GB2386901A - Improved weatherability of flame retardant polyolefin - Google Patents

Improved weatherability of flame retardant polyolefin Download PDF

Info

Publication number
GB2386901A
GB2386901A GB0301386A GB0301386A GB2386901A GB 2386901 A GB2386901 A GB 2386901A GB 0301386 A GB0301386 A GB 0301386A GB 0301386 A GB0301386 A GB 0301386A GB 2386901 A GB2386901 A GB 2386901A
Authority
GB
United Kingdom
Prior art keywords
weight
tert
bis
butyl
hindered amine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB0301386A
Other versions
GB0301386D0 (en
GB2386901B (en
Inventor
Juerg Zingg
Juergen Link
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority claimed from GB0129225A external-priority patent/GB2373507B/en
Publication of GB0301386D0 publication Critical patent/GB0301386D0/en
Publication of GB2386901A publication Critical patent/GB2386901A/en
Application granted granted Critical
Publication of GB2386901B publication Critical patent/GB2386901B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups

Landscapes

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

Abstract

Stabilized thermoplastic polymer, especially polyolefin compositions comprising a flame retardant selected from ammonium polyphosphate, halogenated and/or melamine based flame retardants, and a combination of sterically hindered amine light stabilizers comprising, on 100 parts by weight of total component (c), <SL> <LI>c1) 40 to 95 parts by weight a low molecular weight sterically hindered amine of the hydrocarbyloxyamine or hydroxyhydrocarbyloxyamine class, and <LI>c2) 5 to 60 parts by weight of a high molecular weight secondary or alkylated or polymeric tertiary sterically hindered amine, </SL> and optional further components combine optimum outdoor weathering stability and good flame retardant properties.

