An aqueous hair stying composition comprises:

This invention relates to aqueous hair styling compositions, for example creams, gels and especially aerosol hair styling mousses, which incorporate an oily or fatty material and which have improved strength and durability of hair hold and superior sensory feel.
Hair styling compositions such as hair styling mousses provide human hair with a temporary set which can be removed by water or by shampooing, and function by applying a thin film of a resin or gum onto the hair to adhere adjacent hairs together so that they retain the particular shape or configuration at the time of application.
Conventional hair styling mousses typically utilise a hair setting polymer, water, surfactant and propellant gas, with optional adjuvants such as aesthetic agents, fragrance and hair conditioning agents. The conditioning agents used have included silicone-type materials.
EP 0 523 388 discloses an aqueous hair styling aid or mousse composition incorporating a non-volatile silicone compound or other water-insoluble, emulsifiable conditioning agent. The preferred non-volatile silicone compound is a 3:1 mixture of a low molecular weight polydimethylsiloxane fluid and a higher molecular weight polydimethylsiloxane gum.
EP 0 205 306 discloses the use of high molecular weight silicone materials in styling mousses. These are defined as polydiorganosiloxanes having a viscosity of at least 100,000 cst. The high molecular weight silicone is dissolved in the propellant phase prior to filling the aerosol container.
A problem is that those silicone materials which are typically used as conditioning agents in hair care applications tend to make the hair too soft to form and retain a style.
The present inventors have surprisingly discovered that the strength and durability of hair hold delivered by a hair styling resin in an aqueous hair styling aid such as a hair styling mousse can be significantly increased by the inclusion in the formulation of certain oily or fatty materials. In particular, hair styling aids of the invention provide tough elastic films on the hair which spread more easily on hair to provide more sites for bonding than conventional styling aids. Advantageously, hair styling aids of the invention also exhibit superior sensory feel, in particular improved softness, shine and conditioning. Furthermore, compositions of the invention are able to protect hair against damage, and show a surprising benefit with respect to the reduction of split end formation.
The present invention provides an aqueous hair styling composition comprising:
(i) from 0.1% to 40%, by weight based on total weight, of oily or fatty material, the oily or fatty material including at least one material selected from hydrocarbon oils and glyceride fatty esters.
(ii) from 0.1% to 10%, by weight based on total weight, of a hair styling polymer;
(iii) from 0% to 30%, by weight based on total weight, of an aerosol propellant; and
(iv) from 0% to 5%, by weight based on total weight, of a surfactant.
(i) Oily or Fatty Material
Suitable oily or fatty materials for use in compositions of the invention will generally have a viscosity at ambient temperature of from 10xe2x88x924 to 1.0 Pa.s, preferably from 10xe2x88x923 to 0.5 Pa.s, more preferably from 5xc3x9710xe2x88x923 to 0.15 Pa.s as measured by a Carri-Med CSL2 100 controlled stress rheometer, from TA Instruments Inc.
The oily or fatty material in compositions of the invention includes at least one material selected from hydrocarbon oils and glyceride fatty esters.
Suitable hydrocarbon oils include cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated). Straight chain hydrocarbon oils will preferably contain from about 8 to about 19 carbon atoms. Branched chain hydrocarbon oils can and typically may contain higher numbers of carbon atoms, e.g. from about 5 up to about 70 carbon atoms, preferably from about 8 up to about 50 carbon atoms. Also suitable are polymeric hydrocarbons of alkenyl monomers, such as C2-C6 alkenyl monomers. These polymers can be straight or branched chain polymers. The straight chain polymers will typically be relatively short in length, having a total number of carbon atoms as described above for straight chain hydrocarbons in general. The branched chain polymers can have substantially higher chain length. The number average molecular weight of such materials can vary widely, but will typically be up to about 500, preferably from about 200 to about 400, more preferably from about 300 to about 350.
Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used. Exemplary branched-chain isomers are highly branched saturated or unsaturated alkanes, such as the permethyl-substituted isomers, e.g., the permethyl-substituted isomers of hexadecane and eicosane, such as 2,2,4,4,6,6,8,8-dimethyl-10-methylundecane and 2,2,4,4,6,6-dimethyl-8-methylnonane, sold by Permethyl Corporation. A further example of a hydrocarbon polymer is polybutene, such as the copolymer of isobutylene and butene. A commercially available material of this type is L-14 polybutene from Amoco Chemical Co. (Chicago, Ill., U.S.A.).
