GB2260764A - Stabilizing composition for polymers - Google Patents

Stabilizing composition for polymers Download PDF

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GB2260764A
GB2260764A GB9221154A GB9221154A GB2260764A GB 2260764 A GB2260764 A GB 2260764A GB 9221154 A GB9221154 A GB 9221154A GB 9221154 A GB9221154 A GB 9221154A GB 2260764 A GB2260764 A GB 2260764A
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hydrogen
alkyl
phenyl
case
composition according
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GB9221154D0 (en
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Giovanni Matteini
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Sandoz AG
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Sandoz AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids

Abstract

A stabilizing composition useful as a processing and light stabilizer for polymers such as polyurethane and polyolefins comprises a) a mono- or di- phosphite or mono- or diphosphonite b) a chroman derivative (especially alpha -tocopherol or derivatives thereof); and c) a light stabilizer (component c) selected from (i) a polymer containing at least one hindered amine light stabilizer group, preferably a polysiloxane containing a hindered amine light stabilizer group and/or ii) the combination of an oxanilide and a hindered amino light stabilizer (HALS) compound.

Description

- 3 ') 1 COMPOSITIONS FOR STABILIZING POLYMERS The invention relates to
new compositions for stabilizing polymers, for example, polyurethane.
According to the invention, there is provided a stabilizing composition, useful as a processing and light stabilizer for polymers such as polyurethane comprising:
a) a mono- or di- phosphite or mono- or diphosphonite (component a) b) a chroman derivative (especially cc-tocopherol or derivatives thereof) (component b); and a light stabilizer (component c) selected from i) a polymer containing at least one hindered amine light stabilizer group, preferably polysiloxane containing a hindered amine light stabilizer group (component i) and/or ii) the combination of an oxanilide and a hindered amine light stabilizer (HALS) compound (component ii).
Preferred mono- and di- phosphites for use in a composition according to the invention are those of formula I or 11 /0- R, IR,-0-P O-Rl 0- (H2 CHi-- 0 1 R,- 0- "C P-O-Rl 1 0- CH2 CHi--d (1) (11) 2 Case 153-5550 in which each R, independently is a group derived from an aliphatic, alicyclic or aromatic alcohol containing one or two OH groups.
Aromatic alcohol, in the Specification, include phenols.
Preferred mono- or diphosphonites are selected from compounds of formula III RIP RIO- 0- p R16-0 in which m is 0 or 1; n is 0 or 1; p is 0 or 1; / 0-% ,, P,, 0-% m each R., independently, is a group derived from an aliphatic, alicyclic or aromatic alcohol containing one or two OH groups; whereby the two -OH groups are not positioned to be able to form a P-containing ring; (hereinafter defined as the monovalent significances of Rq); or both groups R. form a group derived from an aliphatic, alicyclic or aromatic alcohol containing two OH groups in such a position that they can form a cyclic group with a single phosphorus atom (hereinafter defined as the divalent significances of Rq):
IR,, is a monovalent or divalent significance of IR,; Y is -0-, -S-, CH(Rj- or -CH4-; where R3 is hydrogen, Cl_.alkyl or COOR4and R4 'SC1_. alkyl. More preferably the mono- 11 3 Case 153-5550 and diphosphonites are diphosphonites, most preferably tetrakis (2,4-tert. butyl phenyl) biphenylene diphosphonite (commercially available as SANDOSTAB P-EPO from SANDOZ Chemicals Ltd.).
Preferably R, is R,' where R,' is a linear or branchedCl-22alkyl or phenyl, unsubstituted or substituted by 1 to 3 linear or branched Cl12alkyl groups (such substitution when present, preferably being Cl4alkyl).
Preferably R. is R3'where R.' is hydrogen or methyl.
Preferably R4 is R4'where R4' 'S Cl-4alky].
Preferred phosphites of component a) are selected from tris(2,4-di-t. butyl phenyl)phosphite, tris(nonylphenyi)phosphite, di- isodecylphenyl phosphite, tril au ryl phosphite, bis (2,6-di-t.butyl-4methyiphenyi)pentaerythrityi diphosphite, bis (2,4-di-t.butyl phenyl)pentaerythrityl diphosphite and distearylpentaerythrityl diphosphite.
