tert-octylphenothiazines, Nallylphenothiazin, N,N,N',N-tetraphenyl-1,4-diaminobut-2ene, N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis(2, 2,6,6-tetramethylpipe6d-4-yl)sebacate,.2,2,6,6tetra methylpi peHdin-4-one, 2,2,6,6-tetramethylpipehdin-4-ol.
2. UV absorbers and light stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotdazoles, for example 2-(2'-hydroxy-5'methylphenyl)-benzothazole, 2-(3',5'-di-tert-butyl-2hydroxyphenyl)benzotHazole, 2-(5-tert-butyl-2'hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3tetramethylbutyl)phenyl)benzotriazole, 2-(3,5'-ditert-butyl-2'hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'methylphenyl)-5-chloro-benzoMazole, 2-(3'-sec-butyl-5'-tert-butyl-2'hydroxyphenyl)benzotriazole, 2-(2'hydroxy-4'-octyloxyphenyl)benzothazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyi)benzotriazole, 2-(3',5'-bis-(ct,adimethylbenzyl)-2'-hydroxyphenyl)benzotazole, 2-(3'-tert-butyl-2hydroxy5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzo tdazole, 2-(3'tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5chloro-benzotazole, 2-(3'-tert-butyl-2-hydroxy-5'(2methoxycarbonylethyl)phenyl)-5-chloro-benzotazole, 2-(3'-tert-butyl-2'hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tertbutyl-5'-[2-(2-ethy[hexyloxy)carbonylethyl]-2'-hydroxyphenyi)benzotriazole, 2-(3'-dodecyi-2-hydroxy-5'-methylphenyi)benzotazole, 2-(3'-tert-butyi2'-hydroxy-5'-(2isooctyloxycarbonylethyi)phenyibenzotriazoi e, 2,2'-methylene-bis[4-(1,1, 3,3tetra methyl butyi)-6-benzothazole-2-yiph enoll; the transesterification product of 2-[3'-tert-butyl-5'-(2methoxycarbonylethyi)-2'-hydroxyphenyq-2H-benzotriazo le with polyethylene glycol 300; [R-CH 2CHi-COO-CH 2 CH2- where R = 3'-tert-butyi-4'-hydroxy-5'2H- benzoth- 2 azol-2-ylphenyl, 2-[2'-hydroxy-3-((x,a-dimethy(benzyi)-5'-(1,1,3,3tetramethyfbutyf)-phenyllbenzothazole; 2-[T-hyd roxy-X-(1, 1,3,3-tetra methyl butyl)-5'-(a,ct-di methylbe no)-p he nyl] benzotriazole.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-tdhydroxy and Thydroxy-4,4-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butyfbenzoyi) resorcinol, benzoyl resorcinol, 2,44-tert-butylphenyl 3,5-di-tert-buty]-4- hydroxybenzoate, hexadecyl 3,5-di-tert-butyi-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyi-4-hydroxybenzoate, 2-methyi-4,6-di-tert-butylphenyI 3,5di-tert-butyi-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl a-cyano-p,p-diphenylacrylate, isooctyl a-cyano-p,p-diphenylacrylate, methyl a-carbomethoxycinnamate, methyl acyano-o-methyi-p-methoxy-cinnamate, butyl (x-cyano-p-methyi-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N-(0-carbomethoxyo-cyanovinyi)-2-methylindoline.
2.5. Nickel compounds. for example nickel complexes of 2,2'-thio-b is-[4(1,1,3,3-tetra methylbutyl)phenoll, such as the 1:1 or 1:2 complex, with or without additional ligands such as nbutylamine, triethanolamine or Ncyclohexyidiethanolamine, nickel d ib utyid ithioca rba mate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4hydroxy-3,5-di-tertbutylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methy(phenyl undecyiketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4pipeddyl)sebacate, bis(2,2,6,6-tetramethyl-4-pipeddyI)succinate, bis(1,2, 2,6,6-pentamethyl-4-piperidyl)sebacate, bis(I-octyloxy-2,2,6,6tetramethyl-4-pipeddyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-pipeddyl) nbutyl-3,5-di-tert-butyl-4-hydroxybenzyimalonate, the condensate of 1-(2hydroxyethyl)2,2,6,6-tetramethyl-4-hydroxypipeddine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4pipeddyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5triazine, tris(2,2,6,6-tetramethyl-4-pipeddyl)nitdlotriacetate, tetrakis(2,2,6,6-tetramethyl-4-pipeddyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylp iperazi none), 4-benzoyl-2, 2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpipeddyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tertbutylb enzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4. 5]decan-2,4-dione, bis(1-octyloxy2,2,6,6-tetramethylpipeddyl)sebacate, bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic condensates of N,N'-bis-(2,2,6,6-tetramethyl-4piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5triazine, the condensate of 2-chloro-4,6-bis(4-nbutyla mino-2,2,6,6-tetra methyl pipe ridyl)-1,3,5-triazine and 1,2-bis (3-aminopropyla min o)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6pentamethylpipeHdyl)1,35-triazine and 1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-tdazaspiro[4.5]decane-2,4dione, 3-dodecyl-l-(2,2,6,6-tetramethyl-4-pipeddyl)pyrrolidin-2,5-dione, 3-dodecyl-l-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyfoxy-2,2,6,6-tetramethylpipeddine, a condensation product of N,N'-bis(2,2,6,6-tetramethyl-4piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6tetramethylpipeddine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl4-pipeddyl)-n-dodecylsuccinimid, N(1,2,2,6,6-pentamethyl-4-piperidyl)-ndodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-1 oxa-3,8-diaza-4-oxospiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2cycloundecyl-l-oxa-3,8-diaza-4-oxospiro [4,51decane und epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-pipeddyloxycarbonyl)-2-(4methoxyphenyl)ethe ne, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4pipeddyl)hexamethylenediamine, diester of 4-methoxy-methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypipeddine, poly[methylpropyl-3oxy-4-(2,2,6,6-tetramethyl-4-pipeddyl)]siloxane, reaction product of maleic acid an hyd rid e-(x-olefin-copolymer with 2,2,6,6-tetramethyl-4aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopipeddine.
