GB2265377A - Phosphonite-hals and phosphite-hals compounds as polymer stabilizers - Google Patents

Phosphonite-hals and phosphite-hals compounds as polymer stabilizers Download PDF

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GB2265377A
GB2265377A GB9304685A GB9304685A GB2265377A GB 2265377 A GB2265377 A GB 2265377A GB 9304685 A GB9304685 A GB 9304685A GB 9304685 A GB9304685 A GB 9304685A GB 2265377 A GB2265377 A GB 2265377A
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formula
phenyl
methyl
group
phosphite
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GB2265377B (en
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Lajos Avar
Peter Staniek
Klaus Stoll
Wolf-Dieter Habicher
Uwe Haehner
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Sandoz AG
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Sandoz AG
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Priority claimed from GB929209759A external-priority patent/GB9209759D0/en
Priority claimed from GB929221279A external-priority patent/GB9221279D0/en
Priority claimed from GB929224522A external-priority patent/GB9224522D0/en
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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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657154—Cyclic esteramides of oxyacids of phosphorus
    • 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
    • C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids
    • 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
    • C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/036—Stabilisers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
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Abstract

A stabilized polymer composition comprises: a) a compound containing a phosphite or phosphonite group and at least one 2,2,6,8-tetraalkylpiperidinyl group (herein defined as component a), and b) a polyolefin which has been produced in the presence of a catalyst which is either i) a supported Zeigler catalyst or ii) a metallocene catalyst, from which polyolefin the catalyst has not been removed (hereinafter component b). The compound a) acts as a processing or light stabilizer. Preparation of some of the compounds used are described.

Description

Phosphonite-HALS and phosphite-HALS compounds as stabilizers The invention relates to the use of certain compounds which may act as processing stabilizers and simultaneously act as light stabilizers in polyurethanes and polyolefins (including polyalkenes) that have been made with a II and above Generation catalyst (e.g.
II to V Generation catalysts).
According to the invention, there is provided a polymer composition comprising: a) a compound containing a phosphite or phosphonite group and at least one (preferably 1 to 4) 2,2,6,6-tetraalkylpiperidinyl groups (hereinafter defined as "component a"), and b) a polyolefin which has been produced in the presence of a catalyst which is either i) a supported Ziegler catalyst or ii) a metallocene catalyst, from which polyolefin the catalyst has not been removed (hereinafter "component b").
Further according to the invention, there is provided a polymer composition comprising a polyurethane or resins capable of forming a polyurethane and a) a compound containing a phosphite or phosphonite group and at least one (preferably 1 to 4) 2,2,6,6tetraalkylpiperidinyl groups (hereinafter defined as component a).
Still further according to the invention, there is provided a coating composition in powder form comprising a polymeric powder coating material to which is applied a compound containing a phosphite or phosphonite group and at least one (preferably 1-4) 2,2,6,6tetraalkylpiperidinyl group (herein defined as component a).
The term "metallocene" is used to describe new catalysts of Generation V and above which are used in the production of polyolefins (especially polyethylenes and polypropylenes) as described, for example, in "Modern Plastics" 10/91 p. 46-49 or in "Makromolekulare Chemie" 192 (1991) 1059-1065.
The supported Ziegler catalysts carriers (such as those supported on a halogencontaining magnesium compound) are well known and are described in Table 1 below.
Preferably component a) is present in an amount of 0.01-5%, more preferably 0.05-2% based on the weight of polymer material (such as polyolefin, polyurethane (or resins capable of forming polyurethane) or polymeric powder coating material present in the composition.