Preferred chroman derivatives are of those of formula IV CH3 33 0:k CM131 CH3 CH3 (IV) in which R2 is -(CH2)3-CH-(CH2)3-CH-(CH2)3-CH-CH3 1 1 1 u13 CH3 jn3 or -CH2-CH2-0-CO-R, where R. is selected from C7-30alkyl, -CH2CH2"S- (C130aikyi) or 4 C(CH3)3 -CH2 -C OH C((H3 Preferred polysiloxanes are compounds of formula V 91 -6alkyl fH2)2-8 0 H CH3 CH3 CH3 3R Case 153-5550 (V) in which na--- 1 to 100, preferably 5 to 30. R is selected from hydrogen, C,_.alkyl, oxygen,-OR, or -CO-R5where R5 is -C(R8)=CH2, C,_.alkyl, phenyl, -COCA, -CH2C.H., -COOC1-12alkyl, COOH, or NR7R8, where R7 is hydrogen, Cl-12alkyl, C,_,cycloalkyl, phenyl, pheny1C1-4alkyl or Cl-12alkylphenyl and R8 'S Cl-12alkyl or hydrogen.
Preferred oxanilides are those of formula V11 (R1 J2 (R1 A N-COM E) R13 R 13 R, 1 13 R,, (V11) Case 153-5550 in which each R,, independently is selected from hydrogen, C,_1.alkyl, C, _1.alkoxy, halogen, hydroxy, phenyl and phenoxy; and each R,., independently, is selected from hydrogen, halogen, hydroxy, C,-. alkyl and C,-.alkoxy; and each R13, independently, is hydrogen or methyl.
Preferably R,, is R,,' where R,,' is selected from hydrogen, hydroxy, Cl4alkyl and Cl-4alkoxy, more preferably R,, is hydrogen.
Preferably R,. is R,,' where R12' is selected from hydrogen, hydroxy, Cl4alkyl and Cl-4alkoxy, more preferably on phenyl group A and B, one R12 is hydrogen and the other R12 is R12"where R,." 'S Cl-4alkyl orCl-4aikoxy. Preferably R12" on ring A is a Cl-4alkyl and on ring B R12" is aCl4alkoxy.
Preferably R13 is hydrogen.
Preferably both R12 groups are ortho to one another.
Preferred HALS compounds are 2,2,6,6-tetramethylpiperidine compounds. More preferred HALS compounds are those of formula V1 (H3 CH3 R N Rio >, R15 CH3 CH 3 V1 6 Case 153-5550 in which R is selected from hydrogen, C,_.alkyl, oxygen or -COR.; where R. is C(RJ=CH2, C,,alkyl, phenyl, -NR7R,, -CO-C6H., -CH2C6H,, -CO0C1- 12alkyl or -COOH; where R7 is hydrogen, Cl-12alky], C5-6C0oalkyl (preferably cyclohexyl), phenyl, phenyl Cl-4alkyl orCl-12alkylphenyl and R. is hydrogen orCl-12alky]; R,5 is hydrogen, Cl-22alkyl, C,-22alkoxy, - N(RJ-CO-CO-R2.; or -NH-C(R3)=N-R21; R3 is hydrogen, Cl-1.alkyl or COOR4where R4 'SC1-,,alkyl R2. is an amide forming group and R21 is Cl-1. alkyl, phenyl, unsubstituted or substituted by 1 to 3 groups selected fromCl-,8a]ky], Cl-4alkoxy and halogen; or IR,. is CH3 CH R18 N-R (CH2)8-1 -0 12 CH3 CH3 and IR,. is hydrogen or Cl,,alkyl; or IR,. and R16together with the C-atom to which they are attached, form a group of formula a) \ C,, ('- (CH2)11 O-C_.', CO- N 2-4alkylene4X)OC1-22alkyl -C (a) Preferably R is R'where R' is hydrogen, C,_4alkyl or -COR.' where R5' 'S Cl-4alkyl or - CO0C1-4alkyl, more preferably R' where R' is hydrogen, methyl or -COCH..
7 Case 153-5550 More preferred 2,2,6,6-tet ram ethyl pipe ri di nyl compounds are of formula W CH3 CH3 ( (CH2)11 0- & W- N 1 _1 CoN-CH2CH200C-laalkyl (M3 CH.9 (V]') where R' is hydrogen, Cl-4alkyl or -CO-R5' where R,,' 'S Cl-4alkyl or -CO- OC1-4alkyl.
