Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
  • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
  • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon

Definitions

• Organic phosphites are known for their antioxidant properties when added to polymers and other organic materials. 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 degradation during their intended use.
• Organic phosphites can be synthesized from variety of alcohols, diols, triols, and alkylphenols. Among them are the commercially significant phosphites, tris (nonylphenyl) phosphite (TNPP) and tris (2, 4-di-t-butylphenyl) phosphite. Historically, these two phosphites have been the low cost stabilizers for the rubber and plastics industry. Recently, however, alkylphenols and phosphites made from them have come under scrutiny due to concerns about them being xeno-estrogenic and bio-accumulative. Therefore suitable replacements for these are desired.
• Polyphosphates with a high hydroxyl number can be suitable in polyurethanes for use as an anti-scorch agent as well as flame lamination additives.
• CHDM phosphites of the general structures described herein can be synthesized with a suitable hydroxyl number so as to be useful additives in polyurethanes.
• Low and high molecular weight polyphosphates of the general structures described herein show excellent compatibility and stabilization in PVC.
• Phosphites of these general structures impart excellent color stability and increase thermal stabilization in PVC.
• alkyl means straight and branched chain saturated acyclic hydrocarbon monovalent groups; said alkyl group may further optionally include one or more suitable substituents independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like.
• straight-chain or branched alkyl groups are C ⁇ o alkyls, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and stearyl groups.
• C ⁇ o alkyls e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepta
• the alkenyl may be interrupted with oxygen, sulfur or nitrogen, non-limiting examples for which the interspersed groups include: -CH 2 -0-CH 2 - -CH 2 -S-CH 2 - -CH 2 -N(CH 3 )-CH 2 - -CH 2 -0-CH 2 CH 2 - -CH 2 CH 2 -0-CH 2 CH 2 -, -CH 2 CH 2 -0- CH 2 CH 2 -0-CH 2 CH 2 - -CH 2 CH 2 -(0-CH 2 CH 2 -) 2 0-CH 2 CH 2 - -CH 2 CH 2 -(0-CH 2 CH 2 -) 3 0-CH 2 CH 2 - -CH 2 CH 2 -(0-CH 2 CH 2 -) 4 0-CH 2 CH 2 - -CH 2 CH 2 -S-CH 2 CH 2 - or -CH 2 CH 2 -N(CH 3 )-CH 2 CH 2 - .
• cycloaliphatic refer to a mono- or polycyclic saturated hydrocarbon monovalent group having from 3 to 1 0 carbon atoms, or a C 7 . 10 polycyclic saturated hydrocarbon monovalent group having from 7 to 1 0 carbon atoms.
• cycloaliphatic may be interrupted with oxygen and/or carbonyl groups (e.g., lactones), or other non-interfering atoms.
• halo or halogen means any atom selected from the group consisting of fluoro, chloro, bromo and iodo.
• CHDM of either the cis or trans isomer may be used as a reactant or combinations thereof. While CH DM is the focus of much of the description of the invention, the invention is not limited to such, and in fact, includes other "cycloaliphatic diol based" derivatives, e.g., cyclopentane dimethanol, cyclopentane diethanol, cyclopentane dipropanol, cyclopentane dibutanol, cyclopentane dipentanol, cyclohexane diethanol, cyclohexane dipropanol, cyclohexane dibutanol, cyclohexane dipentanol, cycloheptane dimethanol, cycloheptane diethanol, cycloheptane dipropanol, cycloheptane dibutanol, cycloheptane dipentanol, cyclooctane
• the cycloaliphatic diol based component is HO-[R 7 ] a - R 8 - [R 9 ] b -OH, Structure I I, where R 7 , R 8 , R 9 , a & b are as defined below.
• R 7 and R 9 are CH 2 groups and a & b are 1 .