2.7. Oxamides, for example 4,4'-dioetyloxyoxanilide, 2,2'diethoxyoxanilide, 2,2'-dioctyloxy5,5'-di-tert-butoxanilide, 2,2'didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'bis(3-dimethylaminapropyf)oxamide, 2-ethoxy-5-tert-butyf-2'-ethoxanifide and its mixture with 2-ethoxy-2'-ethyi-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyi)-1,3,5-triazines, for example 2,4,6-tris(2hydroxy-4-octyloxyphenyi)1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyf)-4, 6-bis(2,4-dimethylphenyi)-1,3,5-thazine, 2(2,4-dihydroxyphenyl)-4,6-bis(2, 4-dimethylphenyl1,3,5-thazine, 2,4-bis(2-hydroxy-4-propyioxyphenyi)-6-(2, 4-dimethylphenyi)-1,3,5-thazine, 2-(2-hydroxy-4-octyloxyphenyi)-4,6bis(4methylphenyi)-1,3,5-tdazine, 2-(2-hydroxy-4-dodecyloxyphenyi)-4,6bis(2,4-dimethylphenyi)1,35-triazine, 2-(2-hydroxy-4-thdecyloxyphenyf)-4, 6-bis(2,4-dimethylphenyf)-1,3,5-thazine, 2[2-hyd roxy-4-(2-hyd roxy-3-b utyloxy-propoxy)phenyl]-4,6-bis(2,4-di methyl)- 1,3,5triazine, 2[2hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyi]-4,6-bis(2,4-dimethyl)1,3,5-thazine, 2-[4(dodecyloxyltddecyloxy-2-hydroxypropoxy)-2-hydroxyphenyll-4,6-bis(2,4-d imethyiphenyl)- 1,35-triazine, 2-[2-hydroxy-4(2-hydroxy-3-dodecyloxy-propoxy)phenyq-4,6bis(2,4-dimethyfphenyl)- 1, 3,5-triazine, 2-(2-hyd roxy-4-hexyloxy)phe nyl-4,6-d i phenyl- 1,3,5-triazine, 2-(2-hycl roxy-4-methoxyphenyi)-4,6di phenyl- 1, 3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyt]-1,3,5-thazine, 2-(2-hydroxyphenyi)-4-(4-methoxyphenyl)-6phenyi1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethyihexyi-l-oxy)-2hydroxypropyioxy]phenyf}-4,6-bis(2, 4dimethylphenyi)-1,3,5-triazine.
3. Metal deactivators, for example N,W-diphenyloxamide, N-salicylalWsalicyloyl hydrazine, N,N'-bis(salicyloyi) hydrazine, N,N-bis(3,5-di-tertbutyf-4-hydroxyphenylpropionyf) hydrazine, 3-salicyloyiamino-1,2,4triazoie, bis(benzyfidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,M-diacetyladipoyl dihydrazide, N,M-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, ths(nonylphenyi) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, ths(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyi) pentaerythritol diphosphite, bis(2,6-ditert-butyi-4-methylphenyi)-pentaerythdtof diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tertbutyi-6-methylphenyi)pentaerythdtol diphosphite, bis(2,4,6-tris(tertbutyf- phenyi)pentaerythhtol diphosphite, tristearyl sorbitol triphosphite, tetra kis (2,4A i-tert-b utylphenyl) 4,4'-biphenylene diphosphonite, 6isooctyloxy-2,4,8,10-tetra-tert-butyi-12H-dibenz[d,g]-1,3,2dioxaphosphocin, bis (2,4A i-tert-butyi-6-methyf phenyl) methyl phosphite, bis(2,4di-tert-butyi-6-methylphenyi) ethyl phosphite, 6-fluoro-2,4,8,10tetra-tert-butyi-12-methyl-dibenz[d,g)-1,3,2-dioxaphosphocin, 2,2',2"nitrilo[thethyitds(3,3',5,5'-tetra-tert-butyi-1,1'-biphenyi-2,2'diyf)phosphite], 2-ethylhexyi(3,3',5,5'-tetra-tert-butyi-1,1'-bipheny1-2, 2'-diyi)phosphite, 5-butyi-5-ethyi-2-(2,4,6-tri-tert-butyiphenoxy)-1,3,2dioxaphosphirane.
