Compositions, methods and uses

Abstract

A composition comprising a pyrolysis oil and, as additives, (a) an antioxidant and (b) one or more stabilizing additives selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, (iii) a quaternary ammonium salt, and mixtures thereof. Also provided are methods and uses for improving the stability of a composition comprising a pyrolysis oil by adding one or more of the additives to the composition.

Description

[Technical field]

[0001] The present invention relates to pyrolysis oil and related methods and uses. In particular, the present invention relates to an additive for improving the stability of compositions containing plastic pyrolysis oil. [Background technology]

[0002] Pyrolysis oil is a fluid produced from the pyrolysis of waste materials, such as plastic waste, biomass, such as agricultural waste, forestry waste, used cooking oil, and algae waste. Examples of waste plastics that can be pyrolyzed to produce plastic pyrolysis oil include polyethylene, polypropylene, polystyrene, polyethylene terephthalate (PET), and rubber (e.g., from tires). The organic liquids produced by the pyrolysis of plastics and other waste materials have a very dark color, an unpleasant odor, and are unstable. However, there is a strong desire to find uses for such oils to avoid such wastes being sent to landfills or polluting the oceans.

[0003] Pyrolysis oil can be used as a feedstock for chemical processing, for example in the production of polymers such as polyethylene. Pyrolysis oil can also be used in fuel oil. The use of pyrolysis oil to produce polymers provides a sustainable alternative to the use of crude oil feedstock.

[0004] The usefulness of pyrolysis oil is limited due to its poor stability, especially when cooled during transportation or storage, which is believed to be due to oxidation of oxygen- or nitrogen-containing species present in the oil, however, precipitation of particles from the bulk oil is also believed to be a problem.

[0005] Pyrolysis oils may be hydrotreated or cracked before further use, which may improve their stability, or may be treated with chemical additives to improve their stability. Summary of the Invention

[0006] The present inventors have discovered that certain compounds are effective in reducing precipitation and / or improving the stability of compositions that include pyrolysis oil.

[0007] According to a first aspect of the present invention, a pyrolysis oil and an additive, (a) an antioxidant, and (b) a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, and mixtures thereof; Compositions are provided that include one or more of:

[0008] In some embodiments, the stabilizing additive (b) may be (iii) a quaternary ammonium salt. Thus, according to a further aspect of the present invention, a pyrolysis oil and an additive, (a) an antioxidant, and (b) a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, (iii) a quaternary ammonium salt, and mixtures thereof. Compositions are provided that include one or more of: [Brief description of the drawings]

[0009] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] A first aspect of the present invention relates to a composition comprising pyrolysis oil. Pyrolysis oil can be obtained by pyrolysis of any kind of waste. The components and properties of the oil vary depending on the type of waste pyrolyzed and the pyrolysis conditions. For example, pyrolysis oil can be obtained from the pyrolysis of plastic waste, agricultural waste, forestry waste, waste cooking oil, and algae waste.

[0011] Preferably, the pyrolysis oil comprises plastic pyrolysis oil. The plastic pyrolysis oil can be obtained from the pyrolysis of any kind of plastic. For example, the pyrolysis oil can be obtained from the pyrolysis of used tires.

[0012] Preferred plastic pyrolysis oils are obtained from the pyrolysis of one or more polymers selected from polyethylene, polypropylene, PET, rubber, and mixtures thereof.

[0013] Preferred plastic pyrolysis oils are obtained from further pyrolysis of one or more polymers selected from polyethylene, polypropylene, PET, rubber, used tires, and mixtures thereof.

[0014] In some embodiments, the pyrolysis oil in the composition of the first aspect may be a hydrotreated pyrolysis oil.

[0015] In some embodiments, the pyrolysis oil in the composition of the first aspect has been processed using a cracking process.

[0016] In a preferred embodiment, the composition of the first aspect comprises pyrolysis oil obtained directly from a pyrolysis plant without refining or further processing.

[0017] In some embodiments, the composition of the first aspect may comprise a blended fuel oil comprising plastic pyrolysis oil and one or more fuel oils from hydrocarbon and / or renewable resources.

[0018] In some embodiments, the composition of the first aspect comprises a blended fuel oil comprising plastic pyrolysis oil and a middle distillate fuel oil.

[0019] The middle distillate fuel oil may include petroleum-based fuel oil, especially middle distillate fuel oil. Such distillate fuel oils usually boil within the range of 110° C. to 500° C., for example 150° C. to 400° C. The middle distillate fuel oil may include atmospheric or vacuum distillates, cracked gas oils, or blends of straight run and refinery streams in any proportions, such as thermally cracked and / or catalytically cracked fractions and hydrocracked fractions.

[0020] Middle distillate fuel oils may include non-renewable Fischer-Tropsch fuels, such as those referred to as gas-to-liquids (GTL), coal-to-liquids (CTL), and oil sands-to-liquids (OTL).

[0021] Middle distillate fuel oils may include renewable fuels, such as biofuel or biodiesel compositions.

[0022] Middle distillate fuel oils may include first generation biodiesel, which includes, for example, esters of vegetable oils, animal fats, and used cooking fats. This form of biodiesel is obtained by transesterification of oils, such as rapeseed oil, soybean oil, safflower oil, palm oil, palm kernel oil, corn oil, peanut oil, cottonseed oil, tallow, coconut oil, Jatropha oil, sunflower seed oil, used cooking oil, hydrogenated vegetable oil, or any mixture thereof, with an alcohol, usually a monoalcohol, in the presence of a catalyst.

[0023] Middle distillate fuel oils may include second generation biodiesel, which is derived from renewable resources such as vegetable oils and animal fats and is often processed in refineries using hydroprocessing such as the H-Bio process developed by Petrobras. Second generation biodiesel may be similar in properties and quality to petroleum-based fuel oil streams, e.g., renewable diesel produced from vegetable oils, animal fats, etc., and is sold by ConocoPhillips as Renewable Diesel and Neste as NExBTL.

[0024] The middle distillate fuel oils used in the present invention may include third generation biodiesel, which utilizes gasification and Fischer-Tropsch technologies, including what is referred to as biomass-to-liquid (BTL). Third generation biodiesel is not significantly different from some second generation biodiesels, but aims to utilize whole plants (biomass), thereby expanding the feedstock base.

[0025] The middle distillate fuel oil may include blends of any or all of the above diesel fuel oils.

[0026] In some embodiments, the middle distillate fuel oil may be a blended diesel fuel containing biodiesel. In such blends, the biodiesel may be present in an amount of, for example, up to 0.5%, up to 1%, up to 2%, up to 3%, up to 4%, up to 5%, up to 10%, up to 20%, up to 30%, up to 40%, up to 50%, up to 60%, up to 70%, up to 80%, up to 90%, up to 95%, or up to 99%.

[0027] In some embodiments, the middle distillate fuel oil may contain a secondary fuel, such as ethanol, however, preferably no ethanol is included in the diesel fuel composition.

[0028] Middle distillate fuel oils may contain a relatively high sulphur content, for example greater than 0.05% by weight, such as 0.1% or 0.2%.

[0029] However, in a preferred embodiment, the sulphur content of the middle distillate fuel oil is at most 0.05% by weight, more preferably at most 0.035% by weight, in particular at most 0.015%. Fuels with even lower concentrations of sulphur are also suitable, for example fuels with less than 50 ppm by weight sulphur, preferably less than 20 ppm, for example 10 ppm or less.

[0030] Various metal species may be present in middle distillate fuel oils. This may be due to contamination of the fuel during production, storage, transportation, or use, or contamination of fuel additives. Metal species may also be intentionally added to the fuel. For example, transition metals may be added as fuel borne catalysts, for example to improve the performance of diesel particulate filters.

[0031] In a preferred embodiment, the middle distillate fuel oil used in the present invention comprises sodium and / or calcium, preferably sodium, which is typically present in a total amount of 0.01 to 50 ppm, preferably 0.05 to 5 ppm, preferably 0.1 to 2 ppm, for example 0.1 to 1 ppm.

[0032] Other metal-containing species may also be present as contaminants, for example, through corrosion of metal and metal oxide surfaces by acidic species present in the fuel or derived from the lubricating oil. During use, fuels such as diesel fuels are constantly in contact with metal surfaces, for example, in the fuel supply system of a vehicle, in a fuel tank, in a fuel conveyance, etc. Typically, metal-containing contaminants may include transition metals, such as zinc, iron, and copper, other Group I or II metals, and other metals such as lead.

[0033] In addition to metal-containing contaminants that may be present in middle distillate fuel oils, metal-containing species may also be intentionally added to the fuel. For example, metal-containing fuel-generated catalytic species may be added to aid in the regeneration of particulate traps, as is known in the art.

[0034] Metal-containing contaminants can be in the form of insoluble particles, or soluble compounds or complexes, depending on their source. Metal-containing fuel-generated catalysts are often soluble compounds or complexes, or colloidal species.

[0035] In some embodiments, the middle distillate fuel oil may contain a metal-containing species including an in-fuel generated catalyst. Preferably, the in-fuel generated catalyst contains one or more metals selected from iron, cerium, platinum, manganese, Group I and Group II metals, such as calcium and strontium. Most preferably, the in-fuel generated catalyst contains a metal selected from iron and cerium.

[0036] In some embodiments, the middle distillate fuel oil may contain metal-containing species including zinc, which may be present in an amount of from 0.01 to 50 ppm, preferably from 0.05 to 5 ppm, more preferably from 0.1 to 1.5 ppm.

[0037] The composition of the first embodiment comprises one or more of: (a) an antioxidant; and (b) a stabilizing additive.

[0038] In some embodiments, the composition of the first aspect comprises (a) an antioxidant. A mixture of two or more antioxidants may be present.

