Title of Invention

A COMPOSITION

Abstract This invention discloses blends of phosphites comprising bis-(2,4-dicumylphenyl) pentaerythritol diphosphite and hindered phenol antioxidants useful as .stabilizers against thermooxidative degradation of polymers during melt processing. Polymer compositions comprising the blends show improved resistance to thermooxidative degradation during melt processing as measured by melt flow index and yellowness index.
Full Text

Blends of Phosphates and Antioxidants Technical Field
This invention pertains generally to synergistic blends of phosphates and hindered phenols with or without other additives as stabilizers for polymers. Background of the Invention
The invention described herein pertains generally to synergistic blends of certain phosphates and hindered phenols as stabilizers for polymers. These blends may be used with other polymer additives.
Various prior art references teach the incorporation of additives into organic polymeric materials. These additives can include polymer stabilizers such as antioxidants, UV absorbers and light stabilizers, metal deactivators, peroxide scavengers, basic co-stabilizers, lactones, nucleating agents, fillers and reinforcing agents, amino propionate derivatives, politicizes, lubricants, emulsifiers, pigments and dyes, optical brighteners, flame-proofing agents, antistatic agents, blowing agents, cross-linking agents, ant blocking agents, slip agents, processing aids, and thiosynergists.
In particular, certain phosphites have been used in combination with hindered phenols as additives in polymers for stabilization against thermooxidative deterioration. What is illustrated in this invention are novel blends of phosphites and hindered phenols useful as polymer additives. The novel blends of phosphites and hindered phenols of this invention show superior performance in stabilizing polymers against thermooxidative deterioration as compared with prior art phosphite/ hindered phenol blends. Summary of the Invention
In accordance with the present invention, there is provided a composition useful as a polymer additive comprising a blend of bias-{2,4-dicumylphenyl) pentaerythritol diphosphite, optionally, one or more additional phosphites, and one or more hindered phenols. As compared with prior art phosphite/hindered phenol blends, the blends of this invention show unexpectedly superior performance in stabilizing polymers against thermooxidative deterioration during processing as indicated by melt flow index.

It is therefore an object of this invention to provide blends of phosphites and hindered phenols comprising bus-(2,4-dicumylphenyl) pentaerythritol diphosphite, said blends being useful, when added to polymers, as stabilizers against thermooxidative degradation during processing of a polymer composition comprising the polymer and the blend.
In general, the present invention provides a composition which comprises bis-{2,4-dicumylphenyl) pentaerythritol diphosphite, optionally, at least one additional phosphite; and at least one hindered phenol antioxididant.
This and other objects of this invention will be evident when viewed in light of the drawings, detailed description, and appended claims. Detailed Description of the Invention
It has been discovered that blends of bus-{2,4-dicumylphenyl) pentaerythritol diphosphite (DOVERPHOS S-9228), optionally at least one additional phosphite, and at least one hindered phenol antioxidant provide better protection against polymer degradation during processing as evidenced by changes in melt flow and may provide better resistance to yellowing than do the current commercially available additive blends.
A non-limiting list of exemplary additional phosphites that may be used in this invention would include tries-(2,4-di-t-butylphenyl) phosphite (DOVERPHOS S-480), distearyl pentaerythritol diphosphite (DOVERPHOS S-680), trisnonylphenyl phosphite (DOVERPHOS 4), phenyl disobey phosphite (DOVERPHOS 7), biphenyl isodecyl phosphite (DOVERPHOS 8), trephine phosphite (DOVERPHOS 10), treasury phosphite (DOVERPHOS 53), alkyl (C12-C15) biphenyl A phosphite (DOVERPHOS 613). alkyl (C10) biphenyl A phosphite (DOVERPHOS 675), bias-(2,4-di-t-butylphenyl) pentaerythritol diphosphite (ULTRANOX 626), 2-butyl-2-ethyl-1,3-propanediol 2,4,6-tri-t-butylphenol phosphite (ULTRANOX 641), bis-(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (PEP 36), testacies-(2,4-di-t-butylphenyl) 4,4'-diphenylenediphosphonite (P-EPQ), 2,2'-ethylidene bias-(4,6-di-t-butylphenyl)fluorophosphonite (ETHANOX 398), bis-(2,4-di-t-butyl-6-methylphenyl) ethyl phosphite (IRGAFOS 38) and 2,2',2"-nitrilotriethanol trigs[3,3',5,5'-tetra-tert-butyl-1,r-biphenyl-2,2'-diyl)-phosphite(IRGAFOS12).

