WO2010076278A1

WO2010076278A1 - Phosphorus based dispersants for inorganic particles in polymer matrices

Info

Publication number: WO2010076278A1
Application number: PCT/EP2009/067850
Authority: WO
Inventors: Paragkumar Nathalal Thanki; Lijun Xu; Subhash Shivaling Nashte; Deepak M. Rane; Neeraj Kumar Gupta; Michael Tinkl
Original assignee: Basf Se
Priority date: 2009-01-05
Filing date: 2009-12-23
Publication date: 2010-07-08

Abstract

The present invention relates to a melt process for the preparation of a synthetic polymer composition, comprising (a) a synthetic polymer, especially a polyolefin, (b) an inorganic filler and (c) a phosphorus based dispersing agent. The present invention relates also to the compositions prepared by this process, to articles made there from and to the use of the phosphorous compounds as a dispersing agent for inorganic fillers in a synthetic polymer matrix during melt processing.

Description

Phosphorus Based Dispersants for Inorganic Particles in Polymer Matrices

The addition of fillers, in particular inorganic fillers to organic materials, especially polymers, is known and is described for example in Hans Zweifel (editor), Plastics Additives Handbook, 5th Edition, pages 901-948, Hanser Publishers, Munich 2001. The use of fillers in polymers has the advantage that it is possible to bring about improvement in, for example, the mechanical properties, especially the density, hardness, rigidity (modulus) or reduced shrinkage of the polymer.

Using extremely small filler particles (with one dimension < 200 nm), so-called nano-scale fillers, mechanical properties, heat distortion temperature stability or flame retardant property of the polymers can be improved with a much lower concentration, typically 2 to 10 % by weight compared to 20 to 50 % by weight with the normal micro-scale filler particles.

Dispersion of mineral filler particles in polymers is a major issue. Currently two approaches are applied and both are having major limitations. In one approach the filler particles are pre- treated with dispersant/coupling agents prior to compounding. This approach involves an additional process step and that is additional cost. In another approach the polymeric dispersants are used as melt additives during compounding of the fillers with polymers. In this approach the content of dispersant is as high as 4% and contributes to significant costs. Moreover, these dispersants do not help to reduce the viscosity of the filled systems and thus amount to higher energy consumption during the processing of filled polymers.

Surprisingly it has been found that the limitations of both existing approaches can be overcome by using phosphorus based dispersants which function as melt additives, thereby significantly improving the extent of dispersion. One aspect of the invention is a process for the preparation of a synthetic polymer composition which comprises melt mixing at a temperature between 120° C and 290° C a) a synthetic polymer, b) an inorganic filler, and c) a phosphinic acid compound of formulae (I), (II) or (III) or a phosphonic acid compound of formula (IV)

O O O

FL- -P- -OR₁ (I). R,- -P — -RJ -P- -R, (H) or

OR₁ OR₁

O O

M

FL- -P- RJ -P- -R₃' (III) or R₂- — P- -OR₁' (IV) m

OR₁ OR₁' OR₁ where

Ri and Ri' are independently hydrogen;

straight or branched chain CrC₅oalkyl; straight or branched chain C₂-C₅₀alkyl interrupted by one to three -0-, -NR-, -COO-,

-OCO-, -CONR- or C₆-Ci₂arylene groups; straight or branched chain Ci-C₅₀alkyl substituted by one to three -OR, -NRR',

-COOR, -CONRR' or C₆-Ci₂aryl groups; straight or branched chain C₂-C₅oalkyl both interrupted and substituted by one to six of said groups; where each of the aryl or arylene groups are unsubstituted or are substituted by one to three straight or branched chain Ci-Ci₂alkyl or -OR groups;

-(CH₂CH₂O)_n-CH₂CH₂OH where n is from 1 to 100; or R₁ and Ri' are an alkali or alkali earth metal;

R₂ is

C₅-Ci₈cycloalkyl; straight or branched chain Ci-C₅₀alkyl; straight or branched chain Ci-Csoalkyl substituted by C₆-Ci₂aryl; straight or branched chain C₂-C₅₀alkyl interrupted by one to three -O-, -NR-, -COO-, -OCO-, -CONR-, C₆-Ci₂arylene, C₅-Ci₈cycloalkylene or C₅-Ci₈cycloalkenylene groups; straight or branched chain Ci-C₅oalkyl substituted by one to three -OR, -NRR', -COOR, -CONRR' groups; straight or branched chain C₂-C₅₀alkyl both interrupted and substituted by one to six of said groups; straight or branched chain Ci-C₅₀alkyl substituted by C₆-Ci₂aryl which is substituted by one to three straight or branched chain Ci-Ci₂alkyl or -OR groups; C₆-Ci₂aryl substituted by one to three straight or branched chain C₄-Ci₂alkyl or

-OR groups;

-(CH₂CH₂O )_n-CH₂CH₂OH where n is from 1 to 100; or

3-0X0-1 ,3-dihydroisobenzofuran-1-yl which is unsubstituted or is substituted by one to three straight or branched chain Ci-Ci₂alkyl, -OR or -COOR groups; R₃ and R₃' are independently hydrogen;

C₅-Ci₈cycloalkyl;

straight or branched chain Ci-Csoalkyl; straight or branched chain C₂-C₅₀alkyl interrupted by one to three -0-, -NR-, -COO-,

-OCO-, -CONR-, C₆-Ci₂arylene, C₅-Ci₈cycloalkylene or C₅-Ci₈cycloalkenylene groups; straight or branched chain Ci-C₅oalkyl substituted by one to three -OR, -NRR',

