GB2306478A - Substituted biphosphines and 3-12 membered cyclic phosphines, process for their preparation and their use as stabilising additives in polymer compositions - Google Patents

Substituted biphosphines and 3-12 membered cyclic phosphines, process for their preparation and their use as stabilising additives in polymer compositions Download PDF

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GB2306478A
GB2306478A GB9619916A GB9619916A GB2306478A GB 2306478 A GB2306478 A GB 2306478A GB 9619916 A GB9619916 A GB 9619916A GB 9619916 A GB9619916 A GB 9619916A GB 2306478 A GB2306478 A GB 2306478A
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polymeric material
compounds
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Peter Staniek
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Clariant Finance BVI Ltd
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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
    • C08K5/50—Phosphorus bound to carbon only
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/504—Organo-phosphines containing a P-P bond
    • 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
    • C07F9/6568—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 atoms as the only ring hetero atoms
    • C07F9/65683—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 atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine

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  • General Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Description

2306478 case i-)3-b886 Phosphorus Compounds This invention relates to the
use of certain phosphorus-containing compounds that can act at low concentrations as stabilizers for polymeric materials against degradation caused by heat or mechanical stress. They are especially suitable for polyolefins which have been made with a H and higher generation catalyst (e.g. H to V generation catalysts).
According to the invention there is provided a new cyclic compound of the formula )P-RI alla) wherein n is 4 or 5 RI is -(4-phenyl)phenyl, -(2,4,4-trimethyl)-pentyl, menthyl, norbornyl, pinenyl, cyclo-pentyl, cyclooctyl or cyclododecyl According to the invention there is provided a process for preparing compounds of formulae II, Ill, and IIIIa W1 2 -p (H) Rel ) P-R'I)M (In) 2 Case 153-5886 P-RJ)n (Ifia) in which R, is as defined above each R', independently is selected from linear or branched C,-30alkyl, C,- 12Cycloalkyl, C2-2.alkenyl, C2A,alkoxyalkyl, C2-19alkanoyImethylene, C7- 30alkaryll C7-3.aralkyl, C124heteroaryl where any one of the above substituents of R', are unsubstituted or are substituted by 1 to 3 groups selected from C,A2alkyl, -OR4, -NR4R5, -COR4, -COOR4 and CO(NR4R,); and C6.30aryl, unsubstituted or substituted by 1 to 5 groups is selected from CM2alkyl, C,-8alkoxy, CS-6CYCloalkyl, phenyl or phenoxy, -OR4, -NR4R,. -COR41 -COOR4 and -CO(NR4R,) R4 and R, independently are selected from hydrogen, C,_,Mkyl (linear or branched), CS-12CYcloalkyl, C6-24aryl,C7-30alkaryl or C7.3Walkyl; m is 3 to 12, preferably 4-6; n is as defined above which comprises reacting either a secondary phosphine of the formula W, WIPH or a primary phosphine of the formula W,PH2 with a halogen, preferably chlorine or bromine, optionally in the presence of an acid acceptor, for example, an oxide, hydroxide, or carbonate of an alkali or alkaline earth metal or an amine, preferably a tertiary amine, optionally in the presence of an inert solvent. Secondary phosphines result in compounds of formula R. Primary phosphines result in compounds of formulae HI and Ma. Advantageously, this process uses as 3 Case 153-5886 starting materials alkyl phosphines which are in larger scales more readily available than the halophosphines that are used in the art.
According to the invention, there is provided a polymeric composition comprising:
a) at least one compound of formula H, M or Ma (these compounds hereinafter being called "component a") - p R11 2 (I1) R11 ) P-W,) m (In) > P-R 1).
(II[Ia) wherein R1q W,, m and n are as defined above and b) a polymeric material (hereinafter called "component W').
Component b) according to the invention include homopolymers, copolymers and polymer blends of..