Preferably component a) is a compound of formula I
in which R is hydrogen; oxygen; -OH; C, 24alkyl; -O-C1 24alkyl; -O-OO-O1.24alkyl; -O-CO-phenyl or -COR15; where R15 is -C(R3)=CH2, C1-6alkyl, phenyl, CO-C1-24alkyl, -CO-phenyl, -NR7R8, -OH2-O6H5, -OO-OO1.12alkyl or -COOH;R3 is hydrogen or O1.4alkyl; R7 is hydrogen, C1 12alkyl, C5-6cycloalkyl, phenyl, phenyl-C1 4alkyl or C1-12alkylphenyl and R8 is O1.12alkyl or hydrogen, each R1, independently, is -CH3 or -CH2(C1-4alkyl) or both groups R1 form a group -(CH2)5-; each R2, independently, is -CH3 or -CH2(C14alkyl) or both groups R2 from a group -(CH2)5-; each of R4 and R5, independently, is selected from methyl, ethyl, linear or branched C3-24alkyl, C7-24alkaryl, C7-24aralkyl, C5-24cycloalkyl, C6-24aryl and the groups of formula a) and b)
provided only one of R4 and R5 is a group of formula b); or both groups R4 and R5 together form a group of formula c);
in which R4a and R5a, independently, are selected from -R10, and a group of formula a); where R10 is methyl, ethyl, linear or branched C324alkyl, C5-24cycloalkyl, C7-24alkaryl, C7-24aralkyl or C6-24aryl; A is C1-24alkylene, C6-24cycloalkylene, C6-24arylene(preferably phenylene), C7-24aralkylene or a group of formula d)
where n = 0 or 1; each R11, independently, has a significance of R10 or is hydrogen; X2 is a direct bond, -NR3-, -O-, -S- or C1-24alkylene [especially C, 4alkylene (e.g. -(CH2)1-4)] C6-24cycloalkylene, C6-24arylene (preferably phenylene), C7-24alkarylene and C7-24aralkylene, and each X, independently, is a direct bond, -N(R3)-, -O-, or -S-; (preferably a direct bond or -O-).
Preferably R11 is R11', where R11' is hydrogen or C1-8alkyl, more preferably R11", where R11" is hydrogen , methyl, t-butyl or t-octyl.
R is preferably R' where R' is hydrogen, -O-CO-phenyl, C1-18alkyl, C1-18alkoxy, -CO-R,5' or -CO-CH=CH2 where R15' is C1-8alkyl, -CO-C1-8alkyl or -CO-O-C1-4alkyl.
Preferably each R, is methyl and each R2 is methyl.
A is preferably A' where A' is C, 8alkylene, O6.8cycloalkylene, C6-12arylene or a group of formula d'
in which each R11' independently is hydrogen or C1-8alkyl; and 2' is C1-12alkylene, C6-12arylene, -O- or -S-.
Preferably in this Specification any aryl group is phenyl and any arylene group is phenylene unless indicated to the contrary.
Preferred compounds of formula I are selected from compounds of formula Il to VII
and mixtures thereof, where each m is 0 or 1, m, is 0 or 1 and p is 1, 2 or 3 and the other symbols are as defined above.
Compounds of formula II, where R10 is other than phenyl and the X connected to Rro is a direct bond, are new.
Compounds of formula V when m=1 and compounds of formula Ill where X is a direct bond are new. Compounds of formula V where m is 1, A is a group of formula d where X2 is C1 12alkylidene and at least one group R11 is not H, are new.
Preferred compounds of formula 1 are of formula II or Ill, more preferably II.
Preferably each X attached to a tetraalkylpiperidinyl group is -O-.
Preferably in the group -X-R10 X is a direct bond or -O-.
Preferably R10 is R10' where R10' is C1-8alkyl, C5-12aryl, C7-24 aralkyl or C7-24alkaryl, more preferably R10" where R10" is C1-8alkyl, C5-12cycloalkyl, C7-24aralkyl or C7-24alkaryl.
More preferred compounds of formula Ill are of formula XIV and 3.
More preferred compounds of formula V are of formula XIII below.
More preferred compounds of formula I are of formula 1 to 9 below: 1. (2,6-Di-t-butyl-4-methyl-phenyl)-bis(2,2,6,-tetramethylpiperidinyl) phosphite
2. (2,6-Di-t-butyl-4-methyl-phenyl)-bis(N-methyl-2,26,6-tetramethylpiperidinyl)phosphite
3. Tetrakis(N-methyl-2,2, 6,6-tetramethylpiperidinyl)-4, 4'-(3, 3'5, 5'-tetra-t-butyl-phenyl) methane)-diphosphite
4. Bis(2, 2, 6, 6-tetramethylpipe ridinyl)-phenyl-phosphonite
5. Bis(N-methyl-2, 2,6, 6-tetramethylpiperidinyl)-phenyl-phosphonite
6. Bis( 2,2,6,6-tetramethylpiperidi nyl)biphen-4-yl-phosphonite, and
7. Bis(N-methyl 2,2,6,6-tetramethylpiperidinyl)-biphen-4-yl-phosphonite
8. (2,4,6-tri-t-butyl-phenyl)-bis(2,2,6,6-tetramethylpiperidinyl) phosphite
9. (2 ,4,6-tri-t-butyl-phenyl)-bis(N-methyl-2 ,2,6,6-tetra-methyl-piperidinyl)phosphit
Component a) may also be a mixture comprising i) 1-90% of a phosphonite of formula I (preferably a compound of formula II to VII) hereinafter defined as component i); and ii) 99-10% of a phosphite of formula VIII (hereinafter defined as component ii)
where P is 1, 2, or 3, X, is -O- or -NR3 and the other symbols are as defined above.