-COOR, -CONRR' or C₆-Ci₂aryl groups; straight or branched chain C₂-C₅₀alkyl both interrupted and substituted by one to six of said groups; where each of the aryl or arylene groups are unsubstituted or are substituted by one to three straight or branched chain Ci-Ci₂alkyl or -OR groups;

-(CH₂CH₂O)_n-CH₂CH₂OH where n is from 1 to 100; or 3-0X0-1 ,3-dihydroisobenzofuran-1-yl which is unsubstituted or is substituted by one to three straight or branched chain Ci-Ci₂alkyl, -OR or -COOR groups; - A -

or, in formula I, Ri and R₂ together or R₂ and R₃ together are (-CH₂-)_n where n is an integer of from 3 to 7, or together are (-CH₂-)_n which is annulated with 1 or 2 phenylene groups;

or, in formulae Il or III, R₁ and R₃ together or R₁' and R₃' together or R₁ and R₃ together and R₁' and R₃' together are (-CH₂-)_n where n is an integer of from 3 to 7, or together are (-CH₂-)_n which is annulated with 1 or 2 phenylene groups;

R and R' are independently hydrogen or straight or branched chain CrC₁₂alkyl;

R₄ is straight or branched chain CrC₅oalkylene; straight or branched chain CrC₅₀alkylene substituted by one to three -OR, -NRR', -COOR, -CONRR' or C₆-C₁₂aryl groups; straight or branched chain C₂-C₅₀alkylene interrupted by one to three -O-, -NR-, -COO-, -OCO-, -CONR-, C₆-C₁₂arylene or C₅-C₁₈cycloalkylene groups; straight or branched chain C₂-C₅₀alkyene both interrupted and substituted by one to six of said groups; C₅-C₁₈cycloalkylene which is unsubstituted or is substituted by one to three C_rC₆alkyl, -OR, -NRR', -COOR, -CONRR' or C₆-C₁₂aryl groups;

C₅-C₁₈cycloalkylene which is interrupted by one to three -0-, -NR-, -COO-, -OCO-, -CONR- or C₆-C₁₂arylene groups;

C₅-C-i8cycloalkylene which is both interrupted and substituted by one to six of said groups; C₆-C₅₀alkylenecycloalkylene; or

C₆-C₁₂arylene; where each of the aryl or arylene groups are unsubstituted or are substituted by one to three straight or branched chain C-ι-C₁₂alkyl or -OR groups; and m is from 2 to 100.

In a specific embodiment all compounds are added at the same time, i. e. simultaneously. The compounds of formulae (I), (II) and (III) are monomeric, oligomeric or polymeric phosphinic acids or their derivatives. The compounds of formula (IV) represent phosphonic acids or their derivatives. They can be prepared according to standard methods or are partially commercially available.

C₆-Ci₂aryl is for example phenyl, naphthyl or biphenyl.

C₆-Ci₂aryl substituted by one to three d-C^alkyl or -OR groups is for instance tolyl,

xylyl, o-, p- or m-phenol, or is the group

Arylene is a divalent version of aryl.

C₅-Ci₈cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and

also includes bicyclic or polycyclic groups such as

Cycloalkylene is a divalent version of cycloalkyl. Cycloalkenylene is a divalent, unsaturated version of cycloalkyl.

Alkyl is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1- methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetra- methylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl,

1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1 ,1 ,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl.

Alkylene is a divalent version of alkyl. 3-0X0-1 ,3-dihydroisobenofuran-1-yl or phthalide is the group

C6-C₅oalkylenecycloalkylene is a divalent alkylcycloalkyl group terminated at each of the alkyl and cycloalkyl radicals, for example:

Alkali and alkali earth metals are for instance Li, Na, K, Mg, Ca or Ba. Where the metal is divalent, it will be satisfied by two phosphinyloxy groups.

Examples of when in formula I, Ri and R₂ together or R₂ and R3 together are (-CH₂-)_n where n is an integer of from 3 to 7, or together are (-CH₂-)_n which is annulated with 1 or 2 phenylene groups;

or, in formulae Il or III, R₁ and R₃ together or R₁' and R₃' together or R₁ and R₃ together and R₁' and R₃' together are (-CH₂-)_n where n is an integer of from 3 to 7, or together are (-CH₂-)_n which is annulated with 1 or 2 phenylene groups, are:

The term "together are (-CH₂-)_n" means "ring forming with methylene groups".

The compounds of formulae (I) or (II) are partly items of commerce or may be prepared as described in WO 2009/121796.

For example, the phosphinic acid compound is of the formula I and where R₂ is straight or branched chain Ci-C₅₀alkyl; straight or branched chain Ci-C₅₀alkyl substituted by C₆-Ci₂aryl; straight or branched chain C₂-C₅oalkyl interrupted by one to three -O-, -NR-, -COO-, -OCO-, -CONR-, C₆-Ci₂arylene, C₅-Ci₈cycloalkylene or C₅-Ci₈cycloalkenylene groups; straight or branched chain Ci-C₅₀alkyl substituted by one to three -OR, -NRR', - COOR, -CONRR' groups; straight or branched chain C₂-C₅₀alkyl both interrupted and substituted by one to six of said groups.

For instance, the phosphinic acid compound is of the formula I and where R₂ is straight or branched chain Ci-C₅₀alkyl substituted by C₆-Ci₂aryl which is substituted by one to three straight or branched chain C₄-Ci₂alkyl or -OR groups; C6-C"i₂aryl substituted by one to three straight or branched chain C₄-Ci₂alkyl or

-OR groups; or R₂ is 3-oxo-1 ,3-dihydroisobenzofuran-1-yl which is unsubstituted or is substituted by one to three straight or branched chain Ci-Ci₂alkyl, -OR or -COOR groups.

