EP2164933A2 - Flüssige styrolierte phenolzusammensetzungen und herstellungsverfahren dafür - Google Patents

Flüssige styrolierte phenolzusammensetzungen und herstellungsverfahren dafür

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Publication number
EP2164933A2
EP2164933A2 EP08781436A EP08781436A EP2164933A2 EP 2164933 A2 EP2164933 A2 EP 2164933A2 EP 08781436 A EP08781436 A EP 08781436A EP 08781436 A EP08781436 A EP 08781436A EP 2164933 A2 EP2164933 A2 EP 2164933A2
Authority
EP
European Patent Office
Prior art keywords
phenolic
cresol
composition
percent
gas chromatography
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08781436A
Other languages
English (en)
French (fr)
Inventor
Michael E. Gelbin
Jonathan S. Hill
Maurice Power
Jun Dong (John)
Cyril A. Migdal
Gerard Mulqueen
Joseph F. Stieber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SI Group Switzerland CHAA GmbH
Original Assignee
Chemtura Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/069,631 external-priority patent/US8193260B2/en
Application filed by Chemtura Corp filed Critical Chemtura Corp
Publication of EP2164933A2 publication Critical patent/EP2164933A2/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/1006—Compounds containing silicon used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/065—Saturated Compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • the present invention relates to liquid sytrenated phenolic compositions. More particularly, the present invention relates to liquid sytrenated phenolic compositions, to processes for forming liquid styrenated phenolic compositions and to their use in the stabilization of polymers and lubricants.
  • phenolic antioxidants having a liquid physical form in a number of polymer markets, such as thermoplastics, thermoelastomers, rubber, and lubricants.
  • the liquid physical form can only be brought about by heating them to temperatures above their melting points. Examples include octadecyl-S ⁇ -di-fert-butyM-hydroxycinnamate, the melting point of which is in the range from between 48°C and 58°C, and 2,6-di-tert-butyl-p-cresol, whose melting point is approximately 69°C.
  • a major drawback associated with offering a compound that is solid at room temperature in its molten state is that, in order to retain it in a liquid physical form, continued heating is required. Heating, however, is not always sustainable and, therefore, the molten product may cool and form a solid. Once solidified, it becomes all but impossible to transfer the compound out of its storage container, which may be necessary to convey it to the polymer to be stabilized. On the other hand, returning it to a liquid physical form requires re-heating, but re-melting a solid material in a closed container can be a laborious and drawn out process. Thus, the situation can lead to process delays, thereby adding unnecessary cost.
  • Polyurethane foams are commonly made from polyether polyols (polyols), which commonly include one or more antioxidants, and diisocyanates.
  • the antioxidants are typically contained in the polyol component for improved stability and low color.
  • the phenomenon of additives being emitted from automotive interior plastics is sometimes known as fogging. Once deposited, they may cause the windshield or other windows to fog up.
  • fogging Once deposited, they may cause the windshield or other windows to fog up.
  • the concern over automotive interior fog is not simply a matter of safety owing to impaired visibility, but, rather, is also fueled by concern for the health of the car's occupants.
  • polymers e.g., polyurethanes such as foamed polyurethanes, having low fog characteristics compared to industry standard controls.
  • U.S. Patent No. 3,956,247 discloses that the solution halogenation of EPDM (rubbery terpolymer of ethylene, an alpha mono-olefin, and a nonconjugated diene) in the presence of an epoxy compound, such as epoxidized soybean oil, with or without a poly(alkylene ether) glycol yields a halogenated EPDM of excellent viscosity stability and limited gel content.
  • EPDM rubbery terpolymer of ethylene, an alpha mono-olefin, and a nonconjugated diene
  • an epoxy compound such as epoxidized soybean oil
  • a mixture of two parts of nonylated phenyl phosphite and one part of styrenated-p-cresol can be employed as an antioxidant.
  • U.S. Patent No. 5,140,055 discloses that a rubber composition containing a specifically limited imidazole compound or imidazoline compound, or benzimidazole or its specifically limited derivative has a large tan ⁇ at high temperature range, and a tire having a tread using such rubber composition is prevented from being lowered in the value of tan ⁇ due to the temperature rising during the running and has an improved grip performance during the high speed running.
  • the use of Bronsted acid in combination with the imidazole, imidazoline or benzimidazole can obviate the drawback of poor scorch resistance of a rubber composition containing the imidazole, imidazoline or benzimidazole alone.
  • the Bronsted acid to be used includes phenol derivatives, carboxylic acids, sulfonic acids, sulfuric acid and its derivatives, phosphoric acid and its derivatives, cyanuric acid and its derivatives, sulfinic acid, nitric acid and its derivatives, phosphorous acid and carbonic acid and its derivatives.
  • Compounds listed as useful include 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis-4-methyl-6-tert-butylphenol, 4,4'-thiobis-3-methyl-6-tertbutylphenol, styrenated p-cresol, phosphoric acid, phosphoric acid esters, phosphorous acid, and phosphorous acid esters, among many others.
  • U.S. Patent No. 5,466,740 discloses a halogen-containing resin composition made stable to heat and light, by incorporating (a) a calcium-based composite metal hydroxide and a calcium-based composite metal oxide, (b) a ⁇ -diketone compound or metal salt thereof, and optionally (c) an organic acid salt of zinc.
  • the halogen-containing resin composition may contain conventional additives, such as organic tin stabilizers, epoxy stabilizers, phosphorous acid esters, sulfur-containing compound stabilizers, phenolic stabilizers, and antioxidants, e.g., styrenated p-cresol, 2,6-di-tert-butyl-4-methylphenol, butylated anisol, 4,4'-methylenebis (6-tert-butyl-3-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-methylphenol ), l,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4 -hydroxybenzyl)benzene, and tetrakis [3-(4-hydroxy-3,5-di-tert-butylphenyl) propionyloxymethylene]methane.
  • additives such as organic tin stabilizers, epoxy stabilizers, phosphorous acid esters, sulfur-containing compound stabilizers
  • U.S. Patent No. 6,242,562 discloses a process for producing a vinyl chloride polymer that includes the steps of: (A) suspension polymerizing vinyl chloride or a monomer mixture containing vinyl chloride, in an aqueous medium to obtain a polymer slurry; (B) stripping unreacted monomers remaining in the polymer slurry; and (C) subjecting the polymer slurry having passed through the step (B), to dehydration at a temperature of from 8O 0 C to 95 0 C, preferably within 60 minutes after the stripping.
  • vinyl chloride or a monomer mixture containing vinyl chloride, an aqueous medium, a polymerization initiator and a dispersant are charged into a polymerization vessel, and a prescribed polymerization temperature (usually from 30 to 75 0 C) is maintained with stirring to polymerize the vinyl chloride or the monomer mixture.
  • a prescribed polymerization temperature usually from 30 to 75 0 C
  • the polymerization is terminated by, e.g., adding to the reaction mixture an antioxidant having a polymerization inhibitory action, e.g., phenol type antioxidants, such as styrenated p-cresol, among many others.
  • U.S. Patent No. 6,339, 132 discloses a process for regenerating unreacted vinyl chloride monomers including the step of compressing by means of an compressor an unreacted vinyl chloride monomer recovered from a process of vinyl chloride polymer production; and compressing the same in contact with a lubricating oil fed into the compressor.
  • the lubricating oil contains a polymerization inhibitor having a polymerization inhibitory action to the vinyl chloride monomer.
  • Such a polymerization inhibitor may be exemplified by phenol type inhibitors, such as styrenated p-cresol, among many others; amine type inhibitors; sulfur type inhibitors; and phosphorus type inhibitors, which can be used singly or in combination of two or more.
  • phenol type inhibitors such as styrenated p-cresol, among many others
  • amine type inhibitors such as sulfur type inhibitors
  • phosphorus type inhibitors which can be used singly or in combination of two or more.
  • U.S. Patent No. 6,391,065 discloses a water-dilutable UV light absorber composition and method for improving the lightfastness of dyed textiles. The composition is applied to the textiles and includes an ultraviolet light absorbing agent and an organic solvent suitable for dissolving the ultraviolet light absorbing agent.
  • Example 5 of the patent discloses adding 10.0 g of benzyl-benzoate into 20.0 g "Naugard 529" liquid anti-oxidant/solvent(alkylated-styrenated p-cresol) to reduce viscosity.
  • the present invention is directed to a liquid styrenated phenolic composition, comprising: (a) at least one distyrenated phenolic in an amount from about 70 to about 98 percent by total Gas Chromatography area; (b) at least one monostyrenated phenolic in an amount greater than 1 percent, e.g., greater than 5 percent, by total Gas Chromatography area; and (c) at least one tristyrenated phenolic in an amount greater than 1 percent, e.g., greater than 5 percent, by total Gas Chromatography area.
  • the composition comprises the at least one monostyrenated phenolic in an amount less than 10 percent by total Gas Chromatography area and the at least one tristyrenated phenolic in an amount less than 10 percent by total Gas Chromatography area.
  • the composition preferably comprises the monostyrenated phenolic and the tristyrenated phenolic, in combination, in an amount from 5 to 20 percent by total Gas Chromatography area.
  • the composition, as formed has an acid number less than 0.1 mg KOH/gram and has an APHA color value of less than 150, e.g., less than 100.
  • the composition preferably has a viscosity of less than 40,000 cPs at 25°C.
  • the composition optionally further comprises: (d) a diluent in an amount from 0.5 to 20 weight percent, based on the total weight of (a) - (d).
  • the composition may also include a co-stabilizer, which, for example, may be selected from the group consisting of phenolics, phosphites, diaryl amines, and epoxidized vegetable oils.
  • the co-stabilizer is an organophosphite, e.g., tris(nonylphenyl)phosphite.
