(19) TZZ ¥__T (11) EP 2 536 781 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C08K 5/51 (2006.01) 04.04.2018 Bulletin 2018/14 (86) International application number: (21) Application number: 10846288.8 PCT/US2010/053207 (22) Date of filing: 19.10.2010 (87) International publication number: WO 2011/102861 (25.08.2011 Gazette 2011/34) (54) ALKYLPHENOL FREE - LIQUID POLYMERIC PHOSPHITE POLYMER STABILIZERS POLYMERSTABILISATOREN AUF DER BASIS VON ALKYLPHENOLFREIEN FLÜSSIGEN POLYMERPHOSPHITEN STABILISANTS DE POLYMÈRES À BASE DE PHOSPITE POLYMÈRE LIQUIDE SANS ALKYLPHÉNOLS (84) Designated Contracting States: • LANCE, Jacob, M. AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Dover, Ohio 44622 (US) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • STEVENSON, Donald PL PT RO RS SE SI SK SM TR Dover, Ohio 44622 (US) (30) Priority: 19.02.2010 US 306014 P (74) Representative: Abel & Imray Westpoint Building (43) Date of publication of application: James Street West 26.12.2012 Bulletin 2012/52 Bath BA1 2DA (GB) (73) Proprietor: Dover Chemical Corporation (56) References cited: Dover, Ohio 44622-9771 (US) WO-A1-99/48997 DD-A1- 229 995 US-A- 3 133 043 US-A- 3 359 348 (72) Inventors: US-A- 3 855 360 US-A- 5 969 015 • JAKUPCA, Michael US-A1- 2004 183 054 US-A1- 2008 071 016 Canton, Ohio 44709 (US) US-B2- 6 770 693 US-B2- 7 199 170 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 536 781 B1 Printed by Jouve, 75001 PARIS (FR) EP 2 536 781 B1 Description Technical Field 5 [0001] The invention described herein pertains generally to an improved polymer composition which contains at least one liquid polymeric phosphite additive which is selected from the group of all alkyl polymeric phosphites as antioxidant additives and a method for the preparation thereof. Background of the Invention 10 [0002] At least one purpose associated with the addition of a stabilizer to a polymeric resin is to prevent deterioration of the polymers derived from the resin during processing at high temperatures and also to permit the manufacture of products with increased intrinsic quality attributable at least in part to increased resistance to thermal and light degradatio n during their intended use. 15 [0003] Many organic phosphites have been used as stabilizers, and most are based on alkylphenols. Among them are the commercially significant phosphites, tris (nonylphenyl) phosphite (TNPP) and tris (2, 4-di-t-butylphenyl) phosphite. Historically, TNPP has been the primary low cost liquid phosphite stabilizer used in the plastic and rubber industry. Recently, however, plastic and rubber manufactures have been reluctant to use TNPP in their formulation due to concerns that one of the degradation product of TNPP (nonylphenol) may be xenoestrogen. 20 [0004] U.S. Patents 6,541,549 B2 and U.S. 7,199,170 B2 disclose phosphite compounds having a general Structure I as non-xenoestrogenic stabilizers for polymers, although they are still based on an alkylphenol. 25 30 35 [0005] U.S. Patent No. 7,186,853 B2 discloses phosphites comprising substituted or unsubstituted tricyclodecylmethyl 40 groups. The phosphites disclosed also comprise certain alcohols which can be aliphatic, arylalkyl and alkylaryl. [0006] U.S. Patent No. 7,468,410 B2 and WO 07 009,916 disclose tris-(mono-alkyl)phenyl phosphites or a mixture of the general Structure II where each R is the same or different alkyl group having 1 to 8 carbon atoms. Again this is a low molecular weight monophosphite still based on an alkylphenol. [0007] The problem with the mono phosphites or lower molecular weight phosphites described in the mentioned patents 45 are that, the phosphites are still based on an alkylphenol of some type and lower molecular weight phosphites can be extracted easily from the polymer. Alkylphenols are of concern as potential skin irritants or having xenoestrogenic activity. Being easily extracted from a polymer means the phosphite or its degradation products can easily migrate into foods that come into contact with polymer that maybe stabilized with the lower molecular weight or mono phosphites. 50 55 2 EP 2 536 781 B1 5 10 15 [0008] WO 08 028,858 discloses liquid polymeric phosphites of the general structure III wherein L is a linkage between the repeated unit n, comprising C1-C24 alkylene, C2-C24 alkenylene, and oxygen, sulfur or substituted nitrogen (N-R) interrupted C2-C24 alkenylene. The integer m is 0 and 1. 20 25 30 A disadvantage of the polymeric phosphites of this disclosure is that all the polymeric phosphites are based on an 35 alkylphenol of some type. It is preferable to have a polymeric phosphite that does not contain an alkylphenol. Summary of the Invention [0009] The present invention is defined in claims 1-12 as attached. 