Preferred additional phosphites that may be used in conjunction with bis-(2,4-dicumylphenyl) pentaerythritol diphosphite are terraces-(2,4-di-t-butylph6nyl) 4,4'-diphenylenediphosphonite (P-EPQ) and tries-{2,4-di-t-butylphenyl) phosphite (DOVERPHOS S-480).
A non-limiting exemplary list of hindered phenol antioxidants that may be used in this invention would include 2,6-di-t-butyl-4-methylphenol (BHT), 2,6-di-t-butyl-4-ethylphenol, tetra is [ethylene (3,5-di-t-butyl-4-hydroxhydrocinnamate)] methane (DOVERNOX 10), octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate (DOVERNOX 76), tries (3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H, 3H, 5H)-trine (DOVERNOX 3114), and a- tocopherol (Vitamin E).
Preferred hindered phenolic antioxidants are BHT, tetrakis [ethylene (3,5-di-t-butyl-4-hydroxhydrocinnamate)] methane, octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate, tris (3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-tnazine-2,4,6(1H, 3H, 5H)-trione, and Vitamin E.
For blends of phosphites and hindered phenol antioxidants, the hindered phenol antioxidant is added in a synergistic amount, and the weight ratio of phosphite: hindered phenol antioxidant may be between about 100:1 to about 1:100. A preferred range is from about 20:1 to about 1:10. Two or more phosphites and two or more hindered phenol antioxidants may be blended together in order to make the phosphite/hindered phenol antioxidant blend.
For blends comprising bis-(2,4-dicumyiphenyl) pentaerythritol diphosphite, additional phosphites, and hindered phenol antioxidants, the weight ratio of bis-{2,4-dicumylphenyl) pentaerythritol diphosphite to additional phosphites may be any ratio between about 10:1 to about 1 ;10. A preferred range is from about 4:1 to about 1:4. Blends of phosphites and more than one hindered phenol may be used. For example, BHT and tetrakis [ethylene (3,5-di-t-butyM-hydroxhydrocinnamate)] methane may be used in a weight ratio of about 1:1. Other examples of such mixtures are possible, and the weight ratio may be between about 10:1 and about 1:10.

Preferred phosphite/hindered phenol antioxidant blends are blends of bis-(2,4-dicumy I phenyl) pentaerythritol diphosphite with tetrakis [ethylene (3,5-di-t-butyl-4-hydroxhydrocinnamate)] methane.
A non-limiting exemplary list of the polymers in which the blends may be used would include polyolefins, PET, PBT, polystyrene, polyacrylics, polycarbonates, PVC, EPDM, SAN, PPO, SBR, ABS, and nylons. The phosphite/hindered phenol antioxidant blend may be used in any concentration from about 10 ppm to about 10,000 ppm based on the total weight of the polymer and the additives, and the blends may be compounded into the polymers by methods known in the art.
Examples
The best mode for carrying out the invention will now be described for the purposes of illustrating the best mode known to the applicant at the time. The examples are illustrative only and not meant to limit the invention, as measured by the scope and spirit of the claims.
Example 1
This example compares blends of bis-(2,4-dlcumylphenyl) pentaerythritol diphosphite with a hindered phenol antioxidant.
The blend comprised bis-(2,4-dicumylphenyl)pentaerythritol diphosphite.


and a hindered phenol antioxidant. The Ingredients were thoroughly mixed to form the desired well-mixed blend.
The hindered phenol used was tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane:

tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane
The following blends were prepared: Blend 1,
bis-(2,4-dicumylphenyl)pentaerythritol diphosphite (2 parts) tetrakis [methylene {3,5-di-t-butyl-4-hydroxyhydrocjnnamate)] methane (1 part) Blend 2,
bis-{2,4-dicumylphenyl)pentaerythritol diphosphite (1 part) tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane (1 part)

These blends were then added to Prefix 6501 polypropylene at 1000 ppm along with 500 ppm of calcium separate and mixed to form a well-mixed polymer composition. The polymer composition was then subjected to multiple pass extrusion at 280 "C and 60 rpm using a Bartender PL 2000 single screw laboratory extruder. The melt flow (ASTM 1238) was measured after the first and fifth passes with a Tina’s Olsen extrusion lactometer. For comparison, two commercially available blends were also each mixed with polypropylene at 1000 ppm along with 500 ppm of calcium steerages, and the resulting polymer compositions were subjected to multiple pass extrusion at 280 C and 60 rpm.
The commercially available blends were Iran B 215 FF, a 2:1 blend of tris-(2,4-di-t-butylphenyl) phosphite and tetrakis[methylene (3,5-di-t-butyl-4-hydroxhydrocinnamate)] methane, and Oreganos B 225 FF, a 1:1 blend of tris-(2,4-di-t-butylphenyl) phosphite and tetrakis[methylene (3,5-di-t-butyl-4-hydroxhydrocinnamate)] methane. The results are given in Table 1.

As can be seen in Table 1, both blend 1 and blend 2 provide a lower initial and final melt flow than do either of the commercially available blends. An increase in melt flow is indicative of polymer degradation. Therefore, blends 1 and 2 provide better protection against degradation that do the commercial blends.