• R 7 and R 9 independently selected from the group consisting of straight and branched alkylene groups
• R 8 is selected from the group consisting of C 5 . 10 saturated carbocyclic rings
• the invention provides a polymeric polyphosphite containing from 2 to 1 000 repeating units of the formula :
• R 2 is selected from the group consisting of
• Ci alkyl group or C 2 _ 22 alkenyl group which is optionally interrupted or terminated by a C 5 . 10 cycloalkyl or cycloalkenyl group,
• a and b are independently selected from the group consisting of 0 and 1 ;
• Y is a C 2 - 22 alkylene group
• n 1 to 20;
• R 2 is selected from the group consisting of
• Ci alkyl group or 0 2 - 22 alkenyl group which is optionally interrupted or terminated by a C 5 . 10 cycloalkyl or cycloalkenyl group
• each of R 7 and R 9 independently represents a alkylene group
• R 8 is selected from the group consisting of C 5 . 10 saturated carbocyclic rings.
• a and b are independently selected from the group consisting of 0 and 1 ;
• said polyphosphite being terminated adjacent the -P(OR 2 )- group of the formula above by a group R 1 0-, and terminated at the other end of the chain by a group -P(OR 3 )(OR 4 ), in which each of R 1 , R 3 , and R 4 , which may be the same or different, has one of the meanings given for R 2 ;
• the invention provides a polymeric polyphosphite containing from 2 to 1 000 repeating units of the formula:
• each R is independently selected from the group consisting of
• R 8 is selected from the group consisting of C 5 . 10 saturated carbocyclic rings
• a and b are independently selected from the group consisting of 0 and 1 ;
• Y represents a C 2 _ 22 alkylene group
• n 1 to 20;
• said polyphosphite being terminated adjacent the -P(OR 2 )- group of the formula above by a group R 1 0-, and terminated at the other end of the chain by a group -P(OR 3 )(OR 4 ), in which each of R 1 , R 3 , and R 4 , which may be the same or different, has one of the meanings given for R 2 .
• Y preferably represents a -CH 2 CH 2 - or -CH(CH 3 )CH 2 - group, and m is preferably from 5 to 20.
• R 2 represents a C 10 - 20 , especially a C 12 to C 18 , alkyl group, a C 16 to C 18 alkenyl group, or a C 2 .
• 10 polyalkylene glycol chain terminated by a C _ 4 alkyl group for example a polyethylene glycol chain of molecular weight 350 terminated by a methyl group, or a tripropylene glycol chain terminated by a butyl group.
• R 2 represents a C 12 to C 18 alkyl group.
• a preferred group of compounds of the invention are polymeric polyphosphites in which R 2 represents a C 10 -C 20 , especially a C 12 -C 18 , alkyl group, a C 16 to C 18 alkenyl group, or a C 2 .
• each of R 1 , R 3 and R 4 also has one of these meanings, especially a C 12 -C 18 alkyl group; each of R 7 and R 9 independently represents an ethylene or, especially, methylene, group, and a an b represent 1 ; R 8 represents a cyclohexylene group; and if unit B is present, Y represents a -CH 2 CH 2 - or -CH(CH 3 )CH 2 - group, and m is from 5 to 20.
• each R 1 , R 2 , R 3 and R 4 can be the same or different and independently selected from the group consisting of 0,. 2 ⁇ alkyl, C 2 . 22 alkenyl, C 6 . 40 cycloalkyl, C 7 . 40 cycloalkylene, or Y-OH (serving as an end capping moiety) for R 1 , R 2 , R 3 and
• Y is selected from the group consisting of C 2 . 40 alkylene (e.g., ethylene, propylene), C cycloaliphatic carboxylic ester (e.g., caprylactone), and ⁇ 3 . 40 cycloalkyl; x ranges from 8 to 1 ,000; further wherein
• At least one monohydroxy-terminated reactants selected from the group consisting of R 1 -OH, R 2 -OH R 3 -OH and R 4 -OH;
• the polymeric polyphosphites of Structure (III) may be illustrated by Structure (Ilia).