In another embodiment the phosphinic acid is of formula Il or III.

In particular the phosphinic acid is of formula Il or III and R₃ and R₃' are C6-C"i₂aryl; straight or branched chain Ci-C₅₀alkyl; straight or branched chain C₂-C₅oalkyl interrupted by one to three -O-, -NR-, -COO-, -OCO-, -CONR-, C₆-Ci₂arylene, C₅-Ci₈cycloalkylene or C₅-Ci₈cycloalkenylene groups; straight or branched chain Ci-C₅₀alkyl substituted by one to three -OR, -NRR',

-COOR, -CONRR' or C₆-Ci₂aryl groups; straight or branched chain C₂-C₅oalkyl both interrupted and substituted by one to six of said groups; where each of the aryl or arylene groups are unsubstituted or are substituted by one to three straight or branched chain d-C^alkyl or -OR groups; or R₃ and R₃' are 3-oxo-1 ,3-dihydroisobenzofuran-1-yl which is unsubstituted or is substituted by one to three straight or branched chain d-C^alkyl, -OR or -COOR groups.

Preferred is in formulae (I), (II) and (III) when m is a number from 5 to 50;

R and R' are independently hydrogen or straight or branched chain Ci-C₄₀alkyl;

R₂ is C₅-C₆cycloalkyl, straight or branched chain CrC₅oalkyl.

R₃ and R₃' are independently hydrogen, C₅-C₆cycloalkyl, phenyl, straight or branched chain

Ci-C₅₀alkyl; R₄ is straight or branched chain Ci-C₅₀alkylene.

Suitable synthetic polymers are mentioned below.

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, 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 (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and

(ULDPE). Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevated temperature).

b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII 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 π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Na and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1 ), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo- lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi- nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethy- lene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene- acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyal- kylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.

Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, α-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/sty- rene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propy- lene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure including syndiotactic, isotac- tic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers. 9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

1 1. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadi- enes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 1 1 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydan- toins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones or lactides, for example polyethylene terephthalate, polybuty- lene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoates as well as copolyether esters derived from hydroxyl-terminated polyethers, and also polyesters modified with polycarbonates or MBS. Copolyesters may comprise, for example - but are not limited to - polybutylenesuccinate/terephtalate, polybuty- leneadipate/terephthalate, polytetramethyleneadipate/terephthalate, polybutylensuccinate/- adipate, polybutylensuccinate/carbonate, poly-3-hydroxybutyrate/octanoate copolymer, poly- 3-hydroxybutyrate/hexanoate/decanoate terpolymer. Furthermore, aliphatic polyesters may comprise, for example - but are not limited to - the class of poly(hydroxyalkanoates), in par- ticular, poly(propiolactone), poly(butyrolactone), poly(pivalolactone), poly(valerolactone) and poly(caprolactone), polyethylenesuccinate, polypropylenesuccinate, polybutylenesuccinate, polyhexamethylenesuccinate, polyethyleneadipate, polypropyleneadipate, polybutyleneadi- pate, polyhexamethyleneadipate, polyethyleneoxalate, polypropyleneoxalate, polybutylene- oxalate, polyhexamethyleneoxalate, polyethylenesebacate, polypropylenesebacate, polybu- tylenesebacate and polylactic acid (PLA) as well as corresponding polyesters modified with polycarbonates or MBS. The term "polylactic acid (PLA)" designates a homo-polymer of preferably poly-L-lactide and any of its blends or alloys with other polymers; a co-polymer of lactic acid or lactide with other monomers, such as hydroxy-carboxylic acids, like for example glycolic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 4-hydroxy-valeric acid, 5-hydr- oxy-valeric acid, 6-hydroxy-caproic acid and cyclic forms thereof; the terms "lactic acid" or "lactide" include L-lactic acid, D-lactic acid, mixtures and dimers thereof, i.e. L-lactide, D-lac- tide, meso-lacide and any mixtures thereof.

19. Polycarbonates and polyester carbonates. 20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, PoIy- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

Preferably the synthetic polymer is a polyolefin, in particular polypropylene or polyethylene.

For example the inorganic filler is selected from the group consisting of calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.

Preferably the inorganic filler is a silicate, calcium carbonate, talc or an alkaline earth metal oxide or hydroxide.

Typically the filler is present in an amount from 10% to 50% by weight, preferably 20% to

30%, based on the weight of the composition. The dispersing compound, component c) is typically present in an amount from 0.5% to 5% by weight, preferably 1 % to 4%, based on the weight of the composition.

The melt mixing occurs between 120° C and 290° C, preferably 180° C to 280° C, more preferably 180° C to 260° C.

Incorporation of components (b) and (c) and, if desired, further additives into the synthetic polymers is carried out by known methods, for example before or during moulding or else by applying the dissolved or dispersed compounds to the synthetic polymer, if appropriate with subsequent slow evaporation of the solvent. The melt mixing can be carried out in any heatable container equipped with a stirrer, for example in a closed apparatus such as a kneader, mixer or stirred vessel. The incorporation is preferably carried out in an extruder or in a kneader. It is immaterial whether processing takes place in an inert atmosphere or in the presence of oxygen.

The addition and mixing of components (a), (b) and (c) can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders. The process is preferably carried out in an extruder by introducing the additive during processing. Particularly preferred processing machines are single-screw extruders, contrarotating and corotating twin-screw extruders, planetary-gear extruders, ring extruders or cokneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied. Suitable extruders and kneaders are described, for example, in Handbuch der Ku nststoff extrusion, Vol. 1 , Grundlagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4; and Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7. For example, the screw length is 1 - 60 screw diameters, preferably 35 - 48 screw diameters. The rotational speed of the screw is preferably 10 to 600 rotations per minute (rpm), for example 25 - 300 rpm. The maximum throughput is dependent on the screw diameter, the rotational speed and the driving force. The process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.