  • One optional organophosphite is Weston® NPF 705.
  • the co-stabilizer is a dialkylated diphenylamine.
  • the invention is to a polymer article comprising a polymer and any of the above-described styrenated phenolic composition.
  • the polymer may, for example, be selected from the group consisting of polyolefins, PVC, polyurethanes, polyols and elastomers.
  • the polymer is styrene-butadiene rubber.
  • the polymer article preferably comprises a polyol or a polyurethane and the composition exhibits low fog.
  • the invention is a lubricant comprising a base stock of lubricating viscosity and the above-described styrenated phenolic composition.
  • the lubricant composition preferably comprises the base stock in an amount greater than 90 weight percent, and the styrenated phenolic in an amount greater than 0.05 weight percent, based on the weight of the lubricant.
  • the lubricant comprises the lubricant base stock in an amount greater than 95 weight percent, and the styrenated phenolic in an amount from 0.1 to 5 weight percent, based on the weight of the lubricant.
  • the lubricant composition further comprises at least one antioxidant comprising one or more secondary diarylamines having the general formula:
  • the at least one monostyrenated phenolic comprises monostyrenated p-cresol
  • the at least one distyrenated phenolic comprises distyrenated p- cresol
  • the at least one tristyrenated phenolic comprises tristyrenated p-cresol.
  • the at least one monostyrenated phenolic comprises a mixture of monostyrenated o-cresol and monostyrenated p-cresol
  • the at least one distyrenated phenolic comprises a mixture of distyrenated o-cresol and distyrenated p- cresol
  • the at least one tristyrenated phenolic comprises a mixture of tristyrenated o- cresol and tristyrenated p-cresol.
  • the composition may comprise the distyrenated p-cresol in an amount greater than 1 percent by total Gas Chromatography area, and the distyrenated o-cresol in an amount greater than 1 percent by total Gas Chromatography area.
  • the at least one monostyrenated phenolic comprises a mixture of monostyrenated phenol and monostyrenated p-cresol
  • the at least one distyrenated phenolic comprises a mixture of distyrenated phenol and distyrenated p- cresol
  • the at least one tristyrenated phenolic comprises a mixture of tristyrenated phenol and tristyrenated p-cresol.
  • the composition may, for example, comprise the monostyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, the distyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, and the tristyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area.
  • the at least one monostyrenated phenolic comprises a mixture of monostyrenated phenol and monostyrenated o-cresol
  • the at least one distyrenated phenolic comprises a mixture of distyrenated phenol and distyrenated o- cresol
  • the at least one tristyrenated phenolic comprises a mixture of tristyrenated phenol and tristyrenated o-cresol.
  • the composition may, for example, comprise the monostyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, the distyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, and the tristyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area.
  • the invention is to a process for forming a liquid styrenated phenolic composition, comprising the step of reacting styrene with at least one phenolic in the presence of a sulfonic acid catalyst in a reaction vessel at an elevated temperature to form a product mixture comprising at least one distyrenated phenolic in an amount from 70 to 98 percent by total Gas Chromatography area, a monostyrenated phenolic in an amount greater than 1 percent by total Gas Chromatography area, and a tristyrenated phenolic in an amount greater than 1 percent by total Gas Chromatography area.
  • the phenolic preferably has the general formula:
  • R 1 is hydrogen or methyl.
  • the product mixture preferably is a liquid at room temperature.
  • the at least one phenolic may comprise one or more of phenol, p- cresol, o-cresol, a mixture of o-cresol and p-cresol, a mixture of phenol and p-cresol, a mixture of phenol and o-cresol, or a mixture of o-cresol, p-cresol and phenol.
  • the product mixture comprises distyrenated p-cresol in an amount greater than 1 percent by total Gas Chromatography area, and distyrenated o-cresol in an amount greater than 1 percent by total Gas Chromatography area.
  • the product mixture comprises monostyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, distyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, and tristyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area.
  • the product mixture comprises monostyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, distyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, and tristyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area.
  • the product mixture preferably comprises the at least one monostyrenated phenolic in an amount greater than 5 percent by total Gas Chromatography area, and preferably comprises the at least one tristyrenated phenolic in an amount greater than 5 percent by total Gas Chromatography area.
  • the product mixture preferably comprises the monostyrenated phenolic in an amount less than 10 percent by total Gas Chromatography area and the tristyrenated phenolic in an amount less than 10 percent by total Gas Chromatography area.
  • the product mixture preferably comprises the monostyrenated phenolic and the tristyrenated phenolic, in combination, in an amount from 5 to 20 percent by total Gas Chromatography area.
  • the sulfonic acid catalyst employed in the process preferably is selected from the group consisting of trifluoromethane sulfonic acid and trichloromethane sulfonic acid.
  • the sulfonic acid catalyst is selected from the group consisting of methane sulfonic acid, ethane sulfonic acid, methyl trichloromethane sulfonic acid, methyl trifluoromethane sulfonic acid, ethyl trichloromethane sulfonic acid and ethyl trifluoromethane sulfonic acid.
  • the sulfonic acid catalyst optionally is present in an amount ranging from 1 wppm to 1000 wppm, based on the total weight of the styrene, the phenolic and the catalyst added to the reaction vessel.
  • the styrene and the phenolic preferably are reacted at a molar ratio of 1.85: 1 to 2.1 :1, respectively.
  • the product mixture has an acid number of less than 0.1 mg KOH/gram, and preferably has an APHA color value of less than 150, e.g., less than 100.
  • the invention is directed to a process for the preparation of a mixture of styrenated phenolics, e.g., one or more of phenol, o-cresol, and/or p-cresol, that is liquid at room temperature and preferably has a viscosity of less than 40,000 cps at 25°C.
  • the process affords corresponding distyrenated phenolics assaying at 70% minimum by total GC area.
  • the process comprises the step of reacting styrene with one or more phenolics, e.g., one or more of phenol, o-cresol, and/or p-cresol, at a molar ratio of 1.85 to 2.1:1, respectively, in the presence of an acid catalyst, e.g., a sulfonic acid, at elevated temperature, wherein the mixture comprises at least one monostyrenated phenolic, at least one distyrenated phenolic, and at least one tristyrenated phenolic and has an acid number of less than 0.1 mg KOH/gram.
  • an acid catalyst e.g., a sulfonic acid
  • the present invention is directed to a method for stabilizing a polymeric composition
  • a method for stabilizing a polymeric composition comprising including in said composition an effective amount of a mixture of styrenated phenolics, e.g., p-cresol, that is liquid at room temperature and has a viscosity of less than 40,000 cps at 25 0 C, wherein said mixture is prepared by a process yielding distyrenated phenolics, e.g., 2,6-distyryl-p-cresol, with an assay of 70% minimum by total GC area and comprises reacting styrene with a phenolic, e.g., p-cresol, at a molar ratio of 1.85 to 2.1:1, respectively, in the presence of an acid catalyst, e.g., a sulfonic acid catalyst, at elevated temperature, wherein said mixture comprises at least one monostyrenated phenolic, e.g., monostyrenated
  • the present invention is directed to a composition
  • a composition comprising a mixture of styrenated p-cresol species that is liquid at room temperature, has a viscosity of less than 40,000 cps at 25 0 C, comprising 2,6-distyrenated p-cresol assaying at 70% minimum by total GC area percent prepared by a process comprising reacting styrene with p-cresol at a molar ratio of 1.85 to 2.1:1, respectively, in the presence of an acid catalyst at elevated temperature, wherein said mixture comprises monostyrenated-p- cresol, distyrenated-p-cresol, and tristyrenated-p-cresol and has an acid number of less than 0.1 mg KOH/gram.
  • the present invention pertains to styrenated phenolic compositions that are liquids at room temperature.
  • the present invention is directed to a liquid styrenated phenolic composition, comprising at least one distyrenated phenolic in an amount from about 70 to about 98 percent by total Gas Chromatography area; at least one monostyrenated phenolic in an amount greater than 1 percent, e.g., greater than 5 percent, by total Gas Chromatography area; and at least one tristyrenated phenolic in an amount greater than 1 percent, e.g., greater than 5 percent, by total Gas Chromatography area.
  • the composition comprises the at least one monostyrenated phenolic in an amount less than 10 percent (but greater than 1 percent) by total Gas Chromatography area and the at least one tristyrenated phenolic in an amount less than 10 percent (but greater than 1 percent) by total Gas Chromatography area.
  • the composition preferably comprises the monostyrenated phenolic and the tristyrenated phenolic, in combination, in an amount from 5 to 20 percent by total Gas Chromatography area.
  • the styrenated phenolic compositions of the invention preferably have a room temperature viscosity of less than 40,000 cPs.
  • the styrenated phenolics of the present invention are highly stable liquids at room temperature (25 0 C) and typically possess highly desirable color and clarity characteristics, e.g., exhibiting a APHA color value less than 150, e.g., less than 100 or less than 80.
  • APHA color value less than 150, e.g., less than 100 or less than 80.
  • the invention is to processes for forming such styrenated phenolic compositions using a sulfonic acid catalyst.
  • the invention also is directed to polymer articles and lubricants that are stabilized with such styrenated phenolic compositions.
  • the styrenated phenolic compositions of the present invention preferably are prepared by reacting styrene with one or more phenolics, preferably at a molar ratio of from about 1.85:1 to about 2.1:1, respectively, at an elevated temperature in the presence of an acid catalyst, preferably a sulfonic acid catalyst, to provide a mixture of styrenated phenolic species.
  • a preferred sryrene:phenolic molar ratio is from 1.75 to 2.2:1, e.g., from 1.85 to 1.98:1, from 1.9 to 1.98:1, or about 1.95:1.