Example 2
This example compares blends of bis-(2,4-dicumylphenyl) pentaerythritol diphosphite, a hindered phenol antioxidant, and a lactones with other blends. The following blends were prepared:
Blend 3
40 wt% bis-(2,4-dicumylphenyl) pentaerythritol diphosphite
50 wt% tetrakisfmethylene (3,5-di-t-butyl-4-hydroxhydrocinnamate)] methane
10 wt% 5,7-di-t-butyl-3-phenylbenzofuran-2-one
Blend 4
40 wt% bis-(2,4-di-t-butylphenyl) pentaerythritol diphosphite
50 wt% tetrakisfmethylene (3,5-di-t-butyl-4-hydroxhydrocinnamate)] methane
10 wt% 5,7-di-t-butyl-3-phenylbenzofuran-2-one
Blend 5
40 wt% tris (2,4-di-t-butylphenyl) phosphite
50 wt% tetrakisfmethylene (3,5-di-t-butyl-4-hydroxhydrocinnamate)] methane
10 wt% 5,7-di-t-butyl-3-phenylbenzofuran-2-one
Blends 3, 4, and 5 were processed following the procedure of Example 1. The results are shown in Table 2.


The results of Table 2 indicate superior 5-pass melt flow stability of Blend 3, which comprises bis-{2,4-dicumylphenyl) pentaerythritol diphosphite, as compared with the other blends.
Discussion
While the present invention has been directed to just a few stabilized polymer compositions which are primarily polyolefins, there is no need to limit it to such. In fact, any of the polymers known in the art, such as polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyamides, polyphenylene ethers, styrene polymers, polycarbonates, acrylic polymers, polyamides, placental, halide containing polymers and polyolefin photopolymers and copolymers. Additionally included would be mixtures of different polymers, such as polyphenylene ether/styrene resin blends, polyvinyl chloride/ABS or other impact modified polymers, methacrylonitrile containing ABS, and polyester/ABS or polyester plus some other impact modifier may also be used. Such polymers are available commercially or may be made by means well known in the art. However, the phosphite/hindered phenol antioxidant blends of the present invention are particularly useful in thermoplastic polymers, such as polyolefins, polycarbonates, polyesters, polyphenylene ethers and styrene polymers, due to the extreme temperatures at which the thermoplastic polymers are often processed and/or used.

Polymers of monoolefins and deletions, for example would include polypropylene, polyisobutylene, polybutene-1, polymethylpentene-l, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or Norborne, polyethylene (which optionally can be cross linked), for example high density polyethylene (HOPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) may be used. Mixtures of these polymers, for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE), may also be used. Also useful are copolymers of monoolefins and deletions with each other or with other vinyl monomers, such as, for example, ethylene/propylene, LLDPE and its mixtures with LDPE, propylene/butene-1, ethylene/hexane, ethylene/ethyipentene, ethylene/heptanes, ethylene/octane, propylene/butadiene, isobutylene/isoprene, ethylene/alkyd acridities, ethylene/alky! methacrylates, ethylene/vinyl acetate (EVA) or ethylene/acrylic acid copolymers (EAA) and their salts (monomers) and terpolymers of ethylene with propylene and a dynes, such as headpiece, dicyclopentadiene or ethylidene-norbornene; as well as mixtures of such copolymers and their mixtures with polymers mentioned above, for example polypropylene/ethylene-propylene copolymers, LDPE/EVA, LDPE/EAA, LLDPE/EVA and LLDPE/EAA.
Thermoplastic polymers may also include styrene polymers, such as polystyrene, poly-(p-methyl styrene), poly-(a-methyl styrene), copolymers of styrene or a-methyl styrene with dynes or acrylic derivatives, such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/malefic anhydride, styrene/butadiene/ethyl acryl ate, styrene/acrylonitrile/methacrylate; mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example, styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylenes/styrene or styrene/ethylene/propylene/styrene. Styrene polymers may additionally or alternatively include graft copolymers of styrene or a-methyl styrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitriie; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene and malefic anhydride or

multimode on polybutadiene; styrene, acrylonitrile and maleic anhydride or melamine on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and alkyl armlets or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acryl ate/butadiene copolymers, as well as mixtures of with the styrene copolymers indicated above.
Nitrites polymers are also useful in the polymer composition of the invention. These include photopolymers and copolymers of acrylonitrile and its analogs such as methacryionitrile, such as polyacrylonitrile, acrylonitrile/butadiene polymers, acrylonitrile/alkyl acryl ate polymers, acrylonitrile/alkyi methacrylate/butadiene polymers, acrylonitrile/butadiene/styrene (ABS), and ABS which includes methacryionitrile.
Polymers based on acrylic acids, such as acrylic acid, met acrylic acid, methyl methacrylate acid and ethacrylic acid and esters thereof may also be used. Such polymers include polymethylmethacrylate, and ABS-type graft copolymers wherein all or part of the acrylonitrile-type monomer has been replaced by an acrylic acid ester or an acrylic acid amide. Polymers including other acrylic-type monomers, such as acrogenic, methacrolein, acryl amide and methacrylamide may also be used.
Halogen-containing polymers may also be useful. These include resins such as polychloroprene, epichlorohydrin photopolymers and copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, fluorinated polyvinylidene, brominates polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride tercopolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate tercopolymer, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-met acrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymer and internally elasticized polyvinyl chloride.