The synthetic polymers prepared in this way can be employed in a wide variety of forms, for example as foams, films, fibres, tapes, moulding compositions, as profiles or as binders for coating materials, especially powder coatings, adhesives, putties or especially as thick-layer polyolefin mouldings which are in long-term contact with extractive media, such as, for example, pipes for liquids or gases, films, fibres, geomembranes, tapes, profiles or tanks.

The preferred thick-layer polyolefin mouldings have a layer thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm.

If desired, further additives may be added to the polymer composition. Examples are given below. 1. Antioxidants

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylundec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '- methylheptadec-1 '-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-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, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.

1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 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-(α-methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methy- lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1 ,1-bis(5-tert- butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4- methylphenol, 1 ,1 ,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1 ,1-bis(5-tert-butyl-4- hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert- butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopenta- diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha- late, 1 ,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe- nyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,

1 ,1 ,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. Q-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl)sulfide, isooctyl-S^-di-tert-butyl^-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)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-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-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-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-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-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-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-di-tert-butyl-4-hydroxy- phenylpropionyl)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso- cyanurate.

1.1 1. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-S-tert-butyM-hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hvdroxyphenyl)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, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or poly- hydric 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, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N.N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert- butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1 ,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]- undecane.

1.15. Esters of β-(3,5-dicvclohexyl-4-hvdroxyphenyl)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, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 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-butyl-4-hvdroxyphenyl acetic 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, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy- drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau- gard^®XL-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)-p-phenylenediamine, N,N'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)-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-allyldiphenylamine, 4-isopropoxydiphenyl- amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naph- thylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butyl- aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4- octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino- methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra- methyl-4,4'-diaminodiphenylmethane, 1 ,2-bis[(2-methylphenyl)amino]ethane, 1 ,2-bis(phenyl- amino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N- phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenyl- amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl- diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro- 3,3-dimethyl-4H-1 ,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert- butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1 ,4-diaminobut-2-ene.

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hvdroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'- hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy- 5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl- oxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2- methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-meth- oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl- ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy- phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[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-butyl-4'-hydroxy-5'-2H-benzotri-

azol-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)-phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]ben- zotriazole.

2.2. 2-Hvdroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 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 unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphe- nylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinna- mate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycin- namate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-di- phenylacrylate.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[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 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4- piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2- hydroxyethyl)-2,2,6,6-tetramethyl-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-2,6-dichloro-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 ,1'-(1 ,2-ethanediyl)- bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy- 2,2,6,6-tetramethylpiperidine, bis(1 ,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5- di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decane-2,4- dione, bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1 -octyloxy-2,2,6,6- tetramethylpiperidyl)succinate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4- piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1 ,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino- 1 ,2, 2, 6, 6-pentamethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)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-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1 ,2,2,6,6-pentamethyl-4- piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2, 2,6,6- tetramethylpiperidine, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4- piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1 ,3,5-triazine, a condensate of 1 ,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1 ,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1 ,6-hexanediamine and 2,4,6-trichloro-1 ,3,5-triazine as well as N,N-dibutylamine and 4- butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6- tetramethyM-piperidyO-n-dodecylsuccinimide, N-(1 , 2,2,6, 6-pentamethyl-4-piperidyl)-n-dode- cylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]de- cane and epichlorohydrin, 1 ,1-bis(1 , 2,2,6, 6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-me- thoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene- diamine, a diester of 4-methoxymethylenemalonic acid with 1 ,2,2,6,6-pentamethyl-4- hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, a reaction product of maleic acid anhydride-α-olefin copolymer with 2,2,6,6-tetramethyl-4-ami- nopiperidine or 1 ,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6- tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1 ,3,5-triazine, 1 -(2-hydr- oxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexanoyl)- oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Reg. No. 106917-31-1], 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, the reaction product of 2,4-bis- [(i-cyclohexyloxy^^^θ-piperidine^-y^butylaminoj-θ-chloro-s-triazine with N,N'-bis(3-ami- nopropyl)ethylenediamine), 1 ,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4- yl)amino)-s-triazine, 1 ,3,5-tris(N-cyclohexyl-N-(1 ,2,2,6,6-pentamethylpiperazine-3-one-4-yl)- amino)-s-triazine.

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, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides. 2.8. 2-(2-Hydroxyphenyl)-1 ,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- (2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl- oxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-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(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- [2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[2- hydroxy-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-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl- phenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hydr- oxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hy- droxypropoxy)phenyl]-1 ,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl- 1 ,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4- dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxy- phenyl)-1 ,3,5-triazine.

3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)- pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristea- ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6- isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1 ,3,2-dioxaphosphocin, bis(2,4-di-tert- butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1 ,3,2-dioxaphosphocin, 2,2',2"-nitrilo- [triethyltris(3,3^l,5,5^l-tetra-tert-butyl-1 ,1 ^l-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-te- tra-tert-butyl-1 J 4)iphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)- 1 ,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos^®168, Ciba Specialty Chemicals Inc.), tris(no- nylphenyl) phosphite,

(F) H₃₇C₁-_B- -C₁ 18₀H' '37 (G)

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N, N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N, N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxyl- amine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β- dodecylmercapto)propionate. 9. Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

1 1. 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(paramethyl- dibenzylidene)sorbitol, and 1 ,3:2,4-di(benzylidene)sorbitol.

12. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

13. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-431661 1 ; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or 3-[4-(2- acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxy- ethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)ben- zofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-di- methylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di- tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3- dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctyl- benzofuran-2-one. The compositions according to the invention can be advantageously used for the preparation of various shaped articles. Examples are:

1-1 ) Floating devices, marine applications, pontoons, buoys, plastic lumber for decks, piers, boats, kayaks, oars, and beach reinforcements.

I-2) Automotive applications, in particular bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter / filler, fuel pumps, fuel tank, body side mouldings, convertible tops, exterior mirrors, exterior trim, fasteners / fixings, front end module, glass, hinges, lock systems, luggage / roof racks, pressed/stamped parts, seals, side impact protection, sound deadener / insulator and sunroof.

I-3) Road traffic devices, in particular sign postings, posts for road marking, car accessories, warning triangles, medical cases, helmets, tires.

I-4) Devices for plane, railway, motor car (car, motorbike) including furnishings.

I-5) Devices for space applications, in particular rockets and satellites, e.g. reentry shields.

I-6) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters.

11-1 ) Appliances, cases and coverings in general and electric/electronic devices (personal computer, telephone, portable phone, printer, television-sets, audio and video devices), flower pots, satellite TV bowl, and panel devices.

II-2) Jacketing for other materials such as steel or textiles. 11-3) Devices for the electronic industry, in particular insulation for plugs, especially computer plugs, cases for electric and electronic parts, printed boards, and materials for electronic data storage such as chips, check cards or credit cards.

11-4) Electric appliances, in particular washing machines, tumblers, ovens (microwave oven), dish-washers, mixers, and irons.

11-5) Covers for lights (e.g. street-lights, lamp-shades).

II-6) Applications in wire and cable (semi-conductor, insulation and cable-jacketing).

II-7) Foils for condensers, refrigerators, heating devices, air conditioners, encapsulating of electronics, semi-conductors, coffee machines, and vacuum cleaners.

111-1 ) Technical articles such as cogwheel (gear), slide fittings, spacers, screws, bolts, handles, and knobs.

III-2) Rotor blades, ventilators and windmill vanes, solar devices, swimming pools, swimming pool covers, pool liners, pond liners, closets, wardrobes, dividing walls, slat walls, folding walls, roofs, shutters (e.g. roller shutters), fittings, connections between pipes, sleeves, and conveyor belts.

III-3) Sanitary articles, in particular shower cubicles, lavatory seats, covers, and sinks.

III-4) Hygienic articles, in particular diapers (babies, adult incontinence), feminine hygiene articles, shower curtains, brushes, mats, tubs, mobile toilets, tooth brushes, and bed pans.

III-5) Pipes (cross-linked or not) for water, waste water and chemicals, pipes for wire and cable protection, pipes for gas, oil and sewage, guttering, down pipes, and drainage sy- stems.

III-6) Profiles of any geometry (window panes) and siding. 111-7) Glass substitutes, in particular extruded plates, glazing for buildings (monolithic, twin or multiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles, and greenhouse.

111-8) Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.

III-9) Intake and outlet manifolds.

111-10) Cement-, concrete-, composite-applications and covers, siding and cladding, hand rails, banisters, kitchen work tops, roofing, roofing sheets, tiles, and tarpaulins.

IV-1 ) Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.

IV-2) Woven fabrics continuous and staple, fibers (carpets / hygienic articles / geotextiles / monofilaments; filters; wipes / curtains (shades) / medical applications), bulk fibers (applications such as gown / protection clothes), nets, ropes, cables, strings, cords, threads, safety seat-belts, clothes, underwear, gloves; boots; rubber boots, intimate apparel, garments, swimwear, sportswear, umbrellas (parasol, sunshade), parachutes, paraglides, sails, "balloon-silk", camping articles, tents, airbeds, sun beds, bulk bags, and bags.

IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps, ponds, dumps, walls roofing membranes, geomembranes, swimming pools, curtains (shades) / sun-shields, awnings, canopies, wallpaper, food packing and wrapping (flexible and solid), medical packaging (flexible & solid), airbags/safety belts, arm- and head rests, carpets, centre console, dashboard, cockpits, door, overhead console module, door trim, headliners, interior lighting, interior mirrors, parcel shelf, rear luggage cover, seats, steering column, steering wheel, textiles, and trunk trim. V) Films (packaging, dump, laminating, agriculture and horticulture, greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries, and connectors.

VI-1 ) Food packing and wrapping (flexible and solid), bottles.

VI-2) Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs, and cans.

VI-3) Cartridges, syringes, medical applications, containers for any transportation, waste baskets and waste bins, waste bags, bins, dust bins, bin liners, wheely bins, container in general, tanks for water / used water / chemistry / gas / oil / gasoline / diesel; tank liners, boxes, crates, battery cases, troughs, medical devices such as piston, ophthalmic applications, diagnostic devices, and packing for pharmaceuticals blister.

Vl 1-1 ) Extrusion coating (photo paper, tetrapack, pipe coating), household articles of any kind (e.g. appliances, thermos bottle / clothes hanger), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap-closures.

VII-2) Support devices, articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.

VII-3) Furniture in general, foamed articles (cushions, impact absorbers), foams, sponges, dish clothes, mats, garden chairs, stadium seats, tables, couches, toys, building kits (boards / figures / balls), playhouses, slides, and play vehicles.

VII-4) Materials for optical and magnetic data storage.

VII-5) Kitchen ware (eating, drinking, cooking, storing).

