WO2024238274A1 - Alkoxylation of n-(2-hydroxyethyl)-2-pyrrolidone (hep) and 2-pyrrolidone (2-p) - Google Patents

Abstract

The present disclosure provides hydrophobic dispersant compounds which are synthesized from N-(2-hydroxyethyl)-2-pyrrolidone (HEP) and 2-pyrrolidone (2-P). The compounds may be used as additives in a variety of applications including rubber, tire, and agricultural compositions.

Description

ALKOXYLATION OF N-(2-HYDROXYETHYL)-2-PYRROLIDONE (HEP) AND 2- PYRROLIDONE (2-P)

FIELD OF THE DISCLOSURE

[001] The present disclosure is related to a series of pyrrolidone based molecules, their methods of making, and their uses in various applications.

BACKGROUND OF THE DISCLOSURE

[002] In the rubber industry, and more particularly the tire industry, it is known art to add surfactants to elastomeric compositions for the purpose of improving mechanical properties of the elastomeric materials obtained thereby by vulcanization. Similarly, in agricultural and coating applications, surfactants are often needed further enhance and optimize end performance. Surfactants play an important role as dispersing, emulsifying, cleaning, wetting, foaming, and anti-foaming agents in many other practical applications and products including adhesives, paints, coatings, inks, biocides, shampoos, toothpastes, fire suppression compositions, surface cleaners, disinfectants, detergents, foams, waxes, and the like.

[003] In these applications, a class of molecules known as pyrrolidones are used to impart a variety of characteristics which are necessary to meet end industrial and application needs. However, some pyrrolidone-based derivatives may contain features such as corrosivity, toxicity, and other environmentally considerations which further adds to the complexity needed to produce end formulations and work with easily. Hence, there is a need for improvements around pyrrolidone molecules and methods of making these molecules.

SUMMARY OF THE DISCLOSURE

[004] Disclosed are a set of new molecules based on pyrrolidone and methods of making and using the molecules. The molecules are synthesized from N-(2-hydroxyethyl)- 2 -pyrrolidone (HEP) and 2-pyrrolidone (2-P) and have a delicate hydrophobic/hydrophilic balance which makes them useful as surfactants in a variety of applications.

[005] In a first form thereof, the present disclosure provides a composition comprising a pyrrolidone derivative of Formula I or Formula II:

Formula (I)

wherein n = 1 to 30;

Ri is independently a linear or branched Ci to C12 alkyl group, for example a C2 to Cs alkyl group, in particular a C2 to C4 alkyl group;

R2 is selected from an alcohol (-OH), a methoxy (-OMe), an electron rich aryl or heteroaryl ring, or an ether with the formula (-OR3), wherein R3 is an aliphatic chain with from 1-12 carbon atoms, or an aryl or heteroaryl ring.

[006] In a second form thereof, the present disclosure provides a method for synthesizing a pyrrolidone product comprising the step: reacting an N-alkyl pyrrolidone derivative with one or more alkylene oxides in the presence of a catalyst to form the pyrrolidone product; wherein the pyrrolidone product is a pyrrolidone derivative of Formula I or Formula II:

Formula (I)

wherein n = 1 to 30;

Ri is independently a linear or branched Ci to C12 alkyl group, for example a C2 to Cg alkyl group, in particular a C2 to C4 alkyl group;

R2 is selected from an alcohol (-OH), a methoxy (-OMe), an electron rich aryl or heteroaryl ring, or an ether with the formula (-OR3), wherein R3 is an aliphatic chain with from 1-12 carbon atoms, or an aryl or heteroaryl ring.