Description

1 238690 1
Improved Weatherability of Flame Retardant Polyolefin The instant invention pertains to a thermoplastic organic polymer, especially a polyolefin such as thermoplastic polyolefirTPO), stabilized against the deleterious effects of-
light, oxygen and heat and containing a certain flame retardant, which contains a sterically hindered amine of the hydrocarbyloxyamine or hydroxyLydrocarbyloxyamine class and optionally further stabilizers, to the use of these flame retardants and sterically hindered amines for imparting both light stabilization and flame retardant properties, and to a corresponding process for improving light stability and flame retardancy of a thermoplastic organic polymer.
United States Patent No. 5,393,812 does describe polyolefin compositions which are made flame retardant by addition of a halogenated hydrocarbyl phosphate or phosphonate ester flame retardant, and stabilized against weathering with a alkoxyamine functional hindered amine. EP-A-792911 proposes the use of a alkoxyamine functional hindered amine for improving the flame retardant properties of a polyolefin. The activity of alkoxyan, ine functional hindered amines alone as a flame retardant is disclosed in WO 99/00450.
There is still need to improve flame retardant polymer compositions in order to obtain good stability against weathering.
Now it has been found-that optimum stabilization against UV light and weathering and good flame retardant properties, especially for outdoor applications, can be combined in a thermoplastic polymer, especially a polyolefin, polyolefin copolymer or blend thereof such as impact modified polyolefin or thermoplastic polyolefin (TPO), when certain hindered amine stabilizers are used in combination with a specific flame retardant.
It is one of the findings of present invention that an especially improved performance, both in light stability and flame retardancy, may be obtained if the thermoplastic polymer contains, besides the flame retardant, a combination of a conventional sterically hindered amine of high molecular weight with a low molecular weight sterically hindered amine of the hydroxyhydrocarbyloxyamine class. Thus, present invention also pertains to a flame retardant composition stabilized against deleterious effects of light and weathering comprising
- 2 A) a thermoplastic polymer, B) a flame retardant selected from ammonium polyphosphate, halogenated and/or melamin based flame retardants, and C) a combination of sterically hindered amine light stabilizers comprising C1) a low molecular weight sterically hindered amine of the hydroxyhydrocarbyloxyamine class, and C2) a conventional high molecular weight sterically hindered amine.
Detailed Disclosure
The sterically hindered amine light stabilizer of the hydrocarbyloxyamine or hydroxyhydrocarbylexyamine class of component (c) is characterized by its substituent E,-O-
on the amino nitrogen atom (see formula below), wherein E, is preferably C,-C,Balkyl, Cs C12cycloalkyl or C7-C,saralkyl in the sterically hindered amine of the hydrocarbyloxyamine class; and E, is preferably C,-C1Balkyl, Cs-C2cycloalkyl or C7-C,5aralkyl each of which is substituted in the aliphatic part by 1-3 OH groups in the sterically hindered amine of the hydroxyhydrocarbyloxyamine class. The latter type of compound, containing a reactive OH group, may also be used in the form of its reaction product.
The sterically hindered amine light stabilizer of the hydrocarbyloxyamine or hydroxyhydrocarbyloxyamine class of component c usually is a compound containing a group of the formula.
G, EN O-N
G./ \ where G. and C;2-areindependently alkyl of 1 to 4 carbon atoms or are together pentamethylene, and Ei is C,-C,8alkyl, Cs-C,2cycloalkyl or C7-C,5aralkyl; or E, is C,-C,ealkyl, C5-
C,2cycloalkyl or C7-C,5aralkyl each of which is substituted in the aliphatic part by 1
- 3 3 OH groups; or is a reaction product thereof. Preferred is a cyclic sterically hindered amine conforming to the formula G\K:G2
T:%N-O E1 (1)
Gil G2 wherein G., G2 and E, are as defined above; T is a divalent organic radical required to complete formula I to form, together with the hindered amine nitrogen atom and the two quaternary carbon atoms substituted by G. and G2, a five- or six-membered aliphatic ring structure, especially a piperidine ring; or is an oligomeric or polymeric hindered amine molecule made from the reaction of a dialkyi ester or isocyanate with a compound of the formula (I) wherein En contains 1 OH group and T is -CH2-CH(CH)-CH2-; or is a simple diester or urethane derivative of a compound of the formula (I) wherein E, contains 1 OH group and T is -CH2-CH(OH)-CH2-.
In general, effective stabilizing amounts of a compound of component c used are from 0.01 to 10 %, preferably from 0.05 to 5% by weight, especially from 0.1 to 2 % by weight, based on the polymer component (a), of the stabilizer of component (c).
Sterically hindered amines of present component (c) are largely known as light stabilizers (US-5004770; US-5096950; US-5204473; US-5096950; US5300544; US-6117995; US-6271377).
Flame retardants of component (b) are commercial compounds. Most preferred is tris-(2,3-
dibromopropyl)-isocyanurate (b3).
- 4 Halogen-free flame retardants b1 are usually employed in an amount from 1 to about 50 % by weight of the polymer (a), preferably in an amount from 5 to 50 % by weight of the polymer (a). The ratio b1: c is most preferably in the range from 20: 1 to 250: 1.
Halogenated flame retardants b2, b3, b4, b5 and/or b6 are usually employed in a total amount from 0.5 to 40 % by weight of the polymer (a); more preferably 3 to 40%, most preferably 5 to 35% by weight of polymer (a) Most preferred amounts of flame retardants (b) in the compositions of present invention are for b1) the melamin based flame retardant and/or ammonium polyphosphate 20 - 50 %; b2) bis-(hexachlorocyclopentadieno) cyclooctane 5 -20 %; b3) tris-(2,3-dibromopropyl)-isocyanurate 2 -10 %; b4) ethylene-bis-tetrabromophthalimide 1 0 - 40 %; b5) 1,2,5,69,1 Ohexabromo-cyclo-dodecan 2 - 20 %; b6) ethane-1,2-bis(pentabromophenyl) 2 20 %; each amount denotes percent by weight, based on the weight of the polymer (a).
Also of importance in the context of present invention is the use of the frame retardant tris(3-bromo-2,2-(bromomethyl)propyl) phosphate (b7; see below), which is most preferably employed in an amount of 2 - 20, especially 2 - 10, percent by weight, based on the weight of the polymer (a).
The ratio of halogenated flame retardants b2, b3, b4, b5, b6 or b7: c is most preferably in the range from 5: 1 to 100: 1.
Advantageously, halogenated flame retardants such as b2, b3, b4, be, be and/or b7 may be used in combination with an appropriate synergist such as an antimon compound (often Sb2O3), which is commonly added in an amount of 0.5 to 20 % by weight of the polymer (a).
Component a is frequently selected from the following thermoplastic polymers:
! - 5 1. Polymers of monoolefins and dioiefins, for example polypropylene (PP), polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, 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 (MOPE), low density polyethylene (LOPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe-
-rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerization (normally under high pressure and at elevated temperature).
b) catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or Vlil of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either- or c-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(l11) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators may be used, -typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ha and/or his 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 polyisobutyiene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
- 6 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 (LOPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethyiene/hexene copo-
lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethyiene/octene copolymers,' propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethy-
lene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl ace-
tate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copo-
lymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidenenorbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylenepropylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLOPE/EVA, LLDPE/EAA and alter-
nating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Blends of the aforementioned polymers (polyblends), for example PP/EP12)M In the following, the term polyolefin will be used for pure polyolefin homopolymers as well as copolymers and blends thereof.
Preferably, the polyolefin or thermoplastic olefin or polyoleDn (TPO) is the only organic polymer-present in these compositions; mainly it is polyethylene (PE) or polypropylene (PP), especially LDPE, LLDPE or PP, or copolymers of PP and PK.
Especially preferred as component (a) are polymers known as thermoplastic (poly)olefines (TPO), e.g. polypropylene or polyethylene containing an impact modifyer or elastomer component such as EPR etc., or heterophasic copolymers (see e.g. W. Neissl et al., Kunststoffe 83, No. 8,1993).
Examples of polymer compositions in which the instant compounds are effective include flame retardant polyolefins where acidic residues from the decomposition of the halogenated flame retardants deactivate hindered amines not having the N-OR group, roofing
- - 7 membranes, greenhouse films and agricultural mulch films where acidic residues from pesticides interfere with the activity of "normal" hindered amine stabilizers, and in thermoplastic polyolefins where pigment interactions with basic hindered amine stabilizers interfere with painting the substrate surfaces.
Preferably, the compound of present component c is a cyclic sterically hindered amine containing a group of formula (11) and/or (111) CH3 G. CH3 G1
G-CH2_G2 G-CH2G2
-O-11 < (11), -O-N N- (111)
G-CH2 G-CH2
CH3 CH3
in which G is hydrogen or methyl, and G1 and G2, independently of one another, are hydrogen, methyl or together are a substituent =0.
Examples of sterically hindered amines of present component c are described below under classes (a') to (m').
(a') A compound of the formula (1 a) JIG, G11 N, - 0-- G12
G-CH2/t' (1 a) CH3 no in which n, is a number from 1 to 4, G and G., independently of one another, are hydrogen or methyl, G1, is 0, hydroxyl, C,-C,3alkoxy, Cs-C,2cycloalkoxy, C7-C,sphenylalkoxy; or Gil, is C, C1, 3alkoxy, Cs-C12cycloalkoxy or C7-C15phenylalkoxy each of which is substituted in the
- 8 aliphatic part by 1-3 OH groups; Gil, preferably being C-C2alkoxy or cyclohexyloxy or C2 C8hydroxyalkoxy, especially octylaxy, cyclohexyloxy or 2-hydroxy-2-methylpropoxy, and G,2, if n, is 1, is hydrogen, C- C18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, COO and/or CONH groups, or is cyanoethyl, benzoyl, glycidyl7 a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus- containing acid or a monovalent silyl radical, preferably a radical of an. aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an cc,- unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 COOZ2 groups, in which Z,2is H. C'-C20alkyl, C3-C,2alkenyl, CsC7cycloalkyl, phenyl or benzyl, G,2, if n1 is 2, is C2-C2alkylene, C4C2alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloeilphatic or aromatic dicarboxylic acid having 8- 14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZ2groups, G2, if n is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by -COOZ,2, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or is a trivalent silyl radical, preferred radicals including triacyl radicals of nitrilo triacetic acid of benzene tricarboxylic acid, and G2, if n is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid. -
The carboxylic acid radicals mentioned above are in each case taken to mean radicals of the formula (-CO)XR, where x is as defined above for n, and the meaning of R arises from the definition given above.
Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyi, n-undecyl, n-dodecyl,
- - 9 - n-tridecyl, n-tetradecyl, n-hexedecyl or n-octadecyl.
C,-C,8alkoxy G., is, for example, methoxy, ethoxy, propcxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy7 hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexedecyloxy and octadecyloxy. C6-Ci2alkoxy, in particular heptoxy and octoxy, is preferred.
Cs-C,2cycloalkoxy G., is, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. CsCcycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.
C7-Cgphenylalkoxy is, for example, benzyloxy.
G,1 as C,-C,8alkoxy, Cs-C,2cycloalkoxy or C7-C,5phenylalkoxy substituted in the aliphatic part by 1-3 OH groups is a radical formed by abstraction of an carbon-bonded hydrogen atom preferably from 2-methyl-2-propanol (tert.-butanol), 2-propanol, 2,2-dimethyl-1-propanol, 2-
methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanoi, 1-
decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1hexanol, cyclo-
hexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1ethanol; 1,2-ethanediol, 1,2-propanedial, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,2 ... _. _.....