  • the phenolic employed in the reaction with styrene to form the liquid styrenated phenolics of the invention may vary widely, but in preferred embodiments is selected from one or more of phenol, p-cresol, tricresol and o-cresol.
  • Scheme 1 depicts a typical reaction, in which the phenolic is p-cresol.
  • the p-cresol reacts with styrene in the presence of an acid catalyst, preferably a sulfonic acid catalyst, to form monostyrenated p-cresol, distyrenated p-cresol and tristyrenated p-cresol.
  • an acid catalyst preferably a sulfonic acid catalyst
  • the main product in the product mixture is the distyrenated phenolic, (e.g., 2,6-di-styrenated-p-cresol in Sheme 1) assaying at 70% minimum, e.g., 75% minimum, 80% minimum, or 90% minimum, by total Gas Chromatography (GC) area.
  • the distyrenated phenolic of the product mixture and various isomers thereof are referred to herein as the "Di" product.
  • the Di product may be present in the product mixture in an amount ranging, for example, from about 70 to 98%, e.g., from 80 to 95%, from 80 to 92%, from 80 to 85%, from 85 to 95% or from 90 to 95%, as determined by total GC area.
  • minor amounts of the corresponding monostyrenated phenolic ("Mono") and tristyrenated phenolic (“Tri”) are also formed in the reaction process, as illustrated in Scheme 1, above, for p-cresol.
  • Tri Tri compounds and isomers
  • Tri Tri compounds
  • Tri refers to each of these various species collectively, so long as the relevant phenolic has three styryl groups associated therewith.
  • the terms "Mono,” “Di” and 'Tri” as used herein refer to phenolics (e.g., one or more of phenol, p-cresol and/or o-cresol) that have been substituted with one, two or three styryl groups, respectively, including various isomers thereof.
  • the phenolic that is styrenated according to the process may vary widely.
  • Preferred phenolics include phenol, o-cresol, p-cresol and mixtures thereof.
  • the phenolic preferably has the general formula:
  • Ri is hydrogen or methyl
  • the phenolic comprises p-cresol.
  • the at least one monostyrenated phenolic comprises monostyrenated p-cresol
  • the at least one distyrenated phenolic comprises distyrenated p-cresol
  • the at least one tristyrenated phenolic comprises tristyrenated p-cresol.
  • the phenolic comprises a mixture of o-cresol and p-cresol.
  • the at least one monostyrenated phenolic comprises a mixture of monostyrenated o-cresol and monostyrenated p-cresol
  • the at least one distyrenated phenolic comprises a mixture of distyrenated o-cresol and distyrenated p-cresol
  • the at least one tristyrenated phenolic comprises a mixture of tristyrenated o-cresol and tristyrenated p-cresol.
  • the composition or product mixture may comprise the distyrenated p-cresol in an amount greater than 1 percent by total Gas Chromatography area, and the distyrenated o-cresol in an amount greater than 1 percent by total Gas Chromatography area.
  • the phenolic comprises a mixture of phenol and p- cresol.
  • the at least one monostyrenated phenolic comprises a mixture of monostyrenated phenol and monostyrenated p-cresol
  • the at least one distyrenated phenolic comprises a mixture of distyrenated phenol and distyrenated p-cresol
  • the at least one tristyrenated phenolic comprises a mixture of tristyrenated phenol and tristyrenated p-cresol.
  • composition or product mixture may, for example, comprise the monostyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, the distyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, and the tristyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area.
  • the phenolic comprises a mixture of phenol and o- cresol.
  • the at least one monostyrenated phenolic comprises a mixture of monostyrenated phenol and monostyrenated o-cresol
  • the at least one distyrenated phenolic comprises a mixture of distyrenated phenol and distyrenated o-cresol
  • the at least one tristyrenated phenolic comprises a mixture of tristyrenated phenol and tristyrenated o-cresol.
  • composition or product mixture may, for example, comprise the monostyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, the distyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, and the tristyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area.
  • the phenolic may comprises a mixture of phenol, o-cresol and p- cresol, in which case the at least one monostyrenated phenolic comprises a mixture of monostyrenated phenol, monostyrenated o-cresol, and monostyrenated p-cresol.
  • the at least one distyrenated phenolic comprises a mixture of distyrenated phenol, distyrenated o-cresol, and distyrenated p-cresol
  • the at least one tristyrenated phenolic comprises a mixture of tristyrenated phenol, tristyrenated o-cresol and tristyrenated p- cresol.
  • composition or product mixture may, for example, comprise the monostyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, the distyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area, and the tristyrenated phenol in an amount greater than 1 percent by total Gas Chromatography area.
  • the liquid physical form of the styrenated phenolic compositions of the invention is achieved by incorporating two additional reaction products, namely the Mono and Tri products, in the resultant styrenated phenolic composition.
  • the styrenated phenolic compositions of the invention preferably possess improved clarity and have a color value of less than 150 APHA, e.g., less than 100 APHA, or less than 80 APHA.
  • the stabilizers of the present invention will be referred to simply as styrenated phenolic compositions; however, it should be understood that the actual product is a mixture of the Mono, Di, and Tri compositions, as described above.
  • the relative amounts of Mono, Di and Tri compositions formed in the process may be controlled by controlling the relative ratios of the reactants. Generally, for example, an increase in styrene:phenolic molar ratio will tend to favor formation of Tri over Mono. Conversely, lower styreneiphenolic molar ratios will favor the formation of Mono over Tri.
  • the styrene is added to the phenolic, e.g., one or more of phenol, o- cresol and/or p-cresol, rather than adding the phenolic to the styrene, which may undesirably lead to polymerization of the styrene prior to or during addition of the phenolic.
  • the styrene is added to heated phenolic that has been heated to a temperature ranging from 50 to 90 0 C, e.g., from 55 to 85 0 C, from 60 to 8O 0 C, or preferably about 7O 0 C.
  • the reaction is run isothermally, i.e., at a single elevated temperature, throughout the reaction process.
  • the reaction is run at a temperature in the range of from about 40 0 C to about 15O 0 C, more preferably in the range of from about 60 to about 8O 0 C.
  • the formation of the Mono species tends to occur quickly, but the formation of the Di species tends to occur more slowly.
  • the rate of formation of the Di species may be increased, however, by increasing the temperature of the reaction mixture.
  • a two stage temperature scheme is employed, in which the reactants are heated to a first temperature for a first time period, and then the reaction mixture is heated to a second "finishing" temperature for a second time period.
  • the first temperature optionally ranges from 50 to 9O 0 C, e.g., from 55 to 85°C, from 60 to 8O 0 C, or preferably about 7O 0 C, and the first time period may range from 1 to 10 hours, e.g., from 1 to 4 hours, from 2 to 4 hours or from 2.5 to 3.5 hours.
  • the first time period begins when the reactants initially contact one another, e.g., when styrene is first added to the phenolic.
  • the second temperature optionally ranges from 60 to 11O 0 C, e.g., from 70 to 110 0 C, from 75 to 110 0 C, from 80 to 100 0 C, or preferably about 9O 0 C, and the second time period may range from 0.25 to 4 hours, e.g., from 1 to 4 hours, from 2 to 4 hours or from 2.5 to 3.5 hours. Extended heating times may lead to darkening of the resulting reaction mixture and, depending on the intended use, may be undesirable.
  • the difference between the second and first temperatures preferably is greater than 1O 0 C, e.g., greater than 15 0 C, and most preferably is about 2O 0 C.
  • the difference between the second and first temperatures optionally is from 10 to 7O 0 C, e.g., from 10 to 5O 0 C, or from 15 to 25 0 C.
  • the reaction process may occur in a single reactor, where the temperature may be increased from the first temperature to the second temperature, or, alternatively, in two or more separate reactors.
  • the reactants may first be added to a first reactor that is held at the first temperature, and then the resulting mixture directed to a second reactor, which is held at the second temperature for the completion of the process.
  • the temperature may be gradually increased or ramped throughout the reaction process or through a portion of the reaction process.
  • the temperature may be gradually increased, e.g., at a rate of from 0.01 to 2 °C/min, at a rate of from 0.02 to 1 °C/min, or at a rate of from 0.02 to 0.1 °C/min, optionally for a period of time ranging from 0.5 to 8 hours, e.g., from 2 to 8 hours or from 4 to 8 hours.
  • the overall reaction time will normally be in the range of from about one to about seven hours, preferably, in the range of from about three to about four hours.
  • the reaction can be run in a solvent that is inert thereto, which will preferably be a hydrocarbon, such as toluene, benzene, heptane, hexane, and the like.
  • a solvent that is inert thereto which will preferably be a hydrocarbon, such as toluene, benzene, heptane, hexane, and the like.
  • the process may be run in a continuous process, a semi-continuous process or a batch process.
  • styrenation of phenolics preferably occurs in the presence of a catalyst.
  • Suitable catalysts typically have acidic properties, e.g., Br ⁇ nsted acids or Lewis acids.
  • acid catalysts are known to impart a yellow color to styrenated phenolic compositions, which may render them unsuitable for certain applications, e.g., polymer or lubricant applications, in which color is an important criterion.
  • examples of such catalysts include, but are not limited to, boron trifluoride etherate and sulfuric acid.
  • boron trifluoride etherate catalyst is known to give a product with an American Public Health Association (APHA) color index value of more than 150.
  • APHA American Public Health Association
  • liquid styrenated phenolic compositions can be prepared having very low color, if desired.
  • a typical preferred APHA value for the liquid styrenated phenolic compositions of the present invention is an APHA value of less than 150, preferably, an APHA value of less than 100 or less than 80.
  • low color-producing catalysts in this context include, but are not limited to, sulfonic acids and cation exchange resins.