Compounds of formula I can be prepared by reacting one mol of a compound of formula X
with one mol of a compound of formula Xl
or by reacting 2 mols of a compound of formula X with 1 mol of a compound of formula XII R4-X-P(Z)2 (Xll) where Z is Cl, Br or N(R7)z Further, the compounds of formula I to VII can be made by other known methods from known compounds.
Further according to the invention, there is provided a compound of formula XIII
in which the symbols are as defined above. Preferably in the compounds of formula XIII R' is R" where R" is hydrogen or O1.4alkyl.
Further according to the invention there is provided a compound of formula XIV
in which the symbols are as defined above.
Preferred polymeric materials which 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) and polyalkenes and copolymers thereof. Preferred polyalkenes include polypentenes and polybutenes e.g.
poiy-4- methylpentene, poly-3-methylpentene and 3-methylpentene and 3- methyl-bute ne1.
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, Iso nave (-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, Isonol, Metpol, Multron, Multranol, Niax Polyol, Pluracol, Quadrol, Thanol, Voranol and Sumiphen.
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.
The new stabilizer compositions are especially suitable for use in polyolefins and especially a-polyolefins prepared using processing catalysts known as Generation II 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, such as an alcohol or water, which can react with the catalyst residue and inactivate or solubilize the residue, 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 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 I catalysts are titanium halide catalysts and an organo aluminium compound or an organo aluminium halide.
What we mean by Generation II catalysts are Generation I catalysts supported on an organo-magnesium compound or based on an organo chromium compound supported on SiO2.
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-oc-olefins, which are presently under development, belong in the sense of the present invention also to the aforementioned generations of supported catalyst systems. Examples for the microstructure of such highly stereo regular polyolefins are given by syndiotactic polypropylene, isotactic stereoblock polymers, isotactic polypropylene containing steric defects randomly distributed along the polymer chain (socalled anisotactic polypropylene) or stereoirregular stereoblock polymers. Due to the 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, so long as such residues are still present in the polymer even if in a deactivated form.
Because of 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 Mulhaupt 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: TABLE I Polyolefin Catalyst Evolution Generation Example Cat.Act. % Act.Ti Stereoreg. Process Technology (gPP/gTi h atm) (% insol. in heptane) I.TiCl4/AIR3 40 0.01 45% removal of cat.residues and atactic PP TiCI3/AIEt2CI 30 0.1 92% removal of catalyst residues II Mg(OEt2)/TiCl4/AIR3 40000 50% no removal of cat.residues SiO2/Cp2Cr 40000 HDPE (mainly HDPE/LLDPE) Ill Mod.TiCI3cat. 5000 1 95% no purification MgCl2/TiCl4/AIR3 20000 10 92% + ester donor IV MgCl2/TiCl4/AIR3 40000 18 99% no purification + silane donor no extrusion V Bis-indenyl-TiR2 on 40000 100 99% novel PPs, narrow MWD (AlCH3O)2 in which R, in Table 1, is an organo group; HDPE is high density polyethylene, LLDPE is linear low density polyethyene, Cp is cyclopentadienyl, Et is ethyl, PP is polypropylene, MWD is molecular weight distribution and x is an integer above 2.
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 orthioethers, such as described in "Kunststoff-Additive" - Gächter/Müller, Ed. 3,1990 p. 42-50, the contents of which are incorporated herein by reference; acid scavengers such as sodium, magnesium or calcium stearates or lactates hydrotalcite or alkoxylated amines;U.V. stabilizers such as sterically hindered amines (for example Nunsubstituted, N-alkyl or N-acyl substituted 2,2,6,6-tetra-methylpiperidine compounds) [also know as hindered amine light stabilizers -HALS] and U.V. absorbers (e.g. 2-(2'hydroxphenyl)-benztriazoles, 2-hydroxybenzophenones, 1 ,3-bis-(2'-hydroxybenzoyi)benzene salicylates, cinnamates and oxalic acid diamides), U.V. quenchers such as benzoates and substituted benzoates, antistatic agents1 flameproofing agents, lubricants, plasticizers, 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% (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 which is identical with or compatible with the material to be stabilized. Of particular importance is dry-blending of the compositions according to the invention with the polymer or coating 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, fibers and foams by extrusion, injection molding, blow molding, spinning or wire coating.