• R 1 , R 2 , R 3 and R 4 can be the same or different and independently selected from the group consisting of C ⁇ o alkyl, C 2 _ 22 alkenyl, C 6 . 40 cycloalkyl, C 7 . 40 cycloalkylene, or Y-OH (serving as an end capping moiety);
• x ranges from 8 to 1 ,000; further wherein
• R 7 and R 9 independently selected from the group consisting of straight and branched alkylene groups
• R 8 is selected from the group consisting of C 5 . 10 saturated carbocyclic rings
• a and b are integral values independently selected from the group consisting of 0 and 1 ;
• said polymeric polyphosphite is a reaction product of:
• Copolymers of polymeric polyphosphites are synthesized at least in part using CHDM as an illustrative example is shown in Structure (IV).
• each R 1 , R 2 , R 3 , R 4 , R 5 and R 6 can be the same or different and independently selected from the group consisting of ⁇ _ 20 alkyl, C alkenyl, C 6 . 40 cycloalkyl, C 7 . 40 cycloalkylene, or Y-OH (serving as an end capping moiety) for R 1 , R 2 , R 3 , R 4 , R 5 and R 6 ;
• Y is selected from the group consisting of C 2 - 40 alkylene (e.g., ethylene, propylene), C cycloaliphatic carboxylic ester (e.g., caprylactone), and C 3 . 40 cycloalkyl; x ranges from 2 to 1 ,000;
• n 1 to 20;
• At least one monohydroxy-terminated reactants selected from the group consisting of R 1 -OH, R 2 -OH R 3 -OH and R 4 -OH;
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 can be the same or different and independently selected from the group consisting of C ⁇ o alkyl, C 2 _ 22 alkenyl, C 6 . 40 cycloalkyl, C 7 . 40 cycloalkylene, or Y-OH (serving as an end capping moiety) for R 1 , R 2 , R 3 , R 4 , R 5 and R 6 ;
• Y is selected from the group consisting of C 2 - 40 alkylene (e.g., ethylene, propylene), C 2 -4o cycloaliphatic carboxylic ester (e.g., caprylactone), and ⁇ 3 . 40 cycloalkyl; x ranges from 2 to 1 ,000;
• z ranges from 0 to 1 ,000 with the proviso that when z is greater than 1 but less than or equal to 12, then x ranges from 2 to 1 ,000, and with the further proviso that when z is 0, then x is 8 or greater;
• n 1 to 20;
• R 8 is selected from the group consisting of C 5 . 10 saturated carbocyclic rings
• a and b are integral values independently selected from the group consisting of 0 and 1 ;
• said polymeric polyphosphite is a reaction product of:
• At least one monohydroxy-terminated reactants selected from the group consisting of R 1 -OH, R 2 -OH, R 3 -OH, R 4 -OH, R 5 -OH, and R 6 -OH; and at least one dihydroxy-terminated reactant is selected from the group HO-[R 7 ] a -R 8 -[R 9 ] b -OH, and
• the polyalkylene glycol units of the copolymeric polyphosphite are often selected from the group consisting of polyethylene glycol and polypropylene glycol.
• the weight average molecular weight of a copolymeric polyphosphite according to the invention is at least 1 200 to 100,000 and for a polymeric polyphosphite, preferably in the range of from 6,000 to 100,000.
• polymeric polyphosphite of the invention may be characterised as the reaction product of
• the trifunctional reactant is a triaryl phosphine, especially triphenyl phosphine. Preferred meanings for the various substituents are as given above.
• the invention also provides a process for the preparation of a polymeric polyphosphite of the invention, which comprises reacting together in the presence of a base (i) at least one alcohol R 2 OH;
• R 7 and R 9 independently represents a alkylene group
• R 8 is selected from the group consisting of C 5 . 10 saturated carbocyclic rings
• a and b are
• Y represents a C 2 . 22 alkylene group
• m is from 1 to 20.