VII-6) Boxes for CD's, cassettes and video tapes; DVD electronic articles, office supplies of any kind (ball-point pens, stamps and ink-pads, mouse, shelves, tracks), bottles of any volume and content (drinks, detergents, cosmetics including perfumes), and adhesive tapes. VII-7) Footwear (shoes / shoe-soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, artificial joints (human), printing plates (flexographic), printed circuit boards, and display technologies.

VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO₂, mica, nanocomposites, dolomite, silicates, glass, asbestos).

Also an aspect of the invention is a synthetic polymer composition obtainable in a process as described above.

A further embodiment of the present invention relates to a shaped article, in particular a film, pipe, profile, bottle, tank or container, fiber containing a synthetic polymer composition as described above.

Also an aspect of the invention is the use of a phosphinic or phosphonic acid based dispersing agent of formulae (I), (II), (III) or (IV) as described above for dispersing inorganic fillers in a synthetic polymer matrix by melt mixing at a temperature from 120° C to 290° C.

The following examples illustrate the invention.

A) Preparation Examples

Experimental procedures for the preparation of dialkyl phosphinic and alkyl phosphonic acids

Example A1 : Process for the preparation of dioctyl phosphinic acid

A 2 L three-necked reaction flask equipped with a thermometer, reflux condenser, addition funnel and a magnetic stirrer is charged with 700 ml of 1-octene (4.4690 mol) and 1250 ml of 1 ,4-dioxan. Added are 37.5 g of benzoyl peroxide under stirring. Temperature of the reaction mass is raised to 75-95°C. 242 ml of 50% hypo-phosphorous acid (2.2367 mol) is added drop-wise within 1 hour. Then the reaction is continued for 7 hours at the same temperature. After completion of the reaction, the mass is cooled below 5°C, filtered, washed with cold 1 ,4-dioxan and dried in an oven under reduced pressure. 336 g (54% yield) of white, amorphous product is yielded. It is characterized by ¹H and ³¹P NMR and IR spectroscopy. Example A2: Process for the preparation of didecyl phosphinic acid

A 250 ml reaction flask is charged with 50 g of 1-decene (0.3571 mol), 125 ml of 1 ,4-dioxan. Added are 3.75 g of benzoyl peroxide under stirring. Temperature of the reaction mass is raised to 75-95°C. 19 ml of 50% hypo-phosphorous acid (0.1786 mol) is added drop-wise within 1 hour. Then the reaction is continued for 7 hours at the same temperature. After completion of the reaction, the mass is cooled below 5°C, filtered, washed with cold 1 ,4- dioxan and dried in an oven under reduced pressure. 30 g (48.6% yield) of white, amorphous product is yielded.

Example A3: Process for the preparation of ditetradecyl phosphinic acid

A reaction flask is charged with 100 g of 1-tetradecene (0.5102 mol), 250 ml of 1 ,4-dioxan. Added are 7.5 g of benzoyl peroxide under stirring. Temperature of the reaction mass is raised to 75-95°C. 33.7 g of 50% hypo-phosphorous acid (0.2551 mol) is added drop-wise within 1 hour. Then the reaction is continued for 7 hours at the same temperature. After completion of the reaction, the mass is cooled below 5°C, filtered, washed with cold 1 ,4- dioxan and dried in an oven under reduced pressure. 66 g (56% yield) of white, amorphous product is yielded.

Example A4: Process for the preparation of dioctadecyl phosphinic acid A reaction flask is charged with 100 g of 1-octadecene (0.3960 mol), 250 ml of 1 ,4-dioxan. Added are 7.5 g of azo bisisobutyronitrile (AIBN) under stirring. Temperature of the reaction mass is raised to 75-95°C. 21.5 ml of 50% hypo-phosphorous acid (0.1980 mol) is added drop-wise within 1 hour. Then the reaction is continued for 7 hours at the same temperature. After completion of the reaction, the mass is cooled below 5°C, filtered, washed with cold 1 ,4-dioxan and dried in an oven under reduced pressure. 90 g (79.6% yield) of white, amorphous product is yielded.

Example A5: Process for the preparation of decyl phosphonic acid

A reaction flask is charged with 100 g of 1-decene (0.7143 mol), 146 g of phosphorous acid (1.7857 mol), 250 ml of methoxy-ethanol and 8.8 g of azo bisisobutyronitrile (AIBN). Temperature of the reaction mass is raised to 115-125°C and the reaction is continued for 8 hours. Solvent is removed using a rotary evaporator. Crude product is washed with water and crystallized from n-heptane. 65 g (41.1 %) of off white colored product is isolated. Characterization of the same is done by ¹H and ³¹P NMR and IR spectroscopy. Example A6: Process for the preparation of tetradecyl phosphonic acid A round bottom flask is charged with 100 g of tetradecene (0.5102 mol), 104.6 g of phosphorous acid (1.2755 mol), 250 ml of methoxy-ethanol and 6.3 g of te/f-butyl per benzoate. Reaction mass is heated at reflux temperature for 8 hours. After completion of the reaction, solvent is stripped off by vacuum distillation. Crude product is washed with water and then crystallized from n-heptane. 55 g (39%) of off-white product is yielded.

Example A7: Process for the preparation of octadecyl phosphonic acid A round bottom flask is charged with 100 g of 1-octadecene (0.3960 mol), 82 g of phosphorous acid (1.0000 mol), 250 ml of methoxy-ethanol and 7.5 g of te/f-butyl per benzoate. Reaction mass is heated at reflux temperature for 8 hours. After completion of the reaction, solvent is stripped off by vacuum distillation on a rotary evaporator. Crude product is washed with water and then crystallized from n-heptane. 81.9 g (61.9 %) of off-white product is yielded.