[007] In a third form thereof, the present disclosure provides the molecule according to Formula I or Formula II

Formula (I)

wherein n = 1 to 30;

Ri is independently a linear or branched Ci to C12 alkyl group, for example a C2 to Cs alkyl group, in particular a C2 to C4 alkyl group;

R2 is selected from an alcohol (-OH), a methoxy (-OMe), an electron rich aryl or heteroaryl ring, or an ether with the formula (-OR3), wherein R3 is an aliphatic chain with from 1-12 carbon atoms, or an aryl or heteroaryl ring. DETAILED DESCRIPTION

I. Definitions

[008] The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of’ and “consisting of’ can be used in place of “comprising” and “including” to provide for more specific embodiments and are also disclosed. As used in this disclosure and in the appended claims, the singular forms “a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise. The disclosure of percentage ranges and other ranges herein includes the disclosure of the endpoints of the range and any integers provided in the range.

II. N-(2-Hydroxyethyl)-2-Pyrrolidone (HEP) and 2-Pyrrolidone (2-P) Based Compounds [009] Elastomeric compositions across a variety of applications contain alkyl- pyrrolidone derivatives which improve processibility, durability, and other characteristics. Unfortunately, many of these alkyl-pyrrolidone compositions such as N-methyl-2- pyrrolidone, N-butyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, and N-octyl-2-pyrrolidone which can have different levels of irritation and corrosive features. The toxicology and other profile of these alkyl-pyrrolidone derivatives often add to the requirements and complexity necessary for working with these complexes.

[0010] Provided herein are a series of alkyl-pyrrolidone compounds based on N-(2- hydroxyethyl)-2-pyrrolidone (HEP) and 2-pyrrolidone (2-P). HEP requires no Globally Harmonized System (GHS) labeling due to its non-toxicity. The structures of these compounds are shown below in Scheme 1 :

Scheme 1

2-pyrrolidone N-(2-hydroxyethyi)~2-pyrrolidone

(2-P) (HEP) [0011] The alkyl-pyrrolidones N-methyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N- hexyl-2-pyrrolidone, and N-octyl-2-pyrrolidone have a high pH due to the strong basicity of the nitrogen. However, this basicity contributes to increased corrosivity which is undesirable. The present disclosure strikes a balance between reactivity, functionality, environmental hazards, hydrophobicity and hydrophilicity, and corrosivity by substituting the alkyl chain via an alkylene oxide chain.

[0012] In a first embodiment, the alkyl-pyrrolidone compound comprises a HEP derivative having the general formula:

Formula (I)

[0013] In Formula (I), the value for n may be as low as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,

11, 12, 13, 14, 15, or as high as 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, or within any range encompassed by any two of the foregoing values as endpoints. For example, n may be from 1 to 30, from 1 to 25, from 1 to 20, from 1 to 15, from 1 to 10 or from 1 to 5.

[0014] In Formula (I), R1 may be independently a linear or branched Ci to C12 alkyl group, for example a C2 to Cs alkyl group, in particular a C2 to C4 alkyl group. For example, Ri may be a methyl, ethyl, propyl, isopropyl, or butyl group.

[0015] In Formula (I), R2 may be an alcohol (-OH), a methoxy (-OMe), an electron rich aryl or heteroaryl ring, or an ether with the formula (-OR3), wherein R3 is an aliphatic chain with from 1-12 carbon atoms, for example 2 to 10 carbon atoms, in particular 3 to 8 carbon atoms, or an aryl or heteroaryl ring. The aliphatic chain in R2 may specifically have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, or any ranges made from the specified number of carbon atoms.

[0016] In a second embodiment, the alkyl-pyrrolidone compound comprises a 2-P derivative having the general formula:

Formula (II)

[0017] In Formula (II), the value for n may be as low as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or as high as 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 , 28, 29, 30, or within any range encompassed by any two of the foregoing values as endpoints. For example, n may be from 1 to 30, from 1 to 25, from 1 to 20, from 1 to 15, from 1 to 10 or from 1 to 5.

[0018] In Formula (II), Ri may be independently a linear or branched Ci to C12 alkyl group. For example, Ri may be a methyl, ethyl, propyl, isopropyl, or butyl group.