Other useful thermoplastic polymers include photopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bis-glycidyl ethers; polyacetals, such as polyoxymethylene and those polyoxymethylene with contain ethylene oxide as a co monomer; polyacetals modified with thermoplastic polyurethanes, acrylates or methacrylonitrile containing ABS; polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene or polyamides; polycarbonates and polyester-carbonates; polysuifones, polyethersulfones and polyetherketones; and polyesters which are derived from dicarboxylic acid and dolls and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poiy-1,4-dimethyliol-cyclohexaneterephthalate, poly-{2,2,4-{4-hydroxyphenyl)-propane] terephthalate and poly hydroxy benzoates as well as block copolyetheresters derived from polyethers having hydroxyl end groups.
Polyamides and copolyamides which are derived from diamonds and dicarboxylic acids and/or from amino carboxylic acids or the corresponding lacteals, such as polyamide-4, polyamide-6, polyamide-6/6, polyamide-6/10, polyamide-6/9, polyamide-6/12, polyamide-4/6, polyamide-11, polyamide-12, aromatic polyamides obtained by condensation of m-xylene, diamante and acidic acid; polyamides prepared from hexamethylene diamante and isophthalic and/or terephthalic acid and optionally an plasterer as modifier, for example, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyl isophthalamide may be useful. Further copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, incomers or chemically bonded or grafted lassoers; or with polyethers, such as for instance, with polyethylene glycol, polypropylene glycol or polytetramethylene glycols, and polyamides or copolyamides modified with EPDM or ABS may be used.
The resulting stabilized polymer compositions of the invention may optionally also contain various conventional additives, such as the following: (1) Antioxidants
(1.1) Alkalized monophenols, for example: 2,6-di-f-butyl-4-methylphenol,

2-f-butyl-4,6-dimethylphenol, 2,6-di-Nbutyl-4-ethylphenol, 2,6-di-f-butyl-4-/7-butylphenol, 2,6-di-f-butyl-4-butylphenol, 2,6-di-cydopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cydohexylphenol, and 2,6-di-f-butyl-4-methoxymethylphenol.
(1.2) Alkylated hydroquinones, for example, 2,6-di-f-butyl-4-methoxyphenol, 2,5-di-f-butyl-hydroquinone, 2,5-di-f-amyl-hydroquinone, and 2,6-diphenyl-4-octadecyloxyphenol.
(1.3) Hydroxylated thiodiphenyl ethers, for example, 2,2'-thio-bis-(6-f-butyl-4-methylphenol), 2,2'-thio-bis-{4-octylphenol), 4,4'-thlo-bis-(6-f-butyl-3-methylphenol), and4,4'-thio-bis-(6-Nbutyl-2-methylphenol).
(1.4) Alkylidene-bisphenols, for example, 2,2'-methylene-bis-(6-f-butyl-4-methylphenol), 2,2'-methylene-bJs-(6-f-butyl-4-ethylphenol), 2,2'-methylene-bis-[4-methyl-6-(alpha-methylcyclohexyl)phenol], 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-[6-{a-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis-[6-(a,a-dimethylbenzyl)-4-nonylphenol], 2,2'-methylene-bis-(4,6-di-f-butylphenol), 2,2'-ethylidene-bis-{4,6-di-f-butylphenol), 4,4'-methylene-bis-(6-f-butyl-2-methylphenol),
1,1 -bis-(5-f-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-di-(3-Nbutyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris-(5-f-butyl-4-hydroxy-2-methylphenyl)butane,
1,1 -bis-(5-f-butyl-4-hydroxy-2-methylphenyl)-3-dodecylmercaptobutane,
ethylenglycol-bis-[3,3-bis-(3'-f-butyl-4'-hydroxy-phenyl)-butyrate],
di-(3-f-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadi6ne, and
di-[2-(3'-f-butyl-2'-hydroxy-5'-methyl-benzyl)-6-f-butyl-4-methylphenyl]terephthalate.
(1.5) Benzyl compounds, for example, 1,3,5-trls-(3,5-di-f-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis(3,5-di-f-butyl-4-hydroxybenzyl)sulfide,