Example A8: Process for the surface treatment of talc with dioctyl phosphinic acid Surface treatment of talc with dioctyl phosphinic acid is carried out by dispersing 600 g talc in 1400 ml IPA and slowly adding a solution of dioctyl phosphinic acid (3.0 g in 100 ml IPA) at 65°C. This leads to 0.5% loading of dispersant to talc. Further it is stirred at 70⁰C for 1 h. Slurry obtained is filtered after cooling to room temperature and dried at 70⁰C.

B) Application Examples

Materials

Table 1 provides the details of the materials and the source from where they were procured.

Table 1

Component Description Source

TPO Reactor grade thermoplastic olefin Borealis

PP Propylene homopolymer Taiwan

Polypropylene

Compound I Dioctyl phosphonic acid (OPA) Ciba

Untreated CaCO₃ Natural, very fine, high grade Omya China crystalline calcium carbonate powder

Treated CaCO₃ Natural, very fine, surface coated high Omya China grade crystalline calcium carbonate powder

Untreated Mg(OH)₂ Uncoated magnesium hydroxide Albemarle

Treated Mg(OH)₂ Coated magnesium hydroxide Albemarle

The following general procedures are used in the working examples unless otherwise indicated.

Mixing procedure: To 2000 g of the polymer the powdered fillers as indicated below are added, mixed in a high speed mixer, for example Henschel, for a period of about 3 minutes at a speed of 2000 rpm.

Compounding:

In general, this mixture are compounded at 230^°C in a laboratory twin screw corotating extruder, and subsequently collected at room temperature.

Injection molding:

The injection molding is performed with a laboratory scale injection molding machine. The palletized thread is placed in a barrel at 220^°C. After the granulate is completely molten, the melt is injected into a polished mold. The mold temperature is 40^°C. Tensile property:

The tensile properties of polymer specimens are measured according to the standard condition as described in ISO 527.

Flexural modulus:

The flexural modulus of polymer specimens is measured according to the standard condition as described in ISO 178.

Notched Izod impact strength: The notched izod impact strength of polymer specimens is measured according to the standard condition as described in ISO 180.

Results and Discussion Examples B9-B12 In the Examples Ex.B9 to Ex.B12 the polymer employed is polypropylene (PP). The filler applied is calcium carbonate. The type of calcium carbonate is varied, comprising surface untreated and treated. In the case of Ex.B9 the calcium carbonate is surface untreated and produced as a blank control sample. However, in Ex.BI O a commercial surface treated calcium carbonate is employed as a reference. In Ex.B1 1 and Ex.B12 inventive melt dispersants are added at adequate amounts to treat CaCO₃ as indicated in the table below. The tensile strength and elongation of the thermoplastic olefin composition as well as flexural modulus and melt flow rate according to the present invention are listed in following table. Table 2

Ex.B9 Ex.BIO Ex.B11 Ex.B12

PP 70 70 69 66 untreated CaCO₃ 30 0 30 30 treated CaCO₃ 0 30 0 0

Compound I 0 0 1 4

Tensile strength (S) yield (MPa) 29.0 28.6 27.4 19.8

Elongation (S) break (%) 275.2 260.8 254.3 50.9

Flexural modulus (MPa) 1934 2419 2449 2337

Tensile modulus (MPa) 3792 3934 3759 3870

Melt flow rate (g/1 Omin, 2.16kg) 3.16 3.32 3.66 3.14 Examples B13-B16

In the Examples Ex.B13 to Ex.B16 the polymer employed is polypropylene (PP). The filler applied is magnesium hydroxide. The type of magnesium hydroxide is varied, comprising surface untreated and treated. In the case of Ex.B13 the magnesium hydroxide is surface untreated and produced as a blank control sample. However, in Ex.B14 a commercial surface treated magnesium hydroxide is employed as a reference. In Ex.B15 and Ex.B16 the inventive melt dispersant is added at adequate amounts to treat Mg(OH)₂ as indicated in the table below.

The tensile strength and elongation of the thermoplastic olefin composition as well as flexural modulus and melt flow rate according to the present invention are listed in following table. Table 3

Ex.B13 Ex.B14 Ex.B15 Ex.B16

PP 70 70 69 66 untreated Mg(OH)₂ 30 0 30 30 treated Mg(OH)₂ 0 30 0 0

Compound I 0 0 1 4

Tensile strength (S) yield (MPa) 20.2 20.5 20.3 19.5

Elongation (S) break (%) 34.2 121.7 59.2 64.6

Flexural modulus (MPa) 5923 4770 5427 4558

Tensile modulus (MPa) 6197 2966 4510 3878

Melt flow rate (g/1 Omin, 2.16kg) 0.49 3.86 3.38 3.07

Claims

1. A process for the preparation of a synthetic polymer composition which comprises melt mixing at a temperature between 120° C and 290° C a) a synthetic polymer, b) an inorganic filler, and c) a phosphinic acid compound of formulae (I), (II) or (III) or a phosphonic acid compound of formula (IV)

O O O

R; -P- -OR₁ (I). R; -P — -RJ -P- -R, (H) or

R, OR₁ OR₁

O O O R; -P- -Rj -P- -R₃' (III) or R₂- — P- ^"OR/ (IV) m

OR₁ OR₁ OR₁ where

R₁ and R-i' are independently hydrogen;

straight or branched chain Ci-C₅₀alkyl; straight or branched chain C₂-C₅oalkyl interrupted by one to three -0-, -NR-, -COO-,

-(CH₂CH₂O)_n-CH₂CH₂OH where n is from 1 to 100; or R₁ and R₁' are an alkali or alkali earth metal;