[0019] In Formula (II), Ri may be an alcohol (-OH), a methoxy (-OMe), an electron rich aryl or heteroaryl ring, or an ether with the formula (-OR3), wherein R3 is an aliphatic chain with from 1-12 carbon atoms, for example 2 to 10 carbon atoms, in particular 3 to 8 carbon atoms. The aliphatic chain in R2 may specifically have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, or any ranges made from the specified number of carbon atoms. R3 may also be an electron rich aryl or heteroaryl ring.

[0020] Examples of particular embodiments of Formula I and Formula II are provided in the table below.

III. Alkoxylation of N-(2-Hvdroxyethyl)-2-Pyrrolidone (HEP) and 2-Pyrrolidone (2-P) [0021] Provided herein are methods for synthesizing new pyrrolidone based molecules. The pyrrolidone based molecules are synthesized from a pyrrolidone derivative, such as HEP or 2-P, and an alkylene oxide unit, such as ethylene oxide, propylene oxide, or butylene oxide.

[0022] According to a first aspect, the present invention relates to a method for producing a compound by alkoxylation of N-(2-hydroxyethyl)-2-pyrrolidone (HEP). An exemplary scheme of this reaction is given below in Scheme 2.

Scheme 2

[0023] According to a second aspect, the present invention relates to a method for producing a compound by alkoxylation of 2 -pyrrolidone (2-P). An exemplary scheme of this reaction is given below in Scheme 3.

Scheme 3

[0024] In each aspect, the first step involves reacting the pyrrolidone with an alkylene oxide which is denoted by “O-Ri” in Schemes 2 and 3. The value for Ri may independently any linear or branched Ci to C12 alkyl group. For example, Ri may be a methyl, ethyl, propyl, isopropyl, or butyl group.

[0025] In the first reaction step, it is possible to use a combination of different alkylene oxides, i.e., different values of Ri, in the same reaction. The alkylene oxides may combined in this manner such that they form alkylene oxide blocks. These blocks may, for example, be blocks of one alkylene oxide combined with blocks of a second and optionally a third alkylene oxide. The block structures may be achieved by feeding individual alkylene oxides in sequentially into the reaction. The alkylene oxides may also be fed into the reaction simultaneously as a homogenous mixture which results in a random polymer structure without distinct alkylene oxide blocks. [0026] The starting materials including the pyrrolidone derivative and alkylene oxide may be present in a stoichiometric ratio of 0.1: 1.9 to 1.9:0.1. For example, the HEP and butylene oxide may have a stoichiometric ratio of 0.9:1.1, 1.1:0.9 or 1: 1.

[0027] In each aspect, the reaction may be conducted in the presence of a catalyst. The catalyst may be any suitable strong base such as KOH, NaOH , LiOH, CsOH, Ba(OH)2 Ca(OH 2, among others.

[0028] The reaction may be carried out in a reactor that uses a sufficient level of agitation to create a homogenous reaction mixture. Suitable agitation can be achieved by using a mechanical stirrer. The reactor vessel may be coupled to a heating medium to maintain an appropriate reaction temperature. The reactor vessel may be coupled to a cooling bath with any suitable cooling medium to maintain a suitable reaction temperature. The reactor vessel may also be sealed to create a high-pressure environment for conducting the reaction. In some embodiments, the reaction may also be performed in a Venturi loop reactor or a spray tower loop reactor.

[0029] The reaction may be carried out at a temperature as low as 80°C, 90°C, 100°C, 110°C, 120°C, or as high as 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, or within any range encompassed by any two of the foregoing values as endpoints. For example, the reaction may be carried out at a temperature of 130-140°C.

[0030] After the first reaction is deemed complete, the catalyst may be quenched by the addition of an acid. A preferred acid is glacial acetic acid although other organic or inorganic acids may be used.