Especially preferred are the following phosphites:
Tris(2,4-di-tert-butyl phenyl) phosphite (1rgafos"168, Ciba-Geigy), tris(nonylphenyl) phosphite, (CHIC C(CHI (CHIC C(CHI 0 0 CH P-F P-O-CH CHi-N (A) H3C 1 1 2 (B) (CH IC C (CH J3 C(CH (CHIC L_ -j 3 (CHIC C(CHI 0 1 P-O-CH2 CH(C4H.)CH2CH3 (C) 0 (CH IC C(CH3)3 0 0 1 X (CH3 0-P \ 1 P-O C(CHI )3C - 0:)C0 -P- (D) C(CHI (CHIC C(CHI (CH IC 1 OXR -0 H C 0-P P-O 3 X CH 3 C(CH (CH IC CH3 1 _Ut13 H31L;-U (F) F137C5 0-P 1 P-O-Cl8H 0-P-OCH2CH3 (G) 0:)C0 H3C X 1 37 0 0 1.c CH3 H3C \ CH %_ 3 2 5. Hydroxylamines, for example, N,N-dibenzyihydroxylamine, N,N- diethylhydroxylarnine, N,Ndioctylhydroxylamine, N, N-d ilaurylhyd roxylamine, N, N-ditetradecylhyd roxylamine, N,Ndihexadecyihydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxyfamine, Nheptadecyf- N-octadecythydroxyfa mine, N,N-diaikylhydroxylamine derived from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, Wethyl-alphamethyl-nitrone, N-actyi-alpha-heptyf-nitrone, N-lauryi-alpha-undecyinitrone, N-tetradecyf-alpha-tddcyf-nitrone, Nhexadecyi-alpha-pentadecylnitrone, Noctadecyl-alpha-heptadecyl-nitrone, Whexadecyl-aipha-heptadecylnitrone, N-ocatadecyi-alpha-pentadecyi-nitrone, Wheptadecyl-alphaheptadecyl-nitrone, N-octadecyi-alpha-hexadecyf-nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
7. Thiosynergists, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavengers, for example esters of P-thiodipropionic acid, for example the laury], stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disuffide, pentaerythritol tetrakis(pdodecyimercapto)propionate.
9. Polyamide stabilisers, for example, copper salts in combination with iodides andlor phosphorus compounds and salts of divalent manganese.
10. Basic co-stabiiisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zink pyrocatecholate.
11. Nucleating agent, 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 poiycarboxyiic 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). Especially preferred are 1, 3:2,4-bis (X,4'-di methyl benzy] idene)sorbito 1, 1,3:2,4- di(paramethyidibenzylidene)sorbitol, und 1,3:2,4-di(benzyiidene)sorbitai.
12. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, bariumsulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flowcontroi agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S. 4, 325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-431661 1; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2- acetoxyethoxy)phenyi]-5,7-di-tert-butyf-benzofuran-2-one, 5,7-di-tert- butyi-3-[4-(2stearayloxyethoxy)phenyqbenzofuran-2-one, 3,3-bis[5,7-di- tert-butyl-3-(4-[2hydroxyethoxyjphenyi)benzofuran-2-one], 5,7-di-tert-butyl-3(4ethoxyphenyi)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyi)-5,7ditert- butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyIY5,7-di-tert- butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl- benzofuran-2-one, 3(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2- one.
The examples which follow illustrate the invention further. All parts and percentages in the examples as in the remainder of the description and claims are by weight unless stated otherwise. The following abbreviations are used in the examples: GC: Gas chromatography; HPLC High-pressure liquid chromatography; GPC: Gel permeation chromatography; THF: Tetra hydrofuran; MALDI: Matrix Assisted Laser Desorption Ionization;
MS: Mass spectrometry', DSC: Differential thermal analysis; MAO: Methylalurnoxane (manufacturer: Witco); Mn: Number average molar mass (units: g/mol); M": Mass average molar mass (units: g/mol); H-NMR: Nuclear magnetic resonance of the nuclide 'H. 1 torr (= I mmHg) corresponds to a pressure of approximately 133 Pa.