Preferably the ratio of components a) and b) to c) is 3:1 to 12, more preferably 1A.
Preferably the ratio of component a) to component b) is 6:1 to 12, more preferaoly 4A.
10:1 to 12, more preferably Preferably in compositions according to the invention the amounts of components a) to c) are as follows:
30-50% (preferably 40%) component a) 5-20% (preferably 10%) component b) aAl 30-65% (preferably 50%) component c).
If more than one light stabilizer is present in component c) they are preferably an oxanilide and a HALS compound. Preferably the ratio of oxanilide to HALS compound is 3:1 to 12, preferably 2A.
Preferably the compositions according to the invention are in the form of liquid preparations, preferably without plasticizer or solvent.
8 Case 153-5550 According to the invention there is further provided a polymeric composition comprising a polymeric material and a stabilizing amount (preferably 0.2-8% based on the weight of polymeric material) of a stabilizing composition defined above.
Polymeric materials that can be stabilized by a stabilizing composition according to the invention include homopolymers, copolymers and polymer blends of:
Cellulose acetate; Cellulose acetobutyrate; Cellulose acetopropionate; Cresolformaldehyde resin; Carboxymethy1cellulose; Cellulose nitrate; Cellulose propionate; Casein plastics; Casein-formalclehyde; Cellulose triacetate; Ethyl cellulose; Epoxy resins; Methyl cellulose; Melamineformaldehyde resins; Polyamide; Polyamideimide; Polyacrylonitrile; Polybutene-1 and -2; Polybutylacrylate; Poly-(butyleneterephthalate); Polycarbonate; Poly(chlorotrifluoroethylene); Poly(diallylphthalate); Polyethylene; chlorinated Polyethylene; Poly(etherketone); Polyetherimide; Polyethyleneoxide; Polyethersulphone; Poly(ethyleneterephthalate); Polytetrafluoroethylene; Phenolformaldehyde resins; Polyimide; Polyisobutylene; Polyisocyanu rate; Polymethacrylimide; Polymethylmethacrylate; Poly(4-methylpentene-1); Poly(a-methyl styrene); Polyoxymethylene; Polyformaldehyde; Polyacetal; Poly- propylene; Polyphenylene ether; Polyphenylenesulphide; Polyphe nyl ene-sul phone; Polystyrene; Polysulphone; Polyurethane; Polyvinyl acetate; Polyvinyl alcohol; Polyvinylbutyral; chlorinated Polyvinyl chloride; Polyvinylidene chloride; Polyvinylidene fluoride; Polyviny[fluodde; Polyvinylformalclehyde; Polyvinylformalclehyde; Polyvinylcarbazol; Polyvinylpyrroliclone; Silicon polymers; saturated polyester; ureaformaldehyde resins; unsaturated polyester; polyacrylate; polymethacrylate; polyacrylamide; maleinate resins; phenolic resins; aniline resins; furane resins; carbamide resins; epoxide resins and silicon resins.
Examples of suitable copolymers include:
9 Case 153-5550 Acrylon itril e/butadien e/acryl ate; Acrylonitrile/butadiene/styrene; Acrylonitrile/methylmeth- acrylate; Acrylonitrile/styrene/acrylic ester; Acrylonitrile/ethylenepropylenediene/styrene; Acrylonitrile/ chlorinated polyethylene/styrene; Ethylene/ethylacrylate; Ethylenemethacrylic acid ester; Ethylene/propylene; Ethylene/propylene-diene; Ethylenelvinyl acetate; Ethylene/vinyl alcohol; Ethylene/tetrafluoro-ethylene; Tetrafluoroethylene/ hexafluoropropylene; Methacrylate /butadiene/styrene; Melamine/phenol-formaidehyde; Polyester blockamide; Perfluoro-alkoxyalkane; Styrene/acrylonitrile; Styrene/butadiene; Styrene/ maleic acid anhydride; Styrene/a-methylstyrene; Vinylchloride/ethylene; Vinylchloride/ ethylene/methacrylate; Vinylchloride/ethylenelvinyl acetate; Vinylchloridel methyl-methacrylate; Vinylchloride/octylacrylate; Vinylchloride/vinyl acetate; and Vinylchloride/ vinylidene chloride.