[0031] After the first step in each of Schemes 2 and 3, the intermediate product may optionally be further reacted to replace the alcohol with the substituent R2. R2 may be a methoxy (-OMe), an electron rich aryl or heteroaryl ring, or an ether with the formula (- OR3), wherein R3 is an aryl or heteroaryl ring, or an aliphatic chain with from 1-12 carbon atoms, for example 2 to 10 carbon atoms, in particular 3 to 8 carbon atoms. The aliphatic chain in R2 may specifically have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, or any ranges made from the specified number of carbon atoms.

[0032] The electron rich R2 substituent may be added through any suitable reaction procedure known in the art. For example, a transition metal catalyzed cross electrophile coupling or any other electrophilic substitution. IV. Applications of N-(2-Hydroxyethyl)-2-Pyrrolidone (HEP) and 2-Pyrrolidone (2-P) Based Derivatives

A. Rubber Compositions

[0033] The pyrrolidone alkoxylate compounds described herein may be used as dispersants in a variety of rubber or elastomeric applications including, for example, elastomeric tire compositions.

[0034] In addition to the pyrrolidone alkoxylate based compounds described in Sections II and III above, the elastomeric compositions contemplated by the present disclosure may further comprise natural rubbers, synthetic polymers, processing aids, reinforcing fibers, and fillers.

[0035] Suitable natural rubbers include latex or other polymers comprising isoprene.

[0036] Suitable synthetic rubbers include those based upon butadiene rubber latexes and styrene butadiene rubber latexes. Other suitable synthetic rubbers include but not limited to polybutadiene, polychloroprene, also called neoprene, acrylonitrile butadiene rubber (NBR), halogenated polyisobutylene (XIIR), ethylene propylene diene monomer rubber (EPDM), natural rubber, poly-2, 3-dimethyl butadiene, butyl rubber, carboxylated nitrile rubber (XNBR), hydrogenated carboxylated nitrile rubber (HXNBR), and mixtures of at least 2 of the foregoing.

[0037] Processing aids may include, but are not limited to, plasticizers, tackifiers, extenders, chemical conditioners, homogenizing agents and peptizers such as mercaptans, petroleum and vulcanized vegetable oils, resins, rosins, and the like. Accelerators include amines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, thiocarbamates, xanthates, and the like. Cross-linking and curing agents include but are not limited to sulfur, zinc, oxide, and fatty acids.

[0038] Fillers may include but not limited to carbon black and mineral fdlers such as silica and clay.

[0039] Reinforcing fibers may include but not limited to steel cord, steel cord fabrics, polyester, nylon, aramid, tire scrap fibers, or glass cords.

B. Agricultural Compositions [0040] The invention also relates to an agrochemical composition comprising an agrochemical active ingredient and the pyrrolidone alkoxylate compounds described in Section II.

[0041] The term “agrochemical active ingredient” refers to a substance that confers a desirable biological activity to the agrochemical formulation. Typically, the agrochemical active ingredient is a pesticide. Agrochemical active ingredients may be selected from fungicides, insecticides, nematicides, herbicides, safeners, nitrification inhibitors, urease inhibitors, plant growth regulators, micronutrients, biopesticides and/or growth regulators. In one embodiment, the agrochemical active ingredient is an insecticide. In another embodiment, the agrochemical active ingredient is a fungicide. In yet another embodiment the agrochemical active ingredient is a herbicide. The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. Suitable insecticides are insecticides from the class of the carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chloro fenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid diamides, chloronitriles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates, methoxy carbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles. Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphenoxy propionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxy acetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpy ridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas. Suitable plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators. Suitable micronutrients are compounds comprising boron, zinc, iron, copper, manganese, chlorine, and molybdenum.).

[0042] The agrochemical composition typically comprises a biologically, e.g. a pesticidally effective amount of the agrochemical active ingredient. The term "effective amount" denotes an amount of the composition or of the agrochemical active ingredient, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants.