dimethyl-1, 3-propa nediol, 1, 2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexaned iol; glycerol, 1,1,1 -tris (hydroxymethyl)methane, 2ethyl-2-(hydroxymethyl-1,3-propanediol, 1,2,4-
butanetriol or 1,2,6-hexanetriol.
More preferably, G11 is are formed from 2-methyl-2-propanol or cyclohexanol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2cyclohexanediol, 1,3-cyclohexanediol or 1,4-
cyclohexanediol. Most preferred hydroxy substituted Gi is 2-hydroxy-2methylpropoxy.
Exampies of several G,2 radicals are given below.
If G12 is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or f3-(3,5di-tert-butyl-4-hydroxyphenyl)propionyl radical.
- 10 lf GO is a monovalent silyl radical, it is, for exampie7 a radical of the formula -(CjH2j)-Si(Z')2Z", in which j is an integer in the range from 2 to 5, and Z' and Z", independently of one another, are C,-C4alkyl or C-C4alkoxy.
If G,2 is a divalent radical of a dicarboxylic acid, it is, for exampie7 a malonyl7 succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, malecyl, itaconyl7 pUthaloyl, dibutylmalonyl, dibenzylmalonyl7 butyl(3,5-di-tertbutyl-4-hydroxybenzyl)malonyl or bicycloheptenedicarbonyl radical or a group of the formula o it 3C-O my/ CH C C o If G12 is a trivalent radical of a tricarboxylic acid, it is7 for example, a trimellitoyl7 citryl or nitrilotriacetyl radical.
If G,2 is a tetravalent radical of a tetracarboxylic acid7 it is, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
If G,2 is a divalent radical of a dicarbamic acid, it is, for example, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.
Preference is given to compounds of the formula (1a) in which G and G. are hydrogen, G,1 is hydrogen or methyl, n' is 2 and G12 is the diacyl radical of an aliphatic dicarboxylic acid having 4-12 carbon atoms.
(b') A compound of the formula (1 b)
Or l JIG-CH2< G13
GNTG14 (1b) CH3 n2 in which n2 is the number 1, 2 or 3, and G. Gil and G., are as defined under (a'), G13 is hydrogen, C,-C,2alkyl, C2Cshydroxyalkyl, Cs-C7cycloalkyl, C7-C8aralkyl, C,-C,8alkanoyl, C3C5alkenoyl, benzoyl or a group of the formula CH3 G.
G-CH2 I<
G., N G-CH2/r CH3 and G,4, if n2 is 1, is hydrogen, C1-C,8alkyl, C3C8alkenyl, Cs-C7cycloalkyl, C1-C4alkyl which is substituted by ahydroxyl, cyano, alkoxycarbon-yl or carbamide group or group of the formula -CONH-Z, or G,4 is glycidyl, a group of the formula -CH2-CH(OH)-Z or of the formula -CONH Z, in which Z is hydrogen, methyl or phenyl or CH2-OZ4 with Z,4 being hydrogen or C, Cl8alkyl; G14, if n2 is 2, is C2-C12alkylene, C6C12arylene, xylylene, a -CH2-CH(OH)-CH2 group or a -CH2-CH(OH)-CH2-O-D-Ogroup, in which D is C2-C10aikyiene, C8-C,5arylene, C6-C,2cycloalkylene, or, provided that G13 is not alkanoyl, alkenoyl or benzoyl, G,4 can alternatively be 1-oxo-C2-C,2alkylene, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or alternatively the group -CO-, G,4, if n2 is 3, is a group
-. - 12 o 11 CH CH(OH)CH
-CH2CH(OH)CH2 'N N / 2 2
O N /:O
CH2CH(OH)CH2
or, if n2 is 1, G3 and G,4 together can be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 173-dicarboxylic acid.
Some examples for the radicals G13, G14 and D are given below.
Any alkyl substituents are as defined above for (a').
Any Cs-C7cycloalkyl substituents are, in particular, cyclohexyl.
C7-CBaraikyl G13 is, in particular, phenylethy! or especially berzy!.
C2-Cshydroxyalkyl G13 is, in particular, 2-hydroxyethyl or 2hydroxypropyl.
C-C8alkanoyl G13 is, for example, formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexedecanoyl, octadecanoyl, but preferably acetyl, and C3-Csalkenoyl G3 is, in particular, acryloyl. C2-C3alkenyl G4 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl. G4 as a hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted C'C4alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.
Any C2-C12alkylene radicals are, for example, ethylene, propylene, 2,2dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
- - 13 Any C6-C,5arylene substituents are, for example, o-, m- or pphenylene, 1,4-naphthylene or 4,4-diphenylene. C6-C,2cycioalkylene is, in particular, cyclohexylene.
G,4 as 1-oxo-C2-C,2alkylene is preferably a group O CH3 11 1 -C C CH3 (c') A compound of the formula (1c) NAG-CH2 ( 0 L G15
-'4 (1C)
in which n3 is the number 1 or 2, G. G. and G., are as defined under (a'), and Go and G 1s if n3 is 1, are independently C,-C12 alkyl7 C2-C2 alkenyl, C7-C,2 aralkyl, or Go is also hydrogen, or G15 and G Is together are C2-C8alkylene, Cs-C,salkenylene, C2-C3hydroxyalkylene or C4-
C22acyloxyalkylene, and if n3 is 2, G,5 and G is together are the (-CH2) 2C(CH2-)2 group.
C2-Calkylene or C2-Chydroxyalkylene G,s and G Is is, for example, ethylene, 1-
methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2hydroxymethylpropylene.
C4-C22acyloxyalkylene G15 and G,5 is, for example, 2-ethyl-2acetoxymethylpropylene.
(d') A compound of the formula (1d-1), (1d-2) or (1 d-3),
: G;:N, / | (1d-1) G-CH2 ll CH3 0 _ n4 CH3 G. T
G11 o-C-T2 (1 d-2) N-C G-CH2 1 1 >0
CH3 H I G-(J,- O-C-T2
L CH3 0 (31-7 (Id-3) in which n4 is the number 1 or 2, G. G1 and G, are as defined under (a'), G16 is hydrogen, C,-C,2alkyl, allyl7 benzyl, glycidyl or C2-C6alkoxyalkyl, and G17, if n4 is 1, is hydrogen, C,- C2alkyl, C3-Csalkenyl, C7-Cgaralkyl, Cs-C7cycloalkyl, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-C,Oaryl, glycidyl or a group of the formula -(CH2)pCOO-Q or -(CH2)p-O-CO-Q, in which p is l or 2, and Q is C1-C4alkyl or phenyl, and G17, if n4 is 2, is C2-C2alkylene, C4-C12alkenylene, C6C12arylene, a group of the formula -CH2-CH(OH)-CH2-O-D'-O-CH2-CH(OH)-CH2-, in which D' is C2-C,Oalkylene, C6-C1sarylene or C6-C12cycloalkylene, or a group of the formula -CH2CH(OD)CH2-(OCH2-CH(OD)CH2)2-, in which D" is hydrogen, C1-C18alkyl, allyl, benzyl, C2-C,2alkanoyl or benzoyl,
- 15 T, and T2, independently of one another, are hydrogen, C-C1alkyl or unsubstituted or haiogen- or C1-C4alkyl-substituted C6-C10aryl or C7Cgaralkyl, or T. and T2 together with the carbon atom bonding them form a C5-C14cycloalkane ring.
Any C,-C12alkyl substituents are, for example, methyl, ethyl, n-propyl, nbutyl, sec-butyl, tert-
butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or ndodecyl.
Any C1-C,alkyl substituents can be, for example, the abovementioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n- hexedecyl or n-octadecyl Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
C3-Csalkenyl G'7 is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
C7-Cgaralkyl G7, T and T2 are, in particular, phenethyl or especially benzyl. If T1 and T2 together with the carbon atom form a cycloalkane ring, this can be, for example, a cyclo-
pentane, cyclohexane, cyclooctane or cyclododecane ring.
C2-C4hydroxyalkyi G17 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2hydroxybutyl or 4-hydroxybutyl. C6-C10aryl G,7, T. and T2 are, in particular, phenyl or cc- or 5-naphthyl, which are unsubstituted or substituted by halogen or C1-C4alkyl.
C2-C12alkylene G,7 is, for example, ethylene, propylene, 2,2dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
C4-C,2alkenylene G17 is, in particular, 2-butenylene, 2-pentenylene or 3hexenylene.
C6-C12arylene G17 is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
- - 16 C2-C,2alkanoyl D" is, for example, propionyl7 butyryl, octanoyl, dodecanoyl, but preferably acetyl. C2-C,0alkylene, C6-C1sarylene or C6-C, 2cycloalkylene D' have, for example, one of the definitions given for D under (b').
(h') A compound of the formula (1 h) CH3 O G-CH2_4
Gal N G14 ( 1 h) CH3 n6 in which n6 is the number 1 or 2, G and Gal are as defined under (a'), and G,4 is as defined under (bi)r but G14 cannot be -CONH-Z and -CH2-CH(OH)-CH2-O-D-O-.
a) A compound of the formula (1j) G-CH2 4
G-CHID COO --T7 ( 1 i) CH3 n7 wherein G. G., are as defined above and when n7 is l, T7 is hydrogen, C,-C,2alkyl, C3-Csalkenyl, C7-Cgaralkyl, C5C7cycloalkyl, C2 C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-C,0 aryi, glycidyl, a group of the formula -(CH2)-COO-Q or of the formula -(CH2)-O-CO-Q wherein t is 1 or 2, and Q is C,-C4alkyl or phenyl; or
- - when n7 is 2, T7 is (:2-Cl2alkylene, C6-C,2arylene, a group -CH2CH(OH) -CH2-O-X-O-CH2-
CH(OH)-CH2- wherein X is C2-C,Oalkylene, C6-C15arylene or C6-C, 2cycloalkylene, or a group -
CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2- wherein Z' is hydrogen, C1-C18alkyl, allyl, benzyl, C2-
C12alkanoyl or benzoyl.
(k) A compound of the formula (1k) CH3 G-CH2 it, G'1,=0 (1k) G-CH2 CH3 wherein G. G1 are as defined above.
(I) A compound of the formula (11) CH3 G-CH2:
G. -N) (11)
G-CH2/
CH3 wherein G. G1, are as defined above.
(m) A compound of the formula (1 m) CH3 G-CH2 Gs2 Gs1 O-N G-CH2 Gs3 (1 m) _ CH3 _
n8 wherein G is as defined above, n is 1, 2 or 3,
- - 18 if n& is 1, G51 is -G50-O-CO-G56; Gs2 is -3-CO-Gs6; and Gs3 is hydrogen; where Gs6 is alkyl or -
NH-alkyl of 1 to 18 carbon atoms or -NH-cycloalkyl of 5 to 8 carbon atoms; if n3 is 2, Gs1 is alkylene of 1 to 18 carbon atoms, hydroxyalkylene of 3 to 18 carbon atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene or hydroxycycloalkylene of 5 to 8 carbon atorris, alkenylene of 3 to 18 carbon atoms, or a straight or branched chain alkylene of 1 to 4 carbon atoms or hydroxyalkylene of 2 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms; or Go is a divalent acyl radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid or of a dicarbamic acid, preferably an acyl radical of an aliphatic dicarboxylic acid having 2-18 C atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 C atoms, if na is 3, G51 is alkanetrlyl of 1 to 18 carbon atoms, hydroxyalkanetriyl of 3 to 18 carbon atoms, cycloalkanetriyl of 5 to 8 carbon atoms, cycloalkenetriyl of 5 to 8 carbon atoms, alkenetriyl of 3 to 18 carbon atoms, a straight or branched chain alkanetriyl of 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by one or two alkyl of 1 to 4 carbon atoms; if nis20r3 . Gs: is -O-G12; -N(G13)G14; -O-G,s; -CQO-T7; or is a group of one of the formulae CH3 G-CH i G11 N O-Gs4 G-CH2 I
CH3 G-CH2 G1 G1 13 713
G11, N Gss N G-CH2 I
CH3
- 19 CH3 G-CH2:
G11-N I> COO-Gas -O-CO-
G-CH CH3 G18 N At N G19/L N E (A)X-
NON N;\N
G1o/: N E-DlV E GIN:\ and Gs3 is hydrogen or, if Gs2 is -O-G1s, is O-G 1s; .... or Gs2 and Gs3 together are =0; or a group of the formula O _ G-CH2 CH3 where G,1 and GO are as defined above under (a) if n1 is 1; G,3 and Gal are as defined above under (b') if n2 is 1; Gas and G',5 are as defined above under (c) if n3 is 1; Goal G'g, A, E, D'V, x are as defined above under (e); T7 is as defined above under (I) if n7 is 1; Gs4 is as defined for G12 under (a) if n1 is 2; Gss is as defined for G,4 under (b)if n2 is 2; Gs6 is as defined for T7 under a) if n7 is 2.
Of special technical importance is a sterically hindered amine light stabilizer of the hydroxyhydrocarbyloxyamine class, wherein E1 is preferably C1-C1aalkyl, Cs C12cycloalkyl or C7-C,5aralkyl each of which is substituted in the aliphatic part by 1
- 20 3 OH groups, especially 1 OH group.
Components b and c of the instant invention and optional further components may readily be incorporated into the polymer by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the additives may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer The additives may be added to component (a), individually or mixed with one another. If desired, the individual components can be mixed with one another in the melt (melt blending) before incorporation into the material to be stabilized. Components b and/or c and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed stabilizer mixture to the material to be stabilized, with or without subsequent evaporation of the solvent. The additives of component b and/or c as well as further additives can also be added to the material to be stabilized in the form of a masterbatch which contains these components in a concentration of, for example, about 2.5 % to about 25 % by weight; in such operations, the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
_.,. 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 latices. A further possibility for incorporating the stabilizers of the invention into polymers is to add them before, during or directly after the polymerization of the corresponding monomers. In the case of addition prior to or during the polymerization, the stabilizers of the invention can also act as a regulator of the chain length of the polymers (chain terminator) Components b and c of the invention can judiciously be incorporated by the following methods: - as emulsion or dispersion (e g. to latices or emulsion polymers), - as a dry mixture during the mixing in of additional components or polymer mixtures,
- 21 by direct introduction into the processing apparatus (e.g. extruders, internal
mixers, etc), as solution or melt.