4 Case 153-5886 Polyarnide; Polyamideimide; Polyacrylonitrile; Polybutene-1 and -2; Polybutylacrylate; Poly(butyleneterephthalate); Polycarbonate; Poylethylene; chlorinated Polyethylene; Poly(etherketone); Polyetherimide; Polyethyleneoxide; Polyethersulphone; Poly(ethyleneterephthalate); Polytetrafluoroethylene; Polyimide; Polyisobutylene; Polyisocyanurate; Polymethacrylimide; PolymethyImethacry late; Poly(4-methylpentene-1); Poly(wmethyl styrene); Polyoxy methylene; Polyformaldehyde; Polyacetal; Polypropylene; Polyphenylene ether; Polyphenylenesulphide; Polyphenylenesulphone; Polystyrene; Polysulphone; Polyurethane; Polyvinyl acetate; Polyvinyl alcohol; chlorinated Polyvinyl chloride; Polyvinylidene chloride; Polyvinylidene floride; Polyvinylfluoride; Silicon polymers; saturated polyester; unsaturated polyester; polyacrylate; polymethacrylate; polyacrylamide; epoxide resins and silicon resins.
Examples of suitable copolymers include:
Acry lonitrilelbutadienelacry late; Acrylonitrile.Ibutadienelstyrene; AcrylonitrilelmethyImethacrylate; Ethylenelpropylene; Ethylenelvinyl acetate; Ethylenelvinyl alcohol; Ethyleneltetrafluoroethylene; Tetrafluoroethylenelhexafiuoro-propylene; Methacrylatelbutadienelstyrene; Polyesterblockamide; Styrenelacrylonitrile; Styrenelbutadiene; Styrenelotmethylstyrene, Vinylchloridelethylene; Vinylchloridelethylenelmethacry late.
Preferred polymeric materials are polyolefins such as polypropylene; polyethylene (e.g. high density polyethylene, low density polyethylene, linear low density polyethylene or medium density polyethylene), polybutylene, poly-4-methylpentene and copolymers thereof as well as polycarbonate, polystyrene and polyurethane.
Preferably, said polyolefins have been produced in the presence of a Ziegler or metallocene type catalyst which has not been removed.
For the avoidance of doubt, compounds of fonnulae M and ffia are cyclic compounds.
Preferred compounds of formula II and M are of formula Hb or HIb Case 153-5886 p(R" 2 1)] 2 Mb) ) P-Rev I) M.
(Mb) in which each WI independently 'S CM2alkyl, C4-,2cycloalkyl, menthyl, adamantyl, pinenyl, norbornyl or C6A2aryl; and me is 4 or 5.
Another embodiment of the invention is a method for stabilizing polymeric material which comprises incorporating into a polymeric material to be stabilized a stabilizing amount of a compound of formulae E, M and Illa, before, during or after the polymerization step, in solid or molten form, in solution (preferably as a liquid concentrate) or as a solid masterbatch composition.
Another embodiment of the invention is a solid masterbatch comprising 10 to 80% by weight, preferably 40 to 70% by weight, more preferably 15 to 40% by weight, of a compound of formula II, HI or IDa and 90 to 20% by weight, preferably 60 to 30% by weight, more preferably 85 to 60% by weight, of a polymeric material which is identical to or compatible with the polymeric material to be stabilized.
Another embodiment of the invention is a liquid concentrate comprising 10 to 80% by weight of a compound of formula H, III or HIa and 90 to 20% by weight of a solvent.
6 Case 153-5886 The compounds of formulae H, Ill, and Ma may be made from known compounds by known methods. Reviews of such reaction procedures are given in e.g. G. M. Kosolapoff, Organic Phosphorus Compounds, Vol. 1-7, Wiley, New York, 1972 or Houben/Weyl, Methoden der Organischen Chemie, Vol. 12, 4. Auflage, Georg Thieme Verlag, Stuttgart 1963 and corresponding supplementary volumes. The contents of which are incorporated herein by reference.
Compounds of formula H and compounds of formula M are also prepared by a process which comprises reacting either a secondary phosphine of the formula W,W,PlI or a primary phosphine of the formula WPH2 with a halogen, preferably chlorine or bromine, optionally in the presence of an acid acceptor, for example, an oxide, hydroxide, or carbonate of an alkali or alkaline earth metal or an amine, preferably a tertiary amine, optionally in the presence of an inert solvent. Secondary phosphines result in compounds of formula H. Primary phosphines result in compounds of formula M or Ma. Advantageously, this process uses as starting materials alkyl phosphines which are in larger scales more readily available than the halophosphines that are used in the art.
Typically those compounds are prepared from organohalides such as alkylor aryl chlorides or alkyl or arylbromides and PC13 via a Grignard or modified Wurtz reaction; via Friedel-Crafts reaction; by addition of P-H containing compound to multiple bonds; by Arbuzov reaction of diorganophosphinites with organohalides and subsequent reductions; or by derivation from already formed phosphines.