[0043] The agrochemical composition typically contains the agrochemical active ingredient in a concentration of from 1 to 70 wt.%, preferably from 10 to 50 wt.%, more preferably from 20 to 45 wt.% based on the total weight of the agrochemical composition. [0044] The agrochemical composition contains the pyrrolidone alkoxylate compounds according to the present disclosure. The concentration of the polymer in the agrochemical composition is typically from 0.5 to 20 wt.%, preferably from 0.5 to 10 wt.%, more preferably from 1 to 8 wt.% based on the total weight of the agrochemical composition. The concentration of the polymer is typically up to 15 wt.%, more preferably up to 9 wt.%, most preferably up to 7 wt.% based on the total weight of the agrochemical composition. The concentration of the polymer is usually at least 2 wt.%, preferably at least 2.5 wt.% based on the total weight of the agrochemical composition.

[0045] The polymer according to the invention is in one embodiment present in the agrochemical composition in dissolved form, in particular if the agrochemical composition is an aqueous agrochemical composition.

[0046] In one embodiment, the polymer is present as solid particles, such as dispersed particles, especially if the agrochemical composition is a non-aqueous composition, such as a solid composition or an agrochemical composition with a continuous organic phase.

[0047] The weight ratio of the active agrochemical ingredient to the polymer in the agrochemical composition is typically from 5:1 to 30:1, preferably from 7:1 to 20:1.

[0048] The agrochemical composition can be any customary type of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further composition types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International. In one embodiment, the agrochemical composition is a suspension, wettable powder or dusts, and granules. In one embodiment, the agrochemical composition is a suspension concentrate. In one embodiment, the agrochemical composition is an emulsion concentrate. In one embodiment, the agrochemical composition is a soluble liquid aqueous formulation (SL).

[0049] Suitable auxiliaries that may be added to the agrochemical composition are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, crystal growth inhibitors, tackifiers and binders.

[0050] Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. [0051] Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

[0052] Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

[0053] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate. [0054] Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines .

[0055] Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries.

[0056] Suitable thickeners are polysaccharides (e.g., xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.

[0057] Suitable bactericides include bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

[0058] Suitable anti-freezing agents include ethylene glycol, propylene glycol, urea and glycerin.

[0059] Suitable anti-foaming agents include silicones, long chain alcohols, and salts of fatty acids.

[0060] Suitable colorants (e.g., in red, blue, or green) include pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g., alizarin-, azo- and phthalocyanine colorants).

[0061] Suitable tackifiers or binders include polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0062] The agrochemical suspension can in principle be prepared at any pH. Preferably, agrochemical suspensions according to the invention have a pH 4- 9.

[0063] In one embodiment, the invention relates to the use of the polymer according to the present invention for dispersing agrochemical active ingredients in agrochemical compositions, such as in suspensions.

[0064] The composition of any of the beforementioned embodiments contains preferably from 1 to 60 wt.% of the active agrochemical ingredient based on the total weight of the agrochemical composition, with the active agrochemical ingredient preferably having a water solubility of up to 5 g/1 at 20°C, preferably up to 1 g/1 at 20°C, and/or contains from 0.5 to 10 wt.% of the polymer based on the total weight of the agrochemical composition.

[0065] Further encompassed by this invention is a method for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired attack by insects , arachnids or mollusca and/or for regulating the growth of plants, where the agrochemical composition - being one as defined in any of the beforementioned embodiments in this chapter disclosing such compositions - is allowed to act on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and/or on undesired plants and/or the useful plants and/or their habitat.

[0066] Suitable methods of treatment include inter alia soil treatment, seed treatment, in furrow application, and foliar application. Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. In furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow.

[0067] When employed in plant protection, the amounts of agrochemical active applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

[0068] Further encompassed is a seed comprising an agrochemical composition in an amount of from 0.1 g to 10 kg per 100 kg of seed, wherein the agrochemical composition is as defined in any of the beforementioned embodiments in this chapter disclosing such compositions.