The additive combination of present components b and c is useful for many applications, especially outdoor applications, including the following: Thermoplastic olefins (TPO), e.g. paintable thermoplastic olefins Polypropylene molded articles Polyethylene film Molded polypropylene with brominated flame retardants Molded thermoplastic olefin with brominated flame retardants Polethylene film with brominated flame retardants Thermoplastic elastomers with other costabilizers Grease-filled wire and cable insulation Coatings over plastic substrates Polyolefin tanks or containers containing chemicals Polyolefin films with an antifog agent Polyolefin fi ms with IR thermal fillers such as hydrotalcites, e.g. DHT4A Polyolefin films with an antistatic agent Flame-resistant molded polypropylene articles Flame-resistant molded thermoplastic olefins Flameresistant polethylene film Pre-formed films for lamination to plastic substrates Electronic appliance Containers boxes, bins for storage and transportation Automotive applications e.g. dashboard, back board Furniture e.g. stadion seats, public seats Roofing sheets Roofing membranes Flooring materials Liners Profiles, especially window and door profiles
- 22 Geomembranes. The materials containing the stabilizers described herein can be used for the production of moldings, extruded articles, rotomolded articles, injection molded articles, blow molded articles, mono- and multilayer films, extruded profiles, surface coatings and the like.
The resulting stabilized compositions of the invention may optionally also contain various conventional additives, preferably in amounts from 0. 01 to 10%, more preferably from about 0 025 to about 2%, and especially from about 0.1 to about 1% by weight of component (a), such as the materials listed below, or mixtures thereof.
1. Antioxidants 1.1. AlkYlated monophenols, for example 2,6-di-tert-butyl4-methylphenol, 2-tert-butyl-4,6-di-
methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-nbutylphenol, 2,6-di-tert-bu-
tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(methylcyclohexyl)-4,6-dimethyl-
phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-ditert-butyl-4-meth-
oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyi-4-methyiphenoi, 2,4-dimethyP6-( l 'methylundec- 1 '-yi)phenoi, 2,4-dirnethyi-6-( 1'-
methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyitridec-1'-yl)phenol and mixtures there-
of. 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tertbutylphenol, 2,4-dioctyl-
thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-
nonylphenol. 1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxy-
phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6diphenyl-4-octade-
cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4hydroxyanisole, 3,5-di-tert-bu-
tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5di-tert-butyl-4-hy-
droxyphenyl) adipate.
- 23 1.4. Tocopherols, for example cc-tocopherol, Q-tocopherol, ytocopherol, S-tocopherol and mixtures thereof (vitamin E).
1.5. HydroxVlated thiodiphenvl ethers for example 2,2'-thiobis(6-tertbutyl-4-methylphenol), 2,2'-thictis(4-octylphenol), 4,4'-thiobis(6-tertbutyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-
methylphenol), 4,4'-thiobis(3, 6-di-sec-amylphenol), 4,4'-bis(2,6-d imethyl-4-hydroxyphenyl)-
disulfide. 1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6tert-butyl-4-methylphenol), 2,2'-
methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6(cc-methylcyclohexyl)-
phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'methylenebis(6-nonyl-4-
methyiphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'ethylidenebis(4,6-di-tert-butyl-
phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'methylenebis[6-(-methylben-
zyl)-4-nonylphenol], 2,2'-methylenebis[6-(cc,-dimethylbenzyl)-4nonylphenol], 4,4'-methy-
lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2methylphenol), 1,1-bis(5-tert-
butyl-4-hydroxy-2-mthyihenyi)hutane, 2,6-bis(3-tert-butyl-5-methyl-2hydroxybenzyl)-4-
methylphenol, 1,1, 3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1, 1 -bis(5-tert-butyl-4-
hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3, 3-bis(3'-tert-
butyl-4!-hydroxyphenyl)butyrate3, bis(3-tert-butyi-4-hyd rox-y-5-methylphenyl)d icyclopenta-
diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4methylphenyl]terephtha-
late, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tertbutyl-4-hydroxyphe-
nyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-ndodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2methylphenyl)pentane. 1.7. O-, N- and S-benzYl compounds, for example 3,5, 3',5'-tetra-tert-butyl-4,4'-dihydroxydi-
benzyl ether, octadecyl-4-hydroxy-3, 5-all methylbenzylmercaptoacetate, tridecyl-4-hydroxy-
3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4hydroxybenzyl)amine, bis(4-
tert-butyl-3-hydroxy-2,6-dimethylbenzyl)d ithioterephthalate, bis(3, 5-ditert-butyl-4-hydroxy-
benzyl)sulfide, isooctyl-3, 5-di-tert-butyl-4hydroxybenzylmercaptoacetate.
1.8. Hvdroxvbenzvlated malonates, for example dioctadecyl-2,2-bis(3,5-ditert-butyl-2-hy-
droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5methylbenzyl)malonate, di
- 24 dod-ecylmercaptoethyl-2,2-bis(3, 5-di-tert-butyl-4-hydroxybenzyl) malonate, bis[4-( 1,1, 3, 3-tetra-
methylbutyl)phenyl]-2,2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tertbutyl-4-hydroxy-
benzyl)-2,4, 6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4hydroxybenzyl)-2, 3,5,6-tetrame-
thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-ditert-butyl-4-hydroxy-
an ilino)-1,3'S-triazine, 2-octylrnercapto-4, 6-bis (3,5-di-tert-butyl-4hyd roxyanilino)- 1, 3,5-tri-
azine, 2-octylmercapto-4,6-bis(3, 5-di-tert-butyl-4-hydroxyphenoxy)-1, 3, 5-triazine, 2,4,6-tris-
(3,5-d i-tert-butyl-4-hydroxyphenoxy)-1,2, 3-triazine, 1,3,5-tris(3,5-ditert-butyl-4-hyd roxyben-
zyl)isocyanurate7 1, 3,5-tris(4-tert-butyl-3-hyd roxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris-
(3, 5-di-tert-butyl-4-hydroxyphenylethyl)-1, 3, 5-triazine, 1,3, 5-tris(3, 5-d i-tert-butyl-4-hydroxy-
phenylpropionyl)-hexabydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4hydroxybenzyl)iso-
cyanurate. 1.11. Benzvlphosphonates, for example dimethyl-2,5-di-tertbutyl-4-hydroxybenzylphospho-
nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3, 5-di-tert-butyl-4-hy-
d roxybenzyl phosphonate, dioctadecyi-5-tert-butyl-4-hydroxy-3methyibenzyl phosphonate, the calcium salt of the monoethyl ester of 3,5di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4hydroxystearanilide, oclyl N-
(3, 5-di-tert-butyl-4-hydroxyphenyl)carbamate 1.13. Esters of C-(3,5-ditert-butyl-4-hydroxyphenvl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-
nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy-
lene glycol, triethylene glycol, penteerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy-
droxyethyl)oxamide, 3-thieundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-
propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of P-(-tert-butyl-4-hydroxy-3-methylphenvl)proPionic acid with mono- or poly-
hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanedi
- 25 ol, 1,9-nonanediol7 ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene giycol, triethylene giycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis-
(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl-.
olpropane, 4-hydroxymethyl-l -phospha-2, 6,7-trioxabicyclo[2.2.2]octane; 3, 9-bis[2-{3-(3-tert-
butyl-4-hydroxy--methyiphenyl)propionyloxy}-1,1 -dimethylethyl]-2,4,8, 1 0-tetraoxaspiro[5.5]-
undecane. 1.15. Esters of 6-(3,5-dicYclohexyl-4-hydroxvphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri-
ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'bis(hydroxyethyl)ox-
amide, 3-thieundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-
droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1. 16. Esters of 3,5-di-tert-butYI-4-hydroxyphenyl acetic acid with monoor polyhydric aico-
hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycoi, thiodiethylene glycol, diethylene glycol, triethyiene glycol, penteerythritol, tris(hydroxyethyl)isocyanurate, N. N'-bis(hyd roxyethyl) ox-
amide 3-thisundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-
droxymethyl- 1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of 5-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-
butyl-4-hyd roxyphenylpropionyl)hexamethylenediamide, N. N'-bis(3,5-ditert-butyl-4-hyd roxy-
phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4hydroxyphenylpropionyl)hy-
drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionylaxy) ethyl]oxamide (Nau-
gardXL-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-bu-
tyl-p-phenylenediamine, N. N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N. N'-bis( 1 -ethyl-3-
methylpentyl)-p-phenylenediamine, N,N'-bis(1 -methylheptyl)-pphenylenediamine, N. N'-dicy-
clohexyl-p-phenylenediamine, N. N'-diphenyl-p-phenylenediamine, N,N'bis(2-naphthyl)-p
- 26 phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3dimethylbutyl)-N'-phe-
nyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-
phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'dimethyl-N,N'-di-
sec-butyl-p-phenylenediamine, diphenylamine, N-allyidiphenylamine, 4isopropoxy-
diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1napUthylamine, N-phe-
nyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tertoctyldiphenylamine, 4-
n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4dodecanoyl-
aminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-ditert-butyl-4-
* dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (otolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-
oclylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-
octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopro-
pyl/isohexyldiphenylamines, a mixture of mono- and dialkylated tertbutyldiphenylamines, 2.3-dihydro-3,3-dimethyl-4H-l,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tertoctylphenothiazines, a mixture of mono- and dialkylated tert-oclyl-
phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4diaminobut-2-ene, N,N-bis-
(2,2,6,6-tetrarnethyl-piperid-4-yl-hexernethylenediamine, bis(2,2,6,6tetramethylpiperid-4-yl)-
sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2, 2,6,6tetramethylpiperidin-4-ol.
2. UV absorbers and light stabilisers 2.1 2-(2'-Hydroxvphenyl) benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyi)benzo-
triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'tert-butyl-2'-hyd roxyphe-
nyl)benzotriazole, 2-(2'-hydroxy-5'-( 1,1,3,3-tetramethylbutyl)phenyl) benzotriazole, 2-(3',5'-d i-
tert-butyl-2'-hyd roxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'hydroxy-5'-methylphe-
nyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'hydroxyphenyl)benzotriazole, 2-(2'-
hydroxy-4'-oclyloxyphenyl)benzotriazole, 2-(3', 5'-di-tert-amyl-2'hydroxyphenyl)benzatriazole, 2-(3', 5'-bis(alCc-dimethylbenzyl)-2'hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-
(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl5'-[2-(2-ethylhexyl-
oxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tertbutyl-2'-hydroxy-5'-(2-
methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'hydroxy-5'-(2-meth
C- - 27 oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'hydroxy-5'-(2-oclyioxycarbonyl-
ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy) carbonylethyl]-2'-hydroxy-
phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-S'-methylphenyl) benzotriazole, 2-(3'-tert-butyl-
2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'methylenebis[4-( 1,1, 3,3-
tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-bu-
tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2 COO-CH2CH2:, where R = 3'-tert-butyl4'-hydroxy-5'-2H-benzotri azol-2-ylphenyl, 2-[2'-hydroxy-3'-(u, ocdimethylbenzyl)-5'-(1,1, 3, 3-tetramethylbutyl)phenyl]-
benzotriazole; 2-[2'-hydroxy-3'-( 1,1, 3,3-tetramethylbutyl)-5'-(cc,cc-d imethylbenzyl)phenyl]ben-
zotriazole. 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4methoxy, 4-octyloxy, 4-decyl-
oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'dimethoxy derivatives.
2.3. Esters of substituted and Substituted henzoic acids, for example 4tert-butyl,ohenyl salicylate, phenyl salicylate, oclylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben-
zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tertbutyl-4-hydroxybenzo-
ate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tertbutyl-4-hydroxyben-
zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4hydroxybenzoate.
2.4. Acrylates, for example ethyl a-cyano-3,{3-diphenylacrylate, isooctyl a-cyano-3,-diphe-
nylacrylate, methyl cc-carbomethoxycinnamate, methyl -cyano--methyl-pmethoxycinna-
mate, butyl cecyano-,B-methyl-p-methoxycinnamate, methyl cc-carbomethoxyp-methoxycin-
namate and N-(3-carbomethoxy--cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis[4-(1, 1,3,3-tetramethyl-
butyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-
butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-
butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2hydroxy-4-methylphe-
nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5hydroxypyrazole, with or with-
out additional ligands.
- 28 2 6. Conventional sterically hindered amines, for example bis(2,2,6, 6-tetramethyl-4-
piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1, 2,2,6,6-pentamethyl-4-
piperidyl)sebacate, bis( 1,2,276,6-pentamethyl-4-piperidyl) n-butyl-3, 5di-tert-butyl-4-
hyd roxybenzylmalonate, the condensate of 1 -(2-hydroxyethyl)-2,2,6,6tetramethyl-4-
hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'bis(2,2,6,6-
tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6dichloro-1,3,5-
triazine, tris (2,2, 6, 6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-