• Synthesis of the compositions typically involve transesterification in which triphenyl phosphite (or any other suitable alkyl or aryl phosphite) is allowed to react with a monoalkyl alcohol or monoalkenyl alcohol or an alkylene glycol ether (e.g., polyethylene glycol ether or polypropylene glycol ether) and at least one diol or polymeric diol H(OY) m OH wherein Y and m are as hereinafter defined with a suitable base catalyst at temperature between 20 °C and 250°C, and more preferred at temperature between 50 °C and 1 85 °C.
• triphenyl phosphite or any other suitable alkyl or aryl phosphite
• the at least one dihydroxy-terminated reactant comprises at least at least one saturated carbocyclic ring, e.g. , cyclohexane dimethanol.
• monoalkyl alcohols or monoalkenyl alcohols include: decyl, isodecyl, lauryl, tridecyl, isotridecyl, myristyl, pentdecyl, palmyl, stearyl, isotearyl, oleic alcohol, monohydroxyl glycol ethers, etc.
• Suitable base catalysts include sodium hydroxide, sodium methoxide, sodium phenolate, potassium hydroxide, and potassium carbonate.
• the amount of the base catalyst used is within the range of 0.01 to 1 0 weight percent based on the total amount of reactants charged. In a preferred embodiment, the amounts are within 0.1 to 1 .0 weight percent of the reactants.
• the mole ratio of alkyl alcohol or glycol-ether and a diol used in forming the phosphites, with regard to triphenyl phosphite is from about 0.9 to 2.2 moles of the alcohol or glycol ether per mole of triphenyl phosphite and 0.3 to 3.0 mole of the diol per mole of triphenyl phosphite.
• the mole ratio is 2.0 to 1 .0 of an alkyl or alkenyl alcohol or a glycol ether per mole of triphenyl phosphite and the mole ratio of a diol to triphenyl phosphite is 0.5 to 1 .0.
• the structure composition of the phosphites depends on the reaction conditions, for example the temperature, the sequence how the reactants are added, alkyl or alkenyl alcohol or glycol ether or a mixture or alkyl or alkenyl alcohol or glycol ether or a combination of some or all are used, the mole ratio and the concentration of the alkyl or alkenyl alcohols or glycol ether and the diols, and the molecular weight of the diols chosen.
• the phosphorus content of the phosphite can be adjusted by the molecular weight of the diol and the alkyl or alkenyl alcohol or glycol ether chosen.
• the preferred alkyl alcohols used are C 12 to C 18 .
• the preferred alkenyl alcohols used are the C 16 and C 18 .
• the preferred glycol ethers used are Carbowax 350 (monomethylether of polyethylene glycol MW 350, and tripropylene glycol monobutylether.
• the polymeric diols used in the process for the copolymers are those which are commercially available, known as poly glycols.
• the preferred poly glycols are polyethylene or polypropylene glycols, having molecular weight ranging from 200 to 3000, and existing as liquids at room temperature.
• the most preferred are polyethylene glycols, having molecular weight 300 to 400, and polypropylene glycols, having molecular weight of 300 to 1000.
• the organic materials into which the polyphosphites and copolymeric polyphosphites are added are preferably synthetic polymers.
• Non-limiting illustrative examples of such polymers include the following.
• Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-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 (H DPE), high density and high molecular weight polyethylene (H DPE-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), and blends of the polymers described above, regardless of the method of preparation.
• H DPE high density polyethylene
• H DPE-HMW high density and high molecular weight polyethylene
• HDPE- UHMW medium density
• Copolymers of monoolefins and diolefins with each other or with other vinyl monomers such as 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 copolymers, 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,
• LLDPE linear low density
• isobutylene/isoprene copolymers ethylene/vinylcyclohexene 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 previously, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene- acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof
• Hydrocarbon resins for example C 5 -C 9
• hydrogenated modifications thereof e.g. tackifiers
• mixtures of polyalkylenes and starch
• Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi- isotactic or atactic. Stereoblock polymers are also included.
• Copolymers are included, such as 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/butadiene, 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/propylene/diene terpolymer; and block copolymers of st
• Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned above are included, especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH). Further included are hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned previously.
• the homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic. Stereoblock polymers are also included.