A) Preparation of the monomers (HALS) Al) Preparation of 2-(but-3-enyl)-2,6,6-tdmethyl-4-oxopipeddine H H 3 C N """CF12 H 3C' CH3 0 a) 31 g (0.27 mol) of diacetoneamine, 52.8 g (0.54 mol) of 5-hexen-2-one and 17 g (0.15 mol) of calcium chloride are heated to 59C in a 500 ml round-bottom flask with thermometer and reflux condenser. After 5 days, the viscose reaction mixture is discharged into a mixture of sodium hydroxide solution and dichloromethane. The organic phase is separated off and dried over sodium sulfate and filtered and the filtrate is concentrated on a rotary evaporator.
The residue is distilled in vacuo (boiling point: 9WC/2 torr). The yield is 5 g (10%) of 2-(but-3- enyi)-2,6,6-trimethyi-4-oxopipeddine.
H-NMR: 1. 19 (s, br, CH3, 3H), 1.24 (s, br, CH3, 3H), 1.24 (s, br, CH3, 3H), 1.4-1.6 (m, CH2- C=Q 21-1), 1.9 (m, C1-12-C-C=Q 2H), 2.11-2.3 (m, CH2-CO, 4H), 4.9-5.1 (m, CH2=, 2H), 57- 5.9 (m, CH=Q 1 H).
MS: M+ (0), 180 (16), 140 (100), 123 (11), 98 (20), 83 (79), 58 (32), 42 (76).
A1 b) Alternatively, anhydrous ammonia (30 g, 1.76 mol) is introduced in four portions over a period of four days to a well stirred mixture of powdered anhydrous calcium chloride (75 g, 0.67 moi), 5-hexen-2-one (125 g, 1.28 mol) and diacetonalcohol (150 g, 1. 28 mol) at - 47 OC. Then, the homogeneous mixture is heated to 59 OC and stirred for additionally four days. The reaction mixture is poured into 500 mi of an aqueous solution containing 100 g sodium hydroxide. The oil is decanted and the remaining caustic slurry washed with dichloromethane. The compained oil and dichloromethane extracts are dried over anhydrous sodium sulfite. The drying agent is removed by filtration and the filtrate is concentrated on a rotating evaporator. Then, the apparatus is converted for distillation, and the reaction mixture is stirred at 40 "C under reduced pressure (5 mmHg). The remaining solution weights 45 g and consists essentially of a 1:1 mixture of triacetonamine and 2-(but-3-enyl)-2,6,6-trimethyi-4-oxopipeddine. The title product is isolated by distillation (2 mmHg).
H CH A2) Preparation of 2-(but-3-enyi)-2,6,6-tdmethylpiperidine C 2 H 3 CH 3 g (0.026 mol) of 2-(but-3-enyi)-2,6,6-trimethy]-4-oxopiperidine (product from Example All), 4.7 g (0.086 mol) of potassium hydroxide, 6 g (0.19 mol) of hydrazine hydrate and 18.2 g of diethylene glycol are heated at 1300C for 2 hours and then boiled over a water separator at 19WC. The organic phase is distilled (80"C, 10 torr). The yield is 2 g (43%).
H-NMR: 1.08 (s, CH3, 3H), 1. 1 (s, CH3, 3H), 1. 13 (s, CH3, 3H), 1.35 (m, CH2, 6H), 1.5-1.7 (m, CH2, 2H), 2.10-2.1 (m, CH2-C=Q 2H), 4.95.1 (m, CH2=, 2H), 5.7-5.9 (m, CH=, 1 H).
MS: 181 (5), 166 (26), 138 (2), 126 (100), 110 (12), 81 (6), 70 (44), 41 (32).
H A3) Preparation of In a 100 m] round-bottom flask with magnetic stirrer and top-mounted distillation unit, 34.0 g (0.2 mol) of 1,2,2,6,6-pentamethyi-4- aminopipeddine and 36.8 g (0.2 mol) of 10undecenoic acid are heated to 180C with stirring. Following a reaction period of 7 h and removal of the water by distillation, the mixture is cooled to room temperature. Subsequent distillation at 0.03 torr and 20WC gives the title product.
A4) Preparation of 7N N, 0 22.6 g of 1,2,2,6,6-pentamethyi-4-butylaminopiperidine and 11. 1 g of triethylamine are dissolved in 150 mi of methylene chloride. The solution is cooled to WC using ice/NaC]. 20.3 g of (10)-undecenoyl chloride, as a solution in 50 mi of methylene chloride, are added dropwise over 20 minutes. The ice bath is removed and the solution is stirred at room temperature for 1 h, then washed twice with 50 mi of H20 each time, and dried over Na2S04 and the methylene chloride is removed on a rotary evaporator. The residue is distilled in a copper pipe distillation apparatus at 0.02 torr and 170C to give 30 g of the title product.