piperidyl)-1,2, 3,4-butanetetracarboxylate, 1, l '-(1,2-ethanediyl)-bis(3, 3,5,5-tetrame-
thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy2,2,6,6-tetramethyl-
piperidine, bis( 1,2,2, 6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hyd roxy3,5-di-tert-butylbenzyl)-
malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4dione, linear or cyclic condensates of N,N'-bis(2,Z,6,6-tetramethyl-4piperidyl)hexamethylenediamine and 4-
morpholino-2,6-dichioro-1,3,5-triazine, the condensate of 2-chloro-4,6bis(4-n-butylamino-
2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2bis(3aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-nbutylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-
triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4piperidyl)pyrrolidine-2,5-
dione, 3-dodecyl- 1 -(1,2,2,6, 6-pentamethyl-4-piperidyi)pyrrolidine-2,5dione, 5-(2-
ethylhexanoyl)-oxymethyl-3, 3, 5-trimethyl-2-morpholinone, 1, 3, 5-tris(Ncyclohexyl-N-(2,2,6,6-
tetramethylpi perazin-3-on-4-yl)amino)-s-triazine, 1,3,5-tris(Ncyclohexyl-N-(1,2,2, 6, 6-
pentamethylpiperazin-3-on-4-yl)amino)-s-triazine, a mixture of 4hexadecyloxy- and 4-
stearyloxy-2,2,6, 6-tetramethyipiperidine, a condensate of N, N'-bis(2,2, 6,6-tetramethyl-4-
piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5triazine, a condensate of 1,2-bis(3-aminopropylamino)ethane and 274,6trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1,6hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as N,Ndibutylamine and 4-
butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N(2,2,6,6-
tetramethyl-4-piperidyi)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4piperidyl)-n-
dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyi-1-oxa-3,8-diaza-4-oXospiro[4,5]decane, a reaction prod uct of 7,7, 9, 9-tetramethyl-2cycloundecyl-1 -oxa-3,8-diaza-4-oxospiro-
[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4piperidyloxycarbonyl)-2-(4-
methoxyphenyl)ethene, N. N'-bis-formyl-N, N'-bis(2,2,6,6-tetramethyl-4piperidyl)
- 29 hexamethylenediarnine, a diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-
pentamethyl-4-hydroxypiperidine, polymethylpropyl-3-oxy-4-(2,2,6,6tetramethyl-4-piperi-
dyl)]siloxane, a reaction product of maleic acid anhydride--olefin copolymer with 2,2,676-
tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'diethoxyoxanilide, 2,2'-dioctyloxy-
5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxydisubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxvphenyl)-1,3, 5-triazines, for example 2,4, 6-tris(2hydroxy-4-oclyloxyphenyl)-
1,3, 5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4dimethylphenyl)-1, 3,5-triazine, 2-
(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4bis(2-hydroxy-4-propyl-
oxyphenyl)-6-(2,4-dimethylphenyl)- 1,3,5-triazine, 2-(2-hydroxy-4octyloxyphenyl)-4,6-bis(4-
methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2, 4-dimethylphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4, 6-bis(2,4dimethylphenyl)-1, 3,5-triazine, 2-
[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyi]-4,6-bis(2,4-dimethyl)1,3, 5-triazine, 2-[2-
hyd roxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6^bis(2,4-dimethyl)-1, 3, 5-triazine, 2-[4-
(dodecyloxy/tridecylOxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-
dimethylphenyl) 1, 3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3dodecyloxypropaxy)phenyl]-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4, 6-diphenyl-1,3,5-
triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6tris[2-hydroxy-4-(3-
butoxy-2-hydroxypropoxy)phenyl]- 1, 3,5-triazine, 2-(2-hydroxyphenyl)-4(4-rnethoxyphenyl)-6-
phenyl- 1, 3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1 -oxy)-2hydroxypropyloxy] phenyl}-4, 6-
bis(2,4-dimethylphenyl)-1,3,5-triazine. 3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N. N'- bis (salicyloyl)hyd rapine, N. N'-bis(3,5-di-tert-butyl-4hydroxyphenylpropionyl)hyd rapine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dibydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'bis(salicyl-
oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dibydrazide.
- 30 4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos-
phite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl penteerythritol diphosphite7 bis(2,4-di-tertbutylphenyl)penteerythritol diphosphite, bis(2,4-di-
curnylphenyl)penteerythritol diphos ph ite, bis (2,6-d i-tert-b utyl-4methylphenyl)penteeryth ritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)-
penteerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl) penteerythritol diphosphite, tristea-
ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'biphenyiene diphosphonite, 6-iso-
octyloxy-2,4,8,1 0-tetra-tert-butyl-1 2H-dibenz[d,g]-1,3,2dioxaphosphocin, bis(2,4-di-tert-butyl-
6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-
fluoro-274,8,1 0-tetra-tert-butyl-1 2-methyl-dibenzd,g]-1,3,2dioxaphosphocin, 2,2',2"-nitrilo-
[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl(3,3',5,5'-te-
tra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4, 6-tri-tert-butylphenoxy)-
1,3,2-dioxaphosphirane. The following phosphites are especialiy preferred: Tris(2,4-di-tert-butylphenyl) phosphite (irgafos@168, Ciba- Geigy), tris(nonylphenyl) phosphite, (C H3)3C c(C H3)3 (CH3)3C C (CH3)3 (A) H3C C: / i P O-CH2CH2 I N (B) C (CH3)3 C(CH3)3 _
(CH3)3C 3
- 31 (CH3)3C C(CH3)3
p-o CH2CH(C4Hg)GH2CH3 () (CH3)3C
C(CH3)3
(CH3)3C OP. P-O j-C(CH3)3 (D) C(CH3)3(CH3)3c C(CH3)3(CH3)3c 3COP >C p_0 =CH3 (E) C(CH3)3 (CH3)3C
H3C-C-CH3
(F) H37C,a O P\ P O-C H /: 3 (G) 5. Hydroxylamines, for example N,Ndibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-
dioctylLydroxylamine, N,N-dilaurylhydroxylamine, N,Nditetradecylhydroxylamine, N,N-
dibexedecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexedecyl-Noctadecylhydrox-
ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
- - 32 6. Nitrones, for example N-benzyl-alpha-phenylnitrone, N-ethylalpha-methylnitrone, N-oclyl-
alpha-heptylritrone, N-lauryl-alpha-undecylcitrone, N-tetradecyl-alphatridecylnitrone, N-
hexedecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecyinitrone, Nhexedecyl-al-
pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecylalpha-hepta-
decylnitrone, N-octadecyl-alpha-hexedecylnitrone, nitrone derived from N, N-dialkylhydroxyl-
amine derived from hydrogenated tallow amine.
7 Thiosynernists, for example dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavengers, for example esters of 0-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-
benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentserythritol tetrakis(-
dodecylmercapto)propionate. 9. Polyamide stabilizers, for example copper salts in combination with iodides and/or phos-
phorus compounds and salts of divalent manganese.
10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl yanu-rate, urea-derivatives,- hydrazine derivatives, amides, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium almitate, antimony pyrocatecholate or zinc pyrocatecholate.
11. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e. g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1,3:2,4-bis(3',4'dimethylbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzyli-
dene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.
- - 33 12. Fillers and reinforcing aqents, for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives for example plasticizers, lubricants emulsifiers, pigments, rheology additives, catalysts, flow-control 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-4316611;
DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2acetoxyethoxy)-
phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2stearoyloxyethoxy)phe-
nyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-2-hydroxyethoxy] phenyl)benzofuran-2-
one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy3,5-dimethylphe-
nyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4pivaloyloxyphenyl)-5,7-di-tert-butyl-
benzofuran-2-one, 3-(3,4-dimethylphenyi)-5,7-di-tert-butyl-benzofuran-2one, 3-(2,3-di-
methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one. 15. Amine oxides, for example amine oxide derivatives as disclosed in U.S. Patent Nos. 5,844, 029 and 5,880,191, didecyl methyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexedecyl amine oxide. U.S. Patent Nos. 5, 844,029 and 5,880,191 disclose the use of saturated hydrocarbon amine oxides towards the stabilization of thermoplastic resins.
It is disclosed that the thermoplastic compositions may further contain a stabilizer or mixture of stabilizers selected from phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organic phosphorus compounds, alkaline metal salts of fatty acids and thiosynergists. The co-use of amine oxides with other stabilizers towards stabilizing polyolefins is not exemplified.
Further preferred compositions comprise, in addition to components (b) and (c) further additives, in particular phenolic antioxidants, light stabilizers or processing stabilizers.
Particularly preferred additives are phenolic antioxidants (item 1 of the list), further sterically hindered amines (item 2.6 of the list), light stabilizers of the benzotriazole and/or o
- 34 hydroxyphenyltriazine class (items 2.1 and 2.8 of the list), phosphites and phosphonites (item 4 of the list) and peroxide-destroying compounds (item 5.) of the list.
Additional additives (stabilizers) which are also particularly preferred are benzofuran-2-
ones, such as described, for example, in US-A-4,325,863, US-A-4,338,244 or US-A-
5,175,312.
The instant composition can additionally contain another UV absorber selected from the group consisting of the s-triazines, the oxanilides, the hydroxybenzophenones, benzoates and the a-cyanoacrylates. Particularly, the instant composition may additionally contain an effective stabilizing amount of at least one other 2-hydroxyphenyl-2H- benzotriazole; another tris-aryl-s-triazine; or hindered amine or mixtures thereof. Preferred are additional components selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic costabilizers, further light stabilizers like UV absorbers and/or sterically hindered amines, metal passivators, metal oxides, organophosphorus compounds, hydroxlamines. and mixtures thereof; especially Figments, phenolic antioxidants, calcium stearate, zinc stearate, UV absorbers of the 2-(2'-hydroxyphenyl)benzotriazole and 2-(2-
Hydroxyphenyi)-1,3,5-triazine classes, and sterically hindered amines.
The halogenated flame retardants useful as component (B) in compositions of present invention may be selected from organic aromatic halogenated compounds such as halogenated benzenes, biphenyls, phenols, ethers or esters thereof, bisphenols, diphenyloxides, aromatic carboxylic acids or polyacids, anhydrides, amides or imides thereof; organic cycloeiiphatic or polycycloaliphatic halogenated compounds; and organic aliphatic halogenated compounds such as halogenated paraffins, oligo- or polymers, alkylphosphates or alkylisocyanurates. These components are largely known in the art, see e.g. US patents Nos. 4,579,906 (e.g. colt 3' lines 30-41), 5,393,812; see also Plastics Additives Handbook, Ed. by H. Zweifel, 5th Ed., Hanser Publ., Munich 2001, pp. 681-698.
The halogenated flame retardant may be, for example, a chlorinated or brominated compound, e.g. selected from the following compounds:
f - - 35 Chloroalkyl phosphate esters (ANTIBLAZE AB-100, Albright & Wilson; FYROL FR-2, Akzo Nobel), polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.), decabromodiphenyl oxide (DBDPO; SAYTEX 102E), tris[3bromo-2,2-bis(bromomethyl)propyl] phosphate (PB 370@, FMC Corp.), bis(2,3dibromopropyl ether) of bisphenol A (PE68), brominated epoxy resin, ethylene-bis(tetrabromopUthalimide) (SAYTEX BT-93), bis(hexachlorocyclopentadieno)cyclooctane (DECLORANE PLUSH), chlorinated paraffins, 1,2-bis(tribromophenoxy)ethane ( FF680), tetrabromo-bisphenol A (SAYTEX RB100), ethylene bis-(dibromo-norbornanedicarboximide) (SAYTEX@BN-451), bis-(hexachlorocyciopentadieno) cyclooctane, tris-(2,3dibromopropyl)-isocyanurate, ethylene-bis-tetrabromopUthalimide. Preferred as component (B) are brominated flame retardants.
Most preferred flame retardants (B) in these compositions of the invention are B1) melamin based flame retardants and/or ammonium polyphosphate, B2) bis-(hexachlorocyclopentadieno) cyclooctane, B3) tris(2,3-dibromopropyl)-isocyanurate, B4) ethylene-bis-tetrabromophthalimide, B5) 1,2,5,6,9,10-hexabromo-cyclo-dodecan, B6) ethane-1,2bis(pentabromophenyl), B7) tris(3-bromo-2,2-(bromomethyl)propyi) phosphate.
Especially preferred flame retardants (B) in these compositions of the invention are as initially explained for component (b).
f - 36 The flame retardant (B) is often contained in an amount from 0.5 to 50 % by weight of the polymeric substrate (A); more preferred dosages for the most preferred flame retardants (B) are as initially explained for component (b).
The ratio (B): (C) in these compositions is preferably in the range from 20: 1 to 250: 1.
The ratio (C1): (C2) in these compositions is often in the range from 1: 5 to 5: 1. In case that the polymeric substrate (A) is a polyolefin, the low molecular weight component (C1) is preferably used in about the same or in a larger amount than (C2), e.g. 40 - 95 parts by weight of (C1) on 100 total parts by weight of component (C) consisting of (C1) and (C2).