isooctyl-3,5-dl-f-butyl-4-hydroxybenzyI-mercapto-acetate,
bis-{4-f-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate,
1,3,5-tris-(3,5-di-f-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-f-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
dioctadecyl-3,5-di-f-butyl-4-hydroxybenzyl-phosphonate, calcium salt of monoethyl
3,5-di-f-butyl-4-hydroxybenzylphosphonate, and
1,3,5-tris-1,3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
(1.6) Acylaminophenols, for example, 4-hydroxy-lauric acid annelid,
4-hydroxy-stearic acid anilide,
2,4-bis-octyimercapto-6-(3,5-f-butyl-4-hydroxy-anilino)-s-triazine, and octyl-N-{3i5-di-f-butyl-4-hydroxyphenyl)-carbamate.
(1.7) Esters of /3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic acid with monohybrid or polyhedral alcohols, for example, methanol, diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris-hydroxyethyl isocyanurate, thiodiethyleneglycol, and dihydroxyethyl oxalic acid diameter.
(1.8) Esters of l3-(5-t-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohybrid or polyhedron alcohols, for example, methanol, diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentyglycol, tris-hydroxyethyl isocyanurate, thiodiethyleneglycol, and di-hydroxyethyl oxalic acid diamond.
(1.9) Esters of j3-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhedral alcohols, e.g. with methanol, diethyl glycol, octadecanol, triathlon glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris(hydroxyethyl)isocyanurate, thiodiethylene glycol, and N,N'-bis(hydroxyethyl)oxalic acid diamond.
(1.10) Amides of fit-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic acid, for example, N,N'-di-(3,5-di-f-butyl-4-hydroxyphenylpropionyl)-hexamethylendiamine, N,N'-di-(3,5-di-f-butyl-4-hydroxyphenylpropionyl)-trimethylendiamlne, and N,N'-di-(3,5-di-f-butyl-4-hydroxyphenylpropionyl)-hydrazine.
(2) UV absenters and light stabilizers.

(2.1) 2'{2 '-HydroxyphenyO-benzotriazoles, for example, the 5'-methyl-, 3',5'-di-f-butyl-, 5'-”butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3'-, 5'-di-f-butyI-, 5-chloro-3'-f-butyl-5'-methyl-, 3'-sec-butyi-5'-f-butyl-, 4'-octoxy, 3',5'-di-f-amyl-, and 3',5'-bis-(a,a-dimethylbenzyl)-derivatives.
(2.2) 2'Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy- and
2'-hydroxy-4,4'-dimethoxy-derivatives.
(2.3) Esters of substituted and unsubstantiated benzoic acids, for example, phenyl calculate, 4-f-butyl-phenylsalicilate, octylphenyl sailcloth, dibenzoyiresorcinol, bis-(4-”butylben2oyl)-resorcinol, benzoylresorcinoi, 2,4-di-”butyl-phenyl-3,5-di-”butyl-4-hydroxybenzoateand hexadecyl-3,5-di-f-butyl-4-hydroxybenzoate.
(2.4) Acrylates, for example, a-cyano-p,3-diphenylacrylic acid ethyl ester or softly ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-p-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, a-carbomethoxy-p-methoxy-cinnamic acid methyl ester, and N-(3-carbomethoxy-|3-cyano-vinyi)-2-m6thyi-indoline.
(2.5) Nickel compounds, for example, nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyi)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butyl amine, triethanolamine or N-cyclohexyl-di-ethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-”butylbenzylphosphonic acid manually esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoxime such as of 2-hydroxy-4-methyl-pentyl unduly ketoxime, and nickel complexes of 1-ph6nyl-4-lauroyl-5-hydroxy-pyrazol, optionally with additional ligands.
(2.6) Serially hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl)-seakale, bis-(1,2,2,6,6-pentamethylpiperidyl)-separate, /7-butyl-3,5-di-f-butyl-4-hydroxybenzyl malonic acid,
bis-(1,2,2,6,6-pentamethylpiperidyl)ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinct acid, condensation

product of N,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and
4-”octylamino-2,6-dichloro-1,3,5-s-t”azine,
tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,
tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarbonicacid,
1,1 '-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone). Such amines include
hydroxylamine derived from hindered amines, such as
di-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sibilate;
1-hydroxy-2,2,6,6-tetramethyl-4-benzoxypiperidine;
1-hydroxy-2,2,6,6-tetramethyl-4(3,5-di-f-butyl-4-hydroxyhydrocinnamoyloxy)piperidine;
and N-{1 -hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)-c-caprolactam.
(2.7) Oxalic add diamonds, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5-di-/-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-f-butyl-oxaniiide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-exclaimed, 2-ethoxy-5-f-butyl-2'-ethyloxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-f-butyloxanilide and mixtures of o-ethoxy and p-ethoxy as well as of o-ethoxy and p-ethoxy disubstituted oxalates.
(3) Metal deactivators, for example, N,N'-diphenyloxaiic acid diameter, N-suicidal-N'-salicyloylhydrazine, N.N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-f-butyl-4-hydroxyphenylpropionyl)-hydrazine, salicyloylamino-1,2,4-triazole, bis-benzyl den-oxalic acid dihydrazide.
(4) Phospliites and phospttonites, for example trephines phosphite, diphenylalkyi phosphites, phenyldialkyi phosphites, tris(nonylphenyl) phosphite, treasury phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-f-butylphenyl)phosphite, diisodecyi pentaeythritol diphosphite, bis(2,4-di-f-butylphenyl)pentaerythritol diphosphite, tristearyl sorbet troposphere, and tetrakis(2,4-di-f-butylphenyl) 4,4'-biphenyl6ne diphosphonite,
(5) Peroxide scavengers, for example esters of p-thiodipropionic acid, for example the laurel, teary, ministry or trades esters, mercaptobenzimidazoie or the zinc salt of 2-mercaptobenzimida2ole, zinc-dibutyl-dithiocarbamate, dioctadecyldlsulfide, pentaerythritol-tetrakis(3-dodecylmercapto)-propionate.