[0039] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive.

[0040] In some embodiments, the composition of the first aspect comprises (a) an antioxidant, and (b) a stabilizing additive.

[0041] The stabilizing additive may comprise (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, or a mixture thereof.

[0042] In some embodiments, the composition of the first aspect comprises (i) (b) a stabilizing additive comprising an alkoxylated amine compound.

[0043] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (ii) an aldehyde-alkylphenol copolymer.

[0044] In some preferred embodiments, the composition of the first aspect comprises (i) an alkoxylated amine compound and (ii) (b) a stabilizing additive comprising an aldehyde-alkylphenol copolymer.

[0045] In some embodiments, the composition of the first aspect comprises (a) an antioxidant, and (b) a stabilizing additive comprising (i) an alkoxylated amine compound.

[0046] In some embodiments, the composition of the first aspect comprises (a) an antioxidant, and (b) a stabilizing additive comprising (ii) an aldehyde-alkylphenol copolymer.

[0047] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (i) an alkoxylated amine compound and (ii) an aldehyde-alkylphenol copolymer.

[0048] In some embodiments, the composition of the first aspect comprises (iii) (b) a stabilizing additive comprising one or more quaternary ammonium salts.

[0049] In some preferred embodiments, the compositions of the first aspect comprise (i) an alkoxylated amine compound, and (b) a stabilizing additive comprising one or more of (iii) a quaternary ammonium salt.

[0050] In some preferred embodiments, the composition of the first aspect comprises (ii) an aldehyde-alkylphenol copolymer, and (iii) (b) a stabilizing additive comprising one or more of a quaternary ammonium salt.

[0051] In some embodiments, the composition of the first aspect comprises (a) an antioxidant, and (b) a stabilizing additive comprising one or more of (iii) a quaternary ammonium salt.

[0052] In some preferred embodiments, the compositions of the first aspect comprise (a) an antioxidant and (b) a stabilizing additive comprising one or more of (i) an alkoxylated amine compound, and (iii) a quaternary ammonium salt.

[0053] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising one or more of (ii) an aldehyde-alkylphenol copolymer, and (iii) a quaternary ammonium salt.

[0054] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising one or more of (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, and (iii) a quaternary ammonium salt.

[0055] Suitable antioxidants for use herein include phenolic antioxidants, and amino antioxidants.

[0056] Suitable amino-based antioxidants include aromatic amines, hindered amines, N-oxides, polyalkylene polyamines, and polyisobutenyl-substituted succinimides.

[0057] Suitable aromatic amines include diaminobenzenes and alkylated diaminobenzenes, particularly dialkylated and trialkylated diaminobenzenes, such as p-phenylenediamine, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,2-diamine, 2,4,6-triethylbenzene-2,6-diamine, alkylated diphenylamines, diphenylamines and alkylated diphenylamines, such as N,N-diphenyl-1,4-phenylenediamine, and naphthylamines, such as N-phenyl-1-naphthylamine and N-phenyl-2-naphthylamine.

[0058] Suitable hindered amines include secondary and tertiary aliphatic amines, such as dimethylcyclohexylamine and diethylhydroxylamine.

[0059] Suitable N-oxides include TEMPO and its derivatives.

[0060] Polyisobutenyl-substituted succinimides are known to the person skilled in the art and their use as antioxidants is described, for example, in WO 2009 / 016400.

[0061] Preferably, the composition of the first aspect comprises a phenolic antioxidant.

[0062] In some embodiments, the composition of the first aspect comprises amino and phenolic antioxidants.

[0063] Any suitable phenolic antioxidant may be used. Suitable antioxidants are known to those skilled in the art.

[0064] Phenolic antioxidant compounds are meant to include any compound that contains a phenol moiety, i.e., a benzene ring substituted with a hydroxyl group. This can be a very simple compound, such as a benzenediol, an alkyl-substituted phenol, or a benzenetriol. Alternatively, the phenolic antioxidant can be part of a more complex molecule, which may contain two phenol moieties, see, for example, the compounds disclosed in US Patent Application Publication No. 2006 / 0219979.

[0065] Suitable phenolic antioxidant compounds for use in the present invention include those having the formula (I): [ka] (I) (In the formula, R 1 is selected from an optionally substituted alkyl or alkenyl group, an aryl group, an aralkyl group, an ester, a carboxylic acid, an aldehyde, a ketone, an ether, an alcohol, an amine or an amide; R 2 and R 3 are independently selected from hydrogen, an optionally substituted alkyl or alkenyl group, an aryl group, an ester group, a ketone, an aldehyde, a carboxylic acid, an ether, an alcohol, an amine or an amide, and n is an integer from 1 to 5.

[0066] Preferably, R 1 is preferably an alkyl group having 1 to 9 carbon atoms, which may be linear or branched. 1 is selected from methyl, ethyl, isopropyl, and tertiary butyl. 1 and R 2 may together form a cyclic substituent of either an alkyl or aryl. R 2 and R 3 is preferably hydrogen or an alkyl group having 1 to 9 carbon atoms. 2 and R 3is independently selected from hydrogen, methyl, ethyl, tertiary butyl, and isopropyl. Preferably, n is 1, 2, or 3.

[0067] Preferred phenolic antioxidant compounds for use in the present invention are substituted benzene compounds having one or more hydroxyl substituents. Examples include tertiary butyl hydroquinone (TBHQ or MTBHQ), 2,5-di-tertiary butyl hydroquinone (DTBHQ), pyrogallol, pyrocatechol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tertiary butyl-phenol, propyl gallate, and tertiary butyl catechol.

[0068] One particularly preferred phenolic antioxidant for use herein is 2,6-di-tert-butyl-phenol, however, as one skilled in the art will appreciate, commercial sources of this compound often contain mixtures that include tert- and tri-tert-butylphenol.

[0069] In some embodiments, the antioxidant is a reaction product of a carboxylic acid-derived acylating agent and an amine. These compounds are also generally referred to herein as acylated nitrogen-containing compounds. Such additives may additionally or alternatively be defined as stabilizing additives. Thus, the reaction product of a carboxylic acid-derived acylating agent and an amine as defined herein may provide an antioxidant of additive type (a) or a stabilizing additive of additive type (b) in the composition comprising the pyrolysis oil of the first aspect.

[0070] Thus, in a further aspect, the present invention relates to a pyrolysis oil and, as an additive, (a) an antioxidant, and (b) a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, (iii) a quaternary ammonium salt, (iv) a reaction product of a carboxylic acid-derived acylating agent as defined herein with an amine, and mixtures thereof. It is possible to provide a composition comprising one or more of the following:

[0071] Suitable acylated nitrogen-containing compounds can be prepared by reacting a carboxylic acylating agent with an amine and are known to those skilled in the art. Suitable carboxylic acylating agents are hydrocarbyl-substituted acylating agents.

[0072] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: (i) hydrocarbon groups, i.e., aliphatic (which may be saturated or unsaturated, linear or branched, e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) and aromatic (including aliphatic and alicyclic substituted aromatic) substituents, as well as cyclic substituents in which the ring is completed by another portion of the molecule (e.g., two substituents taken together form a ring); (ii) substituted hydrocarbon groups, i.e., substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (e.g., chloro, fluoro or bromo), hydroxy, alkoxy (e.g., C 1- C4 alkoxy), keto, acyl, cyano, mercapto, amino, amido, nitro, nitroso, sulfoxy, nitrile and carboxy), (iii) hetero substituents, i.e., those substituents which, in the context of this invention, have a predominantly hydrocarbon character but contain atoms other than carbon in a ring or chain which ring or chain is otherwise made up of carbon atoms. Heteroatoms include sulfur, oxygen, and nitrogen, and include such substituents as pyridyl, furyl, thienyl, and imidazolyl. In general, no more than two, and preferably no more than one, non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group, and typically there will be no non-hydrocarbon substituents in the hydrocarbyl group.

[0073] A preferred hydrocarbyl-substituted acylating agent is polyisobutenyl succinic anhydride. These compounds are commonly referred to as "PIBSA" and are known to those skilled in the art.

[0074] In such embodiments, the antioxidant is suitably a polyisobutenyl-substituted succinimide.

[0075] Conventional polyisobutenes and so-called "highly reactive" polyisobutenes are suitable for use in the present invention. Highly reactive polyisobutenes in this context are defined as polyisobutenes in which at least 50%, preferably 70% or more of the terminal olefin double bonds are of the vinylidene type as described in EP-A-0565285. Particularly preferred polyisobutenes are those having more than 80 mol% and up to 100 mol% of terminal vinylidene groups, such as those described in US Pat. No. 7,291,758. Preferred polyisobutenes generally have the preferred molecular weight (Mn) ranges as described above for the hydrocarbyl substituents.

[0076] Particularly preferred PIBSA has a PIB molecular weight (Mn) of 300-2800, preferably 450-2300, and more preferably 500-1300.

[0077] In a preferred embodiment, the reaction product of the carboxylic acid derived acylating agent and the amine contains at least one primary or secondary amine group.

[0078] Preferred acylated nitrogen-containing compounds for use herein are prepared by reacting a poly(isobutene)-substituted succinic acid-derived acylating agent (e.g., anhydride, acid, ester, etc.) in which the poly(isobutene) substituent has a number average molecular weight (Mn) of 170 to 2800 with a mixture of ethylene polyamines having 2 to about 9 amino nitrogen atoms, preferably about 2 to about 8 nitrogen atoms, and about 1 to about 8 ethylene groups per ethylene polyamine. These acylated nitrogen compounds are suitably formed by reactions in which the molar ratio of acylating agent:amino compound is 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 2:1 to 1:2, and most preferably 2:1 to 1:1. In a particularly preferred embodiment, the acylated nitrogen compounds are formed by reaction in which the molar ratio of acylating agent to amino compound is from 1.8:1 to 1:1.2, preferably from 1.6:1 to 1:1.2, more preferably from 1.4:1 to 1:1.1, and most preferably from 1.2:1 to 1: 1. This type of acylated amino compound and its preparation are well known to those skilled in the art and are described, for example, in EP-A-0565285 and US-A-5925151.