  • the sulfonic acid may be of the formula:
  • R is selected from the group consisting of hydrogen, an alkyl group, such as, for example, a Ci-C 8 alkyl group (including but not limited to, methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl) a halogen (i.e., F, Cl, Br, I or At), aryl (including but not limited to phenyl, benzyl, o-tolyl, m-tolyl, and p-tolyl), and haloalkyl (including but not limited to trichloromethyl and trifluoromethyl).
  • an alkyl group such as, for example, a Ci-C 8 alkyl group (including but not limited to, methyl, ethyl, n- propyl, isopropyl,
  • Preferred sulfonic acids include, for example, methane sulfonic acid, ethane sulfonic acid, trichloromethane sulfonic acid and trifluoromethane sulfonic acid (triflic acid).
  • the amount of acid catalyst employed in the process will vary widely depending, for example, on the strength of the acid. If triflic acid is employed as the acid catalyst, it is preferably present in an amount ranging from 1 wppm to 1000 wppm, e.g., from 1 wppm to 500 wppm or from 1 wppm to 100 wppm, based on the total weight of the styrene, the phenolic and the catalyst added to the reaction vessel. Greater amounts, e.g., greater than 0.1 weight percent, greater than 1 weight percent, greater than 3 weight percent, or potentially much greater amounts of catalyst may be necessary for other catalysts, e.g., ion exchange resins or weaker acids.
  • the catalyst employed includes a sulfonic acid catalyst, e.g., triflic acid, in combination with one or more phosphites.
  • a sulfonic acid catalyst e.g., triflic acid
  • molar ratios of sulfonic acid to phosphites may range, e.g., from 1 to 5 or from 1 to 100.
  • phosphites that may be employed include trilauryl phosphite, diisodecyl phenyl phosphite, isodecyl diphenyl phosphite, triphenyl phosphite.
  • the above-described processes of the invention form novel styrenated phenolic compositions, which comprise a mixture of Mono, Di, and Tri styrenated phenolics.
  • the Mono and Tri components should each be present at a level greater than 1% by total GC area, optionally no less than 2%, no less than 5% or no less than 10%, based on the total GC area of the product mixture (including peaks corresponding to unreacted styrene and phenolic).
  • a typical Mono component level is in the range of greater than 1 to about 15%, e.g., from about 1 to about 10%, or from about 2 to about 5%, based on the total GC area of the product mixture.
  • a typical level for the Tri component is from about 1 to about 15%, as well, e.g., from about 1 to about 10%, or from about 2 to about 5%, based on the total GC area of the product mixture.
  • the percentage of the combination of the Mono and Tri components will be in the range of from about 2 to about 30 percent based on the total GC area of the product mixture, e.g., from about 5 to about 30 percent, from about 5 to about 20% or from about 5 to about 10%, based on the total GC area of the product mixture.
  • the styrenated phenolic composition of the invention preferably is a liquid. More preferably, the composition (optionally with diluent) has a viscosity less than 40,000 cPs at 25 0 C, e.g., less than 30,000 cPs, less than 25,000 cPs or less than 15,000 cPs at 25 0 C.
  • the styrenated phenolic composition may have a viscosity ranging from 1000 to 40,000 cPs, e.g., from 1,500 to 30,000 cPs or from 2,000 to 30,000 cPs, at 25°C.
  • viscosity refers to Brookfield viscosity at 25°C, as determined by ASTM-D-2393, the entirety of which is incorporated herein by reference.
  • Some conventional styrenated phenolic compositions tend to be solids or unstable slushy compositions containing precipitant. Movement and agitation of styrenated phenolic compositions may further increase precipitant formation.
  • the styrenated phenolic compositions of the invention are non-slushy and preferably do not form any visible solids (precipitant) after 1 week, more preferably after 2 weeks, after 1 month, after 3 months, after 6 months or after 1 year when stored without substantial movement thereof and optionally under nitrogen atmosphere.
  • precipitation amounts are based on styrenated phenolic compositions at room temperature without substantial movement thereof, i.e., resting on in a storage container on a level surface for the relevant period, and preferably under nitrogen atmosphere.
  • acid catalysts preferably are employed in the processes of the invention, the resulting styrenated phenolic composition preferably has a low acid number since the presence of acid in the styrenated phenolic composition may undesirably encourage polymerization of the styrenated phenolic and decrease liquid lifetime.
  • the styrenated phenolic composition has an acid number less than 0.5 mg KOH/gram, e.g., less than 0.2 mg KOH/gram, less than 0.1 mg KOH/gram, less than 0.05 mg KOH/gram or less than 0.01 mg KOH/gram.
  • acid number is determined by titration with a KOH/methanol solution, where the titrant is dissolved in isopropyl alcohol. The acid number is the mg KOH required per gram of sample to achieve a neutral solution.
  • the styrenated phenolic mixtures of the invention are liquids at room temperature even in the absence of any other components, their viscosity may be further reduced by adding a diluent thereto.
  • a diluent is added to the above-described styrenated phenolic composition in order to further reduce its viscosity relative to the composition without diluent.
  • the styrenated phenolic compositions of the present invention may or may not include a diluent.
  • the invention is to a styrenated phenolic composition, comprising: at least one distyrenated phenolic (e.g., 2,6-distyrenated p-cresol), optionally in an amount from 70 to 98 percent by total Gas Chromatography area, at least one monostyrenated phenolic, optionally in an amount greater than 1 percent, e.g., greater than 5 percent, by total Gas Chromatography area, at least one tristyrenated phenolic, optionally in an amount greater than 1 percent, e.g., greater than 5 percent, by total Gas Chromatography area, and a diluent, optionally in an amount ranging from 0.5 to 20 weight percent, e.g., from 1 to 10 weight percent, from 3 to 7 weight percent or about 5 weight percent, based on the total weight of the styrenated phenolic species and the diluent.
  • distyrenated phenolic e.g., 2,6-distyrenated
  • the diluent may be any liquid miscible with the above- described styrenated phenolics that improves the handling properties of the composition, as indicated above.
  • exemplary diluent materials may include, for example, lubricating oils including base stocks obtained by isomerization of synthetic wax and wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of crude oil.
  • Other possible diluents include petroleum oils, mineral oils, and oils derived from coal or shale.
  • Natural materials suitable for use as the diluent may include, for example, animal oils, such as lard oil, tallow oil, vegetable oils including canola oils, castor oils, linseed oils, and sunflower oils.
  • the diluent comprises an epoxidized vegetable oil, such as, but not limited to, epoxidized canola oils, epoxidized castor oils, epoxidized linseed oils, and epoxidized sunflower oils.
  • the lubricating oil comprises a commercially available epoxidized soybean oil such as DRAPEX® 6.8 (Chemtura, Corp., Middlebury, Connecticut, USA).
  • the viscosity of the diluent similarly may vary widely, but preferably is no greater than 5,000, e.g., no greater than 1,000 cPs, no greater than 500 cPs, no greater than 400 cPs or no greater than 350 cPs. In terms of ranges, the diluent preferably has a viscosity ranging from 100 to 500 cPs, e.g., from 200 to 400 cPs or from 260 to 380 cPs, and most preferably about 320 cPs.
  • the diluent preferably has a molecular weight of less than 10,000, e.g., less than 5,000, less than 2,500 or less than 1,500, and optionally ranges from 500 to 1500, e.g., from 750 to 1250, and most preferably is about 1000.
  • molecular weights provided herein are determined through gel permeation chromatography using polystyrene standards.
  • the diluent may hydrolyze and/or polymerize slowly in the presence of acids, alkalis, water or water vapor.
  • the diluent preferably has a low acid number, preferably less than 1.5, e.g., less than 1.0, and preferably about 0.5, as determined by AOCS-Te-2a, the entirety of which is incorporated herein by reference.
  • the diluent also ideally has a very high degree of saturation (a low degree of unsaturation) and preferably has an iodine number (HANUS) less than 2.0, e.g., less than 1.8 or less than 1.5, as determined by AOCS-Tgl-64T, the entirety of which is incorporated herein by reference.
  • HANUS iodine number
  • the amount of diluent added to the styrenated phenolic composition for handling purposes depends on factors such as the end use for the styrenated phenolic composition. In some preferred embodiments, the diluent is added to the styrenated phenolic composition in an amount less than 20 weight percent, e.g., less than 10 weight percent or less than 8 weight percent, based on the total weight of the styrenated phenolics and the diluent.
  • the diluent optionally is added to the styrenated phenolics in an amount ranging from 0.5 to 20 weight percent, e.g., from 1 to 10 weight percent, from 3 to 7 weight percent, or about 5 weight percent, based on the total weight of the styrenated phenolics and the diluent.
  • the invention further pertains to a stabilized thermoplastic or elastomeric resin, wherein one component comprises the styrenated phenolic composition and the other a thermoplastic and/or elastomeric polymer, such as a polyolefin, polyvinyl chloride, SBR, nitrile rubber, and the like.
  • Thermoplastic polymers that can be stabilized by the styrenated phenolic compositions of the present invention may be any thermoplastic known in the art, such as polyolefin homopolymers and copolymers, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrenic polymers and copolymers, polycarbonates, acrylic polymers, polyamides, polyacetals and halide- containing polymers.
  • polymers such as polyphenylene ether/styrenic resin blends, polyvinyl chloride/ABS or other impact modified polymers, such as methacrylonitrile and alpha-methylstyrene containing ABS, and polyester/ABS or polycarbonate/ABS and polyester plus some other impact modifier may also be used.
  • polymers are available commercially or may be made by means well known in the art.
  • the stabilizers of the invention are particularly useful in polyolefins, polyurethanes, and halide-containing polymers.
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene, or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) may be used.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • Mixtures of these polymers for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE), may also be used.