In a polyolefin with main component polyethylene, the low molecular weight part (C1) often will amount about half of the total amount of component (C), e.g. from 40 to about 70, more specifically from 45 to about 55 % by weight of total component (C).
In a polyolefin with main component polypropylene, the low molecular weight part (C1) often will amount rather more than half of the total amount of component (C), e g. from 50 to about 90, more specifically from 60 to about 85 % by weight of total component (C).
Under such conditions in a polyolefin, the low molecular weight component (C1) may also be of the hydrocarbyloxyamine class. Thus, another object of the invention pertains to a composition comprising A) a polgolefin, B) a flame retardant selected from ammonium polyphosphate, halogenated and/or melamin based flame retardants, and C) a combination of sterically hindered amine light stabilizers comprising, on 100 parts by weight of total component (C), C1) 40 to 95 parts by weight a low molecular weight sterically hindered amine of the hydrocarbyloxyamine class, and C2) 5 to 60 parts by weight of a conventional high molecular weight sterically hindered amine.
- 37 The low molecular weight sterically hindered amine of the hydroxyhydrocarbyloxyamine or, where appropriate, hydrocarbyloxyamine class (C1) usually is from the molecular weight range 200 to 1000 g/mol, especially 300 to 800 g/mol. It may be one compound or a mixture of compounds, each fulfilling the molecular weight condition. Especially preferred are, for example,
1 -cyclohexyroxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; bis( 1 octyloxy-2,276,6-tetramethylpiperidin-4-yl) sebacate; bis(1-cyclohexyloxy2,2,6,6-tetramethylpiperidin-4-yl) adipate; 1 -(2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethyl piperidine.
The high molecular weight sterically hindered amine (C2) is of the conventional type containing 2,2,6,6-tetramethyl-4-piperidyl moieties whose nitrogen atoms are unsubstituted (secondary sterically hindered amine) or substituted by alkyl, especially methyl (alkylated tertiary sterically hindered amine) or are part of a polymeric backbone (polymeric tertiary sterically hindered amine). It usually is from the molecular weight range 1200 to 10000 g/mol, especially 1500 to 5000 g/mol. Examples for such compounds useful in the composition of the invention can be found among those listed under item 2.6 above, e.g. the following compounds: Examples for secondary sterically hindered amines of high molecular weight N N (CH2)6 N p IN-(CH2)6 N -H H NON
N (: - 3
CH3H2CH3 n
- 38 _ H H (CH2)6 N- it IN-(CH2)6 N -H _ O -n N? /|< it_ C4H9 N C4H9- N N C4Hg where n is mainly from the range 3-5.
Examples for methvlated tertiary sterically hindered amines of high molecular weight _ qH3 qH3_ H-(CH2)6 N '-NN-(OH)-N -H
with n as defined above;
C - 39 R-NH-(CH2)3-N(R)-(CH2)2-N(R)-(CH2)3-NH-R, wherein R is CH3 CH3
C H/N:'N:' C4Hg (GAS-No. 106990-43-6).
N. - N
Example for polymeric tertiary sterically hindered amine of high molecular weight CH 1 CH3 H--of /N-CH2 CH2 0-CH2 CHIL-O-CH3 (Mn >2500; \CH3 m CH3 GAS-No. 65447-77-0).
Especially preferred compounds of component (C2) are those containing 2,2, 6,6-tetramethyl-
4-piperidyl moieties whose nitrogen atoms are unsubstituted or alkyl, especially methyl substituted.- Especially preferred compounds of component (C2) are also containing triazine moieties as structural backbones In general, component (C) is contained in an amount from 0.01 to 10 %, preferably from 0.05 to 5% by weight, especially from 0.1 to 3 % by weight, based on the polymer component (A).
The weight ratio (C1): (C2) preferably ranges from 1: 1 0 to 1 0; 1; most preferably from 1: 1 to 10:1.
Further components optionally to be used in these compositions of the invention, and methods of using them, are as initially explained.
The following examples are for illustrative purposes only and are not to be construed to limit the instant invention in any manner whatsoever. Room temperature depicts a temperature in the range 20-25 C. Percentages are by weight unless otherwise indicated.
Abbreviations:
- - ( - 40 v. parts by volume w parts by weight Hnmr nuclear magnetic resonance (NMR) of 1H m/z mass spectrometry (atomic units) emu molecular weight in g/mol (= atomic units) Mn number average of molecular weight (usually determined by GPC) PP polypropylene PE polyethylene PE-LD low density polyethylene (LOPE) Stericallv hindered amines of the hvdrocarbyloxyamine or hvdroxyhydrocarbyloxyamine class (present component c) for use in the examples are the compounds o oC17H3s c1 disclosed in example 73 of US pat. No. 6,271,377; > \ N Ike POOH c3 H37Ce-C-NO (CH2)8 OWN-o-C3H,7 H C CH3
3 CH3 H3C
Further stabilizers used in the examples are compounds of formulae A R-NH(CH2)3-N(R)-(CH2)2-N(R)-(CH2)3-NH-R (CAS Registry No. 106990-43-6)
CH3 C, H3
where R is the group C4H/N\-N:/ C4Hg NON B poly [[6-[(1,1,3,3-tetramethyl butyl) amino]-1,3,5-triazine-2,4-diyl][[(2,2,6,6 tetramethyl-4-piperidyl) irnino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] (GAS-No. 70624-18-9) D oligomer (GAS-No. 65447-77-0) of the formula HOBO N-CH2 CH2 OCHz CH20-CH3 Ho: 3-o ITCH CH3 H3C \ O OH G I:
- 42 Compounds c2, c3 and A-G are commercial stabilizers available from Ciba Specialty Chemicals. Example 1
Sample preparation: Polymer powder and stabilizers are pre-mixed (Herschel mixer, 800 rpm, room temperature), pigment powder and flame retardant are added as concentrate in PP and homogenized in a drum mixer. Further homogenization and granulation is achieved by extrusion (Coliin(D twin screw extruder, max 200 C, 100 rpm).
Subsequently, the mixture is processed into a flat film by means of a single screw extruder (max 200 C, 70 rpm) equipped with a corresponding nozzle (sample dimension 2mm thickness, 10 cm width).
Weathering; Punched samples are exposed to accelerated weathering (AtlasO WOM Ci 65, Q.95W/m2(at 34Qnm), 102 min dry, 18 min water spray, 63 C black panel temperature. The effect of weathering on the surface is assessed in the following manner: Visual inspection of chalking (chalking indicates decomposition on the surface).
Gloss: Minolta; degradation of surface reduces the reflection of polarized light (60 gloss as defined in DIN 67530).
E: Colour change (according to DIN 6174).
Formulation: 84 parts by weight of polypropylene-ethylene copolymer (Novolen() PPG 1022), 15 parts by weight of a PE-based flame retardant masterbatch containing 51% by weight of ethylene-bistetrabromophthalimide (b4) and 17 % by weight of Sb2O3, 1 part by weight of TiO2 and 0.2 parts by weight of blue pigment (Cromophtal blue 4GNP) and stabilizers as shown in the following table (amounts given in % by weight of the total formulation) The results are shown in the following table.
- 43
- 44 Table. Surface assessment after weathering for 2000 h - Exp. # Stabilizers Visual Gloss E a* none chalking 3 5.9 b O c unchanged 53 1. 5 0.1% B
0.3%C c* 0.1% B chalking 8 4.6 0 3 / c1 d. O unchanged 51 2.8 0.1% B
e * 0.1% B chalking 8 5.9 1 0.2% E I | I I
* comparative example Samples containing the combination of flame retardant and sterically hindered amine of present invention show no chalking, better gloss and distinctly less colour change than samples wherein present component c has been replaced by another sterically hindered Antoine. Example 2
Samples are prepared and subjected to accelerated weathering as described in example 1.
Formulation: 89 parts by weight of polypropylene-ethylene copolymer (Novolen(0 PPG 1022), 10 parts by weight of a PE based flame retardant masterbatch containing 30% by weight of tris-(2,3-dibromopropyl)isocyanurate (b3) and 15 % Sb2O3, 1 part by weight of TiO2 and 0.2 parts by weight of blue pigment (CromopUtal blue 4GNP)
- 45 and stabilizers as shown in the following table (amounts given in % by weight of the total formulation). The results are shown in the following table.
Table: Surface assessment after weathering for 2000 h Exp. # Stabilizers Visual Gloss E a* none chalking 8 7.5 b 0 3% c1 unchanged 58 1.7 0.2% F
0.3% C
c* 0.1% B chalking 12 6.4 0.2% F
d 013% cB3 unchanged 57 3 0.2% E
e 0 3% c1 unchanged 63 2.3 0.2% E
0.3% C
f * 0. 1% B chalking 14 7.1 0.2% E
.. * comparative example Example 3..DTD: Sample preparation: Polymer powder, flame retardant and stabilizers are pre-mixed (Herschel mixer, 800 rpm, roopm temperature), pigment is added as concentrate in PE-LD and homogenized in a drum mixer. Further homogenization and granulation is achieved by extrusion (Berstorff twin screw extruder (max 220 C, 100 rem).
Test samples (44 x 68 x 2 mm) are obtained by compression moulding (Engel) at a plastification temperature of max 200 C and a forming temperature of 50 C.
fin - 46 Accelerated weathering and assessment of the samples is done as described in example 1.
Formulation: 73 parts by weight of polypropylene-ethylene copolymer (Appryl (D 3060), 25 parts by weight of melamin polyphosphate (flame retardant b1, Melapur P 46), 2 parts by weight of blue pigment masterbatch (10% CromopUtal blue 4GNP in PE-LD) 0.15 parts by weight of a commercial phenolic antioxidant (1: 1 mixture of tris(2,4-di-t butyiphenyl)phosphite and pentaerythritol tetrakis[3-(3,5-di-t-butyl-4 hydroxyphenyl)propionate], available from Ciba Specialty Chemicals) and stabilizers as shown in the following table (amounts given in % by weight of the total formulation). The results are shown in the following table.
Table: Surface assessment after weathering for 1000 h Exp. # Stabilizers Visual Gloss E a 0. 2 % A A, I i i n 5 2 3. 9 b 0.133% A unchanged 19 3.9 _ 0.266% c1 * comparative example Example 4
Sample preparation, accelerated weathering and assessment of the samples is done as described in example 3.
Formulation: 82 parts by weight of polypropylene-ethylene copolymer (Appryl (it) 3060), 12 parts by weight of bis-(hexachlorocyclopentadieno) cyclooctane (flame retardant b2, Dechloran Plus A), 4 parts by weight of Sb203 2 parts by weight of blue pigment masterbatch (10% CromopUtal blue 4GNP in PE-LD)
- 47 0.15 parts by weight of a commercial phenolic antioxidant (1: 1 mixture of tris(2,4-di-t-
butylphenyl)phosphite and penteerythritol tetrakis[3-(3,5-di-t-butyl-4-
hydroxyphenyl)propionate], available from Ciba Specialty Chemicals) and stabilizers as shown in the following table (amounts given in % by weight of the total formulation). The results are shown in the following table.
Table: Surface assessment after weathering for 1000 h _. _. _
Exp. Stabilizers Visual Gloss E a* 0.2% B chalking 7 5.1 0.2% C
_. b 0.2% A unchanged 35 0.7 0.2% c1 * comparative example Example 5
Sample preparation, accelerated weathering and assessment of the samples is done as described in example 3. Formulation Is identical with the one of example 3 except that the melamin polyphosphate flame retardant is replaced by the same amount of ammonium polyphosphate (flame retardant b1; Exolith AP 752). Results are shown in the following table.
Table: Surface assessment after weathering for 1500 h _ _. Exp. # Stabilizers Visual Gloss E _._. a* 0.2% A chalking 5 21.4 0.2% D
b 0.2% A unchanged 28 3.1 0.2% c1 * comparative example
- 48 Example 6
Sample preparation, accelerated weathering and assessment of the samples is done as described in example 3.
Formulation: 92 parts by weight of polypropylene-ethylene copolymer (Appryl (it) 3060), 4 parts byweight of tris(3-bromo-2,2-(bromomethyl) propyl) phosphat (flame retardant, FR 372 from Dead See Bronnine), 2 parts by weight of SbzO3 2 parts by weight of blue pigment masterbatch (10% CromopUtal blue 4GNP in PE-LD) 0.15 parts by weight of a commercial phenolic antioxidant (1: 1 mixture of tris(2,4-di-t butyl phenyi) phosphite and penteerythritol tetrakis[3-(3,5-d i-t-butyl-4 hydroxyphenyl) propionate], available from Ciba Specialty Chemicals) and stabilizers as shown in the following table (amounts given in % by weight of the total formulation). The results are shown in the following table.
Table: Surface assessment after weathering for 1500 h 1 I
Exp. Stabilizers Visua' 'pious a E a* 0.2% B chalking 6 7 6 02%C b 0.2% A unchalking 56 0.4 0.2% c1 comparative example Example 7
Sample preparation, accelerated weathering and assessment of the samples is done as described in example 3.
Formulation: 88 parts by weight of polypropylene-ethylene copolymer (Appryl (D 3060), 8 parts by weight of ethane-1,2-bis(pentabromophenyl) (flame retardant be, Saytex 8010),
- 49 4 - parts by weight of Sb2O3 2 parts by weight of blue pigment masterbatch (10% Cromophtal blue 4GNP in PE-LD) 0.15 parts by weight of a commercial phenolic antioxidant (1: 1 mixture of tris(2,4-di-t butylphenyl)phosphite and penteerythritol tetrakist3-(3,5-di-t-butyl-4 hydroxyphenyl)propionate], available from Ciba Specialty Chemicals) and stabilizers as shown in the following table (amounts given in % by weight of the total formulation). The results are shown in the following table.
Table: Surface assessment after weathering for 750 h _. _ _. _
Exp. # Stabilizers Visual Gloss E _ _ _ _._.,
a* 0 2% B Chalking 10 6.5 0 2% C
_ _.
b 0.13% A Unchanged 38 5.3 0.27% c1 1 0.1 % G
* comparative example