[0079] In some preferred embodiments, the composition comprises a class of compounds formed by the reaction of a polyisobutene-substituted succinic acid derived acylating agent with a polyethylene polyamine. Suitable compounds are described, for example, in WO 2009 / 040583.

[0080] In a preferred embodiment, the reaction product of a carboxylic acid derived acylating agent and an amine (b) includes the reaction product of a polyisobutene substituted succinic acid or anhydride with a polyethylene polyamine selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethylene-heptamine, and mixtures and isomers thereof, wherein the polyisobutene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1000.

[0081] The composition of the first aspect may include a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, or a mixture thereof.

[0082] By stabilizing additives it is meant to refer to ingredients that improve the stability of pyrolysis oil compositions, such as their storage or oxidative stability, or that aid in the dispersion of solids, waxes, or high molecular weight gums within the pyrolysis oil. Suitable stabilizing additives may be known in the art as dispersants.

[0083] The composition may include any alkoxylated amine compound, which is meant to include any compound that includes an amine functionality reacted with at least one alkylene oxide moiety.

[0084] In a preferred embodiment, the alkoxylated amine compound contains more than one alkylene oxide residue.

[0085] Suitably, the alkylene oxide residues include ethylene oxide residues, propylene oxide residues, butylene oxide residues, and mixtures thereof.

[0086] Preferably, the alkoxylated amine compound contains ethylene oxide residues, propylene oxide residues, or a mixture thereof.

[0087] Preferably, the alkoxylated amine compound is an alkoxylated amine, alkoxylated diamine or alkoxylated polyamine.

[0088] Some preferred alkoxylated amine compounds for use herein have the formula A-(RO) n -H, where A is the residue of an amine, RO is the residue of an alkylene oxide, and n is at least 1.

[0089] R is preferably an ethylene, propylene or butylene group. R may be an n-propylene or n-butylene group, or an isopropylene or isobutylene group. For example, R may be -CH2CH2-, -CH2CH(CH3)-, -CH2C ... 2、 It may be -CH(CH3)CH(CH3)- or -CH2CH(CH2CH3)-.

[0090] R may contain a mixture of isomers. For example, if R is propylene, the polyhydric alcohol may contain -CH2CH(CH3)- and -CH(CH3)CH2- moieties in any order within the chain.

[0091] Each R may be the same or different. R may also comprise a mixture of different groups, such as ethylene, propylene, or butylene units. In such embodiments, block copolymer units are preferred.

[0092] Preferably, R is ethylene and / or propylene. More preferably, R is -CH2CH2- or -CH(CH3)CH2-.

[0093] In some preferred embodiments, the alkoxylated amine compound (i) comprises a mixture of ethylene oxide and propylene oxide residues.

[0094] n is at least 1. Preferably, n is 5-1000, preferably 5-500, more preferably 10-400, more preferably 15-300, preferably 20-250, suitably 30-200, preferably 50-150.

[0095] A is the residue of an amine. Preferably, A is the residue of an amino or polyamino compound having at least one NH group. Suitable amino compounds include primary or secondary monoamines having a hydrocarbon substituent of 1 to 30 carbon atoms, or a hydroxyl-substituted hydrocarbon substituent of 1 to about 30 carbon atoms.

[0096] Preferably, A is the residue of a polyamine.

[0097] The polyamine can be selected from any compound containing two or more amine groups. Preferably, the polyamine is a (poly)alkylenepolyamine (which means alkylenepolyamine or polyalkylenepolyamine, in either case including diamines within the meaning of "polyamine"). Preferably, the polyamine is a (poly)alkylenepolyamine, the alkylene moiety having 1 to 6, preferably 1 to 4, most preferably 2 to 3 carbon atoms. Most preferably, the polyamine is a (poly)ethylenepolyamine (i.e. ethylenepolyamine or polyethylenepolyamine).

[0098] Preferably, the polyamine has 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms.

[0099] The polyamines may be selected, for example, from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene-hexamine, hexaethyleneheptamine, heptaethyleneoctamine, propane-1,2-diamine, 2(2-amino-ethylamino)ethanol, N',N'-bis(2-aminoethyl)ethylenediamine (N(CHCHNH)), diphenyl 4,4'-diamine, diaminonaphthalene, phenylenediamine, xylylenediamine, 1,2-diaminopropane and 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane.

[0100] Most preferably, A is the residue of ethylenediamine.

[0101] In some preferred embodiments, the alkoxylated amine compound (i) has the formula (II): [ka] (II) where EO represents an ethylene oxide residue, PO represents a propylene oxide residue, and at least one of a, b, c, d, e, f, g, and h is not 0. Compounds of formula (II) can be prepared by reaction of ethylenediamine with ethylene oxide and propylene oxide (when both are present) in any combination and in any order to provide compounds of formula (II) in which the ethylene oxide and propylene oxide residues attached to the nitrogen of the amine group can be present in any combination and in any order.

[0102] Preferably, each of a, b, c, d, e, f, g, and h is at least 1. Preferably, the sum of a, b, c, d, e, f, g, and h is 10 to 500, preferably 20 to 250, more preferably 40 to 200.

[0103] Those skilled in the art will appreciate that the polymeric compounds of formula (II) are typically in the form of mixtures.

[0104] Some alkoxylated amine compounds suitable for use herein are described in US Pat. No. 6,838,422.

[0105] In some embodiments, the composition of the first aspect may comprise an aldehyde-alkylphenol copolymer.

[0106] Any suitable aldehyde-alkylphenol copolymer may be used and such compounds are known to those skilled in the art.

[0107] Preferably, the aldehyde used to prepare the aldehyde-alkylphenol copolymer is formaldehyde or its reactive equivalent, such as paraformaldehyde, C2-C 10 It is selected from aldehydes and aromatic aldehydes, such as benzaldehyde.

[0108] A preferred aldehyde-alkylphenol copolymer is a copolymer of formaldehyde and an alkylphenol. Preferably, the phenol is mono-substituted with an alkyl group, preferably at the para position. The preferred alkyl group has 1 to 40 carbon atoms, preferably 2 to 36 carbon atoms, more preferably 4 to 30 carbon atoms, for example 6 to 24 carbon atoms.

[0109] In some embodiments, the alkylphenol is a polyisobutenyl (PIB) substituted phenol.

[0110] Polyisobutenyl (PIB) substituted phenols contain hydrocarbyl chains having repeating units. [ka]

[0111] Polyisobutene is prepared by the addition polymerization of isobutene (CH3)2C=CH2. Each molecule of the resulting polymer contains a single alkene moiety.

[0112] Conventional polyisobutenes and so-called "highly reactive" polyisobutenes are suitable for use in the preparation of additive (ii) of the present invention.Highly reactive polyisobutenes in this context are defined as polyisobutenes in which at least 50%, preferably 70% or more of the terminal olefin double bonds are of vinylidene type, as described in EP-A-0565285.Particularly preferred polyisobutenes are those with more than 80 mol% and up to 100% terminal vinylidene groups, such as those described in EP-A-1344785.

[0113] Methods for preparing polyalkylene-substituted phenols, such as polyisobutene-substituted phenols, are known to those skilled in the art and include those described in EP 831141.

[0114] The hydrocarbyl substituent of the PIB substituent preferably has an average molecular weight of from 200 to 3000. Preferably, it has a molecular weight of at least 225, suitably at least 250, preferably at least 275, suitably at least 300, such as at least 325 or at least 350. In some embodiments, the hydrocarbyl substituent of component (c) has an average molecular weight of at least 375, preferably at least 400, suitably at least 475, such as at least 500.

[0115] In some embodiments, the phenol may contain a PIB substituent having an average molecular weight of up to 2800, preferably up to 2600, such as up to 2500 or up to 2400.

[0116] In some embodiments, the phenol may contain a PIB substituent having an average molecular weight of 400-2500, such as 450-2400, preferably 500-1500, suitably 550-1300.

[0117] In some embodiments, the phenol may contain a PIB substituent having an average molecular weight of 200-600.

[0118] In some embodiments, the phenol may contain a PIB substituent having an average molecular weight of 500-1000.

[0119] In some embodiments, the phenol may contain a PIB substituent having an average molecular weight of 700-1300.

[0120] In some embodiments, the phenol may contain a PIB substituent having an average molecular weight of 1000-2000.

[0121] In some embodiments, the phenol may contain a PIB substituent having an average molecular weight of 1700-2600, such as 2000-2500.

[0122] In some preferred embodiments, the aldehyde-alkylphenol copolymer has structure (III) or (IV): [ka] where R is hydrogen or an alkyl group and n is at least 1.

[0123] Preferably, n is 2 to 12, preferably 5 to 9, and R is C3-C24 alkyl, preferably C4-C12 alkyl, in particular isononyl, isobutyl or amyl, C6-C12 aryl or hydroxyaryl or C7-C12 aralkyl.

[0124] As those skilled in the art can understand, aldehyde-alkylphenol copolymers can be prepared from a mixture of monomers, particularly compounds where R is a mixture of alkyl groups. Further suitable aldehyde-alkylphenol copolymers for use in the present invention include compounds of formula (III) in which the terminal phenolic groups are further functionalized, for example, by reaction with fatty acids or amines and aldehydes via the Mannich reaction. Compounds of this type are described, for example, in US Patent Application Publication No. 2007 / 221539.