The compounds of formula I of the invention are both good processing stabilizers and also good light stabilizers in polymeric materials, especially polyolefins.
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.
Preferably the alkyl group in any 2,2,6,6-tetraalkylpiperidinyl group in this specification is OH3, -CH2(C1 4alkyl), or both alkyl groups in the 2,2-position or both groups in the 6,6position form a group -(C H2)5. More preferably the alkyl group is -OH3.
In this specification preferably any 01.24 alkyl group is a C,,alkyl group, more preferably any O1.8aIkyl group is a C1-4alkyl group, most preferably any C,.4alkyl is methyl, ethyl or t-butyl and preferred alkoxy groups are methoxy or ethoxy.
For the avoidance of doubt, in this specification t-butyl means tertiary butyl, (-C(CH3)3).
Preferred powder coatings are described in "The Science of Powder Coatings Chemistry, Formulation and Application" - David A. Bate published SITA - 1990, Vol. 1, the contents of which are incoporated herein by reference, especially pp. 249-277.
The powder coating compositions to which this invention can be applied are any powder coatings known in the art. The powders may be thermoplastic or thermosetting and include any known acrylic polyester, epoxy or urethane powder coatings commonly available. Particularly preferred powder coatings are based on acrylic powders and polyisocyanate resins.
Preferred powder coating are formulations based on epoxy resins for example DER 663 UE, HULS B68, Resiflow PU5, Ceriduol ACA8, Durcal 10 and Black Regal.
Hydroxypolyester resins can be used in polyurethane powder coatings.
Powder lacquers are also described in USP 5,036,144, EP 299 420, USP 4937 288 and JP 91-044588 the contents of which are incorporated herein by reference.
The invention will now be illustrated by the following Examples.
Example 1 Synthesis of biphenyl-bis(2,2,6,6-tetramethyl-piperidinyl)-phosphonite At ambient temperature and under inert conditions, 0.1 mol biphenyl-dichloro-phosphine is added dropwise to a suspension of 0.2 mol of 2,2,6,6-tetramethyl-piperidinol in 100 ml of triethylamine. After the addition has been completed, the mixture is refluxed for 5 hours. The product and the excess triethylamine are extracted twice with 50 ml toluene from the triethylamine hydrochloride at room temperature. From this solution the colorless product is precipitated by the addition of di-isopropyl-ether, filtered, washed with ether and dried in vacuo.
The yield is 56%, 831P:155.5 ppm.
Example 2 A polymeric composition containing 100.0 parts of a 3rd generation polypropylene homopolymer (commerically available as Moplen FLS-20) 0.05 parts Irganox 1010, (tetrakis[methylene-3(3'5'-ditert. butyl-4'hydroxyphenyl)- propionate]methane 0.1 parts calcium stearate, and 0.07 parts biphenyl-4,4'-bis(2,2,6,6-tetramethylpiperidinyl)-phosphonite is mixed by dry blender and extruded at 210"C. This composition is then multiple extruded in a Götffert single screw extruder (270or, d=20mm, I:d=20, 50 min~t compression 1:3) and granulated after chilling the polymer melt in a water bath.The melt flow index (ASTM D-1 238-70, 230"C, 2.16kg) and the yellowness index (ASTM D-1 925-70, on granules) are determined after the first, third and fifth passage.
Example 3 A polymeric composition is prepared as in example 2, except that 0.1 parts instead of 0.07 parts of biphenyl-4,4'-bis(2,2,6,6-tetramethyl-piperidinyl)-phosphonite are used.
Comparative example A: A polymeric composition is prepared as in example 2, except that 0.07 parts of Irgafos 168 are used instead of 0.07 parts of biphenyl-4,4'-bis(2,2,6,6-tetramethyl-piperidinyl) -phosphonite.
Comparative example B: A polymeric composition is prepared as in example 2, except that 0.1 parts of Irgafos 168 are used instead of 0.07 parts of biphenyl-4,4'-bis(2,2,6,6-tetramethyl-piperidinyl) -phosphonite.
Example MFI Yl I pass 3.pass 5.pass I pass 3.pass 5.pass Example 2 2.89 4.35 7.50 -0.7 -0.2 0.9 Example 3 2.55 3.41 4.34 -0.5 0.0 1.6 Comp. ex. A 3.22 5.04 6.89 -1.3 1.1 3.0 Comp. ex. B 3.37 4.54 6.13 -1.5 1.3 2.8 Example 4 A powder coating is made up from a hydroxy group containing acrylate and polyisocyanate. 2% of the compound 1 of Example 1 is added and conventionally worked into the coating by mixing, extruding, milling and sieving.