Preferred polymeric materials that can be stabilized are polyolefins such as polypropylene, polyethylene (e.g. high density polyethylene, low density polyethylene, linear low density polyethylene or medium density polyethylene), polybutylene, poly-4-methylpentene and copolymers thereof and polyurethane.
Preferred polyurethanes are those prepared from isocyanate resins and polyols. Preferred isocyanates are those commercially available as Desmodur, Elastan, Lupranat, Tedimon, Scuranat, Suprasec, Systanat, Hylene, lsonate (-Papi), Multrathane, Nacconate and Sumidur.
Preferred Polyols are those commericially available as Desmophen, Lupranol, Lupraphen, Glendion, Napiol, Scuranol, Caradol, Daltolac, Daltorez, Diorez, Estolan, Propylan, Armol, Bermodol, lsonol, Metpol, Multron, Multranol, Niax Polyol, Pluracol, Quadrol, Thanol, Voranol and Sumiphen.
Case 153-5550 Such polyurethanes are as describes in Saechtling: Kunststoff Taschenbuch 23 Ausgabe - published by Carl Hansen Verlag 1986 (esp. p. 339-410). The contents of this book are incorporated herein by reference.
Further additives that can be added to a stabilizing or a polymeric composition according to the invention include antioxidants, such as sterically hindered phenols, secondary aromatic amines or thioethers, such as described in "Kunststoff-Additive" - Gachter /M0fler, Ed. 3, 1990 p.42-50, the contents of which are incorporated herein by reference; U.V. stabilizers such as sterically hindered amines (for example Nunsubstituted, Walkyl or N-acyl substituted 2,2,6,6-tetra methyl pipe ridi n e compounds) [also known as hindered amine light stabilizers - HALS] and U.V. absorbers (e.g. 2-(2'-hydroxyphenyi) -benztriazoles, 2hydroxybenzophenones, 1,3-bis-(2'-hydroxybenzoyi-) benzene saiicylates, cinnamates and oxalic acid diamides;), U.V. quenchers such as benzoates and substituted benzoates, antistatic agents, flameproofing agents, softeners, nucleating agents, metal deactivators, biocides, impact modifiers, fillers, pigments and fungicides.
Stabilizing compositions according to the invention may be added to the polymeric material before, during or after the polymerization step and may be added in solid or molten form, in solution preferably as a liquid concentrate containing from 10 to 80 % by weight of the composition and 90 to 20 % by weight of solvent or as a solid masterbatch composition containing 10 to 80 % (more preferably 40 to 70 %) by weight of the composition and 90 to 20 % (more preferably 60 to 30 %) by weight of a solid polymeric material which is identical with or compatible with the material to be stabilized.
The stabilizing compositions according to the invention may be incorporated by known methods into the polymeric material to be stabilized. Of particular importance is dry-blending of the compositions according to the invention with the polymer or coating Case 153-5550 shaped polymer particles, e.g. polymer spheres, with the present compositions in the form of a liquid, a solution or a suspension/dispersion. Of particular importance is blending of the compounds with thermoplastic polymers in the melt, for example in a melt blender or during the formation of shaped articles, including films, tubes, fibres and foams by extrusion, injection moulding, blow moulding, spinning or wire coating. The compositions according to the invention are particularly useful for polypropylene and polyethylene articles of every type and polyurethane.
Further, in this specification, where a range is given, the figures defining the range are included therein. Any group capable of being linear or branched is linear or branched unless indicated to the contrary.
For the avoidance of doubt, in this specification t-butyl means tertiary butyl, (-C(CHI).
The new stabilizer compositions are especially suitable for use in polyolefins and especially a- polyolefins prepared using processing catalysts known as Generation 11 to Generation V catalysts and which have not been subjected to a catalyst removal step. By the term "catalyst removal step" used herein is meant a step for the purpose of positively removing the catalyst residues contained in the polymerized polyolefins or treating the polyolefins with the compound which can react with the catalyst residue and inactivate or solubilize the residue, such as alcohols or water, and then removing the inactivated or solubilized catalyst residue by physical means such as filtration, washing and centrifuging. Thus, in the case of suspension polymerization, the step of separating the resulting polymer from a dispersion medium, such as a solvent or a liquefied monomer, does not fall under the above-mentioned definition of the catalyst residue removal step, although the catalyst dissolved in the dispersion medium may be removed by a separation step. The step of adding a small amount of catalyst poisons such as ethers, alcohols, ketones, esters and water to the resulting polymer, to inactivate the catalyst remaining after the 12 Case 153-5550 completion of polymerization, or the step of treating the resulting polymer suspension with gas such as steam or nitrogen to remove the dispersion medium also does not fall under the above-mentioned definition of the "catalyst residue-removal" step.