Compounds of formulae H, HI and HIa of special interest are:
Tetra-tert-butyl-diphosphine Tetra-cyclohexyl-diphosphine, Penta-(4phenyl)phenyl-cyclopentaphosphine, Penta-(2,4,4-trimethyl-pentyl)cyclopentaphosphine Tetra-menthyl-cyclotetraphosphine 7 Tetra-norbomyl-cyclotetraphosphine Tetra-adamantyl-cyclotetraphosphine Tetra-pinenyl-cyclotetraphosphine Tetra-tert-butyl-cyclotetraphosphine Tetra-cyclopentyl-cyclotetraphosphine Tetra-cyclohexylcyclotetraphosphine Tetra-cyclooctyl-cyclotetraphosphine Tetracyclododecyl-cyclotetraphosphine Case 153-5886 The compounds of formulae M and ffia are cyclic compounds in which the P atoms form a ring with a pendant R, or W, group.
Preferably component a) is present in an amount of 0.005-5%, more preferably 0.01-1% based on the weight of the polymer present in the composition.
The term metallocene is used to describe new catalysts of generation V and higher which are used to produce polyolefins (especially polyethylenes and polypropylenes) as described for example in "Modem Plastics" 10191 p. 46-49 and in "Makromolekulare Chernie", 192, 1059 (1991). The supported Ziegler catalysts (such as those supported on a halogen containing magnesium compound) are well known and are described in Table 1 below.
Further additives which may be added to a polymeric composition according to the invention include antioxidants, such as sterically hindered phenols, secondary aromatic amines or thioethers, (as described in "Kunststoff-Additive" - Glichter/MUller, Ed. 3, 1990 p.42-50, the contents of which are incorporated herein by reference); acid scavengers such as sodium, magnesium and calcium stearates and lactates, zinc oxide, hydrotalcite or alkoxylated amines; U.V. stabilizers such as sterically hindered amines (for example N-unsubstituted, N-alkyl or N-acyl substituted 2,2,6,6-tetramethylpiperidine compounds) [also known as hindered amine light stabilizers - HALS] and U.V. absorbers (e.g. 2-(2'hydroxyphenyl)-benztriazoles, 2-bydroxybenzophenones, (2-hydroxyphenyl)triazines, 1,3-bis-(2'-hydroxy-benzoyl)benzene 8 Case 153-5886 salicylates, cinnamates and oxalic acid diamides), U.V. quenchers such as benzoates and substituted benzoates, antistatic agents, flameproofing agents, lubricants, plasticisers, nucleating agents, metal deactivators, biocides, impact modifiers, fillers, pigments and fungicides.
Component a) may be added to the polymeric material before, during or after the polymerization step and may be added in solid or molten form, in solution preferably as a liquid concentrate containing from 10 to 80 % by weight of the compounds of formula H, III or Ma and 90 to 20 % by weight of solvent or as a solid masterbatch composition containing 10 to 80 % (more preferably 40 to 70 %) by weight of the compounds of formula H, III or Ma and 90 to 20 % (more preferably 60 to 30 %) by weight of a solid polymeric material which is identical to or compatible with the material to be stabilized.
Component a) may be incorporated by known methods into the polymeric material to be stabilized. Of particular importance is dry-blending of component a) with the polymer or coating shaped polymer particles, e.g. polymer spheres, or in the form of a liquid, a solution or a suspension/dispersion. Of particular importance is blending of the compounds with thermoplastic polymers in the melt, for example in a melt blender or during the formation of shaped articles, including films, tubes, fibres and foams by extrusion, injection moulding, blow moulding, spinning or wire coating. Component a) is particularly useful for stabilizing polypropylene and polyethylene articles of every type as well as polycarbonate, polystyrene and polyurethane and other polymeric materials, including laquers and powder coatings.
Component a) is especially suitable for use in polyolefins and especially (x-polyolefins prepared using processing catalysts known as Generation H to Generation V catalysts and which have not been subjected to a catalyst removal step. By the term "catalyst removal step" used herein is meant a step for the purpose of positively removing the catalyst residues contained in the polymerized polyolefins or treating the polyolefins with the compound which can react with the catalyst residue and inactivate or solubilize the residue, such as alcohols or water, and then removing the inactivated or solubilized catalyst residue by physical means 9 Case 153-5886 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 is meant by Generation 1 catalysts is titanium halide catalysts and an organo aluminium compound or an organo, aluminium halide.