[0069] Further encompassed by this invention is a method for treating or protecting an animal from infestation or infection by invertebrate pests which comprises bringing the animal in contact with a pesticidally effective amount of the agrochemical composition, where the agrochemical composition is an agrochemical composition as defined in any of the beforementioned embodiments in this chapter disclosing such compositions.

[0070] Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0. 1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying the agrochemical composition on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, the agrochemical composition applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.

[0071] In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.

[0072] When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

[0073] Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g., herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the agrochemical composition as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1: 10 to 10: 1. [0074] The user applies the agrochemical composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a drone (UAV), a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. In one embodiment, 10 to 2000 liters, preferably 20 to 400 liters, of the ready-to- use spray liquor are applied per hectare of agricultural useful area.

[0075] In a further embodiment, either individual components of the composition according to the invention or partially premixed components can be applied jointly (e.g., after tank mix) or consecutively. C. Other Applications

[0076] The present disclosure also contemplates numerous other compositions containing the pyrrolidone alkoxylate derivatives described in Section II. The pyrrolidone based compounds defined by Formulas I and II may, for example, also be used in pharmaceuticals such as binders, coatings, and disintegrants for tablets, or solubilizers for suspensions and solutions.

[0077] The compounds may also be used in cosmetics such as for hair sprays, setting lotions, and conditioning shampoos.

[0078] The compounds may be used in food products such as in stabilizers for beverages.

[0079] The compounds may be used in inks, dyes, paints, surfactants, or plasticizers.

[0080] The compounds may be used in cleaning formulations such as surface cleaners, detergents, sanitizers, and the like.

[0081] The compounds may be used as a solvent for membrane production.

EXAMPLES

[0082] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compositions and/or methods claimed herein are made and evaluated and are intended to be purely exemplary and are not intended to limit the scope of the disclosure. Unless indicated otherwise, parts are parts by weight, temperature is in degrees Celsius or is at ambient temperature, and pressure is at or near atmospheric.

Example 1: Alkoxylation of N-(2-hydroxyethyl)-2-pyrrolidone (HEP) with 1 Mole HEP and 5 Moles of Propylene Oxide (PO)

[0083] 1539 grams of HEP (N-(2-hydroxyethyl)-2-pyrrolidone, CAS# 126-86-3) was charged to a clean, dry, high pressure, stainless steel reactor. Agitation at 250 rpm was started and the reactor charge port was closed and sealed. Oxygen was removed from the reactor by pulling vacuum to <50 mmHg followed by purging 3 times with 90 psig nitrogen. The pressure was checked on the final purge. Next the reactor contents were heated with agitation to 95-100°C. The reactor was then evacuated to <10mmHg and held at 95-100°C for approximately 1 hour to remove water from the catalyst addition. The water was collected in a dry ice trap and until the expected amount (12 grams) of water was collected. The vacuum with nitrogen was then broken and the mixture was heated to 130°C. The required 3461 grams of propylene oxide (PO) was weighted and transferred into a high pressure, stainless steel cylinder under an inert environment. The PO cylinder was then connected to the feed lines and the dip tube of the reactor and was then pressurized with nitrogen. The PO was fed into the reactor through the dip tube at a steady rate over approximately 4 hours. The temperature was maintained at 130°C ± 5°C. After all PO had been added, the mixture was post-reacted at 130°C at constant pressure for approximately 3 hours. The reactor was maintained at 130°C, then vented and evacuated to < lOmmHg. Then the reactor was stripped for 1 hour to remove residual PO. The reactor was cooled to < 60°C. 8 grams of glacial acetic acid (GAA) was charged to neutralize the reaction catalyst. Additional GAA was added as needed to ensure the product is sufficiently neutral (typ. apparent pH of 6-8. Finally, the finished product was discharged from the reactor.