A5) Synthesis of 2,2,6,6-tetramethyl-3,4-dehydro-4-allylpipeddine 0 N Br-CH2-CH=CH2 HCI Zn/DMF r.t 10-30 rrirL HO CH2--CH=CH2 N S002 (or H2SO4) CH2-CH=CH2 N a) To a stirred solution of 5 g of 2,2,6,6-tetramethyl pipe ridon e hydrochloride in 50 ml DIVIF and 6.31 g of allylbromide, 3.75 g of zinc powder are added. An exothermic reaction starts quite rapidly and it ceases within 20 minutes. Then most of the DMF is evaporated using reduced pressure and warming. The residue is then washed with chloroform and alkalized water. The chloroform phase is then collected and dried over Na2SO4, then the solvent is evaporated and the product distillated. During distillation the product crystallizes in the cooler and the receiving flask, yielding 4.3 g of 2,2,6,6-tetramethyl-4-hydroxy-4allylpipeddine.
b) To the produced 2,2,6,6-tetramethyl-4-hydroxy-4-allylpipeddine is added dropwise 7.85 g of thionylchloride at room temperature; then the solution is heated to 50'C for a period of 3 hours. Thionylchloride is evaporated and water followed by NaOH-solution and diethylether is added for extraction. The diethylether phase is dried with Na2SO4, evaporated and distilled under reduced pressure at 45-500C to give 1.8 g of 2,2,6,6-tetramethyl-3, 4-dehydro-4allylpiperidine.
A6) Preparation of 4-(but-3-enyi)-1,2,2,6,6-pentamethy]-3,4dehydropipeddine 0 HO + M9Br", Et20 SOC12 CH3 k-k13 CH3 A Grignard reagent is prepared under argon atmosphere in the normal manner using 0.14 mol of magnesium turnings and 0.14 mol of 4-bromo-l- butene in 80 mi of THF Then a solution of 1,2,2,6,6-pentamethy]-4- oxopiperidine (0.12 mol) in 20 m] of THF is added dropwise. The reaction mixture is stirred overnight and poured into aqueous am moniumch lo ride solution. The THF phase is separated and the water phase extracted with dichloromethane. The organic layers are dried over sodium sulfate and concentrated. After distillation under reduced pressure, 7.2 9 ( 27 %) of 4-(but-3-enyi)-4-hydroxyi-1,2,2,6,6pentamethylpipeddine (bp 7011C/5mmHg) is collected.
Subsequently, 7.2 g of 4-(but-3-enyi)-4-hydroxyi-1,2,2,6,6pentamethylpipeddine are diluted in chloroform and 80 mi of thionyl chloride is added dropwise to the mixture under a blanket of argon. The mixture is heated to 60 OC and kept at that temperature under continued heating for 16 hours. After cooling to room temperature, the excess of thionyl chloride is evaporated and the residue is dissolved in water and then alkalized with an excess of 50 % of sodium hydroxide solution. After extracting the water phase with ether, the solvent is removed and the product is distilled giving 2.5 g (37.5 %) of 4-(but-3-enyi)-1,2,2,6, 6pentamethyl-3,4-dehydro-piperidine, which contains approximately 20 % of 4-(but-Mdienyi)-1,2,2,6,6-pentamethylpiperidine isomer and the isomers were not separated (bp 900C/1 0 mmHg). The isolated product exhibits the following spectral data: 'H NIVIR (500 MHz, CDC13, TMS): 1.0 (d), 1. 1 (s br, -CH3, 6H), 1. 1 (s br, - CH3, 6H), 1.9 (s br, -C5H2, 2H), 2.0 (m, CH2-C=C, 2H), 2.1 (m br, -CH2-piperidine), 2.2 (s, N-CH3, 3H), 4.9-5.1 (m, =CH2, 2H), 5.2 (s br, C3H, 1 H), 57-5.9 (m, -CH=, 1 H). 13 C NMR: 24.7, 26.8, 28.7, 31.7, 33.6, 43.8, 52.5, 54.9, 114.3, 130.4, 130.6 and 138.4. MS mle (rel.int.) for the major compound: W' 207 (1), 192, (100), 151 (12), 136 (13), 119 (4), 108 (3), 96 (2), 77 (4), 72 (3) and 56 (21). The MS mle (rel.int.) for the minor compound shows peaks at M '. 207 (8), 193 (16), 192 (100), 136 (7), 119 (5), 93 (5), 77 (13), 72 (43), 56 (33) and 51 (7).