(6) Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
(7) Basic co “stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, tribally cyan rate, urea derivatives, hydrazine derivatives, amines, polyamides, poiyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, barium stearate, magnesium steerage, sodium ricinoleate, potassium palpitate, antimony pyrocatecholate and zinc pyrocatechoiate.
(8) Lactones, for example, 5, 7-di-t-butyl-3-phenyl-3H-benzofuran-2-one; 5,7-di-cumyl-3-phenyl-3H-benzofuran-2-one; nonyl-3-phenyl-3H-benzofuran-2-one; dinonyl-3-phenyl-3H-benzofuran-2-one; 5-t-butyl-3-phenyl-3H-benzofuran-2-one; 5-cumyl-3-phenyl-3H-benzofuran-2-one; and octyl-3-phenyl-3H-benzofuran-2-one, and other 3-arylbenzofuran-2-ones.
(9) Nucleating agents, for example, 4-f-butyl-benzoic acid, acidic acid, diphenylacetic acid.
(10) Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
(11) Aminoxy propanoate derivatives such as
methyl-3-[N,N-dibenzylaminoxy]propanoate; ethyl-3-[N,N-dibenzylaminoxy]propanoate; 1,6-hexamethylene-bis[3-{N,N-dibenzyiaminoxy)propanoate]; methyl-[2-(methyi)-3(N,N-dibenzylaminoxy)propanoate];
octadecyl-3-[N,N-dibenzyl-aminoxy]propanoicacid; tetrakis[(N,N-dibenzylaminoxy)ethyl carbonyl oxymethyl]methane; octadecyi-3-[N,N-diethylaminoxy]propanoate; 3-[N,N-dibenzyiaminoxy]propanoic acid potassium salt; and 1,6-hexamethylene bis[3-(N-aliyl-N-dodecyl aminoxy)propanoate].
(12) Other additives, for example, plasticizers. lubricants, emulsifiers, pigments, optical
brighteners, flame-proofing agents, anti-static agents, blowing agents and thiosynergists
such as diiaurylthiodipropionate or distearyithiodipropionate.
Hindered phenolic antioxidants may also be present in the polymer composition. Use of bis-aralkylphenyl pentaerythritol diphosphites of the present invention may result in

enhanced polymer protection by reducing the formation of color resulting from the presence of the phenols. Such phenolic antioxidants include in addition to those specifically mentioned previously, n-octadecyi-3,5-di-f-butyl-4-hydroxyhydrocinnamate, neopentaneterayl tetrakis-(3,5-di-f-butyl-4-hydroxyl-hydrocinnamate), di-n-octadecyl-3,5-di-f-butyl-4-hydroxybenzyl-phosphonate, 1,3,5-tris(3,5-di-f-butyl-4-hydroxybenzyi-)isocyanurate, thiodiethyiene-bis(3,5-di-f-butyl-4-hydroxyhydrocinnamate),
1,3,5-trimethyl-2,4,6-tris(3,5-di-f-butyl-4-hydroxybenzyl)benzene, 3,6-di-oxaoctamethylene bis(3-methyl-5-f-butyl-4-hydroxyhydrocinnamate), 2,6-di-”butyl-p-cresol, 2,2'-ethyl idene-bis(4,6-di-f-butylphenol), 1,3,5-tris-(2,B-di-methyl-4-f-butyl-3-hydroxybenzyl)isocyanurate, 1,1,3-tris-(2-methyl-4-hydroxy-5-f-butylphenyl)butane, 1,3,5-tris[2-(3,5-di-f-butyl-4-hydroxyhydrocinnamoloxy)-ethyl]-isocyanurate,
3,5-di-(3,5-di-f-butyl-4-hydroxybenzyl)-mistily,
hexamethylene-bis(3,5-di-Nbutyl-4-hydroxyhydrocinnamate),
1-{3,5-di-f-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,
N,N'-hexamethylene-bis(3,5-di-f-butyl-4-hydroxyhydro-cinnamamide), calcium
bis(ethyl-3,5-di-f-butyl-4-hydroxybenzylphosphonate), ethylene
bis[3,3-di(3-f-butyl-4-hydroxyphenyl)butyrate], octyi
3,5-di-f-butyl-4-hydroxybenzylmercaptoacetate,
bis(3,5-di-Nbutyl-4-hydroxyhydrocinnamoyl)hydrazine, and
N,N'-bis-[2-(3,5-f-butyl-4-hydroxyhydroxocinnamoyloxy)-ethyll-oxamide, and preferably
neopentanetetrayltetrakis(3,5-di-f-butyl-4-hydroxyhydrocJnnamate),
n-octadecyl-3,5-di-f-butyl-4-hydroxyhydrocinnamate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-f-butyl-4-hydroxy-benzyl)benzene,
1,3,5-tris-(3,5-di-”butyl-4-hyd”oxybenzyl)isocyanurate, 2,6-di-f-butyl-p-cresol or
2,2' -ethyl idene-bis(4,6-di-f-butylphenol).
Other additives, such as oxazaphospholidines, may additionally or alternatively be present. Likewise, the instant compounds prevent color formation when hindered amine light stabilizers are present, such hindered amines including

bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-n-butyl-2-{3,5-di-f-butyl-4-hydroxy-ben2yl) ammoniate; bis(2,2,6,6-tetramethyl-4-piperidy!) seakale; dimethylsuccinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol; and polymers of 2,4-dichloro-6-octylamino-s-tria2ine with N'-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene thiamine.
The invention has been described with reference to preferred and alternate embodiments. Obviously, modifications and alterations will occur to others upon the reading and understanding of the specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.




1. A composition which comprises:
bus-(2,4-dicumylphenyl) pentaerythritol diphosphite; optionally, at least one additional phosphates; and at least one hindered phenol antioxididant.
2. The composition of claim 1, wherein said at least one additional phosphite is selected
from the group consisting of tris-(2,4-di-t-butylphenyl) phosphite, dietary pentaerythritol
diphosphite, trisnonylphenyl phosphite, phenyl disobey phosphite, diphenyl isodecyl
phosphite, trephine phosphite, treasury phosphite, alkyl (C12-C15) biphenyl A phosphite,
alkyl (C10) biphenyl A phosphite, bis-{2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2-
butyl-2-ethyl-1,3-propanediol 2,4,6-tri-t-butylphenol phosphite, bis-(2,6-di-t-butyl-4-
methyl phenyl) pentaerythritol diphosphite, terraces-{2,4-di-t-butylphenyl) 4,4'-
diphenylenediphosphonite, 2,2'-ethylidene bis-(4,6-di-t-butylphenyl) fluorophosphonite,
bis-(2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, and 2,2',2"-nitrilotriethanol
tris[3,3*,5,5'-tetra-tert-butyl-1,r-biphenyl-2,2 -idyll)-phosphite.
3. The composition of claim 1 wherein
a phosphite / hindered phenol antioxidant weight ratio is from 100:1 to 0.01:1.
4. The composition of claim 1 wherein
the hindered phenol antioxidant is selected from the group consisting of 2,6-di-t-butyl-4-methylphenoi, terraces [methyiene(3,5-di-t-butyl-4-hydroxhydrocinnamate)]methane, octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate, tris (3,5-di-t-butyM-hydroxybenzyl)-1,3,5-triazine-2,4,6(1 H, 3H, 5H)-triune, and a-tocopherol.
5. The composition of claim 1 wherein
said at least one additional phosphite is not present.
6. The composition of claim 1 wherein
a bis-(2,4-dicumylphenyl) pentaerythritol diphosphite/additional phosphite weight ratio is from 10:1 to 1:10.
7. The composition of claim 1, further comprising:

a polymer selected from the group consisting of polyolefins, polyesters,
polyurethane’s, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrene polymers, polycarbonates, acrylic polymers, polyamides, placental, halide containing polymers and mixtures thereof.
8. The composition of claim 7, wherein the concentration of phosphates and hindered
phenol antioxidants in the composition is from about 10 ppm to about 10,000 ppm.
9. A composition which comprises:
a polymer;
bis-(2,4-dicumylphenyl) pentaerythritol diphosphite; optionally, at least one additional phosphite; and a hindered phenol antioxidant.
10. The composition of claim 9, wherein said at least one additional phosphite is selected
from the group consisting of tris-(2,4-di-t-butylphenyl) phosphite, dipteral pentaerythritol
diphosphite, trisnonylphenyl phosphite, phenyl disobey phosphite, diphenyl isodecyl
phosphite, trephine phosphite, treasury phosphite, alkyl (C12-C15) bisphenoi A phosphite,
alkyl (C10) bisphenoi A phosphite, bis-{2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2-
butyl-2-ethyi-1,3-propanediol 2,4,6-tri-t-butylphenol phosphite, bis-(2,6-dJ-t-butyl-4-
methylphenyi) pentaerythritol diphosphite, tetra is-{2,4-di-t-butylphenyl) 4,4'-
diphenylenediphosphonite, 2,2'-ethylidene bis-(4,6-di-t-butylphenyl) fluorophosphonite,
bis-(2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, and 2,2',2"-nitrilotriethanol
tris[3,3',5,5'-tetra-tert-butyl-1,r-biphenyi-2,2'-diyl)-phosphite.
11 .The composition of claim 9 wherein
a phosphite / hindered phenol antioxidant weight ratio is from about 100:1 to about 1:100. 12. The composition of claim 9 wherein
the hindered phenol antioxidant is selected from the group consisting of 2,6-di-t-butyl-4-methylphenol, tetra is [ethylene(3,5-di-t-butyl-4-hydroxhydrocinnamate)]methane, octadecyl 3,5-di-t-butyM-hydroxyhydrocinnamate, tris (3,5-di-t-butyl-4-hydroxyben2yl)-1,3,5-tria2ine-2,4,6(1 H, 3H, 5H)-triune, and a-tocopherol.