[0125] The aldehyde-alkylphenol copolymer preferably has a number average molecular weight of 500 to 20,000, preferably 1,000 to 10,000, more preferably 1,500 to 5,000, for example, 2,000 to 3,500.

[0126] In some embodiments, the composition of the first aspect comprises, as an additive, (iii) one or more quaternary ammonium salts.

[0127] Preferably, the quaternary ammonium salt additive is the reaction product of a compound containing a tertiary amine group and a quaternizing agent.

[0128] Any suitable quaternizing agent may be used. The quaternizing agent may suitably be selected from ester and non-ester.

[0129] Suitable quaternizing agents include esters of carboxylic acids, dialkyl sulfates, benzyl halides, hydrocarbyl-substituted carbonates, hydrocarbyl-substituted epoxides which may be combined with acids, alkyl halides, alkyl sulfonates, sultones, hydrocarbyl-substituted phosphates, hydrocarbyl-substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or its salts, or mixtures thereof.

[0130] In some preferred embodiments, the quaternizing agents used to form the quaternary ammonium salt additives of the present invention are esters.

[0131] Preferred ester quaternizing agents are represented by formula (XI): [ka] (XI) (wherein R is an optionally substituted alkyl, alkenyl, aryl or alkylaryl group; R 1 is a C1-C22 alkyl, aryl or alkylaryl group. The compound of formula (XI) is preferably an ester of a carboxylic acid capable of reacting with a tertiary amine to form a quaternary ammonium salt.

[0132] Suitable quaternizing agents include carboxylic acid esters with a pKa of 3.5 or less.

[0133] The compounds of formula (XI) are preferably esters of carboxylic acids selected from substituted aromatic carboxylic acids, α-hydroxycarboxylic acids and polycarboxylic acids.

[0134] In some preferred embodiments, the compound of formula (XI) is an ester of a substituted aromatic carboxylic acid, and thus R is a substituted aryl group.

[0135] Preferably, R is a substituted aryl group having 6 to 10 carbon atoms, preferably a phenyl group or a naphthyl group, and most preferably a phenyl group. R is suitably selected from the group consisting of carboalkoxy, nitro, cyano, hydroxy, SR. 5 or NR 5 R 6 R is substituted with one or more groups selected from 5 and R 6 Each of R may be hydrogen or an optionally substituted alkyl, alkenyl, aryl, or carboalkoxy group. 5 and R 6 Each of R is hydrogen or an optionally substituted C1-C22 alkyl group, preferably hydrogen or a C1-C16 alkyl group, preferably hydrogen or a C1-C10 alkyl group, more preferably hydrogen or a C1-C4 alkyl group. 5 is hydrogen, and R 6 is hydrogen or a C1-C4 alkyl group. Most preferably, R 5 and R 6 are both hydrogen. Preferably, R is an aryl group substituted with one or more groups selected from hydroxyl, carboalkoxy, nitro, cyano, and NH2. R may be a polysubstituted aryl group, such as trihydroxyphenyl. In some embodiments, R may be a hydrocarbyl-substituted aryl group, such as an alkyl-substituted aryl group. In some embodiments, R may be an aryl group substituted with hydrocarbyl groups, such as hydroxy and alkyl groups, as described, for example, in EP 2631283.

[0136] Preferably, R is a mono-substituted aryl group. Preferably, R is an ortho-substituted aryl group. Suitably, R is substituted with a group selected from OH, NH2, NO2 or COOMe. Preferably, R is substituted with an OH or NH2 group. Suitably, R is a hydroxy-substituted aryl group. Most preferably, R is a 2-hydroxyphenyl group.

[0137] Preferably, R1 R is an alkyl, aralkyl or alkaryl group. 1 R may be a C1-C16 alkyl group, preferably a C1-C10 alkyl group, suitably a C1-C8 alkyl group. 1 R may be a C7-C16 aralkyl group or an alkaryl group, and is preferably a C7-C10 aralkyl group or an alkaryl group. 1 may be methyl, ethyl, propyl, butyl, pentyl, benzyl or an isomer thereof. 1 is benzyl or methyl. Most preferably, R 1 is methyl.

[0138] Particularly preferred compounds of formula (XI) are the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n-propyl salicylate, and i-propyl salicylate, and butyl salicylate, preferably methyl salicylate.

[0139] In some embodiments, the compound of formula (XI) is an ester of an α-hydroxycarboxylic acid. In such embodiments, the compound has the following structure: [ka] (In the formula, R 7 and R 8 are the same or different and each is selected from hydrogen, alkyl, alkenyl, aralkyl or aryl. Compounds of this type suitable for use herein are described in EP 1 254 889.

[0140] Examples of compounds of formula (XI) in which RCOO is the residue of an α-hydroxycarboxylic acid include methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of 2-hydroxyisobutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of 2-hydroxy-2-methylbutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of 2-hydroxy-2-ethylbutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl-, and allyl esters of lactic acid; and methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl-, phenyl-, and allyl esters of glycolic acid. Of the above, a preferred compound is methyl 2-hydroxyisobutyrate.

[0141] In some embodiments, the compound of formula (XI) is an ester of a polycarboxylic acid. This definition is meant to include dicarboxylic acids and carboxylic acids with three or more acidic moieties. In such embodiments, RCOO is preferably present in the form of an ester, i.e., one or more additional acidic groups present in the R group are in esterified form. However, embodiments in which not all acidic groups are esterified are also included within the present invention. Mixed esters of polycarboxylic acids may also be used. Preferred esters are C1-C4 alkyl esters.

[0142] The ester quaternizing agent may be selected from diesters of oxalic acid, diesters of phthalic acid, diesters of maleic acid, diesters of malonic acid, or diesters of citric acid. One particularly preferred compound of formula (XI) is dimethyl oxalate.

[0143] In a preferred embodiment, the compound of formula (XI) is an ester of a carboxylic acid having a pKa of less than 3.5. In such embodiments where the compound contains more than one acidic group, it is meant to refer to the first dissociation constant.

[0144] The ester quaternizing agent may be selected from esters of a carboxylic acid selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid, 2,4,6-trihydroxybenzoic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, acetylenedicarboxylic acid, glutaconic acid, muconic acid, citraconic acid, mesaconic acid, itaconic acid, tartronic acid, mesoxalic acid, tartaric acid, oxaloacetic acid, dioxosuccinic acid, alpha-hydroxyglutaric acid, diphenic acid, and 2,6-naphthalenedicarboxylic acid.

[0145] The ester quaternizing agent may be selected from esters of carboxylic acids selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid, and 2,4,6-trihydroxybenzoic acid.

[0146] Preferred ester quaternizing agents include dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.

[0147] In some preferred embodiments, the quaternizing agent used to form the quaternary ammonium salt additive of the present invention is an ester selected from dimethyl oxalate, methyl 2-nitrobenzoate, and methyl salicylate, preferably dimethyl oxalate and methyl salicylate.

[0148] Suitable non-ester quaternizing agents include dialkyl sulfates, benzyl halides, hydrocarbyl-substituted carbonates, hydrocarbyl-substituted epoxides optionally in combination with acids, alkyl halides, alkyl sulfonates, sultones, hydrocarbyl-substituted phosphates, hydrocarbyl-substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or its salts, or mixtures thereof.

[0149] Preferred non-ester quaternizing agents include dialkyl sulfates, benzyl halides, hydrocarbyl-substituted carbonates, hydrocarbyl-substituted epoxides in combination with acids, alkyl halides, alkyl sulfonates, sultones, hydrocarbyl-substituted phosphates, hydrocarbyl-substituted borates, N-oxides, chloroacetic acid or its salts, or mixtures thereof.

[0150] In some embodiments, quaternary ammonium salts may be prepared, for example, from alkyl or benzyl halides (particularly chlorides), which are then subjected to an ion exchange reaction to provide a different anion as part of the quaternary ammonium salt. Such methods may be suitable for preparing quaternary ammonium hydroxides, alkoxides, nitrites, or nitrates.

[0151] Suitable alkyl halides for use herein include chlorides, bromides, and iodides.

[0152] Suitable benzyl halides include chloride, bromide, and iodide. The phenyl group, especially when chloride is used, may be substituted, for example, with one or more alkyl or alkenyl groups. The preferred compound is benzyl bromide.

[0153] Dialkyl sulfates suitable for use herein as quaternizing agents include those containing alkyl groups having 1 to 10, preferably 1 to 4 carbon atoms in the alkyl chain. A preferred compound is dimethyl sulfate.

[0154] Suitable hydrocarbyl substituted carbonates may contain two hydrocarbyl groups which may be the same or different. Each hydrocarbyl group may contain from 1 to 50 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms, suitably from 1 to 5 carbon atoms. Preferably, the or each hydrocarbyl group is an alkyl group. Preferred compounds of this type include diethyl carbonate and dimethyl carbonate.

[0155] Suitable hydrocarbyl-substituted epoxides have the formula: [ka] (In the formula, R 1 , R 2 , R 3 and R 4 each independently is hydrogen or a hydrocarbyl group having 1 to 50 carbon atoms. Examples of suitable epoxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and stilbene oxide. Hydrocarbyl epoxides are used as quaternizing agents in combination with acids.

[0156] In some embodiments, the compound containing a tertiary amine group also contains an acidic functional group. In these embodiments, when an epoxide is used as the quaternizing agent, it is not necessary to add a separate acetic acid. However, in other embodiments, an acid, such as acetic acid, may be used.

[0157] Particularly preferred epoxide quaternizing agents are propylene oxide and styrene oxide, which may be combined with an additional acid.

[0158] Suitable alkyl sulfonates include those having 1 to 20, preferably 1 to 10, and more preferably 1 to 4 carbon atoms.