A7) Preparation of 1-(but-3-enyi)-2,2,6,6-tetramethylpiperidine A mixture of 2,2,6,6-tetramethylpipeddine (14.1 g, 0.1 mol) and 4-bromo-l- butene (16.2 g, 0. 12 mol) in dioxane (11 m]) is refluxed for 1 day at 100 C. Then a piece of sodium is added and the mixture i stirred for additional 3 days at 100 'C. The insoluble substances are separated by filtration and dioxane is removed under reduced pressure. Then diethyl ether is added and the organic layer washed with aqueous sodium carbonate, dried over anhydrous sodium sulfate and concentrated. Distillation under reduced pressure affords 3 g (15.4 %) of 1-(but-3-enyi)-2,2,6,6tetramethyi-pipeddine (bp 62 C/10 mmHg). The product contains approximately 17.5% isomer, i.e. 1 -(but-2-enyl)-2,2,6,6-tetra methyl p iperid ine and the isomers are not separated. 'H NMR (500 MHz, CD03, TMS): 5.7 (m, =CH, 1 H), 4.9 (m, =CH2, 2H), 2.4 (m, -N-CH2-, 2H), 2.1 (m, =C-CH2-, 2H), 1.45 (m, C4H2, 2H), 1.3 (mbr, C3H2 and C5H2, 4H), 0.9 (s, CH3, 12H). 13 C NMR: 137, 114.7, 54.5, 44.5, 41,1, 40.3, 31.4 and 17.7. MSM/e (rel.int.) for the major compound: 195 (2), 180 (27), 154 (100), 124 (16), 112 (5), 83 (7), 69 (69), 41 (59) and for the minor compound: 195 (5), 180 (100), 154 (1.5), 124 (15), 109 (7), 82 (5), 70 (27) and 55 (42).
A8) 1-(3,5-di-tert-buty]-4-hydroxybenzyi)-4-but-3-enyi-2,2,6,6tetramethyl-3,4- dehydropiperidine 0 HO + SOC12 N N 2Br N BULi 2 >4H2Br H a) Preparation of 4-hydroxyi-4-(but-3-enyi)-2,2,6,6-tetramethylpipeddine:
A Grignard reagent is prepared under nitrogen atmosphere in the normal manner using 0.5 mol of magnesium turnings and 0.49 mol of 4-bromobuten in 200mi of diethylether. Then a solution of 0.245 mol of 2,2,6,6-tetra methyl p iperidone in diethylether is added dropwise to maintain refluxing. The reaction mixture is stirred for 12 h at room temperature and then the solution is acidified to pH 1 with 10% hydrochloridic acid. The aqueous phase is separated after washing it twice with diethylether. Then the aqueous phase is alkalized with an excess of ammonia solution and then the aqueous phase extracted with chloroform. The chloroform is then separated, dded and the solvent removed and 21 g (43.5 6/o) of 4-hydroxyl-4-(but-3enyl)-2,2,6,6-tetramethyipiperidine is obtained by vacuum distillation; 72 -76 "C/3mmHg.
b) Preparation of 4-(but-3-enyl)-2,2,6,6-tetramethyl-3,4dehydropipeddine: To a solution of 21 g of 4-hydroxyl-4-(but-3-enyl)-2,2, 6,6-tetramethylpiperidine in 210 ml of chloroform is added dropwise 219 g of thionyl chloride within 30 minutes at 50 "C. The mixture is kept at this temperature for 4 hours under stirring. After cooling to 25 OC, the excess of thionyl chloride is evaporated in vacuo. The residue is dissolved in 50 mi of water and then alkalized with an excess of sodiumhydroxide solution. After extracting the aqueous phase with ether, the solvent is removed and the product distilled giving 12.9 g of 4-(but3enyl)-2,2,6,6-tetramethyl-3,4-dehydropiperidine at 80 OC/10 mmHg.
c) Preparation of 1-(methylene-2,6-di-tert-butylphenol)-4-(but-3-enyl)-2, 2,6,6tetramethyldehydro-piperidine:
To (5.6 g, 31 mmol) of 4-(but-3-enyl)-2,2,6,6-tetramethyl-3,4dehydropiperidine is added dropwise n-BuLi (10.3 ml of a 2.5 M solution in hexane, 26mmol), and the reaction mixture is vigorously stirred for 30 minutes at -60 OC. Then (7.7 g, 26mmol) of 4-bromomethyl-2,6-ditert-butyl phenol diluted in 15 ml of hexane is added dropwise. After completed addition the reaction mixture is allowed to warm to room temperature, stirred over night and washed three times with water. The organic layer is dried over sodium sulfate and solvent is evaporated. Then the excess 2, 2,6,6-tetramethylpipeddine is evaporated at 50OC/1 mmHg. The residue is dissolved in 50 ml mixture of hexane/water (1: 1) and then acidified with HCI, whereby the desired product falls out as a salt. The salt is separated by filtration. After extracting the salt with ether and water which has been alkalized with sodium hydroxide, 2 g of raw 1(methylene-2, 6-di-tert-butylphenol)-4-(but-3-enyl)-2,2,6,6-tetramethylpiped dine are obtained.