What we mean by Generation 1 catalysts are titanium halide catalysts and an organo aluminium compound or an organo aluminium halide.
What we mean by Generation 11 catalysts are Generation 1 catalysts supported on an organo magnesium compound or based on an organo chromium compound supported onSA.
What we mean by a Generation III catalyst is a Ziegler type complex catalyst supported on a halogen containing magnesium compound.
What we mean by a Generation IV catalyst is a Generation III catalyst with a silane donor.
What we mean by Generation V catalysts is a bis-indenyl organo titanium compound supported on alumoxane or bis cyclopentadienyl titanium halides activated by aluminium alkyl compound.
Further generations of highly specific catalysts, especially useful for manufacturing highly stereoregular poly-a-olefins, which are presently underdevelopment, belong in the sense of the present invention also to the aforementioned generations of supported catalyst systems. Examples for the microstructure of such highly stereoregular polyolefins are given by syndiotactic polypropylene, isotactic stereoblock polymers, isotactic polypropylene containing stearic defects randomly distributed along the polymer chain (so called anisotactic polypropylene) or stereoirregular steroblock polymers. Due to the 13 Case 153-5550 rapid progress in the development of newer generation catalyst systems the commercial significance of these polymers with novel, highly interesting properties increases more and more. However, residues of such further catalyst generations, as long as they contain metals of the 3d, 4d and 5d series of the periodic system supported analogously to the earlier catalyst generations, can also cause disadvantageous properties in the polymer, as long as such residues are still present in the polymer even if in a deactivated form. Due to this, it can therefore be expected that the new compositions according to the invention are also suitable for overcoming such disadvantageous properties of the polymer. This means that any disadvantageous interaction between processing stabilizers and the aforementioned residues of catalysts of further generations, particularly the hydrolysis of phosphites and phosphonites, is most effectively inhibited.
These generations of catalysts are described in the Twelfth Annual International Conference on Advances in the stabilization and Controlled Degradation of Polymers held in Luzern, Switzerland, 21-23 May 1990 in an article on pages 181 to 196 inclusive by Rolf M01haupt entitled "New Trends in Polyolefin Catalysts and Influence on Polymer Stability". The contents of this article is incorporated herein by reference and especially Table I on page 184 describing the Generation of Catalysts:
14 Case 153-5550 TABLE 1 Polyolefin Catalyst Evolution Generation Example Cat.Act. % Act.Ti Stereoreg. Process Technology (gPP/gTi h atm) (%hept.ins.) 1. TiCI4/AIR, 40 0.01 45% removal of cat.residues and atactic PP TiCl./AIEt2Cl 30 0.1 92% removal of catalyst residues 11 Mg(OEtJITO4/AIR, 40000 50% no removal of cat.residues.
S'02/CP2Cr 40000 HDPE (mainly H13PE/LI-13PE) Ill Mod.MC13cat. 5000 1 95% no purification MgC1J04/AIR3 20000 10 92% + ester donor IV MgC12/TiCI4/AIR3 40000 18 99% no purification + silane donor no extrusion V Bis-indeny]-TiR, on 40000 100 99% novel PPs, narrow MWID (AICH30)2 in which R is an organo group; HDPE is high density polyethylene, LLDPE is linear low density polyethyene, Cp is cyclopentadienyl, Et is ethyl, PP is polypropylene, MWID is molecular weight distribution and x is an integer above 2.
Case 153-5550 Polymeric compositions according to the invention have both good stabilizing properties and good light fastness properties.
The invention will be illustrated by the following Example.
16 Example
Samples preparation Ground formulation:
parts by weight parts by weight Case 153-5550 thermoplastic polyurethane (TPU) granules ("Pellethane 2355-65W from Dow Chemical, USA) Additive and "CarrieC' parts of Additive being light stabilizing compounds 1 or 11 or non-light stabilizing additives A and B being liquid, are previously incorporated in a solid and opaque system (the so-called "CarrieC) consisting of:
37.0 parts by weight SBS granules ("Cariflex TR1 102" from Shell Chemical, U.K.) 19.5 parts by weight LIDPE powder MFI:70 from Verplast, Italy -24.7 parts by weight PE WAX 520 from BASF, Germany &-ak 8.8 parts by weight an antiblocking agent Silica compound ("Syloblock 44" from Grace, USA) 100.0 parts by weight Note: The Tarrier" enables TPU to be used to mould opaque sporting shoe soles.