[0159] Suitable sultones include propane sultone and butane sultone.

[0160] Suitable hydrocarbyl-substituted phosphates include monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates, and O,O-dialkyldithiophosphates. Preferred alkyl groups have 1 to 12 carbon atoms.

[0161] Suitable hydrocarbyl-substituted borate groups include alkyl borates having 1 to 12 carbon atoms.

[0162] Preferred alkyl nitrites and alkyl nitrates have from 1 to 12 carbon atoms.

[0163] Preferably, the non-ester quaternizing agent is selected from dialkyl sulfates, benzyl halides, hydrocarbyl-substituted carbonates, hydrocarbyl-substituted epoxides optionally in combination with additional acids, chloroacetic acid or salts thereof, and mixtures thereof.

[0164] Particularly preferred non-ester quaternizing agents for use herein are hydrocarbyl-substituted epoxides in combination with an acid. These may include embodiments in which a separate acid is provided, or in which the acid is provided by the tertiary amine compound that is quaternized. Preferably, the acid is provided by the tertiary amine molecule that is quaternized.

[0165] Preferred quaternizing agents for use herein include dimethyl oxalate, methyl 2-nitrobenzoate, methyl salicylate, chloroacetic acid or its salts, and styrene oxide or propylene oxide, optionally in combination with an additional acid.

[0166] In some embodiments, a mixture of two or more quaternizing agents may be used.

[0167] To form the quaternary ammonium salt additive, a quaternizing agent is reacted with a compound that contains a tertiary amine group.

[0168] Any suitable compound that contains a tertiary amine group can be used.

[0169] The compound comprising at least one tertiary amine group may be selected from: (1) The reaction product of a hydrocarbyl-substituted acylating agent with a compound containing at least one tertiary amine group, and a primary amine, a secondary amine, or an alcohol group; (2) Mannich reaction products containing tertiary amine groups; (3) a polyalkylene-substituted amine having at least one tertiary amine group, and (4) Simple alkylamines and alkanolamines.

[0170] Examples of quaternary ammonium salts and methods for preparing them are described in the following patents: U.S. Patent Application Publication No. 2008 / 0307698, U.S. Patent Application Publication No. 2008 / 0052985, U.S. Patent Application Publication No. 2008 / 0113890, and U.S. Patent Application Publication No. 2013 / 031827.

[0171] The preparation of some suitable quaternary ammonium salt additives of type (1), in which the compound contains at least one tertiary amine group, is described in WO 2006 / 135881, U.S. Patent Application Publication No. 2020 / 0024536 and WO 2011 / 095819.

[0172] The preparation of quaternary ammonium salts of type (2), in which the compound contains at least one tertiary amine group, is described in US Patent Application Publication No. 2008 / 0052985.

[0173] The preparation of quaternary ammonium salt additives of type (3), in which the compound contains at least one tertiary amine group, is described, for example, in US Patent Application Publication No. 2008 / 0113890.

[0174] The preparation of some suitable quaternary ammonium salt additives of type (4), in which the compound contains at least one tertiary amine group, is described, for example, in WO 2016 / 016641.

[0175] Other suitable quaternary ammonium salts include the quaternized terpolymers described, for example, in U.S. Patent Application Publication No. 2011 / 0258917, the quaternized copolymers described, for example, in U.S. Patent Application Publication No. 2011 / 0315107, and the acid-free quaternized nitrogen compounds disclosed in U.S. Patent Application Publication No. 2012 / 0010112.

[0176] In some embodiments, the present invention does not encompass acid-free quaternized nitrogen compounds. In a preferred embodiment, the quaternary ammonium salt additive of the present invention comprises a distinct anion and a distinct cation.

[0177] In some embodiments, the quaternary ammonium compounds for use in the present invention are the quaternized reaction products of fatty acids (eg, oleic acid) and dimethylaminopropylamine.

[0178] Further suitable quaternary ammonium compounds for use in the present invention include those described in the Applicant's co-pending applications WO 2011 / 095819, WO 2013 / 017889, WO 2015 / 011506, WO 2015 / 011507, WO 2016 / 016641 and WO 2017 / 017454.

[0179] Preferably, additive (iii) comprises a quaternary ammonium salt that is the quaternized reaction product of a hydrocarbyl-substituted succinic acid derived acylating agent and a compound capable of reacting with the acylating agent and that contains a tertiary amine group.

[0180] Preferably, the hydrocarbyl-substituted acylating agent is a hydrocarbyl-substituted succinic acid derived acylating agent.

[0181] For the avoidance of doubt, quaternized reaction products are meant to refer to reaction products that contain a tertiary amine and are subsequently quaternized to form a quaternary ammonium group. The quaternary ammonium salt additive is formed by reacting a quaternizing agent with the reaction product of a hydrocarbyl-substituted succinic acid derived acylating agent and a compound capable of reacting with the acylating agent and that contains a tertiary amine group.

[0182] Suitable hydrocarbyl-substituted succinic acid derived acylating agents and means for their preparation are well known in the art. For example, a common method for preparing hydrocarbyl-substituted succinic acid acylating agents is by reacting maleic anhydride with an olefin using a chlorination route or a thermal route (the so-called "ene" reaction).

[0183] Exemplary hydrocarbyl-based substituent groups include n-octyl, n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, chlorooctadecyl, triicontanyl, and the like. The hydrocarbyl-based substituents can be made from homopolymers or interpolymers (e.g., copolymers, terpolymers) of mono- and diolefins having 2 to 10 carbon atoms, such as ethylene, propylene, butane-1, isobutene, butadiene, isoprene, 1-hexene, 1-octene, and the like. Preferably, these olefins are 1-monoolefins. Alternatively, the substituents may be made from other sources, such as monomeric high molecular weight alkenes (e.g., 1-tetra-contene), aliphatic petroleum fractions such as paraffin wax and its cracked analogs, white oils, synthetic alkenes such as those produced by the Ziegler-Natta process (e.g., poly(ethylene) grease), and other sources known to those skilled in the art. Any unsaturation in the substituents can be reduced or removed, if necessary, by hydrogenation according to procedures known in the art.

[0184] Preferably, the hydrocarbyl substituents are predominantly saturated, i.e., they contain no more than one carbon-carbon unsaturated bond for every 10 carbon-carbon single bonds present, and most preferably, they contain no more than one carbon-carbon non-aromatic unsaturated bond for every 50 carbon-carbon bonds present.

[0185] The hydrocarbyl substituent of the succinic acid derived acylating agent preferably contains at least 10, more preferably at least 12, such as at least 30 or at least 40 carbon atoms. It may contain up to about 200 carbon atoms. Preferably, the hydrocarbyl substituent of the acylating agent has a number average molecular weight (Mn) of 170 to 2800, such as 250 to 1500, preferably 500 to 1500, more preferably 500 to 1100. An Mn of 700 to 1300 is particularly preferred.

[0186] Those skilled in the art will be familiar with standard techniques for measuring number average molecular weight, such as vapor pressure osmometry, end group titration, proton NMR, boiling point elevation, freezing point depression (cryoscopy), and gel permeation chromatography (GPC).

[0187] The hydrocarbyl-substituted succinic acid derived acylating agent may comprise a mixture of compounds, for example a mixture of compounds having different hydrocarbyl substituents may be used.

[0188] A preferred hydrocarbyl-based substituent is polyisobutene. Such compounds are known to those skilled in the art.

[0189] A preferred hydrocarbyl-substituted succinic acid derived acylating agent is polyisobutenyl succinic anhydride. These compounds are commonly referred to as "PIBSA" and are known to those skilled in the art.

[0190] Conventional polyisobutenes, as well as the so-called "highly reactive" polyisobutenes, are suitable for use in the present invention. Suitable highly reactive polyisobutenes are as defined above.

[0191] Other preferred hydrocarbyl groups include those containing internal olefins, for example as described in the applicant's published application, WO 2007 / 015080.

[0192] As used herein, internal olefins refers to olefins that contain primarily non-alpha double bonds, i.e., beta or higher olefins. Preferably, such materials are substantially entirely beta or higher olefins, e.g., containing less than 10 wt. % alpha olefins, more preferably less than 5 wt. % or less than 2 wt. % alpha olefins. Exemplary internal olefins include Neodene 1518IO available from Shell.

[0193] Internal olefins may be known as isomerized olefins and may be prepared from alpha olefins by isomerization processes known in the art or may be available from other sources. The fact that they are also known as internal olefins reflects that they do not necessarily have to be prepared by isomerization.

[0194] The preferred hydrocarbyl-substituted succinic acid derived acylating agents for use in the preparation of the additive (iii) of the present invention are polyisobutenyl-substituted succinic anhydrides, or PIBSA. Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300-2800, preferably 450-2300, more preferably 500-1300.

[0195] Hydrocarbyl-substituted succinic acid derived acylating agents are suitably prepared by reacting maleic anhydride with an alkene, such as polyisobutene. The resulting product (such as PIBSA) still contains a double bond. The maleic anhydride is present in the resulting molecule as a succinic acid moiety. This initial product is monomaleated PIBSA.

[0196] Monomaleated PIBSA has structure (A) or (B). [ka]

[0197] The double bond in the monomaleated product can react with an additional molecule of maleic anhydride to form a bismaleated PIBSA having structure (C) or (D). [ka]

[0198] Thus, it is possible to provide a hydrocarbyl group substituted with more than one succinic acid moiety.

[0199] Those skilled in the art will appreciate that the additives used in the present invention typically comprise a mixture of compounds and are prepared from a mixture of monomaleated and bismaleated PIBSA, which can be defined by the level of bismaleation.

[0200] One way this can be determined is by calculating the average number of succinic acid moieties per molecule of the acylating agent.

[0201] Monomaleated PIBSA has one succinic acid moiety per module.