• 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, such as styrene on polybutadiene, styrene and alkylacrylates or methacrylates on butadiene, styrene and acrylonitrile on ethylene/
• Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact- modified with butyl acrylate.
• Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals 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 above.
• Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• 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, 6/1 0, 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
• Polyureas Polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
• Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly- 1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
• Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
• Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acrylates, urethane acrylates or polyester acrylates.
• Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
• Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
• Aqueous emulsions of natural or synthetic rubber e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
• the stabilized polymer compositions of the invention may also contain from about 0.001 % to 5%, preferably from 0.01 % to 2%, and most preferably from 0.025% to 1 % of other conventional stabilizers, a non-limiting exemplary list is provided below.
• Thioesters a non-limiting exemplary list including dilauryl thiodipropionate and distearyl thiodipropionate.
• Aromatic amine stabilizers a non-limiting exemplary list including as N, N'-diphenyl-p- phenylene-diamine.
• additives such as lubricants, antistatic agents, antiblocking agents, slip agents, fire retardants, nucleating agents, impact modifiers, blowing agents, plasticizers, fillers, dyes, and pigments may be used in an amount appropriate and in combination of the invented polymeric diphosphites to modify a selected property of the polymer, such as alkanolamines, a non-limiting exemplary list including triethanolamine and triisopropanolamine.
• 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-butyl-4- isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethyl- phenol, 2,6- dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 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 '-
• 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.
• 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(
• 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-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
• esters of -(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, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3- thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 - phos
• esters of -(5-tert-butyl-4-hvdroxy-3-methylphenyl)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, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3- thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 - phospha
• esters of ⁇ -(3,5-dicvclohexyl-4-hydroxyphenyl)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)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7- trioxabicyclo[2.2.2]oct
• 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)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7- trioxabicyclo[2.2.2]octane.
• Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-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'-dicyclohexyl- p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N, N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)
• diphenylamine N-allyldiphenylamine, 4- isopropoxydiphenylamine, N-phenyl-1 -naphthylamine, N-(4- tert-octylphenyl)-1 - naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di- tert- butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'- diaminodiphenylmethane, N,N
• 2-(2'-Hydroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2- (2'-hydroxy-5'-(1 , 1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5- chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl- 5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'- hydroxy-4'-octy
• esters of substituted and unsubstituted benzoic acids for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert- butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl, 3,5-di-tert-butyl-4- hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4- hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.
• [01 1 1 ] Acrylates, for example ethyl a-cyano- , -diphenylacrylate, isooctyl-a-cyano- ⁇ , ⁇ - diphenylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano- -methyl-p-methoxycinnamate, butyl a-cyano- -methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and ⁇ -( ⁇ - carbomethoxy p-cyanovinyl)-2-methylindoline.
• Stericallv 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
• 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-(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-propyloxyphenyl)-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)
• Metal deactivators for example ⁇ , ⁇ '-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, ⁇ , ⁇ '-diacetyladipoyl dihydrazide, N, N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
• Phosphines for example 1 ,3-bis(diphenylphosphino)-2,2-dimethyl-propane.
• [01 1 8] Hydroxy/amines for example N,N-dibenzylhydroxylamine, ⁇ , ⁇ -diethylhydroxylamine, N, N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, ⁇ , ⁇ -ditetradecylhydroxylamine, N, N- dihexadecylhydroxylamine, ⁇ , ⁇ -dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, ⁇ , ⁇ -dialkylhydroxylamine derived from hydrogenated tallow amine.
• Nitrones for example N-benzyl-a-phenylnitrone, N-ethyl-a-methylnitrone, N-octyl-a- heptylnitrone, N-lauryl-a-undecylnitrone, N-tetradecyl-a-tridecylnitrone, N-hexadecyl-a- pentadecylnitrone, N-octadecyl-a-heptadecylnitrone, N-hexadecyl-a-heptadecylnitrone, N-ocatadecyl- a-pentadecylnitrone, N-heptadecyl-a-hepta-decylnitrone, N-octadecyl-a-hexadecylnitrone, nitrone derived from ⁇ , ⁇ -dialkylhydroxylamine
• Peroxide scavengers for example esters of ⁇ -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( - dodecylmercapto)propionate.