Preparation:
g of the above blend (of the carder and additive) are homogeneously processed on a two-roll laboratory open mill (Meccaniche Moderne, Italy) at 1 1TA 15C for about 5-7 17 minutes.
Case 153-5550 The resulting rough crepe (2-3 mm thick) is hand-cut by scissors in very small irregular pieces and added to 900 g of TPU granules in a laboratory tumbler and tumbled for about 5 minutes.
This mixture is then fed to the hopper of a "Negri & Bossi V5-8FA" (Italy) laboratory injection moulding machine. Operating at a temperature of 200-220C (cold mould) 1.5 mm thick specimens are moulded for the subsequent accelerated light degradation exposure.
Light exposure The above specimens are exposed in an Atlas Weather-0-MeterWRCi 65, cam 7(LISA) (Black panel 63'C; 50% R.H., according to ASTM D 2565), for 20-70- 162 hours and visually examined for comparative yellowing discoloration and classified by the Vool Blue Scale" (ranking from 8, the best (no discoloration) to 1, the worst (total discoloration)):
Carrier + Additive After 20 h After 70 h After 162 h 6 4 4 6 5 4 A 5 3 2 B 5 3 2 Additive used:
18 Additive 1 is a) 50% of a composition comprising 57% of the compound QNI+CO-CONH-C2H2E OG2H5 29% of (CHX) \k, r CHP" CH2 C-0 CH3 CH3 CH CH3 3 H where R is nCl2H25and n-C14H2. (Composition A); and 14% xylene and Case 153-5550 b) 5 0% of a composition comprising 80% trilaurylphosphite and 20% a- tocopherol (Composition B).
Additive 11 is a composition comprising a) 50% of Composition B and b) 50% of po lym ethyl propyl 3-oxy [4(2,2,6,6-tetramet hyl) pipe ridi nyll siloxane, a compound of the formula 19 PH2 H cCH3 CR3 CH3 RI CH3 where na is a number from 1 to 30.
Additive A is TPU alone ("Pellethane 2355-65D") from Dow Chemical, USA.
Additive B is 90% TPU + 10% Carrier.
Case 153-5550

Claims (12)

CLAIMS:
1.
Case 153-5550 A stabilizing composition comprising:
a) a mono- or di- phosphite or mono- or diphosphonite (component a) b) a chroman derivative (component b); and c) a light stabilizer (component c) selected from i) a polymer containing at least one hindered amine light stabilizer group (component i) and/or ii) the combination of an oxanilide and a hindered amine light stabilizer (HALS) compound (component ii).
2. A stabilizing composition according to Claim 1 in which the mono- or di- phosphites are of formula I or 11 0-131 RI-0-P, O-R, 0- CH2 CH,--- 0 1 % R,- 0- P C P- 0- IR, 1 CHi----d ()- CH2 (1) (11) in which each R, independently is a group derived from an aliphatic, alicyclic or aromatic alcohol containing one or two OH groups.
3. A stabilizing compositions according to Claim 1 in which the mono- or diphosphonites are selected from compounds of formula III 21 Case 153-5550 R10- 0- p Rje-0 in which m is 0 or 1; n is 0 or 1; p is 0 or 1; P-1%,,, P, 0-% m each Rq, independently, is a group derived from an aliphatic, alicyclic or aromatic alcohol containing one or two OH groups; whereby the two -OH groups are not positioned to be able to form a P-containing ring; (hereinafter defined as the monovalent significances of Rq); or both groups R. form a group derived from an aliphatic, alicyclic or aromatic alcohol containing two OH groups in such a position that they can form a cyclic group with a single phosphorus atom (hereinafter defined as the divalent significances of R,):
R,. is a monovalent or divalent significance of IR,; Y is -0-, -S-, -CH(R3)- or C^-', where R3 is hydrogen or Cl_.alkyl or COOR4and R4 'SC1_.alky].