Example 2: Alkoxylation of N-(2-hydroxyethyl)-2-pyrrolidone (HEP) with 1 Mole HEP and 4 Moles of Butylene Oxide (BO)

[0084] 1547 grams of HEP (N-(2-hydroxyethyl)-2-pyrrolidone, CAS# 126-86-3) was charged to a clean, dry, high pressure, stainless steel reactor. To the same reactor, 17 grams of 45% KOH was charged. Agitation was started at 250 rpm and the reactor charge port was closed and sealed. Oxygen was removed from the reactor by pulling vacuum to <50 mmHg followed by purging 3 times with 90 psig nitrogen. The reactor pressure was checked with the final purge. The reactor contents were heated with agitation at 95-100°C. Then the reactor was evacuated to <10 mmHg and held at 95-100°C for approximately 1 hour to remove water from the catalyst addition. The water was collected in a dry ice trap and until the expected amount (12 grams) of water was collected. The vacuum with nitrogen was then broken and the mixture was heated to 140°C. 3454 grams of BO was weighted into a high-pressure stainless-steel cylinder under an inert environment. The BO cylinder was then connected to the feed lines and the dip tube of the reactor and pressurized with nitrogen. The BO was then fed into the reactor through the dip tube at a steady rate over approximately 5 hours. The temperature was maintained at 140°C ± 5°C. After all the BO had been added the mixture was post-reacted at 130°C to a constant pressure for approximately 4 hours. Then, with the reactor temperature was maintained at 140 °C, the reactor was vented and evacuated to < lOmmHg. The reactor was stripped reactor for 1 hour to remove residual BO. The reactor was cooled to < 60°C. 8 grams of glacial acetic acid (GAA) was charged to neutralize the reaction catalyst. Additional GAA was added as needed to ensure the product is sufficiently neutral (typ. apparent pH of 6-8. Finally, the finished product was discharged from the reactor.

Example 3: Alkoxylation of N-(2-hydroxyethyl)-2-pyrrolidone (HEP) with 1 Mole HEP, 2 Moles of Ethylene Oxide (EQ) and 3 Moles of Butylene Oxide (BO)

[0085] 1489 grams of HEP (N-(2-hydroxyethyl)-2-pyrrolidone, CAS# 126-86-3) was charged to a clean, dry, high pressure, stainless steel reactor. To the same reactor, 17 grams of 45% KOH was charged. Agitation was started at 250 rpm and the reactor charge port was closed and sealed. Oxygen was removed from the reactor by pulling vacuum to <50 mmHg followed by purging 3 times with 90 psig nitrogen. The reactor pressure was checked with the final purge. The reactor contents were heated with agitation to 95-100°C. Then the reactor was evacuated to <10 mmHg and held at 95-100°C for approximately 1 hour to remove water from the catalyst addition. The water was collected in a dry ice trap and until the expected amount (12 grams) of water was collected. Then the vacuum was broken with nitrogen and the mixture was heated to 140°C. The required 1017 grams of ethylene oxide (EO) was weighted into a high pressure, stainless steel cylinder under an inert environment. Then the EO cylinder was connected to the feed lines and dip tube of the reactor and was then pressurized with nitrogen. Nitrogen was added to the reactor to raise the pressure to 35 psig. The EO was fed into the reactor through the dip tube at a steady rate over approximately 1.5 hours. The reactor temperature was maintained at 145°C ± 5°C.

Then the temperature was maintained at 145°C and the mixture was post-reacted at constant pressure for 30-60 minutes. The reactor was cooled to 140°C and vented to 2-5 psig. The required 2494 grams of BO was then weighed into a high pressure, stainless steel cylinder under an inert environment. Then the BO cylinder was connected to the feed lines and dip tube of the reactor and was then pressurized with nitrogen. The BO was fed into the reactor through the dip tube at a steady rate for approximately 4 hours. The temperature was maintained at 140°C ± 5°C. After all BO had been added, the mixture was post-reacted at 130°C at a constant pressure for approximately 3 hours. The reactor temperature was maintained at 140°C, then the reactor was vented and evacuated to < 10 mmHg. The reactor was stripped for 1 hour to remove residual BO. The reactor was cooled to < 60°C. 8 grams of glacial acetic acid (GAA) was charged to neutralize the reaction catalyst. Additional GAA was added as needed to ensure the product is sufficiently neutral (typ. apparent pH of 6-8. Finally, the finished product was discharged from the reactor.