Claims (9)

- t-- - 50 WHAT IS CLAIMED IS:
1. A flame retardant composition stabilized against deleterious effects of light and weathering comprising a) a thermoplastic polymer, b) a flame retardant selected from ammonium polyphosphate, halogenated and/or melamin based flame retardants, and c) a combination of sterically hindered amine light stabilizers comprising c1) a low molecular weight sterically hindered amine of the hydroxyhydrocarbyloxyamine class, and c2) a high molecular weight secondary or alkylated or polymeric tertiary sterically hindered amine.
2. Composition according to claim 1, wherein component (a) is a polyolefin.
3. A flame retardant composition stabilized against deleterious effects of light and weathering comprising a) a polyolefin, b) a flame retardant selected from ammonium polyphosphate, halogenated and/or melamin based flame retardants, and c) a combination of sterically hindered amine light stabilizers comprising, on 100 parts by weight of total component (c), c1) 40 to 95 parts by weight a low molecular weight sterically hindered amine of the hydroxyLydrocarbyloxyamine or hydrocarbyloxyamine class, and c2) 5 to 60 parts by weight of a high molecular weight secondary or alkylated or polymeric tertiary sterically hindered amine.
4. Composition according to claim 1 or 3, wherein component (b) is selected from b1) melamin based flame retardants and/or ammonium polyphosphate, b2) bis-(hexachlorocyclopentadieno) cyclooctane, b3) tris(2,3-dibromopropyl)-isocyanurate, b4) ethylene-bis-tetrabromophthalimide,
c b5) 1,2,5,6,9,10-hexabromo-cyclo-dodecane, be) ethane-1,2bis(pentabromophenyl), b7) tris(3-bromo-2,2-(bromomethyl)propyl) phosphate.
5. Composition according to claims 1 or 3, wherein the low molecular weight stericaily hindered amine of the hydrocarbyloxyamine or hydroxyLydrocarbyloxyamine class (c1) is from the molecular weight range 200 to 1000 g/mol, and the high molecular weight sterically hindered amine (c2) is from the molecular weight range 1200 to 10000 g/mol.
6. Composition according to claims l or 3 containing component (b) in an amount from 0.5 to 50 % by weight, and component (c) in an amount of 0.01 to 10 % by weight, each based on the weight of component (a).
7. Composition according to claims 1 or 3 additionally containing one or more further components selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic costabilizers, metal passivators, metal oxides, organophosphorus compounds, hydroxylamines, further light stabilizers and mixtures thereof.
8. Composition according to claims 1 or 3 additionally containing one or more further _......
components selected from pigments' phenolic antioxidants, calcium stearate, zinc stearate, stericaily hindered amides, UV absorbers of the 2-hydroxy-benzophenone, 2-(2'-
hyd roxyphenyl)benzotriazole and/or 2-(2-hydroxyphenyl)-1, 3, 5-triazine classes.
9. Molded or extruded article comprising a composition according to claims 1 or 3.
GB0301386A 2000-12-12 2001-12-06 Improved weatherability of flame retardant polyolefin Expired - Fee Related GB2386901B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP00811174 2000-12-12
GB0129225A GB2373507B (en) 2000-12-12 2001-12-06 Improved weatherability of flame retardant polyolefin