The powder coating is applied directly to primed metal panel by electrostatic spraying.
The resulting plates are exposed to a UVCON apparatus (UV fluorescent light 313 nm for 8 hours at 700C and 4 hours at 500C) to test for accelerated weathering.
Examples 5-9 By a method according to Example 2, polymeric compositions are prepared by mixing: 100.0 parts linear low density polyethylene (LLDPE, d=0.920g/cm3) 0.02 parts Irganox 1010 0.10 parts calcium stearate 0.07 parts stabilizer as listed below by pre-extrusion at 170 C and multiple extrusion at 240"C- The following are the stabilizers used:: Example 5 phenyl-bis(1 ,2,2,6,6-pentamethylpiperidinyl)-phosphonite; Example 6 biphenyl-bis(1 ,2,2,6,6-pentamethylpiperidinyl)-phosphonite; Example 7 2,4-di -tert-butyl-phenyl-bis(1 ,2,2,6,6-pentamethylpiperidinyl)-phosphite; Example 8 2,6-di-tert-butyl-4-methyl-phenyl-bis(1 ,2,2,6,6-pentamethylpiperidinyl)- phosphite; Example 9 2,4,6-tri-tert-butyl-phenyl-bis(1 ,2,2,6, 6-pentamethylpiperidinyl)-phosphite; Comp. ex. C tris(2,4-di-tert-butyl-phenyl)phosphite (commercial processing stabilizer) Comp. ex. D butanoic acid, polymer with 4-hydroxy-2,2,6,6-tetramethyl-1 -piperidine- ethanol (commercial light stabilizer) Comp. ex.E no additional stabilizer The results can be seen in Table 2 below: Table 2 Example MFI Yl I pass 3.pass 5.pass I pass 3.pass 5.pass Example 5 1.01 0.78 0.49 -1.1 -1.2 3.8 Example 6 1.02 0.77 0.49 -0.9 2.7 5.5 Example 7 0.96 0.77 0.56 1.5 3.2 6.1 Example 8 0.99 0.74 0.50 0.3 0.9 2.0 Example 9 1.02 0.60 0.58 0.9 2.2 4.3 Comp. ex. C 0.92 0.66 0.45 1.8 2.4 3.0 Comp. ex. E 0.74 0.50 0.35 4.2 5.2 5.6 From the pellets of the pre-extrusion of Examples 5-9 approximately 150 lim cast film samples are prepared on a Reiffenhäuser extruder and exposed to artificial weathering in an Atlas Weather-O-Meter with a WOM 65 cycle (dry conditions).
The photooxidative degradation is followed by measuring the carbonyl Index (C=O-lndex) by FT-IR-Spectroscopy and the mechanical properties (elongation at break (ELB) according to DIN 53455 after distinct periods.
The results can be seen in Table 3 Table 3 Example C=O-lndex after 200h 600h 1000h 1250h 1500h Example 5 0.008 0.009 0.016 0.022 0.025 Example 7 0.001 0.004 0.010 0.015 0.020 Example 8 0.000 0.001 0.001 0.002 0.003 Example 9 0.001 0.003 0.010 0.013 0.018 Comp. ex. D 0.007 0.025 0.044 0.054 0.066 Comp. ex. E 0.060 > 0.5 Example retained elongation at break (%) after 200h 600h 1 OOOh 1250h 1 SOOh ExampleS 102 106 110 105 87 Example 7 101 103 103 98 79 Example 8 100 101 101 101 100 Example 9 101 105 103 92 40 Comp. ex. D 106 103 80 58 31 Comp. ex. E 94 0 Examples 10-12 In test vials, mixtures containing 98% of an acrylic powder coating material and 2% of the stabilizer listed below are dry blended and heated to 1 60 C. After 3h and 6h, turbidity and color change were determined.
Example 10 2, 4-di-tert-butyl-phenyl-bis(1 ,2,2,6, 6-pentamethylpiperdinyl)-phosphite; Example 11 2,6-di-tert-butyl-4-methyl.phenyl-bis(1 ,2,2,6,6-pentamethylpiperdinyl) phosphite; Example 12 2,4,6-tri-tert-butyl-phenyl-bis(1 ,2,2,6,6-pentamethylpiperdinyl)-phosphite; Comp. ex. F no additional stabilizer The results can be seen in Table 4 below Table 4 Example Turbidity Color Change 3h/6h 3h16h Example 10 none/none trace yellow/trace yellow Example 11 none/none none/none Example 12 none/none none/none Comp. ex. F none/none trace yellow/slight yellow

Claims (16)

  1. Claims: 1. A composition comprising: a) a compound containing a phosphite or phosphonite group and at least one 2,2,6,6-tetraalkylpiperidinyl group (herein defined as component a), and b) a polyolefin which has been produced in the presence of a catalyst which is either
    i) a supported Ziegler catalyst or
    ii) a metallocene catalyst, from which polyolefin the catalyst has not been removed (hereinafter component b).