  • copolymers of monoolefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene/propylene, LLDPE and its mixtures with LDPE, propylene/butene-1, ethylene/hexene, ethylene/ethylpentene, ethylene/heptene, ethylene/octene, propylene/isobutylene, ethylene/butane-1, propylene/butadiene, isobutylene, isoprene, ethylene/alkyl acrylates, ethylene/alkyl methacrylates, ethylene/vinyl acetate (EVA) or ethylene/acrylic acid copolymers (EAA) and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene- norbornene; as well as mixtures of such
  • Halogen-containing polymers e.g., PVC
  • poly(vinyl chloride) and PVC are intended to include both homopolymers and copolymers of vinyl chloride, i.e., vinyl resins containing vinyl chloride units in their structure, e.g., copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate; copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile; copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or anhydrides thereof, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride; post-chlorinated polymers and copolymers of vinyl chloride; copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such
  • polyvinyl chloride and "PVC” as employed herein are also intended to include graft polymers of PVC with EVA, ABS, and MBS.
  • Preferred substrates are also mixtures of the above-mentioned homopolymers and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM, and polylactones.
  • Vinyl acetate, vinylidene dichloride, acrylonitrile, chlorofluoroethylene and/or the esters of acrylic, fumaric, maleic and/or itaconic acids may be mentioned as preferred examples of monomers that are copolymerizable with vinyl chloride.
  • polyvinyl chloride can be chlorinated having a chlorine content of up to 70% by weight. This invention applies particularly to the vinyl chloride homopolymers.
  • PVC will also be understood to include recyclates of halogen-containing polymers that have suffered damage by processing, use or storage.
  • the polymers may also include styrenic polymers, such as polystyrene, poly- (p-methylstyrene), poly-( ⁇ -methylystyrene), copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/maleic anhydride, styrene/maleimide, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methylacrylate, 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 styren
  • Styrenic polymers may additionally or alternatively include graft copolymers of styrene or ⁇ -methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene and copolymers thereof; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers,
  • Nitrile polymers are also useful in the polymer composition of the invention. These include homopolymers and copolymers of acrylonitrile and its analogs, such as polymethacrylonitrile, polyacrylonitrile, acrylonitrile/-butadiene polymers, acrylonitrile/alkyl acrylate polymers, acrylonitrile/alkyl methacrylate/butadiene polymers, and various ABS compositions as referred to above in regard to styrenics. [0071] Polymers based on acrylic acids, such as acrylic acid, methacrylic acid, methyl methacrylic 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 acrolein, methacrolein, acrylamide and methacrylamide may also be used.
  • Other useful polymers include homopolymers 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 which contain ethylene oxide as a comonomer; 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; polysulfones, polyethersulfones and polyetherketones; and polyesters which are derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly- 1 ,4dimethylo
  • Polyamides and copolyamides which are derived from bisamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4/6, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m-xylene bisamine and adipic acid; polyamides prepared from hexamethylene bisamine and isophthalic or/and terephthalic acid and optionally an elastomer as modifier, for example poly-2,4,4 trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide may be useful.
  • copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; 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.
  • Suitable elastomeric polymers include solution styrene-butadiene rubber (SSBR), styrene-butadiene rubber (SBR), natural rubber (NR), polybutadiene (BR), ethylene-propylene co- and terpolymers (EP, EPDM), and acrylonitrile-butadiene rubber (NBR).
  • the rubber composition is comprised of at least one diene-based elastomer, or rubber.
  • Suitable conjugated dienes are isoprene and 1,3- butadiene and suitable vinyl aromatic compounds are styrene and ⁇ - methyl styrene.
  • the rubber is a sulfur curable rubber.
  • Such diene-based elastomer, or rubber may be selected, for example, from at least one of cis-l,4-polyisoprene rubber (natural and/or synthetic, and preferably natural rubber), emulsion polymerization prepared styrene/butadiene copolymer rubber, organic solution polymerization prepared styrene/butadiene rubber, 3,4-polyisoprene rubber, isoprene/butadiene rubber, styrene/isoprene/butadiene terpolymer rubber, cis-l,4-polybutadiene, medium vinyl polybutadiene rubber (35 percent to 50 percent vinyl), high vinyl polybutadiene rubber (50 percent to 75 percent vinyl), styrene/isoprene copolymers, emulsion polymerization prepared styrene/butadiene/acrylonitrile terpolymer rubber and butadiene/acrylonitrile copoly
  • An emulsion polymerization derived styrene/butadiene might be used having a relatively conventional styrene content of 20 percent to 28 percent bound styrene or, for some applications, an e-SBR having a medium to relatively high bound styrene content, namely, a bound styrene content of 30 percent to 45 percent.
  • Emulsion polymerization prepared styrene/butadiene/acrylonitrile terpolymer rubbers containing 2 to 40 weight percent bound acrylonitrile in the terpolymer are also contemplated as diene- based rubbers for use in this invention.
  • the solution polymerization prepared SBR typically has a bound styrene content in a range of 5 to 50 percent, preferably 9 to 36 percent.
  • Polybutadiene elastomer may be conveniently characterized, for example, by having at least a 90 weight percent cis-l,4-content.
  • the one or more polymers preferably comprise a stabilizing amount of the styrenated phenolic composition of the present invention.
  • stabilizing amount or an “effective amount” of the styrenated phenolic composition of the invention is meant when the polymer composition containing such styrenated phenolic composition shows improved stability in any of its physical or color properties in comparison to an analogous polymer composition which does not include the styrenated phenolic composition.
  • improved stability include improved stabilization against, for example, molecular weight degradation, color degradation, and the like from, for example, melt processing, weathering, and/or long term field exposure to heat, light, and/or other elements.
  • an improved stability is meant one or both of lower initial color or additional resistance to weathering, as measured, for example, by initial yellowness index (YI), or by resistance to yellowing and change in color, when compared to a composition without the stabilizer additive.
  • YI initial yellowness index
  • the desired stabilizing amount of the styrenated phenolic composition will vary widely depending on the polymer employed and the intended use for the polymer article at issue, in some exemplary embodiments, the styrenated phenolic composition is present in the polymer in an amount less than 5 weight percent, e.g., less than 1 weight percent, less than 1000 wppm, less than 500 wppm or less than 100 wppm, based on the total weight of the polymer and the styrenated phenolic composition.
  • the styrenated phenolic composition may be present in the polymer in an amount from 10 wppm to 5 weight percent, e.g., from 100 wppm to 1 weight percent, from 100 to 5000 wppm, or from 150 wppm to 1000 wppm, based on the total weight of the polymer and the styrenated phenolic composition. Stabilization of Lubricants
  • the styrenated phenolic compositions of the invention are also useful for the stabilization of lubricants, such as lubricating oil base stocks.
  • a lubricant composition comprising a lubricant base stock, preferably in an amount greater than 90 weight percent, e.g., greater than 95 weight percent or greater than 99 weight percent, based on the weight of the lubricant composition; and a styrenated phenolic composition, preferably in an amount greater than 0.05 weight percent, e.g., greater than 0.5 weight percent or greater than 1 weight percent, based on the weight of the lubricant composition.
  • the lubricant composition preferably comprises the styrenated phenolic composition in an amount from 0.05 to 10 weight percent, e.g., in an amount from 0.1 to 5 weight percent, or in an amount from 0.5 to 1 weight percent, based on the weight of the lubricant composition.
  • the styrenated phenolic composition preferably comprises the distyrenated phenolic (e.g., 2,6-distyrenated p-cresol) in an amount from about 70 to 98%, e.g., from 80 to 95%, from 80 to 92%, from 80 to 85%, from 85 to 95% or from 90 to 95%, by total Gas Chromatography area, monostyrenated phenolic in an amount greater than 1 percent, e.g., greater than 5 percent, by total Gas Chromatography area, and tristyrenated phenolic in an amount greater than 1 percent, e.g., greater than 5 percent, by total Gas Chromatography area.
  • distyrenated phenolic e.g., 2,6-distyrenated p-cresol
  • monostyrenated phenolic in an amount greater than 1 percent, e.g., greater than 5 percent, by total Gas Chromatography area
  • tristyrenated phenolic in an amount greater than 1 percent
  • the styrenated phenolic composition optionally further comprises a diluent, as described above.
  • the lubricating oil base stock may be any natural or synthetic lubricating oil base stock fraction having a kinematic viscosity at 100 0 C of about 2 to about 200 cSt, more preferably about 3 to about 150 cSt, and most preferably about 3 to about 100 cSt.
  • the lubricating oil base stock can be derived, for example, from natural lubricating oils, synthetic lubricating oils, or mixtures thereof.
  • Suitable lubricating oil base stocks include base stocks obtained by isomerization of synthetic wax and wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude oil.
  • Natural lubricating oils include animal oils, such as lard oil, tallow oil, vegetable oils including canola oils, castor oils, linseed oils, and sunflower oils, for example, petroleum oils, mineral oils, and oils derived from coal or shale.
  • the lubricating oil is an epoxidized vegetable oil, such as, but not limited to, epoxidized canola oils, epoxidized castor oils, epoxidized linseed oils, and epoxidized sunflower oils (e.g., DRAPEX® 6.8, Chemtura Corporation, Middlebury, Connecticut, USA).
  • epoxidized vegetable oil such as, but not limited to, epoxidized canola oils, epoxidized castor oils, epoxidized linseed oils, and epoxidized sunflower oils (e.g., DRAPEX® 6.8, Chemtura Corporation, Middlebury, Connecticut, USA).
  • Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and interpolymerized olefins, gas-to-liquids prepared by Fischer- Tropsch technology, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, homologs, and the like.
  • Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof, wherein the terminal hydroxyl groups have been modified by esterification, and etherification, for example.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with a variety of alcohols.
  • Esters useful as synthetic oils also include those made from C 5 to Qg monocarboxylic acids and polyols and polyol ethers.
  • Other esters useful as synthetic oils include those made from copolymers of ⁇ -olefins and dicarboxylic acids which are esterified with short or medium chain length alcohols.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils, comprise another useful class of synthetic lubricating oils.
  • the lubricating oil may be derived from unrefined, refined, re-refined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar and bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
  • a natural source or synthetic source e.g., coal, shale, or tar and bitumen
  • Refined oils are similar to unrefined oils, except that refined oils have been treated in one or more purification steps to improve one or more properties.
  • Suitable purification techniques can include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, percolation, and the like, all of which are well-known to those skilled in the art.
  • Re-refined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
  • Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks.
  • Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
  • Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process.
  • the resulting isomerate product is typically subjected to solvent dewaxing and fractionation to recover various fractions having a specific viscosity range.
  • Wax isomerate is also characterized by possessing very high viscosity indices (VI), generally having a VI of at least 130, preferably at least 135 or higher as determined by ASTM D-2270, the entirety of which is incorporated herein by reference, and, following dewaxing, a pour point of about -2O 0 C or lower.
  • VI very high viscosity indices
  • the lubricating oil used in the practice of the present disclosure can be selected from any of the base oils in Groups I-V as broadly specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • the five base oil groups are described in Table 1.
  • Group I >0.03 and/or ⁇ 90 80 to 120
  • PAOs polyalphaolefins
  • the styrenated phenolic compositions of the present disclosure are especially useful as components in many different lubricating oil compositions.
  • the additives can be included in a variety of oils with lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
  • the additives can be included in crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines.
  • the compositions can also be used in gas engine lubricants, steam and gas turbine lubricants, automatic transmission fluids, gear lubricants, compressor lubricants, metal- working lubricants, hydraulic fluids, and other lubricating oil and grease compositions.
  • the desired stabilizing amount of the styrenated phenolic composition in the lubricant composition will vary widely depending on the lubricating base stock employed and the intended use for the lubricant composition at issue, in some exemplary embodiments, the styrenated phenolic composition is present in the lubricant composition in an amount less than 10 weight percent, e.g., less than 1 weight percent, less than 0.5 weight percent, or less than 0.1 weight percent, based on the total weight of the lubricant base stock and the styrenated phenolic composition.
  • the styrenated phenolic composition may be present in the lubricant base stock in an amount from 0.01 to 10 weight percent, e.g., from 0.1 to 5 weight percent or from 0.1 to 2 weight percent, based on the total weight of the lubricant base stock and the styrenated phenolic composition.
  • the resulting lubricating composition When blended into a lubricant base stock, the resulting lubricating composition preferably has a high degree of oxidative stability.
  • Oxidative stability may be quantified by pressure differential scanning calorimetry (PDSC).
  • PDSC examines an oil's oxidative stability under thin-film oxidation conditions.
  • OIT oxidation induction time
  • Oil giving longer OIT is generally considered more resistant to oxidation.
  • each test oil was pre-treated with 50 ppm of oil soluble iron derived from ferric naphthenate.
  • the lubricant compositions of the invention have a 16O 0 C PDSC OIT that is greater than 20 min., e.g., greater than 30 min., greater than 40 min., greater than 50 min, or greater than 55 min.
  • the lubricant optionally has a 185 0 C PDSC OIT that is greater than 2 min., e.g., greater than 5 min., greater than 8 min., or greater than 10 min.
  • Oxidative stability also may be quantified by rotary pressure vessel oxidative test (RPVOT) according to ASTM D2272, the entirety of which is incorporated herein by reference.
  • the lubricant composition has an RPVOT OIT greater than 100 min., e.g., greater than 200 min., or greater than 300 min.
  • the lubricant compositions of the invention also preferably have a reduced tendency to form deposits than an analogous lubricant composition without the styrenated phenolic compositions of the present invention.
  • Deposit formation may be quantified, for example, by a Thermo-oxidation Engine Oil Simulation Test (TEOST) at moderately high temperature (MHT) according to ASTM D7097, the entirety of which is incorporated herein by reference.
  • the TEOST simulates the effect of engine operating conditions on the oxidation and deposit-forming tendencies of lubricant compositions.
  • the lubricant compositions of the invention provide TEOST MHT values less than 100 mg, e.g., less than 75 mg, less than 60 mg, or less than 55 mg.
  • the invention further relates to a stabilized thermoplastics and/or elastomeric resins and/or lubricant compositions, where one component comprises the styrenated phenolic composition of the invention and the other a polymer or lubricant base stock such as those described above, and where the styrenated phenolic composition is used with a co-stabilizer, for example, phenolics, aromatic amines, phosphites and phosphonites, hydroxylamines, alkylamine-N-oxides, lactones, thioethers, epoxidized vegetable oils, e.g., epoxidized soybean oil, and the like.
  • a co-stabilizer for example, phenolics, aromatic amines, phosphites and phosphonites, hydroxylamines, alkylamine-N-oxides, lactones, thioethers, epoxidized vegetable oils, e.g., epoxidized soybean oil, and the
  • thermoplastic resins and lubricants stabilized by the styrenated phenolic composition of the present invention may optionally contain an additional stabilizer or mixture of stabilizers selected from the group consisting of the phenolic antioxidants, hindered amine stabilizers, the ultraviolet light absorbers, phosphites, phosphonites, alkaline metal salts of fatty acids, the hydrotalcites, metal oxides, epoxydized soybean oils, the hydroxylamines, the tertiary amine oxides, lactones, thermal reaction products of tertiary amine oxides, and the thiosynergists. Phenolics, diaryl amines, and organophosphites are particularly preferred.
  • Phenolics that can be employed as optional co-stabilizers in the practice of the present invention include, but are not limited to:
  • Alkylated monophenols for example: 2,6-di-tert-butyl-4-methylphenol, 2- tert-butyl-4,6-dimethylphenol, 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-( ⁇ - methylcyclohexyl)-4,6 dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6,- tricyclohexyphenol, 2,6-di-tert-butyl-4-methoxymethylphenol.
  • Alkylated hydroquinones for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4- octadecyloxyphenol.
  • Hydroxylated thiodiphenyl ethers for example, 2,2'-thio-bis-(6-tert-butyl- 4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert-butyl-3- methylphenol), 4,4'-thio-bis-(6-tert-butyl-2-methylphenol).
  • Alkylidene-bisphenols for example, 2,2'-methylene-bis-(6-tert-butyl-4- methylphenol), 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis-(4- methyl-6-( ⁇ -methylcyclohexyl(phenol), 2,2'-methylene-bis-(4-methyl-6- cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-(6- nonyl-4-methylphenol), 2,2'-methylene-bis-(6-( ⁇ -methylbenzyl)-4-nonylphenol), 2,2'- methylene-bis-(6-( ⁇ , ⁇ -dimethylbenzyl)-4-nonyl-phenol), 2,2'-methylene-bis-(4,6-di-tert- butylphenol), 2,2'-ethylidene-(
  • Benzyl compounds for example, l,3,5-tris-(3,5-di-tert-butyl-4- hydroxybenzyl)-2,4,6-trimethylbenzene, bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl 3 , S-di-tert-butyM-hydroxybenzyl-rnercaptoacetate, bis-(4-tert-butyl-3 -hydroxy- 2,6-dimethylbenzyl)dithiol-terephthalate, l,3,5-tris-(3,5-di-tert-butyl-4- hydroxybenzyl)isocyanurate, l,3,5-tris-(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, calcium salt
  • Acylaminophenols for example, 4-hydroxy-lauric acid anilide, 4-hydroxy- stearic acid anilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid with monohydric or polyhydric alcohols for example, methanol, diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris-hydroxyethyl isocyanurate, thiodiethyleneglycol, di-hydroxyethyl oxalic acid diamide.
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols for example, methanol, diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris-hydroxyethyl isocyanurate, thidiethyleneglycol, dihydroxyethyl oxalic acid diamide.
  • esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols e.g., with methanol, diethylene glycol, octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N-bis(hydroxyethyl) oxalic acid diamide.
  • Amides of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid for example, N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylen-diamine, N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-di-(3,5- di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.
  • Aromatic amines that are useful as co-stabilizers in the practice of the present invention can be represented by the general formula
  • R 1 -NH-R 2 where R 1 and R 2 may be, but are not necessarily, identical.
  • R 1 and R 2 can be independently selected from the group consisting of (i) aromatic carbon, (ii) aliphatic Ri and aromatic R 2 carbon atoms, and (iii) aromatic carbon linked to a second nitrogen atom to give a phenylene diamine.
  • Ri is aliphatic, it can be straight chain or branched and can have from one to twelve carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof. It is preferred that, where Ri is aliphatic, it be a straight or branched chain aliphatic group having from one to eight carbon atoms, and more preferred that it have from one to four carbon atoms.
  • the amine antioxidants can be hydrocarbon substituted diarylamines, such as, aryl, alkyl, alkaryl, and aralkyl substituted diphenylamine antioxidant materials.
  • hydrocarbon substituted diphenylamines include substituted octylated, nonylated, and heptylated diphenylamines and para- substituted styrenated or ⁇ -methyl styrenated diphenylamines.
  • the sulfur-containing hydrocarbon substituted diphenylamines such as p-(p-toluenesulfonylamido)- diphenylamine, i.e.,
  • Ar and Ar' are independently selected aryl radicals, at least one of which is preferably substituted with at least one alkyl radical.
  • the aryl radicals can be, for example, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, and the like.
  • the alkyl substituent(s) can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isomers thereof, and the like.