Publications (3)

Publication Number Publication Date
GB0301386D0 GB0301386D0 (en) 2003-02-19
GB2386901A true GB2386901A (en) 2003-10-01
GB2386901B GB2386901B (en) 2004-03-31

Family

ID=27790073

Family Applications (1)

Application Number Title Priority Date Filing Date
GB0301386A Expired - Fee Related GB2386901B (en) 2000-12-12 2001-12-06 Improved weatherability of flame retardant polyolefin

Country Status (1)

Country Link
GB (1) GB2386901B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1767576A1 (en) * 2004-07-09 2007-03-28 Mitsui Chemicals, Inc. Resin composition and use thereof
WO2015044785A3 (en) * 2013-09-27 2015-06-11 Basf Se Polyolefin compositions for building materials
US11976186B2 (en) 2018-06-15 2024-05-07 Borealis Ag Flame retardant polyolefin composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5844026A (en) * 1997-06-30 1998-12-01 Ciba Specialty Chemicals Corporation N,N',N''-tris{2,4-bis Hydrocarbyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)alkylamino!-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamines, their isomers and bridged derivatives and polymer compositions stabilized therewith
WO1999000450A1 (en) * 1997-06-30 1999-01-07 Ciba Specialty Chemicals Holding Inc. Flame retardant compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5844026A (en) * 1997-06-30 1998-12-01 Ciba Specialty Chemicals Corporation N,N',N''-tris{2,4-bis Hydrocarbyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)alkylamino!-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamines, their isomers and bridged derivatives and polymer compositions stabilized therewith
WO1999000450A1 (en) * 1997-06-30 1999-01-07 Ciba Specialty Chemicals Holding Inc. Flame retardant compositions

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1767576A1 (en) * 2004-07-09 2007-03-28 Mitsui Chemicals, Inc. Resin composition and use thereof
EP1767576A4 (en) * 2004-07-09 2008-08-20 Mitsui Chemicals Inc Resin composition and use thereof
WO2015044785A3 (en) * 2013-09-27 2015-06-11 Basf Se Polyolefin compositions for building materials
AU2014326295B2 (en) * 2013-09-27 2017-11-30 Basf Se Polyolefin compositions for building materials
US10428204B2 (en) 2013-09-27 2019-10-01 Basf Se Polyolefin compositions for building materials
US10669403B2 (en) 2013-09-27 2020-06-02 Basf Se Polyolefin compositions for building materials
US11976186B2 (en) 2018-06-15 2024-05-07 Borealis Ag Flame retardant polyolefin composition

Also Published As

Publication number Publication date
GB0301386D0 (en) 2003-02-19
GB2386901B (en) 2004-03-31

Similar Documents

Publication Publication Date Title
KR100805296B1 (en) Flame retardant polymer composition
EP1749051B1 (en) Flame-retardants
DE60302494T2 (en) Agriculturally applicable articles
JP4406869B2 (en) Flame retardant composition
JP4389248B2 (en) Flame retardant composition
KR101994057B1 (en) Sterically hindered amine stabilizer
AU2004275997A1 (en) Stabilization of photochromic systems
DE60319695T2 (en) STABILIZED OBJECTS
CA2498975A1 (en) Flame retardant compositions
GB2386901A (en) Improved weatherability of flame retardant polyolefin

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee

Effective date: 20101206