[0202] Bismaleated PIBSA has two succinic acid moieties per molecule.

[0203] A mixture containing monomaleated PIBSA and bismaleated PIBSA in a 1:1 molar ratio contains an average of 1.5 succinic acid moieties per PIBSA molecule.

[0204] The average number of succinic acid moieties per molecule of acylating agent is sometimes referred to in the art as the "P value."

[0205] Suitably, the quaternary ammonium salt additive is prepared from a hydrocarbyl-substituted succinic acid derived acylating agent containing an average of 1 to 2 succinic acid moieties per molecule.

[0206] In some preferred embodiments, the present invention may involve the use of quaternary ammonium salts derived from hydrocarbyl-substituted acylating agents that contain an average of at least 1.2 succinic acid moieties per molecule.

[0207] As one of ordinary skill in the art would understand, a single molecule cannot have 1.2 succinic acid moieties. At least 1.2 succinic acid moieties refers to the average number of succinic acid moieties per molecule of acylating agent, calculated as the sum of all succinic acid moieties present in a sample divided by the total number of molecules of acylating agent having one or more succinic acid moieties present in the sample.

[0208] Preferably, the hydrocarbyl-substituted succinic acid derived acylating agents contain on average at least 1.21 succinic acid moieties per molecule, more preferably at least 1.22 succinic acid moieties per molecule.

[0209] In some embodiments, the hydrocarbyl-substituted succinic acid derived acylating agent may contain at least 1.23 or at least 1.24 succinic acid moieties per molecule.

[0210] In some embodiments, the hydrocarbyl-substituted succinic acid derived acylating agent may contain at least 1.25, at least 1.26, or at least 1.27 succinic acid moieties per molecule.

[0211] In some embodiments, the hydrocarbyl-substituted succinic acid derived acylating agent may contain at least 1.28, at least 1.29, or at least 1.30 succinic acid moieties per molecule.

[0212] A succinic moiety is meant to include residues of succinic acid present in either the diacid or anhydride form.

[0213] The hydrocarbyl-substituted succinic acid derived acylating agent is reacted with a compound capable of reacting with the acylating agent and containing a tertiary amine group, which is quaternized to provide a quaternary ammonium salt additive.

[0214] Examples of suitable compounds that can react with hydrocarbyl-substituted succinic acid derived acylating agents and contain a tertiary amine group include, but are not limited to, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, and N,N-dimethylaminoethylamine. Nitrogen- or oxygen-containing compounds that are condensed with acylating agents and further have a tertiary amino group further include aminoalkyl-substituted heterocyclic compounds such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3'3-aminobis(N,N-dimethylpropylamine). Other classes of nitrogen or oxygen containing compounds that may be condensed with an acylating agent and have a tertiary amino group include, but are not limited to, triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-dimethylaminoethanol, N,N-diethylaminopropanol, N,N-diethylaminoethanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine, N,N,N-tris(aminoethyl)amine, N,N-dibutylaminopropanol, N,N-diethyl ... N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl 1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol, N,N,N'-trimethylaminoethylethanolamine and 3-(2-(dimethylamino)ethoxy)propylamine.

[0215] Preferably, the compound capable of reacting with a hydrocarbyl-substituted succinic acid derived acylating agent and containing a tertiary amine group has formula (XII) or (XIII): [ka] (In the formula, R 2 and R 3are the same or different alkyl, alkenyl, aryl, alkaryl or aralkyl groups having 1 to 22 carbon atoms, X is a bond or an optionally substituted alkylene group having 1 to 20 carbon atoms, n is 0 to 20, m is 1 to 5, R 4 is hydrogen or C1-C 22 It is an amine of the alkyl group.

[0216] When a compound of formula (XII) is used, R 4 is preferably hydrogen or C-C 16 Alkyl groups, preferably C1-C 10 R is an alkyl group, more preferably a C1-C6 alkyl group. 4 When R is alkyl, it may be linear or branched. It may be substituted, for example with hydroxy or alkoxy substituents. Preferably, R 4 is not a substituted alkyl group. More preferably, R 4 is selected from hydrogen, methyl, ethyl, propyl, butyl and their isomers. Most preferably, R 4 is hydrogen.

[0217] When a compound of formula (XIII) is used, m is preferably 2 or 3, most preferably 2, and n is preferably 0 to 15, preferably 0 to 10, more preferably 0 to 5. Most preferably, n is 0, and the compound of formula (XIII) is an alcohol.

[0218] Preferably, the hydrocarbyl-substituted acylating agent is reacted with a diamine compound of formula (XII).

[0219] R 2 and R 3 are the same or different alkyl, alkenyl, aryl, alkaryl, or aralkyl groups having 1 to 22 carbon atoms. In some embodiments, R 2 and R 3 can be linked together to form a ring structure, such as a piperidine, imidazole, or morpholine moiety. Thus, R 2 and R3 R can be taken together to form an aromatic and / or heterocyclic moiety. 2 and R 3 may be a branched alkyl or alkenyl group. Each may be substituted, for example with hydroxy or alkoxy substituents.

[0220] Preferably, R 2 and R 3 Each of C1-C 16 Alkyl groups, preferably C1-C 10 R is an alkyl group. 2 and R 3 may be independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or any isomer thereof. 2 and R 3 are each independently C1-C4 alkyl. 2 is methyl. Preferably, R 3 is methyl.

[0221] X is a bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. In preferred embodiments, when X is an alkylene group, the group may be linear or branched. The alkylene group may include a ring structure therein. For example, it may be substituted with a hydroxy or alkoxy substituent. In some embodiments, X may include a heteroatom in the alkylene chain, for example, X may include an ether functional group.

[0222] X is preferably an alkylene group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example 2 to 6 carbon atoms or 2 to 5 carbon atoms. In some preferred embodiments, X is an unsubstituted alkylene group. Most preferably, X is an ethylene, propylene or butylene group, especially a propylene group.

[0223] Examples of compounds of formula (XII) suitable for use herein include 1-aminopiperidine, 1-(2-aminoethyl)piperidine, 1-(3-aminopropyl)-2-pipecoline, 1-methyl-(4-methylamino)piperidine, 4-(1-pyrrolidinyl)piperidine, 1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1-methylpyrrolidine, N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-dibutylethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-dimethyl-1,3-diaminopropane, N,N,N'-trimethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N,N'-triethylethylenediamine, 3-methyl-4-(2-aminoethyl)pyrrolidine, 4-(1-pyrrolidinyl)piperidine, 1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1-methylpyrrolidine, N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-dibutylethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-dimethyl-1,3-diaminopropane, N,N,N'-trimethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N,N'-triethylethylenediamine, 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, 3,3-aminobis(N,N-dimethylpropylamine), 3-(2-(dimethylamino)ethoxy)propylamine, or combinations thereof.

[0224] In some preferred embodiments, the compound of formula (XII) is selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine, or a combination thereof.

[0225] Examples of compounds of formula (XIII) suitable for use herein include, but are not limited to, triethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamine)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylamino-ethanol, N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol, and N,N,N'-trimethylaminoethylethanolamine.

[0226] In some preferred embodiments, the compound of formula (XIII) is selected from triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamine)ethoxy]ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, or a combination thereof.

[0227] A particularly preferred compound of formula (XII) is N,N-dimethyl-1,3-diaminopropane (dimethylaminopropylamine).

[0228] When a compound of formula (XIII) is reacted with a succinic acylating agent, the resulting product is a succinate ester. 4When reacting with a compound of formula (XII) where R is hydrogen, the resulting product may be a succinimide or a succinamide. 4 When reacted with a compound of formula (XII) where is not hydrogen, the resulting product may be an amide.

[0229] To form the quaternary ammonium salt additive (iii), the hydrocarbyl-substituted succinic acid derived acylating agent is reacted with a compound capable of reacting with the acylating agent and containing a tertiary amine group, and the reaction product is then quaternized by reaction with a quaternizing agent.

[0230] The reaction product of the acylating agent and the compound containing a tertiary amine group is preferably reacted with at least one molar equivalent of quaternizing agent per mole of tertiary amine group present in the reaction product.

[0231] In some embodiments, the reaction product of the acylating agent and the compound containing a tertiary amine group may be reacted with more than 1 molar equivalent of quaternizing agent per mole of tertiary amine group present in the reaction product, preferably at least 1.2 molar equivalents of quaternizing agent per mole of tertiary amine group, more preferably at least 1.5 molar equivalents of quaternizing agent, suitably at least 1.7 molar equivalents of quaternizing agent, for example at least 1.9 molar equivalents of quaternizing agent.

[0232] In some embodiments, the reaction product of the acylating agent and the compound containing a tertiary amine group can be reacted with 2 or 3 or more molar equivalents of quaternizing agent per mole of tertiary amine group present in the reaction product, and preferably at least 2.1 molar equivalents of quaternizing agent.

[0233] In some embodiments, the reaction product of the acylating agent and the compound containing a tertiary amine group is reacted with greater than 2.2 molar equivalents of quaternizing agent per mole of tertiary amine group present in the reaction product, e.g., from 2.3 to 4 molar equivalents, from 2.3 to 3 molar equivalents, or from 2.3 to 2.7 molar equivalents, or from 2.5 to 3 molar equivalents of quaternizing agent per mole of tertiary amine group present in the reaction product.

[0234] To form some preferred quaternary ammonium salt additives of the present invention, a compound of formula (XI) is reacted with a compound formed by the reaction of a hydrocarbyl-substituted acylating agent with an amine of formula (XII) or (XIII).

[0235] The compound of formula (XII) or formula (XIII) is as described above.

[0236] Preferably, an amine of formula (XII) or (XIII) is reacted with a hydrocarbyl-substituted succinic acid derived acylating agent, such as succinic acid or succinic anhydride.