What is meant by Generation H catalysts is Generation 1 catalysts supported on an organo magnesium compound or based on an organo chromium compound supported on S'02.
What is meant by a Generation IIII catalyst is a Ziegler type complex catalyst supported on a halogen containing magnesium compound.
What is meant by a Generation IV catalyst is a Generation HI catalyst with a silane donor.
What is meant 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-(x-olefins, which are presently under development, are included in the concept of II and higher Generation catalysts, as well as the abovementioned generations of supported catalyst systems.
Case 153-5886 Examples for the microstructure of such highly stereoregular polyolefins are given by syndiotactic polypropylene, isotactic stereoblock polymers, isotactic polypropylene containing stearic defects randomly distributed along the polymer chain (so called anisotactic polypropylene) or stereoirregular 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 is increasing. However, residues of such further catalyst generations, as long as they contain metals of the 3d. 4d and 5d series of the periodic system supported analogously to the earlier catalyst generations, can also cause disadvantageous properties in the polymer, as long as such residues are still present in the polymer even if in a deactivated form. In view to this, it can therefore be expected that component a) according to the invention is 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 is most effectively inhibited.
These generations of catalysts are described in the publication of the Twelfth Annual International Conference on Advances in the Stabilization and Controlled Degradation of Polymers held in Luzem, Switzerland, 21-23 May 1990 in an article on pages 181 to 196 inclusive by Rolf Millhaupt 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:
1 11 TABLE I Polyolefin Catalyst Evolution Case 153-5886 Generation Example Cat.Act. % Act.Ti Stereoreg. Process (g PP/g (% insol. in Technology Ti h aim) heptane) I TiCI4/AIR3 40 0.01 45% removal of catalyst residues and atactic PP TiCIAlEt2C1 30 0.1 92% removal of catalyst residues II Mg(OR2)/TiCI,,l 40000 --- 50% no removal AIR3 of catalyst residues Si02/Cp2Cr 40000 HDPE (mainly HDPE/ LLDPE) ill Mod.MC13cat. 5000 1 95% no MgClyMC1.1AIR3 20000 10 92% purification + ester donor IV MgC12/TW14/AIR3 40000 18 99% no + silane donor purification no extrusion v Bis-indenyl-Tilk, 40000 100 99% novel PPs, on (AICH30). narrow M" R is an organo group; HDPE is high density polyethylene, LLDPE is linear low density polyethyene, Cp is cyclopentadienyi, Et is ethyl, PP is polypropylene and MWD is molecular weight distribution and x is an integer above 2 (preferably 2-100).
Further, in this specification, where a range is given, the figures defining the range are included therein. Any group capable of being linear or branched is linear or branched unless indicated to the contrary.
For the avoidance of doubt, in this specification t-butyl means tertiary butyl, (-C(CHI).
12 Case 153-5886 The invention will now be illustrated by the following Examples.
Example 1
Synthesis of Penta-biphenylyl-cyclopentaphosphine 1 1.1 51 1 Under nitrogen 25.5 g biphenyl-dichlorophosphine (isomeric mixture from the Friedel-Crafts reaction of biphenyl and phosphorus trichloride, >90% 4-biphenyl-dichlorophosphine) are dissolved in 100 mL tetrahydrofurane (THF) and 2.4 g magnesium turnings are added with ice cooling. After 30 min the ice bath is removed and the reactants stirred 20 h at ambient temperature. 60 mL acetone are added and the yellowish precipitate is filtered off. The crude product is agitated with 100 mL 0.5 molar hydrochloric acid to remove magnesium residuals, filtered, washed with water and acetone and dried.
Yield 50 %, mp.: 227-2290 C, &("P)= 14.1 ppin and 17.5 ppm 13 Case 153-5886 Example 2
Synthesis of Penta-(2,4,4-trimethyl-pentyl)-cyclopentaphosphine ((TW-P),) p p P-P Under nitrogen and ice cooling, 32.0 g bromine are added to a mixture of 74.1g tributylamine and 58.5 g of a 50 wt% solution of 2,4,4-trimethyl- pentylphosphine in toluene. Then the mixture is heated to reflux for a short time. After addition of 50 mL water, the phases are separated and the aqueous layer extracted two times with 10 mL toluene. The combined organic phases are dried over sodium sulfate and the solvent is stripped off in vacuo. The brownish crude product is distilled in a Kugelrohr apparatus at 2STC/0.05 mm Hg.