• esters of ⁇ -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( - dodecyl
• Polvamide stabilizers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
• 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.
• 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 ric
• 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.
• ionic copolymers e.g., 1 ,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1 ,3:2,4-di(paramethyldibenzylidene)sorbitol, and 1 ,3:2,4-di(benzylidene)sorbitol.
• Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
• Benzofuranones and indolinones such as 3-[4-(2- acetoxyethoxy)phenyl]-5,7-di-tert- butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyl-oxyethoxy)phenyl]benzofuran-2-one, 3,3'- bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)- benzofuran-2-one], 5,7-di-tert-butyl-3-(4- ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7- di-tert-butylbenzofuran-2-one
• the preferred thick-layer polyolefin moldings have a layer thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm.
• compositions according to the invention can be advantageously used for the preparation of various shaped articles.
• end-use applications include, but are not limited to: Floating devices, marine applications, pontoons, buoys, plastic lumber for decks, piers, boats, kayaks, oars, and beach reinforcements; 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 moldings, convertible tops, exterior mirrors, exterior trim
• Still further applications include: Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes; 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; and Membranes, insulation, covers and seals for roofs, tunnels, dumps, ponds, dumps, walls roofing membranes, geomembranes,
• Additional applications include: 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; Food packing and wrapping (flexible and solid), bottles; Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs, and cans; and 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.
• 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
• 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.
• compositions comprising as component (a) fibers and fabrics used in nonwoven medical fabric and related apparel (surgical gowns, drapes, bandages), construction fabrics (house wrapping, roofing, swimming-pool wrapping) and home furnishing (carpets, table linens, shower curtains).
• 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 composition as described above.
• the organic materials to be protected are preferably organic polymers, particularly synthetic polymers.
• Thermoplastic materials in particular polyolefins, are particularly advantageously protected.
• the excellent effectiveness of the polymeric compounds of the phosphites as processing stabilizers (heat stabilizers) should be emphasized.
• they are advantageously added to the polymer before or during processing thereof.
• other polymers for example elastomers
• lubricants or hydraulic fluids can also be stabilized against degradation, for example light-induced or thermo-oxidative degradation. Elastomers are given in the above list of possible organic materials.
• Example #1 The apparatus in Example #1 was used. 1 00 grams (0.69mol) of cyclohexane dimethanol, triphenyl phosphite (237g, 0.76 mol), a mixture of lauryl and myristyl alcohol with a hydroxyl number of about 280, (1 90g, 0.95 mol), and and 0.4 grams of potassium hydroxide were added. The mixture was mixed well and heated to approximately 150 °C under nitrogen and held at the temperature for 1 hour. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 180 °C over a course of 1 hour. The reaction contents were held at 1 80 °C under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a non-viscous liquid.
• Example #1 The apparatus in Example #1 was used. 20 grams (0.14mol) of cyclohexane dimethanol, 7g polypropylene glycol 400 (0.02m) triphenyl phosphite (1 00g, 0.32mol), stearyl alcohol (1 88g, 0.70mol) and 0.4 grams of potassium hydroxide were added. The mixture was mixed well and heated to approximately 1 50C under nitrogen and held at the temperature for 1 hour. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 180 °C over a course of 1 hour. The reaction contents were held at 1 80 °C under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a solid.
• Example #1 The apparatus in Example #1 was used. 20 grams (0.14mol) of cyclohexane dimethanol, 7g polypropylene glycol 400 (0.02m), triphenyl phosphite (1 00g, 0.32mol), a mixture of lauryl and myristyl alcohol with a hydroxyl number of about 280 (136g, 0.69 mol) and 0.4 grams of potassium hydroxide were added. The mixture was mixed well and heated to approximately 150C under nitrogen and held at the temperature for 1 hour. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 1 80 °C over a course of 1 hour. The reaction contents were held at 180 °C under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a non-viscous liquid.