40 [0010] Herein are described liquid polymeric phosphites of the general Structure IV as stabilizers for polymers during processing. 45 50 wherein 1 2 3 4 each R , R , R and R can be the same or different and independently selected from the group consisting of C 1-20 55 alkyl, C3-22 alkenyl, C 6-40 cycloalkyl, C 7-40 cycloalkylene, C 1-20 methoxy alkyl glycol ethers, C 1-20 alkyl glycol ethers, and or Y-OH (serving as an end capping moiety) Y is selected from the group consisting of C 2-40 alkylene, C 2-40 alkyl lactone, (e.g., ethylene, propylene, caprylactone), 3 EP 2 536 781 B1 7 8 9 -R -N(R )-R - (e.g., C2-40 alkyl diamines and C2-40 alkyl triamines), wherein R7, R8 and R9 are independently selected from the group previously defined for R1, R2, R3 and R4, now further including H; 5 m is an integral value ranging from 2 to 100 inclusive; and x is an integral value ranging from 1 to 1,000. [0011] Depending on reaction conditions and components, it is also possible to synthesize Structure V: 10 15 wherein 20 each R1, R2, R3 and R4 are as defined previously; Y is as defined previously; and m is as defined previously. 25 [0012] The polymeric phosphites of the general Structures IV or V are suitable for stabilization of organic materials against oxidative, thermal or actinic degradation. [0013] The most preferred polymeric diphosphites or polymeric phosphites are the ones that do not have or contain aromatic groups or alkylphenol groups. 30 [0014] The advantages of the liquid high molecule weight dimeric and the polymeric phosphites are very low volatility, no migration out of the polymer being stabilized, very difficult to extract from the polymer being stabilized. These advan- tages can translate into no plate out during polymer extrusion (no die lip build up) and no migration into food from polymers that are used in food packaging. It is extremely advantageous to have a liquid polymeric phosphite that has excellent hydrolytic stability and one that is not based on alkylphenols. 35 Detailed Description of the Invention [0015] As used herein, and unless otherwise stated, the term "alkyl" means straight and branched chain saturated acyclic hydrocarbon monovalent groups; said alkyl group may further optionally include one or more suitable substituents 40 independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like. Specific non-limiting examples of straight-chain or branched alkyl groups are C1-20 alkyls, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and stearyl groups. It is recognized that the alkyl may be interrupted with oxygen, sulfur or nitrogen, examples for which include: CH3-O-CH2CH2-, CH3-S-CH2CH2-, CH3-N(CH3)-CH2CH2-, CH3-O-CH2CH2-O-CH2CH2-, CH3-(O- 45 CH2CH2-)2O-CH2CH2-, CH3-(O-CH2CH2-)3O-CH2CH2- or CH3-(O-CH2CH2-)4O-CH2CH2-. [0016] As used herein, and unless otherwise stated, the term "alkenyl" means straight and branched chain unsaturated acyclic hydrocarbon monovalent groups; said alkenyl group may further optionally include one or more suitable substit- uents independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like. Specific non-limiting examples of the straight-chain or branched alkenyl groups are those having 2 to 30 carbon 50 atoms wherein the position of the double bond may vary, such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, and octadecenyl groups. It is once again, recognized that the alkenyl may be interrupted with oxygen, sulfur or nitrogen, examples for which include: -CH2-O-CH2-, -CH2-S-CH2-, -CH2-N(CH3)-CH2-, CH2-O-CH2CH2-, -CH2CH2-O-CH2CH2-, -CH2CH2-O- CH2CH2-O-CH2CH2-, -CH2CH2-(O-CH2CH2-)2O-CH2CH2-, -CH2CH2-(O-CH2CH2-)3O-CH2CH2-, -CH2CH2-(O- 55 CH2CH2-)4O-CH2CH2-, -CH2CH2-S-CH2CH2- or -CH2CH2-N(CH3)-CH2CH2-. [0017] As used herein, and unless otherwise stated, the terms "cycloaliphatic" refer to a mono- or polycyclic saturated hydrocarbon monovalent group having from 3 to 10 carbon atoms, or a C 7-10polycyclic saturated hydrocarbonmonovalent group having from 7 to 10 carbon atoms. Specific non-limiting examples of the cycloaliphatic or cyclic alkyl groups which 4 EP 2 536 781 B1 may have substituents are cycloalkyl groups having 5 to 7 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl groups, and the alkylcycloalkyl groups having 6 to 11 carbon atoms wherein the position of the alkyl group may vary, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimeth- ylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylcycloheptyl, and 5 diethylcycloheptyl groups.