Yield: 75 % colorless viscous liquid, 8("P)= -5 to + 30 ppm, complex multiplett ((TMP-P),); -67.5 ppm (2 Peaks, (TW-P)4 ca. 2 %) Comparative Example A Application of substances of the Examples 1 and 2 as processing stabilizers in a mixture consisting of:
parts 3rd generation polypropylene homopolymer 14 Case 153-5886 0.05 part Tetrakis(methylen-3(3',5'-di-tert-butyl-4'hydroxyphenyl)propionate)methane 0.01 part Calcium stearate and 0.04 or 0. 07 part of a compound of formula Ifia or of a comparative substance (Sandostab P-WQ of Clariant International Ltd., formerly Sandoz Ltd.), are dry blended and homogenized by extrusion in a single screw extruder at 210' C. The resulting pellets are extruded five times in a Gijttfert single screw extruder (d= 20 mm, I1d= 20, 50 min-', compression L3) at 27TC and the melt flow index (MFI, ASTM D-1238-70) as well as the Yellowness Index (ASTM D-1925-70) are determined after the first, third, and fifth extrusion passage. The data.obtained are summarized in the following table.
Substance Parts Melt Flow Index of Example No. Stabilizer [m!llO min] Yellowness Index extrusion passage extrusion passage 1. 3. 5. 1. 3. 5.
Sandostab P-EIQ 0.04 2.45 4.13 6.31 0.3 1.1 2.1 0.07 1.91 2.57 3.75 -0.1 0.8 1.5 1 0.04 2.01 2.85 3.65 1.1 1.5 1.9 0.07 1.94 2.87 3.65 0.9 0.8 0.9 2 0.04 2.46 3.18 3.81 1.3 1.5 1.9 Case 153-5886 Example 3
Synthesis of Tetra-cyclohexyl-cyclotetraphosphine 01 p j r Under nitrogen and ice cooling, 6.4 g bromine are added to a mixture of 5. 5 g anhydrous potassium carbonate and 4.65 g cyclohexylphosphine in 15 mL toluene. Then the mixture is heated to reflux for a short time. After addition of 10 mL water the solid is filtered off and washed two times with 5 mL methanol and dried in vacuo. Yield: 43 % colorless crystals. mp. 227-2300C, 8("P)-- -67.1 ppm.
Example 4
Synthesis of Tetra-cyclohexyl-biphosphine Q p P-'o d 16 Case 153-5886 Under nitrogen and ice cooling, 3.2 g bron-fine are added to 7.9 g dicyclohexylphosphine in 10 mI, triethylamine and 10 mL toluene. Then the mixture is heated to reflux for 15 min., 10 mL water are added, and the solid is filtered off and washed two times with 5 mL methanol and dried in vactio. Yield: 36 % colorless crystals, mp.: 168-170 C 17 Case 153-5886

Claims (10)

1. A compound of the formula HIa )P-Rdn (IHa) wherein n is 4 or 5; R, is -(4-phenyl)phenyl or -(2,4,4-trimethyl)-pentyl, menthyl, norbornyl, pinenyl, cyclopentyl, cyclooctyl or cyclododecyl
2. A process for preparing compounds of formula H, compounds of formula M and compounds of formula Ma p L \WI /R, (H) 2 ) P-R'I)n, (I11) ) P-RI)n (I111a) 18 Case 153-5886 in which R, is as defined above each R', independently is selected from linear or branched Cl-30alkyl, CS- 12CYCloalkyl, C2-24alkenyl, C2-,,alkoxyalkyl,C2-lgalkanoylmethylene, C7-3. alkaryl, C7-30aralkyl, C4-24heteroaryl where any one of the above substituents of R', are unsubstituted or are substituted by 1 to 3 groups selected fromC,-,2alkyl, -OR41 -NR4Rs, -COR41 -COOR, and CO(NR4R,); and C6.30aryl, unsubstituted or substituted by 1 to 5 groups R3 selected fromC,-12alkyl, C,-.alkoxy, C,-,cycloalkyl, phenyl or phenoxy, -OR4, - NR4R,, -COR4, -COOR4 and CO(NIZ4R5); R4 and R, independently are selected from hydrogen, Cl-3.alkyl (linear or branched), C5-12CYCloalkyl, C6.24aryl,C7.30alkary] orC7-30aralkyl; m is 3 to 12, preferably 4-6; n is as defined above which comprises reacting either a secondary phosphine of the formula W,W, PlI or a primary phosphine of the formula W,PH2 with a halogen, preferably chlorine or bromine, optionally in the presence of an acid acceptor, for example, an oxide, hydroxide, or carbonate of an alkali or alkaline earth metal or an amine, preferably a tertiary amine, optionally in the presence of an inert solvent.