Claims

WHAT IS CLAIMED IS

1. A composition comprising a pyrrolidone derivative of Formula I or Formula II: Formula (I)

wherein n = 1 to 30;

Ri is independently a linear or branched Ci to C12 alkyl group;

R2 is selected from an alcohol (-OH), a methoxy (-OMe), an electron rich aryl or heteroaryl ring, or an ether with the formula (-OR3), wherein R3 is an aliphatic chain with from 1-12 carbon atoms, or an aryl or heteroaryl ring.

2. The composition of claim 1, wherein n = 1 to 20.

3. The composition of claim 1 or 2, wherein n = 1 to 10.

4. The composition of any of claims 1 to 3, wherein n = 1 to 5.

5. An elastomeric tire composition comprising: a natural or synthetic rubber, and the composition according to any of claims 1 to 4.

6. An agricultural composition comprising: a biocide, and the composition of any of claims 1 to 5.

7. The agricultural composition of claim 6, further comprising a solvent.

8. A plasticizer composition comprising the composition of any of claims 1 to 4.

9. A surface cleaning composition comprising the composition of any of claims 1 to 4.

10. A method for synthesizing a pyrrolidone product comprising the step: reacting pyrrolidone starting material with one or more alkylene oxides in the presence of a catalyst to form the pyrrolidone product; wherein the pyrrolidone product is a pyrrolidone derivative of Formula I or Formula II:

Formula (I)

wherein n = 1 to 30;

Ri is independently a linear or branched Ci to C12 alkyl group;

R2 is selected from an alcohol (-OH), a methoxy (-OMe), an electron rich aryl or heteroaryl ring, or an ether with the formula (-OR3), wherein R3 is an aliphatic chain with from 1-12 carbon atoms, or an aryl or heteroaryl ring.

11. The method of claim 10, wherein the pyrrolidone starting material is N-(2- hydroxyethyl)-2-pyrrolidone.

12. The method of claim 10 or 11, wherein the pyrrolidone starting material is 2- pyrrolidone (2-P).

13. The method of any of claims 10 to 12, wherein the alkylene oxide is ethylene oxide.

14. The method of any of claims 10 to 13, wherein the alkylene oxide is propylene oxide.

15. The method of any of claims 10 to 14, wherein the alkylene oxide is butylene oxide.

16. The method of any of claims 10 to 15, wherein the alkylene oxide is isobutylene oxide.

17. The method of any of claims 10 to 16, wherein the alkylene oxide is pentylene oxide.

18. The method of any of claims 10 to 17, wherein the alkylene oxide is a mixture of propylene oxide and butylene oxide.

19. The method of any of claims 10 to 18, wherein the reaction step results in random alkoxylation.

20. The method of any of claims 10 to 19, wherein the reaction step produces alkylene oxide blocks.

21. The method of any of claims 10 to 20, wherein the catalyst is potassium hydroxide.

22. The method of any of claims 10 to 21, wherein the reaction step is carried out at a temperature of 90-160°C.

23. The molecule according to Formula I or Formula II

Formula (I)

wherein n = 1 to 30;

Ri is independently a linear or branched Ci to C12 alkyl group;

R2 is selected from an alcohol (-OH), a methoxy (-OMe), an electron rich aryl or heteroaryl ring, or an ether with the formula (-OR3), wherein R3 is an aliphatic chain with from 1-12 carbon atoms, or an aryl or heteroaryl ring.

24. The molecule of claim 23, wherein n = 1 to 20.

25. The molecule of claim 23 or 24, wherein n = 1 to 10.

26. The molecule of any of claims 23 to 25, wherein n = 1 to 5.