    2. A composition comprising a polyurethane or resins capable of forming a polyurethane and a) a compound containing a phosphite or phosphonite group and at least one 2,2,6,6-tetraalkylpiperidinyl group (hereinafter defined as component a).
    3. A composition according to claim 1 or claim 2 in which component a) is present in an amount of 0.01-5%, based on the weight of polymer present in the composition.
    4. A composition according to any one of the preceding claims in which component a) is a compound of formula I
    R is hydrogen; oxygen; -OH; C1-24alkyl; -O-C1 24alkyl; -O-CO-C1 8alkyl; -O-CO-phenyl or -COR15; where R15 is -C(R3)=CH2, C1-6alkyl, phenyl, -CO-C1-24alkyl -CO-phenyl, -NR7R8, -CH2-C6H5, -CO-OC1-12alkyl or -COOH; R3 is hydrogen or C1-4alkyl;R7 is hydrogen, C1-12alkyl, C5-6cycloalkyl, phenyl, phenyl-C1-4alkyl or C1-12alkylphenyl and R8 is C1-12alkyl or hydrogen, each R, independently, is -CH3 or -CH2(C, 4alkyl) or both groups R, form a group -(CH2)5-; each R2, independently, is -CH3 or -CH2(C1-4alkyl) or both groups R2 from a group -(CH2)5-; each of R4 and R5 independently are selected from methyl, ethyl, linear or branched C3-24alkyl, C7-24alkaryl, C7-24aralkyl, C5-24cycloalkyl, C7-24aryl and the graoups formula a) and b)
    provided only one of R4 and R5 is a group of formula b); or both groups R4 and R5 together form a group of formula c);
    in which R4a and R5a, independently, are selected from -R10, or a group of formula a); and where R10, is methyl, ethyl, linear or branched C324alkyl, C5-24cycloalkyl, C7-24alkaryl, C7-24aralkyl or C6-24aryl; A is C1-24alkylene, C6-24cycloalkylene, C6-24arylene, C7-24aalkylene or a group of formula d)
    where n = O or 1 each R11 independently has a significance of R10 or is hydrogen; X2 is a direct bond, -NR3-, -O-, -S- or C1-24alkylene, C6-24cycloalkylene, C6-24arylene, C7-24alkarylene and C7-24aralkylene, and each X independently is a direct bond -N(R3)-, -O-, or -S-.
    5. A composition according to claim 4 in which R11 is R"", where R11" is methyl, t-butyl or t-octyl.
    6. A composition according to claim 4 or claim 5 in which R is R' where R' is hydrogen, -O-CO-phenyl, C1-24alkyl, C, 24alkoxy, -CO-R5' or -CO-CH=CH2 where P5, is C1-8alkyl -CO-C1-8alkyl or -CO-O-C1-4alkyl.
    7. A composition according to any one of claims 4 to 6 in which each R, is methyl and each R2 is methyl.
    8. A composition according to any one of claims 4 to 7 in which the compounds of formula I are selected from compounds of formula II to VII
    and mixtures thereof, where each m is O or 1, m1 is O or 1 and p is 1, 2 or 3 and the other symbols are as in claim 4.
    9. A composition according to any one of claims 4 to 8 in which the compounds of formula I are of formula 1 to 9 below: 1. (2,6-D i-t-butyl-4-methyl-phenyl)-bis(2,2 ,6 ,6-tetramethylpiperidi nyl) phosphite
  2. 2. (2, 6-Di-t-butyl-4-methyl-phenyl)-bis(N-methyl-2, 2, 6,6-tetramethylpiperidinyl)- phosphite
  3. 3. Tetrakis(N-methyl-2,2,6,6-tetramethylpiperidinyl)-4,4'-(3,3'5,5'-tetra-t-butyl -phenyl) methane)-diphosphite
  4. 4. Bis(2,2,6,6-tetramethylpiperidinyl)-phenyl-phosphonite
  5. 5. Bis(N-methyl-2,2, 6,6-tetramethylpiperidinyl)-phenyl-phosphonite
  6. 6. Bis( 2,2,6, 6-tetramethylpiperidinyl)biphen-4-yl-phosphonite, and
  7. 7.Bis(N-methyl 2,26,6-tetramethylpiperidinyl)-biphen-4-yl-phosphonite
  8. 8. (2,4,6-tri-t-butyl-phenyl)-bis(2,2,6,6-tetramethylpiperidinyl) phosphite
  9. 9. (2,4,6-tri-t-butyl.phenyl)-bis(N-methyl-2,2,6,6-tetra-methyl-piperidinyl)phosphite
  10. 10. A composition according to any one of the preceding claims in which Component a) is a mixture comprising
    i) 1-90% of a phosphonite of formula I; and
    ii) 99-10% of a phosphite of formula VIII (hereinafter defined as component ii)
    where p is 1, 2, or 3, X1 is -O- or -N(R3) and the other symbols are as defined in claim 1.