4. A stabilizing composition according to any one of the preceding claims in which the chroman derivatives are selected from compounds of formula IV 22 Case 153-5550 C'H3 HO R2 a13 C113 CH, (IV) in which R2 is -(CH2)3-CH-(CH2)3-CH-(CH2)3-CH-CH3 1 CH3 CH3 CH3 or -CH 2-CH2-0-CO-R6where R6 'Sselected from C7-30alky], -CH2CH2-S-(C1- 30alkyi) or C(CH3 -CH2-0OH C(CH3b
5. A stabilizing composition according to any one of the preceding claims in which the polysiloxanes are selected from compounds of formula V 23 Case 153-5550 9, -,aikyi 1 4 ? 0.)% fH2)2 - 8 0 H CH3 CH3 K' "' CH3 CH3 RI (V) in which na 1 to 100, R is selected from hydrogen, Cl_.alkyl, oxygen -CO- R5 or OR,, where R. is -C(RJ=CH2, Cl_.alkyl, phenyl, -COCK, -CH2C66H.. - CO0C1-12alkyl, COOH or NR7R,3, where R7 is hydrogen, Cl-12alky], C5-6C0o aikyl, phenyl, phenyl Cl-4alkyl or Cl-12alkylphenyl and R. is Cl-12alkyl or hydrogen.
6. A stabilizing composition according to any one of the preceding claims in which the oxanilides are of formula V11 /& N- CO 00 1 B R R13 1 R,, R13 R, 1 (R1 A (V11) in which each R,, independently is selected from hydrogen, Cl-1.alkyl, Cl- 18alkoxy, halogen, hydroxy, phenyl and phenoxy; and 24 Case 153-5550 each R12, independently, is selected from hydrogen, halogen, hydroxy, Cl,, alkyl and Cl_.alkoxy; and each R13, independently, is hydrogen or methyl.
7. A stabilizing composition according to Claim 6 in which R,, is R,,' where R,,' is selected from hydrogen, hydroxy, C,-4alkyl andCl-4alkoxy; R12is R12' where R12' is selected from hydrogen, hydroxy, Cl-4alkyl andCl4alkoxy; and R,. is hydrogen.
8. A stabilizing composition according to any one of the preceding claims in which the HALS compoound is of formula V1 CH3 CH3 R N R18 R15 CH3 (H (V1) in which R is selected from hydrogen, Cl_.alkyl, oxygen, -COR5 or OR,; where R5 is C(RJ=CH2, Cl_.alkyl, phenyl, -NRA, -CO-C61-15, -CH2C61-15, - CO0C1-1.alkyi or -COOH; where R7 is hydrogen, Cl-12alkyl, Q,-6cycloalkyl phenyl, phenyl Cl-4alkyl or Cl-12alkylphenyl and R8 is hydrogen orCl-12alkyl; R15 is hydrogen, Cl-22alky], Cl-22alkoxy, -N(R),5-CO-CO-R20; or - NWC(R)5=WR21; Case 153-5550 R3 is hydrogen, Cl-1.alkyl or -COOR4where R4 'SC1_.alkyl R20 is an amide forming group and R21 is Cl-1.alky], phenyl, unsubstituted or substituted by 1 to 3 groups selected from Cl-1.alkyl, Cl,aRoxy and halogen; or R,. is (M CH3 RIO W- R "C()0"(CH2)8'12 CO.0 CM3 CH3 R16 is hydrogen or Cl_.alkyl; or JR,. and R16 together with the C-atom to which they are attached, form a group of formula a) r (CH2)11 O-C./ ce.. 1 / \ CO- N-C2-4a1Wene-(X)OC,-22alky It
9. A stabilizing composition substantially as herein described with reference to the Example.
10. A polymeric composition comprising a polymeric material and a stabilizing amount of a composition according to any one of the preceding claims.