A9) Preparation of 4-(2-(3-cyclohexenyl)ethyldimethylsiloyl)-1,2,2,6,6pentamethyipipeddine -31 2 + 2 &2 N &2 &3 &3 A solution of 1,2,2,6,6-pentamethyl-4-oxo-pipeddine ( 10 g, 0.06 mol) and imidazol (4.1 g, 0.06 mol) in DMF (60 mQ is reacted with 2-(3cyclohexenyl)-ethyldimethylchlorosilane) (13.8 g, 0.06 mol) and then stirred overnight at room temperature under a blanket of argon. The reaction mixture is treated with water and extracted with diethylether (2 x 150 mL). The combined organic phases are washed with water several times and dried over sodium sulfate. The solvents are removed under reduced pressure to leave an organic oil. Distillation under reduced pressure affords 7.9 g (38.9%) of 4-(2-(3cyclohexenyl)ethyldimethylsiloxyl)1,2,2,6,6-pentamethylpipeddine as a white liquid (bp 150 OC/3 mmHg).
A10) (2,2,6,6-Tetramethyl-3,4-dehydropipeddine-4-yi)-(4-vinylphenyl)methan + THE SOCI-1- N 11 H2 H 2M9CI H 2 N N I I H H N I H CH213r a) (2,2,6,6-Tetramethyi-4-hydroxypiperidine-4-yi)-(4-vinylphenyl)-methane (1) is prepared according to the procedure described in example A5(a) but using the equivalent amount of 4vinyibenzyfbroMide instead of allylbromide. The same compound is obtained using the same educt in a procedure as described in example A8(a). b) Heating the above product together with thionyl chloride according to the procedure described in example A8(b) yields (2,2,6,6-Tetramethyi-3,4-dehydropiperidine-4-yi)(4vinylphenyi)-methane.
A1 1) Following the pathway described in example A7 but using an equivalent amount of 11 bromo-1 -undecene instead of 4-bromo-1 -butene yields 1 -(undec-1 0-enyl)-2,2,6,6tetramethyfpiperidine.
A12) Preparation of 1-benzyl-2,2,6,6-tetramethyi-3,4-dehydropipeddine 75 g of concentrated sulfuric acid is added in portions to 24.5 g (0.15 mol) of 2,2,6,6tetra methyl p iperidi nol. The mixture is warmed to 100 0 C and stirred for 1.5 h. Then the mixture is allowed to cool down to room temperature and is added dropwise to a solution of 100 g sodium hydroxide in 250 mi of water. The water phase is extracted three times with 200 mi of dichloromethane. The combined organic extracts are dried over sodium sulfate and the solvent removed by evaporation. The residue is distilled to give 12.3 g (53 %) of 2,2,6,6tetra methyl-3,4-de hyd rop iperid ine (bp. 149 0 C/760 mmHg). Then 38 g of benzyl bromide is added to 12.3 g (0. 08 mol) of the prepared 2,2,6,6-tetramethyi-3,4-dehydropipeddine and heated at 150 0 C for 3.5 h. The excess benzy! bromide is removed by evaporation and the residue is dissolved in benzene, washed with aqueous potassium carbonate and dried over anhydrous potassium carbonate. The benzene is removed and the residue distilled to give 1 8.2g (41 %) of 1benzyi-2,2,6,6-tetramethyi-3,4-dehydropipeddine (bp. 115 OC/4 mmHg). H NMR (500 MHz, WC13, TMS): 1.0 (s br, -CH3, 6H), 1.1 (s br, - CH3, 6H), 2. 0 (s br, -WH2piperidine, 2H), 3.8 (m, -CH2phenyl, 2H), 5.6 (m br, -CH=qH-, 2H), 7.1-7.4 (m, phen 1, 5H). 13 C NMR: 41.1, 47.5, 53.5, 55.8, 120.2, 125,6, 126.6, 127.8, 136.7 and 146.3. MS mle (rel.int.): 229 (3), 214 (95), 172 (2), 145 (6), 122 (2), 91 (100), 65 (15) and 41 (10).