  11. 11. A process for preparing a compound of formula I comprising reacting one mol of a compound of formula X
    with one mol of a compound of formula Xl
    or by reacting 2 mols of a compound of formula X with 1 mol of a compound of formula XII R4-X-P(Z)2 (XII) where Z is Cl, Br or N(R7)2
  12. 12. A compound of formula XIII
    in which R' is as defined in claim 6 and the other symbols are defined in claim 4.
  13. 13. A compound according to claim 12 of formula XIV
    in which R' is R" where P" is hydrogen or C alkyl.
  14. 14. A composition according to claim 1 and any one of the claims 3-13 when appendent to claim 1 in which the polyolefins that can be stabilized are polyolefins such as polypropylene, polyethylene, polybutylene, poly-4-methylpentene and copolymers thereof.
  15. 15. A composition according to claim 2 or any one of claims 3-13 when appendant to claim 2 in which the polyurethanes are those prepared from isocyanate resins and polyols.
  16. 16. A powder coating composition comprising a polymeric powder coating material to which is applied a compound containing a phosphite or phosphonite group and at least one 2,2,6,6-tetraalkylpiperidinyl group.
GB9304685A 1992-03-11 1993-03-08 The use of phosphonite-HALS and phosphite-HALS compounds for the stabilisation of polyolefins Expired - Fee Related GB2265377B (en)

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GB929209759A GB9209759D0 (en) 1992-05-06 1992-05-06 Improvements in or relating to organic compounds
GB929221279A GB9221279D0 (en) 1992-10-09 1992-10-09 Organic compounds
GB929224522A GB9224522D0 (en) 1992-11-23 1992-11-23 Organic compounds
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EP0651006A1 (en) * 1993-10-29 1995-05-03 Montell North America Inc. Piperidinyl phosphite compositions and polyolefin compositions containing them
FR2715161A1 (en) * 1994-01-14 1995-07-21 Sandoz Sa Powder coating compositions and stabilized powder coatings.
GB2288398A (en) * 1994-04-13 1995-10-18 Ciba Geigy Ag Monomeric and oligomeric bisphenyl-HALS phosphites as stabilizers
GB2288397A (en) * 1994-04-13 1995-10-18 Ciba Geigy Ag HALS phosphonites as stabilizers
FR2718742A1 (en) * 1994-04-13 1995-10-20 Ciba Geigy Ag Phosphites and phosphoramides of hindered amine light stabilizing compounds useful as stabilizers.
GB2293827A (en) * 1994-10-06 1996-04-10 Sandoz Ltd Stabilizer composition for polymers
FR2728573A1 (en) * 1994-12-22 1996-06-28 Ciba Geigy Ag HALS-PHOSPHORAMIDES AS STABILIZERS
NL1000919C2 (en) * 1995-08-03 1997-02-04 Dsm Nv Powder paint composition.
US5654430A (en) * 1994-04-13 1997-08-05 Ciba-Geigy Corporation Oligomeric aliphatic HALS phosphites and HALS phosphonites as stabilizers
EP0816442A2 (en) * 1996-06-25 1998-01-07 Ciba SC Holding AG Stabilizing agents for powder coatings
WO2002033009A1 (en) * 2000-10-16 2002-04-25 Ciba Specialty Chemicals Holding Inc. Stabilizers for powder coatings
US6593485B1 (en) 1994-10-06 2003-07-15 Clariant Finance (Bvi) Limited Stabilizer composition

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Cited By (30)

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US5607989A (en) * 1993-10-29 1997-03-04 Montell North America Inc. Piperidinyl phosphite compositions and polyolefin compositions containing them
EP0651006A1 (en) * 1993-10-29 1995-05-03 Montell North America Inc. Piperidinyl phosphite compositions and polyolefin compositions containing them
FR2715161A1 (en) * 1994-01-14 1995-07-21 Sandoz Sa Powder coating compositions and stabilized powder coatings.