  • the co- stabilizer comprises at least one antioxidant comprising one or more secondary diarylamines having the general formula:
  • the oxidation stability of a lubricating oil comprising one or more Group I, Group ⁇ , Group HI, Group rV or synthetic lubricating base stocks of varying viscosity grades may be increased by adding thereto: (i) the styrenated phenolic composition of the invention (e.g., in an amount from about 0.01 to about 10 weight percent, based on the total weight of the lubricant including antioxidants) and (ii) one or more diarylamines of the above structure (e.g., in an amount from about 0.01 to about 10 weight percent, based on the total weight of the lubricant composition including antioxidants) .
  • the content ratio of the styrenated phenolic to the secondary diarylamine can be in practically all proportions. In illustrative embodiments, the ratio will be in the range of 1:99 to 00:1 parts by weight and more preferably, 90:10 to 10:90 parts by weight.
  • Preferred hydrocarbon-substituted diarylamines are those disclosed in U.S. Patent Numbers 3,452,056 and 3,505,225, the entire disclosures of which are incorporated by reference herein.
  • the preferred hydrocarbon-substituted diarylamines can be represented by the following general formulas:
  • Rn is selected from the group consisting of phenyl and p-tolyl radicals
  • Ri 2 and R 13 are independently selected from the group consisting of methyl, phenyl, and p-tolyl radicals;
  • Ri 4 is selected from the group consisting of methyl, phenyl, p-tolyl, and neopentyl radicals; R 15 is selected from the group consisting of methyl, phenyl, p-tolyl, and 2-phenylisobutyl radicals; and, R 16 is a methyl radical.
  • Rn through R 1S are independently selected from the radicals shown in Formula I and R 17 is selected from the group consisting of methyl, phenyl, and p-tolyl radicals;
  • X is a radical selected from the group consisting of methyl, ethyl, C 3 -Ci 0 sec-alkyl, ⁇ , ⁇ -dimethylbenzyl, ⁇ -methylbenzyl, chlorine, bromine, carboxyl, and metal salts of the carboxylic acids where the metal is selected from the group consisting of zinc, cadmium, nickel, lead, tin, magnesium, and copper; and,
  • Y is a radical selected from the group consisting of hydrogen, methyl, ethyl, C 3 - Cio sec-alkyl, chlorine, and bromine.
  • Rn is selected from the group consisting of phenyl or p-tolyl radicals
  • Ri 2 and Ri 3 are independently selected from the group consisting of methyl, phenyl, and p-tolyl radicals;
  • Ri 4 is a radical selected from the group consisting of hydrogen, C 3 -Ci O primary, secondary, and tertiary alkyl, and C 3 -Ci 0 alkoxyl, which may be straight chain or branched; and
  • X and Y are radicals selected from the group consisting of hydrogen, methyl, ethyl, C 3 -C 1O sec-alkyl, chlorine, and bromine.
  • Ri 8 is selected from the group consisting of phenyl and p-tolyl radicals
  • Ri 9 is a radical selected from the group consisting of methyl, phenyl, p-tolyl and 2- phenyl isobutyl;
  • R 20 is a radical selected from the group consisting of methyl, phenyl, and p-tolyl.
  • R 2I is selected from the group consisting of hydrogen, ⁇ , ⁇ -dimethylbenzyl, ⁇ -methylbenzhydryl, triphenylmethyl, and ⁇ , ⁇ p-trimethylbenzyl radicals;
  • R 22 is selected from the group consisting of phenyl or p-tolyl radicals
  • R 23 is selected from the group consisting of methyl, phenyl, and p-tolyl radicals.
  • R 24 is selected from the group consisting of methyl, phenyl, p-tolyl, and 2-phenylisobutyl radicals.
  • a second class of amine antioxidants comprises the reaction products of a diarylamine and an aliphatic ketone.
  • the diarylamine aliphatic ketone reaction products that are useful herein are disclosed in U.S. Patent Numbers 1,906,935; 1,975,167; 2,002,642; and 2,562,802. Briefly described, these products are obtained by reacting a diarylamine, preferably a diphenylamine, which may, if desired, possess one or more substituents on either aryl group, with an aliphatic ketone, preferably acetone, in the presence of a suitable catalyst.
  • diarylamine reactants include dinaphthyl amines; p-nitrodiphenylamine; 2,4-dinitrodiphenylamine; p- aminodiphenylamine; p-hydroxydiphenylamine; and the like.
  • acetone other useful ketone reactants include methylethylketone, diethylketone, monochloroacetone, dichloroacetone, and the like.
  • a preferred diarylamine-aliphatic ketone reaction product is obtained from the condensation reaction of diphenylamine and acetone (NAUGARD A, Chemtura Corporation), for example, in accordance with the conditions described in U.S. Patent Number 2,562,802.
  • the commercial product is supplied as a light tan-green powder or as greenish brown flakes and has a melting range of 85°C to 95°C.
  • a third class of suitable amines comprises the N,N' hydrocarbon substituted p-phenylene diamines.
  • the hydrocarbon substituent may be alkyl or aryl groups, which can be substituted or unsubstituted.
  • alkyl unless specifically described otherwise, is intended to include cycloalkyl. Representative materials are: N-phenyl-N'-cyclohexyl-p-phenylenediamine;
  • N,N -diphenyl-p-phenylenediamine
  • N,N'-di-beta naphthyl-p-phenylenediamine N,N'-di-beta naphthyl-p-phenylenediamine; mixed diaryl-p-N,N'-bis-(l-ethyl-3- methylpentyl)-p-phenylenediamines; and
  • a fourth class of amine antioxidants comprises materials based on quinoline, especially, polymerized l,2-dihydro-2,2,4-trimethylquinoline (Naugard Super Q,
  • Phosphites and phosphonites useful as co-stabilizers in the practice of the present invention include, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, and tetrakis(2,4-di-tert-butylphenyl)4,4'- biphen
  • Lactones that can be employed as co-stabilizers in the practice of the present invention include those of the structure: wherein
  • R 1 and R 2 are independently selected from the group consisting of hydrogen; chloro; hydroxy; C 1 -C 25 alkyl; C 7 -C 9 -phenylalkyl; unsubstituted or C 1 -C 4 alkyl- substituted phenyl; unsubstituted or C 1 -C 4 alkyl-substituted Cs-C 8 cycloalkyl; C 1 -C 18 alkoxy; Ci-C 18 alkylthio; Ci-C 4 alkylamino; di-(Ci-C 4 alkyl)amino; Ci-C 25 alkanoyloxy; C 1 -C 25 alkanoylamino; C 3 -C 2 S alkenoyloxy; C 3 -C 2 S alkanoyloxy which is interrupted by oxygen, sulfur, or >N — R 8 ; C 6 -C 9 cycloalkylcarbonyloxy; benzoyloxy or Ci-Ci 2 alkyl- substituted
  • R 8 is hydrogen or Ci-C 8 alkyl
  • R 3 and R 4 are independently selected from the group consisting of hydrogen, C 1 - C 8 alkyl, C 1 -C 4 alkoxy, halogen, a group
  • n 1 or 2 or a group
  • radicals A are independently selected from the group consisting of Ci -Cg alkyl and Ci-C 8 alkoxy.
  • Thioethers that are useful as co-stabilizers in the practice of the present invention can be of the structure:
  • Ri 8 is a straight or branched chain alkyl moiety of 1 to 20 carbon atoms
  • Ri 9 is a straight or branched chain alkylene moiety of 1 to 8 carbon atoms.
  • Ri 8 can, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and isomers thereof; and Ri 9 can, for example, be methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and isomers thereof.
  • Ri 8 be a straight or branched chain alkyl moiety of 8 to 18 carbon atoms and that R 19 be a straight or branched chain alkylene moiety of 1 to 4 carbon atoms. It is more preferred that R 19 be ethylene, i.e., -CH 2 -CH 2 -.
  • R 18 is as described above, and R ⁇ and R 20 are independently selected straight or branched chain alkylene moieties of 1 to 8 carbon atoms. It is preferred that R 1 9 and R 20 be independently selected straight or branched chain alkylene moieties of 1 to 4 carbon atoms. It is more preferred that R 2 o be methylene, i.e., -CH 2 -, and that R ⁇ be ethylene, i.e., -CH 2 -CH 2 -.
  • Preferred thioethers that are useful in the practice of the present invention are exemplified by products such as distearylthiodipropionate (Naugard DSTDP, Chemtura Corporation), dilaurylthiodipropionate (Naugard DLTDP, Chemtura Corporation), pentaerythritol tetrakis( ⁇ -laurylthiopropionate) (Naugard 412S, Chemtura Corporation), and pentaerythritol octylthiopropionate (Naugard 2140, Chemtura Corporation).
  • the optional co-stabilizer of the present invention can also be a trialkyl amine oxide, as, for example, GENOXTM EP(commercially available from Chemtura Corporation) and described in U.S. Patent Nos. 6,103,798; 5,922,794; 5,880,191; and 5,844,029, the entireties of which are incorporated herein by reference.
  • GENOXTM EP commercially available from Chemtura Corporation
  • Another co-stabilizer may be a hydroxylamine, as, for example, N 9 N- dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N 9 N- dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl- N-octadecylhydroxylamine, N,N-dioctylhydroxylamine, N,N-di-tert-butylhydroxylamine, N-cyclohexylhydroxylamine, N-cyclododecylhydroxylamine, N 9 N- dicyclohexylhydroxylamine, N,N-didecylhydroxyl
  • the co-stabilizers described herein for combination with the styrenated phenolic compositions of the invention preferably are present in an amount effective to improve composition stability.