Claims (9)

WHAT IS CLAIMED IS:
1. A compound of the formula V, VI, VII or Wil R2 R 3 R4 R5 - N R5 (V) H // c R7 R, H2C R2 R 3 )L- R6-N HC - NR9 (V1) (C H2-C=CH 2 /- j H W7/ R, 0 R2 R3 R6 - N -R E-C=CH2 (V1 1) H W7 R, R2 R3 R 1,7 R R 21 / 18 R6-N -0-Si-R 20 (VIII) R W7 R, 19 in which IR,, R2 and R3 are Cl-COlkyl; or R2 and R3 together are C4- C11alkylene; R4 is hydrogen; R5 is hydrogen, OH, Cl-C18alkyl, C3-C12aikenyl, acryloyloxy, acryloylamido, or is a radical of the formula -X-(CO)i-R8, where i is 0 or 1; or R4 and R5 together are =Q R6 is hydrogen, Cl-C18alkyl, C3-C8211kenyl, C7-C11phenylalkyl, or C7Cilphenylalkyl substituted on the phenyl ring by Cl-C12alkyl andlor OH; the index j is a number from the range 1-12; R5 is Cl-C8alkylene; W7 is Cl-C4alky]; or W7 together with R, is C4-Cl jalkyiene; R8 is Cl-C18alkyl, C3-C12alkenyl, C7-C15phenylalkyl, C8-C15phenylalkenyl, C7-C15phenylalkyl substituted in the phenyl moiety by Cl-C4alkyl or Cl-C4alkoxy, or is phenyl or Cl-COlkyl- or Cl-C4alkoxy-substituted phenyl; R9 is Cl-C12alkyl or C5-Cl2CYCloalkyl; R9 is hydrogen, Cl-C12alkyl or C5-Cl2CYcloalkyl; R18 and R19, independently of one another, are Cl-C8alkyl; R20 is C3C18aikenyl, C7-C18cycloalkenylalkyl or C7-C18bicycloalkenylalkyl; R17 and R21 are hydrogen, or R17 together with R21 is a chemical bond; R22 is C2C16alkylene, phenylene, phenylene- or cyclohexylene-interrupted C2Cloalkylene, or alkylene-phenylene of a total of 2-16 carbon atoms; X is NH-, -NIR9- or -0-; or the compound 1 -(b ut-3-enyi)-2,2,6,6-tetra methyl piperid i ne.
2. A compound of the formula V according to claim 1, of the formula Va R2 R3 R4 R6-N 1< R 5 (Va) H) R, // C-(CH 2 M H2C in which m is a number from the range 18; R, is methyl or ethyl; R2 and R3 are as defined for R, or together are C4-C11alkylene; R4 is hydrogen and R5 is hydrogen or a radical of the formula -X-(CO)i-R8; the index i being 0 or 11; or R4 and R5 together are =Q % is hydrogen or Cl-C18alkyl; R8 is Cl-C18alkyl, C7-C15phenylaikyl, C7-C15phenylaikyl substituted in the phenyl moiety by Cl-COlkyl or Cl-C4aikoxy, or is phenyl or Cl-COlkyl- or Cl-CORoxysubstituted phenyl; R9 is Cl-C12alkyl or C5-Cl2CYCloalkyl; and X is -NH-, -NR9- or -0-.
3. A composition comprising A) an organic material sensitive to oxidative, thermal andlor actinic degradation and B) as stabilizer at least one compound according to claim 1.
4. A composition according to claim 3, wherein the organic material is a synthetic organic polymer, especially a thermoplastic polymer.
5. A composition according to claim 3, comprising the stabilizer (component B) in an amount of from 0.01 to 50% based on the weight of the organic material to be stabilized.
6. A composition according to claim 3, comprising as additional component C one or more conventional additives.
7. The use of a compound according to claim 1 for stabilizing organic material against oxidative, thermal or actinic degradation or build-up.
8. A method of stabilizing organic material against thermal, oxidative andfor actinic degradation or build-up, which comprises adding to said material at least one compound according to claim 1.
9. A method according to claim 8 in which the organic material is a thermoplastic polymer, wherein a compound of the formula V, VI, V[] andlor V1 11 is admixed and the mixture obtained is heated.
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Publication number Priority date Publication date Assignee Title
WO2016105988A1 (en) * 2014-12-22 2016-06-30 3M Innovative Properties Company Sterically hindered amine and oxyalkyl amine light stabilizers
US10000626B2 (en) 2014-12-22 2018-06-19 3M Innovative Properties Company Sterically hindered amine and oxyalkyl amine light stabilizers

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Publication number Priority date Publication date Assignee Title
WO1996018667A2 (en) * 1994-12-12 1996-06-20 Rhone Poulenc Chimie New silicon compounds with sterically hindered cyclic amine functions useful for the light and heat stabilization of polymers
WO1998049231A1 (en) * 1997-04-25 1998-11-05 Aristech Chemical Corporation Copolymers of propylene with polymerizable hindered amine light stabilizers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996018667A2 (en) * 1994-12-12 1996-06-20 Rhone Poulenc Chimie New silicon compounds with sterically hindered cyclic amine functions useful for the light and heat stabilization of polymers
WO1998049231A1 (en) * 1997-04-25 1998-11-05 Aristech Chemical Corporation Copolymers of propylene with polymerizable hindered amine light stabilizers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016105988A1 (en) * 2014-12-22 2016-06-30 3M Innovative Properties Company Sterically hindered amine and oxyalkyl amine light stabilizers
US10000626B2 (en) 2014-12-22 2018-06-19 3M Innovative Properties Company Sterically hindered amine and oxyalkyl amine light stabilizers
US10450332B2 (en) 2014-12-22 2019-10-22 3M Innovative Properties Company Sterically hindered amine and oxyalkyl amine light stabilizers

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