[0237] Suitably, about one equivalent of amine is added per succinic acid moiety present in the acylating agent, and thus the ratio of amines used will typically depend on the average number of succinic acid moieties present in each molecule of the acylating agent.

[0238] Preferred quaternary ammonium salts for use herein are formed by reacting methyl salicylate or dimethyl oxalate, or propylene oxide, optionally in combination with an acid, with the reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine. Mixtures of two or more of such quaternary ammonium salts may also be used.

[0239] A preferred quaternary ammonium salt for use herein is the quaternary ammonium salt of the reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

[0240] Particularly preferred quaternary ammonium salts for use herein are formed by reacting methyl salicylate or dimethyl oxalate with the reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

[0241] In one preferred embodiment, the polyisobutylene-substituted succinic anhydride contains an average of at least 1.2 succinic acid moieties per molecule.

[0242] Antioxidants, when present, are preferably included in the composition of the first aspect in an amount of at least 10 ppm, preferably at least 20 ppm, more preferably at least 50 ppm, such as at least 70 ppm.

[0243] When present, antioxidants may be included in the composition of the first aspect in an amount of up to 10000 ppm, preferably up to 5000 ppm, more preferably up to 2000 ppm, such as up to 1000 ppm.

[0244] The stabilising additive, when present, is preferably included in the composition of the first aspect in an amount of at least 10 ppm, preferably at least 20 ppm, more preferably at least 50 ppm, for example at least 70 ppm.

[0245] When present, the stabilising additive may be included in the composition of the first aspect in an amount of up to 10000 ppm, preferably up to 5000 ppm, more preferably up to 2000 ppm, such as up to 1000 ppm.

[0246] The alkoxylated amine compound, when present, is preferably included in the composition of the first aspect in an amount of at least 5 ppm, preferably at least 10 ppm, more preferably at least 20 ppm, such as at least 40 ppm.

[0247] When present, the alkoxylated amine compound may be included in the composition of the first aspect in an amount of up to 7000 ppm, preferably up to 3000 ppm, more preferably up to 1500 ppm, such as up to 800 ppm.

[0248] The aldehyde-alkylphenol copolymer, when present, is preferably included in the composition of the first aspect in an amount of at least 5 ppm, preferably at least 10 ppm, more preferably at least 20 ppm, such as at least 30 ppm.

[0249] When present, the aldehyde-alkylphenol copolymer may be included in the composition of the first aspect in an amount of up to 5000 ppm, preferably up to 3000 ppm, more preferably up to 1000 ppm, such as up to 700 ppm.

[0250] In this specification, all references to ppm refer to parts per million by weight.

[0251] In a preferred embodiment, the stabilizing additive (b) comprises 1 part (by weight) of the alkoxylated amine compound (i) and 0.5 to 2.5 parts (by weight) of an aldehyde-alkylphenol copolymer.

[0252] The stabilizing additive may also include a carrier or diluent. Preferred carriers and diluents are aromatic hydrocarbon compounds, especially C 10 It is an alkylnaphthalene.

[0253] In a preferred embodiment, the composition of the first aspect comprises from 100 to 1000 ppm, preferably from 250 to 750 ppm, of an antioxidant, and / or from 100 to 1000 ppm, preferably from 250 to 750 ppm, of a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, and mixtures thereof.

[0254] In a preferred embodiment, the composition of the first aspect contains 100 to 1000 ppm, preferably 250 to 750 ppm, of an antioxidant, and / or 0 to 500 ppm, preferably 100 to 300 ppm, of an alkoxylated amine compound, and / or 0 to 500 ppm, preferably 100 to 300 ppm, of an aldehyde-alkylphenol copolymer.

[0255] In a preferred embodiment, the composition of the first aspect contains 50 to 500 ppm, preferably 125 to 325 ppm, of one or more quaternary ammonium salts, and suitably the quaternary ammonium salt is a polyisobutenyl-substituted succinimide ammonium salt, for example, a quaternary ammonium salt of a reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

[0256] In a preferred embodiment, the composition of the first aspect comprises 200 to 400 ppm, preferably 275 to 375 ppm, of a polyisobutenyl-substituted succinimide, such as a polyisobutene-substituted succinic acid or a reaction product of succinic anhydride with a polyethylene polyamine, preferably selected from ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene-heptamine, and mixtures and isomers thereof, preferably tetraethylene pentamine, and preferably the polyisobutene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1000.

[0257] In some embodiments, the composition of the first aspect can be used as a middle distillate fuel oil. The composition may therefore contain one or more additional additives, such as those commonly found in diesel fuels. These include, for example, antioxidants, dispersants, detergents, metal deactivating compounds, wax anti-settling agents, cold flow improvers, cetane improvers, dehazers, stabilizers, demulsifiers, antifoam agents, corrosion inhibitors, lubricity improvers, dyes, markers, fuel oil combustion improvers, metal deactivators, odor masks, drag reducers, and conductivity improvers. Examples of suitable amounts of these various additives are known to those skilled in the art.

[0258] Surprisingly, it has been found that the inclusion of (a) an antioxidant and / or (b) a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, or a mixture thereof, improves the storage stability of compositions comprising pyrolysis oil.

[0259] According to a second aspect of the present invention, there is provided a method for improving the stability of a composition comprising pyrolysis oil, comprising the steps of: (a) antioxidants, and (b) a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, and mixtures thereof; The method includes adding to the composition one or more additives selected from:

[0260] According to a further aspect of the present invention, there is provided a method for improving the stability of a composition comprising pyrolysis oil, comprising the steps of: (a) antioxidants, and (b) a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, (iii) a quaternary ammonium salt, and mixtures thereof. The method includes adding to the composition one or more additives selected from:

[0261] According to a third aspect of the present invention, there is provided a method for improving the stability of a composition comprising pyrolysis oil, comprising: (a) antioxidants, and (b) a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, and mixtures thereof; The use of one or more additives selected from the following is provided:

[0262] According to a further aspect of the present invention, there is provided a method for improving the stability of a composition comprising pyrolysis oil, comprising: (a) antioxidants, and (b) a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, (iii) a quaternary ammonium salt, and mixtures thereof. The use of one or more additives selected from the following is provided:

[0263] Preferred features of the second and third aspects are as defined in relation to the first aspect. Further preferred features of the invention are set out below.

[0264] One or more additives may be added to the composition containing the pyrolysis oil at any time, preferably as soon as possible after synthesis of the oil, and preferably before the oil cools.

[0265] The methods and uses of the present invention improve the stability of compositions containing pyrolysis oil.

[0266] Preferably, the method and use improves the stability of compositions comprising plastic pyrolysis oils.

[0267] Preferably, the method and use improves the storage stability of compositions comprising pyrolysis oil.

[0268] Preferably, the method and use improves the storage stability of compositions comprising plastic pyrolysis oil.

[0269] Improved storage stability suitably translates to reduced deterioration of the oil during storage, which can be observed in a variety of ways.

[0270] In some embodiments, improved stability may result in reduced discoloration upon storage.

[0271] In some embodiments, the increased stability may result in reduced precipitation.

[0272] In some embodiments, the increased stability may reduce or prevent an increase in viscosity.

[0273] In some embodiments, improved stability may reduce the formation of gums and particles in compositions that include pyrolysis oil.

[0274] In some embodiments, improved stability may provide improved filterability, especially after storage.

[0275] In some embodiments, the improved stability may provide improved low temperature properties for compositions including pyrolysis oil.

[0276] One method for measuring the increased stability is described in Example 1, where the sediment from the pyrolysis oil over time is collected by filtration and the residue on the surface of the storage container is examined.

[0277] Preferably, the methods and uses of the present invention reduce the formation of insoluble residues in the pyrolysis oil by at least 5% by weight, preferably by at least 10% by weight, for example by at least 15% by weight.

[0278] The invention will now be further described with reference to the following non-limiting examples. EXAMPLES

[0279] The following additives were added at 500 mg / L to commercially available plastic pyrolysis oil. [Table 1]

[0280] The storage stability of the oils containing the additives was compared to that of the oils without them. During the 28 day storage period, the compositions were kept at a minimum temperature of 15°C.

[0281] The tests involved agitating the cans to disperse the sediment, extracting 500 ml from each can, and filtering through a nitrocellulose filter (0.8 μm). The filters were then dried with 2,2,4-trimethylpentane, which is known to wash away any residual pyrolysis oil without dissolving the sediment. Filters were weighed before and after filtration to quantify the amount present.

[0282] The results are shown in Table 1 and the filter paper is shown in Figure 1. [Table 2] EXAMPLES

[0283] Compositions were prepared by adding the following additives to the plastic pyrolysis oil: [Table 3]

[0284] Dispersant 1 is as defined in Example 1.

[0285] Antioxidant 1 is a phenolic antioxidant containing at least 75% by weight of 2,6-di-tertiary-butyl-phenol and up to 25% by weight of tertiary and tri-tertiary-butyl-phenol.

[0286] After a storage period of 4 weeks, 500 ml of each fuel was filtered through a nitrocellulose filter (0.8 μm).

[0287] The filter was then washed with 2,2,4-trimethylpentane, which is known to wash away any residual pyrolysis oils without dissolving the deposits, and then dried.

[0288] To quantify the amount of insoluble material present, the filter paper was weighed before and after filtration.

[0289] After filtration, the adherent insoluble material remaining in the storage bottle was then dissolved in triple solvent (1:1:1-acetone:toluene:methanol) and transferred to a pre-weighed beaker.

[0290] The solvent was then evaporated and the content of adhering insoluble matter was determined.