R₂ is

C₅-C₁₈cycloalkyl; straight or branched chain CrC₅oalkyl; straight or branched chain Ci-C₅₀alkyl substituted by C₆-Ci₂aryl; straight or branched chain C₂-C₅oalkyl interrupted by one to three -O-, -NR-, -COO-, -OCO-, -CONR-, C₆-Ci₂arylene, C₅-Ci₈cycloalkylene or C₅-Ci₈cycloalkenylene groups; straight or branched chain Ci-C₅₀alkyl substituted by one to three -OR, -NRR',

-COOR, -CONRR' groups; straight or branched chain C₂-C₅oalkyl both interrupted and substituted by one to six of said groups; straight or branched chain Ci-C₅oalkyl substituted by

which is substituted by one to three straight or branched chain d-C^alkyl or -OR groups;

C6-Ci₂aryl substituted by one to three straight or branched chain C₄-Ci₂alkyl or -OR groups;

-(CH₂CH₂O)_n-CH₂CI-I₂OI-I where n is from 1 to 100; or

3-0X0-1 ,3-dihydroisobenzofuran-1-yl which is unsubstituted or is substituted by one to three straight or branched chain Ci-Ci₂alkyl, -OR or -COOR groups;

R₃ and R₃' are independently hydrogen;

C₅-Ci₈cycloalkyl;

-OCO-, -CONR-, C₆-Ci₂arylene, C₅-Ci₈cycloalkylene or C₅-Ci₈cycloalkenylene groups; straight or branched chain Ci-C₅₀alkyl substituted by one to three -OR, -NRR',

-(CH₂CH₂O)_n-CH₂CH₂OH where n is from 1 to 100; or

3-0X0-1 ,3-dihydroisobenzofuran-1-yl which is unsubstituted or is substituted by one to three straight or branched chain Ci-Ci₂alkyl, -OR or -COOR groups; or, in formula I, Ri and R₂ together or R₂ and R₃ together are (-CH₂-)_n where n is an integer of from 3 to 7, or together are (-CH₂-)_n which is annulated with 1 or 2 phenylene groups;

2. A process according to claim 1 where the phosphinic acid compound is of the formula I and where R₂ is straight or branched chain CrC₅oalkyl; straight or branched chain Ci-C₅₀alkyl substituted by C₆-Ci₂aryl; straight or branched chain C₂-C₅oalkyl interrupted by one to three -O-, -NR-, -COO-, -OCO-, -CONR-, C₆-Ci₂arylene, C₅-Ci₈cycloalkylene or C₅-Ci₈cycloalkenylene groups; straight or branched chain Ci-C₅₀alkyl substituted by one to three -OR, -NRR', -

COOR, -CONRR' groups; straight or branched chain C₂-C₅oalkyl both interrupted and substituted by one to six of said groups.

3. A process according to claim 1 where the phosphinic acid compound is of the formula I and where R₂ is straight or branched chain Ci-C₅₀alkyl substituted by C₆-Ci₂aryl which is substituted by one to three straight or branched chain C₄-Ci₂alkyl or -OR groups; C6-Ci₂aryl substituted by one to three straight or branched chain C₄-Ci₂alkyl or

-OR groups; or R₂ is 3-0X0-1 ,3-dihydroisobenzofuran-1-yl which is unsubstituted or is substituted by one to three straight or branched chain d-C^alkyl, -OR or -COOR groups.

4. A process according to claim 1 where the phosphinic acid is of formula Il or III.

5. A process according to claim 1 where the phosphinic acid is of formula Il or III and R₃ and R₃' are

straight or branched chain Ci-C₅₀alkyl; straight or branched chain C₂-C₅oalkyl interrupted by one to three -0-, -NR-, -COO-, -OCO-, -CONR-, C₆-Ci₂arylene, C₅-Ci₈cycloalkylene or C₅-Ci₈cycloalkenylene groups; straight or branched chain Ci-C₅₀alkyl substituted by one to three -OR, -NRR', -COOR, -CONRR' or C₆-Ci₂aryl groups; straight or branched chain C₂-C₅₀alkyl both interrupted and substituted by one to six of said groups; where each of the aryl or arylene groups are unsubstituted or are substituted by one to three straight or branched chain Ci-Ci₂alkyl or -OR groups; or R₃ and R₃' are 3-oxo-1 ,3-dihydroisobenzofuran-1-yl which is unsubstituted or is substituted by one to three straight or branched chain Ci-Ci₂alkyl, -OR or -COOR groups.

6. A process according to any preceding claim wherein m is a number from 5 to 50;

R and R' are independently hydrogen or straight or branched chain Ci-C₄₀alkyl; R₂ is C₅-C₆cycloalkyl, straight or branched chain CrC₅oalkyl.

R₃ and R₃' are independently hydrogen, C₅-C₆cycloalkyl, phenyl, straight or branched chain d-Csoalkyl; R₄ is straight or branched chain Ci-C₅₀alkylene.

7. A process according to any preceding claim wherein the synthetic polymer is a polyolefin.

8. A process according to claim 7 wherein the polyolefin is polypropylene or polyethylene.

9. A process according to any preceding claim 1 wherein the inorganic filler is selected from the group consisting of calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.

10. A process according to claim 9 wherein the inorganic filler is a silicate, calcium carbonate, talc or an alkaline earth metal oxide or hydroxide.

11. A synthetic polymer composition obtainable in a process according to claim 1.

12. An article made from a synthetic polymer composition according to claim 1 1.

13. Use of a phosphinic or phosphonic acid based dispersing agent of formulae (I), (II), (III) or (IV) according to claim 1 for dispersing inorganic fillers in a synthetic polymer matrix by melt mixing at a temperature from 120° C to 290° C.