3. A polymeric composition comprising a) at least one compound of formula H, Ifi or Ifia (these compounds hereinafter being called "component a") 19 Case 153-5886 --p _i 2 Rll \WI (H) ) P-R'I)m (III) ) P-R,), (II1a) wherein R,, R,, m and n are as defined above and b) a polymeric material (hereinafter called "component V).
4. A composition according to claim 3 in which component a) is present in an amount of 0.005-5%, based on the weight of polymer present in the composition.
5. A composition according to claim 3 in which component a) is present in an amount of 0.0 1 - 1 % based on the weight of the polymer present in the composition.
Case 153-5886
6. A composition according to claim 3 in which the polymeric material is selected from polyolefins, polyesters, polyamide, polystyrene, polyurethanes, polyacrylates, polymethacrylates, epoxide resins, silicon polymers, including copolymers and blends thereof
7. A composition according to claim 3 in which the polymeric material is a polyolefin which has been produced in the presence of a supported Ziegler catalyst or a metallocene catalyst which has not been removed.
8. A composition according to claim 3 which further comprises additives selected from the group consisting of antioxidants, acid scavengers, hydrotalcite or alkoxylated amines; U.V. stabilizers and U.V. absorbers, U.V. quenchers, antistatic agents, flameproofing agents, lubricants, plasticisers, nucleating agents, metal deactivators, biocides, impact modifiers, fillers, pigments and fungicides.
9. A solid masterbatch composition comprising 10 to 80 % by weight of a compound of formula H, Ill or Ma and 90 to 20 % by weight of a polymeric material which is identical to or compatible with the polymeric material to be stabilized.
10. A method for enhancing the stability of a polymeric material against degradation caused by beat or mechanical stress comprising incorporating into the polymeric material a stabilizing quantity of a compound of formula H, HI or ffia in solid or molten form, in solution or as a solid masterbatch composition.
GB9619916A 1995-09-28 1996-09-24 Phosphorus compounds Expired - Fee Related GB2306478B (en)

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US7067569B2 (en) 2000-07-14 2006-06-27 Clariant Finance (Bvi) Limited Mixtures of phosphorus-containing compounds used as polymer stabilizers
US8519035B2 (en) 2007-09-04 2013-08-27 Basf Se Cyclic phosphines as flame retardants
US10414985B2 (en) 2014-03-27 2019-09-17 Basf Se Heptaphosphorus-derived compounds as flame retardants

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US7083743B2 (en) 1999-12-20 2006-08-01 Clariant Finance (Bvi) Limited Mixture of phosphanes and chromane derivatives
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JP4599169B2 (en) * 2002-12-04 2010-12-15 チバ ホールディング インコーポレーテッド Process for the synthesis of cycloorganylphosphane and di (alkali metal / alkaline earth metal) oligophosphanedides
DE102004000058A1 (en) * 2004-12-01 2006-06-08 Kuraray Specialities Europe Gmbh Organophosphine-stabilized polymer blends
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US7067569B2 (en) 2000-07-14 2006-06-27 Clariant Finance (Bvi) Limited Mixtures of phosphorus-containing compounds used as polymer stabilizers
US8519035B2 (en) 2007-09-04 2013-08-27 Basf Se Cyclic phosphines as flame retardants
US10414985B2 (en) 2014-03-27 2019-09-17 Basf Se Heptaphosphorus-derived compounds as flame retardants

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ITRM960662A1 (en) 1998-03-27
JPH09124672A (en) 1997-05-13
FR2739381B1 (en) 1999-06-11
DE19638924A1 (en) 1997-04-03
IT1285791B1 (en) 1998-06-24
ES2152760A1 (en) 2001-02-01
GB9619916D0 (en) 1996-11-06
ES2152760B1 (en) 2001-11-01
FR2739381A1 (en) 1997-04-04
CH691059A5 (en) 2001-04-12
GB2306478B (en) 1998-12-09

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