• Example #1 The apparatus in Example #1 was used. 38 grams (0.29 mol) of cyclohexane dimethanol, triphenyl phosphite (200g, 0..64 mol), a mixture of lauryl and myristyl alcohol (1 83g, 0.93 mol) polypropylene glycol 400 (1 10, 0.28) and 0.4 grams of potassium hydroxide were added. The mixture was mixed well and heated to approximately 150 °C under nitrogen and held at the temperature for 1 hour. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 180 °C over a course of 1 hour. The reaction contents were held at 1 80 °C under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a non-viscous liquid. Comparative Example #8 (non-CHDM polyphosphite)
• Example #1 The apparatus in Example #1 was used. PPG 400 (95g, 0.237mol), triphenyl phosphite (73g, 0.235mol), a mixture of lauryl and myristyl alcohol with a hydroxyl number of about 280, (47g, 0.235 mol), and 0.8 grams of potassium hydroxide were added. The mixture was mixed well and heated to 160-1 62°C under nitrogen and held at the temperature for 1 hour. The pressure was then gradually reduced to 0.3 mmHg and the temperature was increased to 170-1 72°C over a course of 1 hour. The reaction contents were held at 1 70-1 72 °C under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to 50 °C. The product was a clear, colorless liquid.
• Characteristics of the various synthesized additives may be characterized at least in part by the following tables.
• the solid phosphites of the invention can be blended with higher melting point materials to increase the melting point of the phosphites.
• the phosphite from Example #1 was used for all of the examples below. Table 2
• the cycloaliphatic diol-based polyphosphite performed better in extrusion stability as measured by melt flow index and yellowness index in polypropylene, even at lower concentrations than a non-saturated aliphatic diol phosphite.
• the cylcoaliphatic diol-based polyphosphite performed as well or better in extrusion stability as measured by melt flow index and yellowness index in high density polyethylene, even at lower concentrations than a non-cylcoaliphatic diol-based polyphosphite.
• the cyloaliphatic diol-based polyphosphate performed better in extrusion stability as measured by melt flow index and yellowness index in linear low density polyethylene than a non-saturated aliphatic diol phosphite.
• Example #1 The apparatus in Example #1 was used. 45 grams (0.31 mol) of cyclohexane dimethanol, triethyl phosphite (60g, 0.36mol), a mixture of lauryl and myristyl alcohol with a hydroxyl number of about 280, (87g, 0.44 mol), polypropylene glycol with an average molecular weight of 400 (5g, 0.013mol), and 0.5 grams of sodium methoxide were added. The mixture was mixed well and heated to approximately 1 60 °C. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 1 80°C over the course of 1 hour. The reaction contents were held at 1 80 °C under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a non- viscous liquid.
• Example #1 The apparatus in Example #1 was used. 25 grams (0.1 7 mol) of cyclohexane dimethanol, triphenyl phosphite (1 14g, 0.37mol), a mixture of lauryl and myristyl alcohol with a hydroxyl number of about 280, (92g, 0.47 mol), polycaprolactone with an average molecular weight of 400 (68g, 0.1 7mol), and 0.5 grams of potassium hydroxide were added. The mixture was mixed well and heated to approximately 1 60 °C. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 1 80°C over the course of 1 hour. The reaction contents were held at 1 80 °C under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a non- viscous liquid.
• Example #1 The apparatus in Example #1 was used. 87 grams (0.75 mol) of cyclohexane diol, triphenyl phosphite (284g, 0.92mol), 98% lauryl alcohol, (236g, 1 .27 mol), polypropylene glycol with an average molecular weight of 400 (6g, 0.015mol), and 0.5 grams of potassium hydroxide were added. The mixture was mixed well and heated to approximately 1 60 °C. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 180 °C over the course of 1 hour. The reaction contents were held at 1 80 °C under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a viscous liquid.