US5654430A (en) * 1994-04-13 1997-08-05 Ciba-Geigy Corporation Oligomeric aliphatic HALS phosphites and HALS phosphonites as stabilizers
GB2288398B (en) * 1994-04-13 1998-09-09 Ciba Geigy Ag Monomeric and oligomeric bisphenyl-HALS phosphites as stabilizers
FR2718742A1 (en) * 1994-04-13 1995-10-20 Ciba Geigy Ag Phosphites and phosphoramides of hindered amine light stabilizing compounds useful as stabilizers.
FR2718741A1 (en) * 1994-04-13 1995-10-20 Ciba Geigy Ag Phosphonites of hindered amine light stabilizing compounds useful as stabilizers.
GB2288398A (en) * 1994-04-13 1995-10-18 Ciba Geigy Ag Monomeric and oligomeric bisphenyl-HALS phosphites as stabilizers
GB2288397B (en) * 1994-04-13 1997-12-17 Ciba Geigy Ag HALs phosphonites as stabilizers
NL1000133C2 (en) * 1994-04-13 1996-05-13 Ciba Geigy HALS phosphites and HALS phosphoramides as stabilizers.
FR2718743A1 (en) * 1994-04-13 1995-10-20 Ciba Geigy Ag Bisphenyl phosphites of hindered amine light stabilizing compounds monomers and oligomers useful as stabilizers.
NL1000132C2 (en) * 1994-04-13 1996-07-23 Ciba Geigy HALS phosphonites as stabilizers.
BE1008991A3 (en) * 1994-04-13 1996-10-01 Ciba Geigy Ag PHOSPHITES phosphoramides COMPOUNDS STABILIZERS AND IN THE LIGHT OF TYPE USE AS STABILIZERS hindered amine.
BE1009087A3 (en) * 1994-04-13 1996-11-05 Ciba Geigy Ag Phosphonites COMPOUNDS STABILIZERS IN THE LIGHT TYPE USE AS STABILIZERS hindered amine.
NL1000131C2 (en) * 1994-04-13 1996-12-03 Ciba Geigy Monomeric and oligomeric bisphenyl-HALS phosphites as stabilizers.
BE1009490A5 (en) * 1994-04-13 1997-04-01 Ciba Geigy BISPHENYLPHOSPHITES COMPOUNDS STABILIZERS IN THE LIGHT TYPE hindered amine MONOMERS AND USE AS STABILIZERS OLIGOMERS.
US5665273A (en) * 1994-04-13 1997-09-09 Ciba-Geigy Corporation Hals phosphonites as stabilizers
GB2288397A (en) * 1994-04-13 1995-10-18 Ciba Geigy Ag HALS phosphonites as stabilizers
US6593485B1 (en) 1994-10-06 2003-07-15 Clariant Finance (Bvi) Limited Stabilizer composition
GB2293827B (en) * 1994-10-06 1997-05-07 Sandoz Ltd Stabilizer composition for polymers
FR2725451A1 (en) * 1994-10-06 1996-04-12 Sandoz Sa NOVEL STABILIZING COMPOSITION FOR POLYMERIC MATERIALS
GB2293827A (en) * 1994-10-06 1996-04-10 Sandoz Ltd Stabilizer composition for polymers
FR2728573A1 (en) * 1994-12-22 1996-06-28 Ciba Geigy Ag HALS-PHOSPHORAMIDES AS STABILIZERS
BE1009841A3 (en) * 1994-12-22 1997-10-07 Ciba Geigy Ag HALS-AS STABILIZERS phosphoramides.
NL1001958C2 (en) * 1994-12-22 1997-05-30 Ciba Geigy Ag HALS phosphoramides as stabilizers.
WO1997006218A1 (en) * 1995-08-03 1997-02-20 Dsm N.V. Powder paint composition
NL1000919C2 (en) * 1995-08-03 1997-02-04 Dsm Nv Powder paint composition.
EP0816442A2 (en) * 1996-06-25 1998-01-07 Ciba SC Holding AG Stabilizing agents for powder coatings
EP0816442A3 (en) * 1996-06-25 1998-06-17 Ciba SC Holding AG Stabilizing agents for powder coatings
WO2002033009A1 (en) * 2000-10-16 2002-04-25 Ciba Specialty Chemicals Holding Inc. Stabilizers for powder coatings

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