11. A polymeric composition comprising 0.2-8% of a stabilizing composition according to any one of Claims 1 to 9.
26 Case 153-5550
12. A polymeric composition substantially as herein described with reference to the Example.
GB9221154A 1991-10-11 1992-10-08 Stabilizing composition for polymers Withdrawn GB2260764A (en)

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GB2278362A (en) * 1993-05-24 1994-11-30 Sandoz Ltd Processing stabiliser compositions
GB2283490A (en) * 1993-11-03 1995-05-10 Sandoz Ltd Processing stabilizers for polymers
WO1996017886A1 (en) * 1994-12-06 1996-06-13 Basf Aktiengesellschaft Stabilized styrene/butadiene block copolymers
GB2263280B (en) * 1992-01-17 1996-07-31 Sandoz Ltd Use of a phosphonite and optionally a phosphite for clarifying propylene polymers
EP0781805A1 (en) * 1995-12-29 1997-07-02 General Electric Company Stabilized thermoplastic polymer composition
EP0805178A1 (en) * 1996-05-03 1997-11-05 Ciba SC Holding AG Tocopherol-containing composition as stabiliser for thermoplastic materials
US5695689A (en) * 1994-10-04 1997-12-09 Bayer Aktiengesellschaft Polyether polyols stabilized with tocopherol
US5969014A (en) * 1997-09-23 1999-10-19 Clariant Finance (Bvi) Limited Synergistic polyamide stabilization method
WO2000052090A1 (en) * 1999-02-26 2000-09-08 Yoshitomi Fine Chemicals, Ltd. Polymeric material composition and stabilizer composition both containing spirochroman compound
US20120146257A1 (en) * 2010-12-13 2012-06-14 Cytec Technology Corp. Processing additives and uses of same in rotational molding

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US7083743B2 (en) 1999-12-20 2006-08-01 Clariant Finance (Bvi) Limited Mixture of phosphanes and chromane derivatives
DE19961464A1 (en) * 1999-12-20 2001-06-21 Clariant Internat Ltd Muttenz Mixtures containing phosphane and chromane derivatives are useful as stabilizers against the thermo-oxidate decomposition of polymers.
EP1521794B1 (en) * 2002-07-05 2010-01-06 Sabic Innovative Plastics IP B.V. Weatherable polycarbonates comprising oxanilide structural units, method, and articles made therefrom
KR102081524B1 (en) * 2015-09-16 2020-02-25 미쯔이가가꾸가부시끼가이샤 Polymerizable composition for optical materials, optical material and plastic lens obtained from the composition

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DE3725926A1 (en) * 1987-08-05 1989-02-16 Basf Ag Mixture for the stabilisation of polyurethanes
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2263280B (en) * 1992-01-17 1996-07-31 Sandoz Ltd Use of a phosphonite and optionally a phosphite for clarifying propylene polymers
GB2278362B (en) * 1993-05-24 1997-08-13 Sandoz Ltd Processing stabiliser composition for polymers
GB2278362A (en) * 1993-05-24 1994-11-30 Sandoz Ltd Processing stabiliser compositions
GB2283490A (en) * 1993-11-03 1995-05-10 Sandoz Ltd Processing stabilizers for polymers
US5695689A (en) * 1994-10-04 1997-12-09 Bayer Aktiengesellschaft Polyether polyols stabilized with tocopherol
WO1996017886A1 (en) * 1994-12-06 1996-06-13 Basf Aktiengesellschaft Stabilized styrene/butadiene block copolymers
US6362258B1 (en) 1995-12-29 2002-03-26 General Electric Company Stabilized thermoplastic polymer composition
EP0781805A1 (en) * 1995-12-29 1997-07-02 General Electric Company Stabilized thermoplastic polymer composition
EP0805178A1 (en) * 1996-05-03 1997-11-05 Ciba SC Holding AG Tocopherol-containing composition as stabiliser for thermoplastic materials
US5844027A (en) * 1996-05-03 1998-12-01 Ciba Specialty Chemicals Corporation Stabilizer composition for thermoplastic materials
US5969014A (en) * 1997-09-23 1999-10-19 Clariant Finance (Bvi) Limited Synergistic polyamide stabilization method
WO2000052090A1 (en) * 1999-02-26 2000-09-08 Yoshitomi Fine Chemicals, Ltd. Polymeric material composition and stabilizer composition both containing spirochroman compound
US20120146257A1 (en) * 2010-12-13 2012-06-14 Cytec Technology Corp. Processing additives and uses of same in rotational molding
US11312043B2 (en) * 2010-12-13 2022-04-26 Cytec Technology Corp. Processing additives and uses of same in rotational molding

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GB9221154D0 (en) 1992-11-25
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FR2682392A1 (en) 1993-04-16
DE4233973A1 (en) 1993-04-15
ITRM920734A0 (en) 1992-10-12
JPH05214254A (en) 1993-08-24
ITRM920734A1 (en) 1994-04-12

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