• Example #1 The apparatus in Example #1 was used. 60 grams (0.42 mol) of cyclohexane dimethanol, triphenyl phosphite (284g, 0.92mol), stearyl alcohol, (293g, 0.85 mol), 1 ,6 hexane diol (49g, 0.42mol), and 1 .5 grams of potassium hydroxide were added. The mixture was mixed well and heated to approximately 1 60 °C. The pressure was then gradually reduced to 0.3 mm Hg and the temperature was increased to 1 80°C over the course of 1 hour. The reaction contents were held at 1 80 °C under the vacuum for 2 hours at which point no more phenol was distilling out. The vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature. The product was a viscous liquid.
• Characteristics of the various synthesized additives in Examples #13 - #16 may be characterized at least in part by the following.
• the pressure was then gradually reduced to 0.3 mm Hg and the temperature was held to 150 °C over a course of 1 hour.
• the reaction contents were held at 150°C under the vacuum for 2 hours at which point no more phenol was distilling out.
• the vacuum was then broken by nitrogen and the crude product was cooled to ambient temperature.
• the product was a non-viscous liquid.
• Example #1 The apparatus of Example #1 was used to synthesize a high molecular weight ( ⁇ 14,000 M.W.) polyphosphite having CH DM using the identical experimental conditions and quantities of reactants found in Example #17 above.
• n is a number from 1 to 6
• R is a divalent linking group.
• FDA Food and Alcohol Administration
• LLDPE linear low density polyethylene
• both patent example phosphites were compounded into linear low density polyethylene (LLDPE) at a concentration of 2500 ppm. These were then compression molded into sheets of a thickness of 20 mils. These sheets were cut into discs having a diameter of 1 .5 inches (3.8 cm). Five discs of each were then placed into separate clean dry jars with spacers in between each disc to ensure that the 1 0% ethanol solution could touch both sides of the discs.
• LLDPE linear low density polyethylene
• the discs were then exposed to the 10% ethanol for 2 hours at a temperature of 1 00 °C.
• the discs and spacers were then removed and the solution was analyzed to measure the amount of phosphite that had migrated from the LLDPE discs into the 1 0% ethanol.
• CHDM improves the hydrolytic stability of the phosphite additive in that the CH DM rigid structure does not bend due to its saturated ring. It additionally is essentially "odor-free.”
• One embodiment employs approximately 1 0% by weight of polypropylene glycol (“PPG") in combination with 90% CHDM by weight. The PPG prevents crosslinking and keeps the phosphite a liquid. The increased amounts of CHDM additionally increases the percentage of phosphorus in the molecule, which provides a performance
• the preferred ratio is approximately 1 :1 :1 while a more preferred ratio will have the dihydroxy-terminated reactant as the limiting reagent with a slight molar excess of the monofunctional chain stopper. While the graphic depiction is stylized and believed to be an accurate description, the unpredictable nature of chemical reactions prohibits any depiction with absolutely certainty. What is illustrated however, is that while it is possible to have some hydroxy termination in the polyphosphite, i.e., some of the above monofunctional hydroxy moieties may be replaced by dihydroxy moieties. However, by controlling the molar ratio of reactants, the amount of hydroxyl groups at a chain end is preferably limited to no more than 1 -2 chains within the molecule, depending on the amount of excess chain stopper.
• polymeric polyphosphite is a reaction product of:
• At least one monohydroxy-terminated reactant at least one dihydroxy-terminated reactant selected from the group
• R 7 is a linear or branched alkylene
• R 8 is a saturated carbocyclic ring having from 5 to 1 0 carbon atoms in the ring
• R 9 is a linear or branched alkylene, and further wherein a and b are integral values ranging from 0 and 1 ;
• a trifunctional reactant comprising at least one phosphorus moiety; and isolating said alkylphenol-free phosphite.

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• 2014
  • 2014-06-19 JP JP2016521568A patent/JP2016525156A/ja active Pending
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  • 2014-06-19 EP EP14813504.9A patent/EP3010961A1/en not_active Withdrawn
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