13. The composition of claim 9 wherein
said at least one additional phosphite is not present.
14. The composition of claim 9 wherein
a bis-(2,4-dicumylphenyl) pentaerythritol diphosphite/additional phosphite weight ratio is from about 10:1 to about 1:10.
15. The composition of claim 9, wherein
the polymer is selected from the group consisting of polyolefins, polyesters, polyurethane’s, polyalkylene terephthalates, polysulfones, polyimides. polyphenylene ethers, styrene polymers, polycarbonates, acrylic polymers, polyamides, polyacetals, halide containing polymers and mixtures thereof.
16. The composition of claim 9, wherein the concentration of phosphates and hindered phenol antioxidants in the composition is from about 10 ppm to about 10,000 ppm.
17. A method for improving the thermo oxidative stability of a polymer composition comprising the steps of:
obtaining an amount of polymer;
adding an amount of bis-(2,4-dicumylphenyl) pentaerythritol diphosphite to said polymer;
optionally, adding an amount of at least one additional phosphite to said polymer; adding an amount of a hindered phenol antioxidant to said polymer; and mixing to form a well-mixed polymer composition.
18. The method of claim 17, wherein said at least one additional phosphite is selected
from the group consisting of tris-(2,4-di-t-butylphenyl) phosphite, dietary pentaerythritol
diphosphite, trisnonylphenyl phosphite, phenyl disobey phosphite, diphenyl isodecyl
phosphite, trephines phosphite, treasury phosphite, alkyl {C12-C15) biphenyl A phosphite,
alkyl (C10) biphenyl A phosphite, bus"(2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2-
butyl-2-ethyl-1,3-propanediol 2,4,6-tri-t-butylphenol phosphite. bis-(2,6-di-t-butyl-4-
methyl phenyl) pentaerythritol diphosphite, retraces-(2,4-di-t-butylphenyl) 4,4*-
diphenylenediphosphonite, 2,2*-ethylidene bis-{4,6-di-t-butylphenyl) fluorophosphonite,
bis-(2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, and 2,Z,2"-nitrilotriethanol
tris[3,3\5,5'-tetra-tert-butyl-1,r-biphenyl-2,2-diyl)-phosphite.

19. The method of claim 17 wherein
the hindered phenol antioxidant is selected from the group consisting of 2,6-di-t-butyl-4-methyiphenol, terraces methyiene[(3,5-di-t-butyl-4-hydroxhydrocinnamate)]methane, octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate, tris (3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1 H, 3H, 5H)-triune, and a-tocopherol.
20. The method of claim 17, wherein
the polymer is selected from the group consisting of polyolefins, polyesters, polyurethane, poiyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrene polymers, polycarbonates, acrylic polymers, .; polyamides, polyacetals, halide containing polymers and mixtures thereof.
21. A composition which comprises bis-(2,4-dicumylphenyl) pentaerythritol diphosphite; substantially as herein described and exemplified.


Documents:

505-mas-2000-abstract.pdf

505-mas-2000-claims filed.pdf

505-mas-2000-claims granted.pdf

505-mas-2000-correspondnece-others.pdf

505-mas-2000-correspondnece-po.pdf

505-mas-2000-description(complete) filed.pdf

505-mas-2000-description(complete) granted.pdf

505-mas-2000-form 1.pdf

505-mas-2000-form 26.pdf

505-mas-2000-form 3.pdf

505-mas-2000-form 5.pdf

505-mas-2000-other documents.pdf


Patent Number 201851
Indian Patent Application Number 505/MAS/2000
PG Journal Number 05/2007
Publication Date 02-Feb-2007
Grant Date 31-Aug-2006
Date of Filing 30-Jun-2000
Name of Patentee M/S. DOVER CHEMICAL CORPORATION
Applicant Address 3676 DAVIS ROAD N W DOVER,OH 44622
Inventors:
# Inventor's Name Inventor's Address
1 DARYL STEN 6125 SANDY RIDGE CIRCLC N W NORTH CANTON OH-44720
2 DONALD R STEVENSON 6125 SANDY RIDGE CIRCLC N W NORTH CANTON OH-44720
3 MARC NOLEN 6125 SANDY RIDGE CIRCLC N W NORTH CANTON OH-44720
4 SATYAN R KODALI 6125 SANDY RIDGE CIRCLC N W NORTH CANTON OH-44720
PCT International Classification Number C08K 5/15
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 09/353,000 1999-07-13 U.S.A.