  • the amount is generally less than about 5 weight percent based on the total weight of the resin or lubricant and is preferably at least about 50 ppm based on the weight of the resin or lubricant.
  • the stabilizer combinations of this invention stabilize resins and lubricants especially during high temperature processing or high temperature applications with relatively little change in melt index and/or color, even though, for polymer applications, the polymer may undergo a number of extrusions.
  • the instant stabilizers may readily be incorporated into the resins by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom.
  • the stabilized compositions of the invention may optionally contain from about 0.001 to about 5%, preferably from about 0.0025 to about 2%, and especially from about 0.005% to about 1%, by weight of various conventional additives, such as those described previously, or mixtures thereof.
  • Fog data were gathered by performing a test designated as Windscreen Fogging Characteristics of Trim Materials in Motor Vehicles on suitable polyurethane foam test specimens.
  • the test method is also known as DEST 75 201 Method B.
  • Di- isodecylphthalate (DIDP) was used as reference.
  • the test calls for exposing test specimens at 100 0 C for 16 hours.
  • the styrenated phenolic compositions e.g., styrenated p-cresol compositions
  • the term "low fog” is defined as a fog deposit after heating for 160 hours at 100 0 C in the range of from about 0.01 to about 0.4 mg, preferably from about 0.02 to about 0.1 mg.
  • Oxidation Induction Temperature was recorded as onset temperature on heating test specimens, under oxygen, from 30 — 300 0 C using a heating rate of 8°C/min.
  • This example illustrates the stabilizer efficacy of 2,6-distyryl-p-cresol in the presence of a phosphite stabilizer, as compared to a control comprising a blend of octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate and a phosphite stabilizer.
  • the base polymer was a C4-copolymer linear low density polyethylene powder with a melt index (MI) of 1, having a density of 0.918 g/cm 3 .
  • the base formulation also contained 500 ppm of zinc stearate as an acid scavenger.
  • This example illustrates the stabilizer efficacy of 2,6-distyryl-p-cresol, in the presence of a phosphite stabilizer, as determined by measuring retention of color. The result is compared to a control comprising a blend of octadecyl 3,5-di-t-butyl-4- hydroxyhydrocinnamate and the same phosphite stabilizer.
  • the base polymer was a C4-copolymer linear low density polyethylene powder with a melt index (MI) of 1, having a density of 0.918 g/cm 3 .
  • the base formulation also contained 500 ppm of zinc stearate as an acid scavenger. All formulations were made up by adding tris nonylphenyl phosphite in combination with either 2,6-distyryl-p-cresol or octadecyl 3,5-di-t-butyl-4- hydroxyhydrocinnamate to the base formulation (see Table 8 for additional details).
  • the thus-stabilized resin formulation was then extruded from a 19 mm diameter Brabender single-screw extruder at 60 rpm, with the temperature set to
  • the first extrusion pass was performed under inert atmosphere.
  • the extrudate was cooled by passing it through an ice water bath and then pelletized. These pellets were re-extruded, albeit under air, using the same RPM, temperature, and pelletizing conditions as before, for up to five additional passes. The results of this testing are shown in Table
  • e-SBR 1502 type resin was used.
  • the coagulation agents were as follows: 7.5 mol% H 2 SO 4 and 5 mol% Al 2 (SO 4 ) S in water.
  • e-SBR test specimens containing the stabilizer(s) shown in Table 9 were prepared and then placed in an oven at IOOEC for the oven aging experiments.
  • Mooney viscosities were measured on a viscTech Mooney viscometer from 30 gram samples (Temp: 100 0 C; 1 min preheat time @ no rotation; measurement time 4 minutes after preheat). Mooney viscosity was measured on each formulation before oven aging, and then at regular intervals once the SBR test specimens had been exposed in the oven at 100 0 C. The results from this testing are shown in Table 9. Table 9
  • Example 8 Synthesis of 2,6-distyryl-p-cresol (Two Reactor System) [0140]
  • This example illustrates a reaction system comprising two reactors and providing for a two tiered temperature profile for forming styrenated p-cresol.
  • 50 Kg (110.2 Ib, 462.2 moles) p-cresol was pumped from a preheated drum into a 50 gallon glass lined steel jacketed reactor equipped with an agitator, thermowell, and a pump around loop for sampling and acid injection.
  • the p-cresol was heated to about 60 0 C followed by the addition of 1.6 to 8.3 g (5.53e-05 to 1.07e-02 moles) of trifluoromethane sulfonic acid via a syringe in an injection port of the pump around loop.
  • 93.9 Kg (207 Ib, 901.6 moles) styrene was fed through a mass flow meter at a constant rate over a 3 to 4 hour reaction time where the reactor temperature was maintained at 7O 0 C.
  • the molar ratio of styrene to p-cresol fed was maintained at 1.95.
  • Example 9 Synthesis of 2,6-Distyryl-p-cresoI (Single Reactor) [0141]
  • This example illustrates a reaction system comprising a single reactor for forming styrenated p-cresol.
  • Example 9 was run in a manner similar to Example 8, with the exception that a single reactor was used for the 7O 0 C reaction and the 90 0 C finishing reaction and clay addition were used.
  • the styrene feed was fed over time periods ranging from 2.5 to 4 hours.
  • the amount of triflic acid used ranged from 1.7 to 2.6 g.
  • the molar ratio of styrene to p-cresol was maintained at 1.95.
  • the composition of the resulting styrenated p-cresol composition was as follows:
  • This example illustrates the stabilization properties of the styrenated phenolic (p-cresol) compositions of the invention in a passenger car motor oil.
  • the stabilizing ability of two styrenated p-cresol compositions (COM 1 & COM 2) of the present invention were determined.
  • the compositions of the COM 1 and COM 2, by total GC area, are provided below.
  • COM 1 and COM 2 were blended, respectively, with a passenger car motor oil (PCMO), specifically a 5W20 ELSAC GF-4 prototype (0.6 wt.% P) containing a Group II base stock.
  • PCMO passenger car motor oil
  • BLENDS IA and 2A contained 0.5 weight percent of COM 1 and COM 2 styrenated p-cresol compositions, respectively, based on the total weight of the respective blends.
  • Two additional blends (BLENDS IB and 2B, respectively) were also formed containing 1.5 weight percent of COM 1 and COM 2 styrenated p-cresol compositions, respectively, based on the total weight of the respective blends.
  • BLENDS IA and 2A were analyzed by pressure differential scanning calorimetry (PDSC) at 160 0 C and the results compared.
  • BLENDS IB and 2B were analyzed by PDSC at 185°C.
  • An approximate 185 0 C PDSC value for the comparison PCMO sample was determined from the 16O 0 C PDSC OIT value by reducing the 16O 0 C PDSC OIT value by 50% for every 1O 0 C increase.
  • TEOST Thermo-oxidation Engine Oil Simulation Test
  • This example illustrates the stabilization properties of the styrenated p-cresol compositions of the invention in an industrial turbine oil.
  • the stabilizing ability of styrenated p-cresol compositions COM 1 and COM 2 of the present invention were determined in an industrial turbine oil (ITO) base stock (AO free, Group II base stock).
  • ITO industrial turbine oil
  • the resulting blends, designated BLEND 1C and BLEND 2C contained 1.0 weight percent of COM 1 and COM 2, respectively, based on the total weight of the respective blends.
  • BLENDS 1C and 2C were analyzed by rotary pressure vessel oxidative test (RPVOT) according to ASTM D2272, the entirety of which is incorporated herein by reference.
  • RVOT rotary pressure vessel oxidative test
  • This example compares the color stabilizing effects of styrenated phenolic compositions, specifically the styrenated p-cresol composition COM 1 of Example 10, with comparative antioxidants, such as Naugard PS-48 (or Irganox 1135), Anox 1315, Irganox 1076 (or Anox PP 18) or Isonox 132, in the formation of polyurethane foams.
  • the comparative antioxidants did not form foams having good color stability over an extended period of time at above room temperatures.
  • BHT butylated hydroxytoluene, di- tert-butyl-para-cresol
  • a common antioxidant is also known to have poor color stability
  • the above antioxidants were blended into a polyester polyol (Fomrez 2C53), which is commonly reacted with isocyanates to form polyurethanes, in amounts ranging from 8 wt.% to 22 wt.%, as indicated in Table 16, below.
  • Foams produced from the polyester polyol containing Isonox 132 (2,6-di-tert-butyl-4-sec-butylphenol) have demonstrated discoloration problems over an extended period of time at above room temperature.
  • the polyester polyols containing various antioxidants in different amounts were prepared by heating Fomrez 2C53 containing no antioxidant in an oven at 7O 0 C for three hours, followed by mixing with various antioxidants as indicated below.
  • Samples 1-7 were sent to a testing company, which reacted the polyol with TDI (toluene diisocyanate) to form foams for color stability testing.
  • Sample 7, containing 0.482 wt.% styrenated phenolics gave the best performance
  • Sample 6, containing 0.241 wt.% styrenated phenolics gave the second best performance.
  • Foams formed from Samples 1-5 failed the color stability tests over an extended period of time at above room temperature.
  • stable foams would be expected when combining the styrenated phenolics of the invention with polyether polyols for polyurethane applications.
  • Example 13 Preparation of Low Colored Phenolic Stabilizers by Styrenation of o- Cresol and o-Cresol/p-Cresol Mixtures
  • 2-Methyl-4,6-di-(l-phenylethyl)-phenol has previously been prepared by the Aluminum catalyzed reaction of o-Cresol and Styrene. Under the disclosed conditions, conversions to the desired compound are low (ca. 75%) and the reaction product is highly coloured (11 Gardner) requiring that 2-methyl-4,6-di-(l-phenylethyl)-phenol be purified by distillation prior to use as an antioxidant in synthetic polymers.

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