[0291] The total amount of insoluble material recovered for each composition is shown in Table 3. [Table 4] EXAMPLES

[0292] Further exemplary compositions were prepared by adding the following additives to the plastic pyrolysis oil: [Table 5]

[0293] Additive 2 was a polyisobutenyl-substituted succinimide ammonium salt and was prepared as follows.

[0294] Polyisobutenyl succinic anhydride (PIBSA) was prepared by adding polyisobutylene (M n A 1000 ml flask was prepared by charging 700 g (0.7 mol) of maleic anhydride (1000 ml). The starting materials were heated to 120° C. with stirring and the nitrogen flush was repeated. The reaction temperature was increased to 190° C. and maleic anhydride (82.4 g, 0.84 mol, 1.2 eq.) was charged over 1 h. After maintaining the temperature at 190° C. for an additional 1 h, the temperature was increased to 200-208° C. and held in this range for 8 h. A vacuum (<30 mbar) was then applied for 2.5 h while maintaining the reaction temperature to reduce the level of residual maleic anhydride to 0.05 wt.% or less. The reaction was cooled to below 80° C. and then discharged from the reactor.

[0295] The PIBSA prepared as above was charged into a nitrogen-flushed jacketed reactor equipped with an overhead stirrer and heated to 120°C. 3-(Dimethylamino)propylamine (DMAPA) (1 equivalent relative to anhydride groups) was charged slowly while maintaining the reaction temperature at 120-130°C. After stirring for an additional hour at 120°C, the reaction temperature was raised to 140°C and held for 3 hours with simultaneous distillation of water. Methyl salicylate (2.1 equivalents relative to anhydride groups) was added in one portion and heating was continued at 140°C for 10 hours. The reactants were diluted with Aromatic 150 solvent to a total solids content of 60% by weight before being discharged from the reactor.

[0296] Additive 3 was a polyisobutenyl-substituted succinimide and was prepared as follows.

[0297] The reaction setup is a 1 L jacketed glass reactor equipped with a Dean-Stark condenser, overhead stirrer, dropping funnel, and nitrogen inlet. 600 g of PIBSA (HR 750mw PIB, 0.768 mol) and 483.33 g of Aromatic A150 solvent were transferred to the reactor. The mixture was stirred and heated to 65° C. to form a homogeneous liquid. Tetraethylenepentamine (138.12 g, 0.729 mol) was then charged to the reactor via the dropping funnel over 1 hour. The temperature of the mixture was increased to 135° C. and held for 1 hour to distill water. The temperature of the mixture was then increased to 165° C. and held for 3 hours. After distillation was complete, the product was cooled and transferred to storage (1208.32 g).

[0298] The storage stability of pyrolysis oil compositions G, H, and I was tested as described in Example 2. The amount of insoluble matter (leachable and attached matter) recovered for each composition, including the total amount, is shown in Table 5. [Table 6]

[0299] These results show that the amount of adhesive insoluble matter produced by plastic pyrolysis oil during storage is significantly reduced when the additives of the present invention are used. The results for compositions H and I also show that additives 2 and 3 (500 mg / l treat rate) also significantly reduce the total amount of insoluble matter produced. Thus, these additives may be effective in improving the stability of compositions containing pyrolysis oil.

Claims

1. Pyrolytic oil, and as an additive (a) Antioxidants, and (b) Stabilizing additives selected from (i) alkoxylated amine compounds, (ii) aldehyde-alkylphenol copolymers, (iii) quaternary ammonium salts, and mixtures thereof. A composition comprising one or more of the following.

2. The composition according to claim 1, wherein the pyrolysis oil is a plastic pyrolysis oil.

3. The composition according to claim 1, comprising an antioxidant.

4. The composition according to claim 3, wherein the antioxidant is a phenolic antioxidant.

5. The composition according to claim 4, wherein the phenolic antioxidant is selected from tert-butylhydroquinone (TBHQ or MTBHQ), 2,5-di-tert-butylhydroquinone (DTBHQ), pyrogallol, pyrocatechol 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butylphenol, propyl gallate, and tert-butylcatechol.

6. The composition according to claim 3, wherein the antioxidant is polyisobutenyl-substituted succinimide.

7. The composition according to claim 1, wherein the antioxidant comprises an amino-based antioxidant.

8. The composition according to claim 1, comprising a stabilizing additive.

9. The composition according to claim 8, wherein the stabilizing additive comprises an alkoxylated amine compound.

10. Alkoxylated amine compounds are given by formula (II): 【Chemistry 1】 (II) The composition according to claim 9, comprising a compound of (wherein EO represents an ethylene oxide residue, PO represents a propylene oxide residue, and at least one of a, b, c, d, e, f, g, and h is not 0).

11. The composition according to claim 8, wherein the stabilizing additive comprises an aldehyde-alkylphenol copolymer.

12. Aldehyde-alkylphenol copolymer, structure (III) or (IV): 【Chemistry 2】 The composition according to claim 11, having (wherein R is hydrogen or an alkyl group, and n is at least 1).

13. The composition according to claim 8, wherein the stabilizing additive comprises (iii) a quaternary ammonium salt.

14. The composition according to claim 13, wherein the quaternary ammonium salt is a reaction product of methyl salicylate or dimethyl oxalate and a reaction product of polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

15. A method for improving the stability of a composition containing pyrolysis oil, (a) Antioxidants, and (b) Stabilizing additives derived from (i) alkoxylated amine compounds, (ii) aldehyde-alkylphenol copolymers, (iii) quaternary ammonium salts, and mixtures thereof. A method comprising the step of adding one or more additives selected from to the composition.

16. The method according to claim 15, wherein the pyrolysis oil is a plastic pyrolysis oil.

17. The method according to claim 15, comprising an antioxidant.

18. The method according to claim 17, wherein the antioxidant is a phenolic antioxidant.

19. The method according to claim 18, wherein the phenolic antioxidant is selected from tert-butylhydroquinone (TBHQ or MTBHQ), 2,5-di-tert-butylhydroquinone (DTBHQ), pyrogallol, pyrocatechol 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butylphenol, propyl gallate, and tert-butylcatechol.

20. The method according to claim 17, wherein the antioxidant is polyisobutenyl-substituted succinimide.

21. The method according to claim 15, wherein the antioxidant includes an amino-based antioxidant.

22. The method according to claim 15, comprising a stabilizing additive.

23. The method according to claim 22, wherein the stabilizing additive comprises an alkoxylated amine compound.

24. Alkoxylated amine compounds are given by formula (II): 【Chemistry 1】 (II) The method according to claim 23, comprising a compound of (wherein EO represents an ethylene oxide residue, PO represents a propylene oxide residue, and at least one of a, b, c, d, e, f, g, and h is not 0).

25. The method according to claim 22, wherein the stabilizing additive comprises an aldehyde-alkylphenol copolymer.

26. Aldehyde-alkylphenol copolymer, structure (III) or (IV): 【Chemistry 2】 The method according to claim 25, wherein R is hydrogen or an alkyl group, and n is at least 1.

27. The method according to claim 22, wherein the stabilizing additive comprises (iii) a quaternary ammonium salt.

28. The method according to claim 27, wherein the quaternary ammonium salt is a reaction product of methyl salicylate or dimethyl oxalate and a reaction product of polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

29. The method according to claim 15, wherein the improvement in stability is an improvement in storage stability.

30. - Reduce discoloration during storage, - Reduced precipitation, - Reduction of gum and particle formation, - Improved filtration, and - Improved low-temperature characteristics The method according to claim 15, wherein one or more of the following are provided.

31. To improve the stability of compositions containing pyrolysis oil, (a) Antioxidants, and (b) Stabilizing additives selected from (i) alkoxylated amine compounds, (ii) aldehyde-alkylphenol copolymers, (iii) quaternary ammonium salts, and mixtures thereof. Use of one or more additives selected from the following.

32. The use according to claim 31, wherein the pyrolysis oil is a plastic pyrolysis oil.

33. The use according to claim 31, comprising an antioxidant.

34. The use according to claim 33, wherein the antioxidant is a phenolic antioxidant.

35. The use according to claim 34, wherein the phenolic antioxidant is selected from tert-butylhydroquinone (TBHQ or MTBHQ), 2,5-di-tert-butylhydroquinone (DTBHQ), pyrogallol, pyrocatechol 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butyl-phenol, propyl gallate, and tert-butylcatechol.

36. The use according to claim 33, wherein the antioxidant is polyisobutenyl-substituted succinimide.

37. The use according to claim 31, wherein the antioxidant includes an amino-based antioxidant.

38. The use according to claim 31, comprising a stabilizing additive.

39. The use according to claim 38, wherein the stabilizing additive comprises an alkoxylated amine compound.

40. Alkoxylated amine compounds are given by formula (II): 【Chemistry 1】 (II) The use according to claim 39, comprising a compound of (wherein EO represents an ethylene oxide residue, PO represents a propylene oxide residue, and at least one of a, b, c, d, e, f, g, and h is not 0).

41. The use according to claim 38, wherein the stabilizing additive comprises an aldehyde-alkylphenol copolymer.

42. Aldehyde-alkylphenol copolymer, structure (III) or (IV): 【Chemistry 2】 The use according to claim 41, comprising (wherein R is hydrogen or an alkyl group, and n is at least 1).

43. The use according to claim 38, wherein the stabilizing additive comprises (iii) a quaternary ammonium salt.

44. The use according to claim 43, wherein the quaternary ammonium salt is a reaction product of methyl salicylate or dimethyl oxalate and a reaction product of polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

45. The use according to claim 31, wherein the improvement in stability is an improvement in storage stability.

46. - Reduce discoloration during storage, - Reduced precipitation, - Reduction of gum and particle formation, - Improved filtration, and - Improved low-temperature characteristics The use according to claim 31, which provides one or more of the following.

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