Particularly preferred hydrocarbon oils are the various grades of mineral oils. Mineral oils are clear oily liquids obtained from petroleum oil, from which waxes have been removed, and the more volatile fractions removed by distillation. The fraction distilling between 250xc2x0 C. to 300xc2x0 C. is termed mineral oil, and it consists of a mixture of hydrocarbons, in which the number of carbon atoms per hydrocarbon molecule generally ranges from C10 to C40. Suitable commercially available materials of this type include Sirius M40 (carbon chain length C10-C30, viscosity 5.5xc3x9710xe2x88x923 Pa.s), Sirius M85 (carbon chain length C10-C40, viscosity 2.7xc3x9710xe2x88x922 Pa.s) and Sirius M340 (carbon chain length C15-C40, viscosity 1.5xc3x9710xe2x88x921 Pa.s), all available from Silkolene.
By xe2x80x9cglyceride fatty estersxe2x80x9d is meant the mono-, di-, and tri-esters formed between glycerol and long chain carboxylic acids such as C8-C22 carboxylic acids. A variety of these types of materials are present in vegetable and animal fats and oils, such as camellia oil, coconut oil, castor oil, safflower oil, sunflower oil, peanut oil, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil. These have various ranges of carbon chain lengths depending on the source, typically between about 12 to about 18 carbon atoms. Synthetic oils include trimyristin, triolein and tristearin glyceryl dilaurate. Specific examples of preferred materials for inclusion in compositions of the invention as sources of glyceride fatty esters include camellia oil, coconut oil, sunflower oil, peanut oil, palm oil and soybean oil.
Other suitable oily or fatty materials which may be present in combination with the hydrocarbon oils and/or glyceride fatty esters in compositions of the invention include other fatty esters.
In general, fatty esters are characterised by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols, e.g., monocarboxylic acid esters, polyhydric alcohol esters, and di- and tricarboxylic acid esters. The hydrocarbyl radicals of the fatty esters can also include or have covalently bonded thereto other compatible functionalities, such as amides and alkoxy moieties, such as ethoxy or ether linkages.
Monocarboxylic acid esters include esters of alcohols and/or acids of the formula Rxe2x80x2COOR in which Rxe2x80x2 and R independently denote alkyl or alkenyl radicals and the sum of carbon atoms in Rxe2x80x2 and R is at least 10, preferably at least 20.
Specific examples include, for example, alkyl and alkenyl esters of fatty acids having aliphatic chains with from about 10 to about 22 carbon atoms, and alkyl and/or alkenyl fatty alcohol carboxylic acid esters having an alkyl and/or alkenyl alcohol-derived aliphatic chain with about 10 to about 22 carbon atoms, and mixtures thereof.
The monocarboxylic acid ester need not necessarily contain at least one chain with at least 10 carbon atoms, so long as the total number of aliphatic chain carbon atoms is at least 10. Examples include isopropyl myristate, hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyl adipate.
Di- and trialkyl and alkenyl esters of carboxylic acids can also be used. These include, for example, esters of C4-C8 dicarboxylic acids such as C1-C22 esters (preferably C1-C6) of succinic acid, glutaric acid, adipic acid, hexanoic acid, heptanoic acid, and octanoic acid. Examples include diisopropyl adipate, diisohexyl adipate, and diisopropyl sebacate. Other specific examples include isocetyl stearoyl stearate, and tristearyl citrate.
Polyhydric alcohol esters include alkylene glycol esters, for example ethylene glycol mono and di-fatty acid esters, diethylene glycol mono- and di-fatty acid esters, polyethylene glycol mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid esters, polypropylene glycol monooleate, polypropylene glycol monostearate, ethoxylated propylene glycol monostearate, polyglyceryl poly-fatty acid esters, ethoxylated glyceryl monostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters.
The oily or fatty material may be present in compositions of the invention as a single material or as a blend, provided that there is included at least one material selected from hydrocarbon oils and glyceride fatty esters as described above.
Blends are particularly preferred since these appear to give optimum benefits in respect of style longeveity and sensory feel.
Examples of blends which have been found useful in compositions of the invention are hydrocarbon oil/fatty ester blends and hydrocarbon oil/fatty ester/fatty ester blends. The hydrocarbon oil:fatty ester(s) weight ratio in such blends may suitably range from 1:0.01 to 0.01:1, preferably from 1:0.1 to 0.1:1, most preferably from 3:1 to 1:3. Specific examples of blends of this type include blends of mineral oil and soybean oil and blends of mineral oil, soybean oil and isopropyl myristate. Particularly preferred is a blend of mineral oil, soybean oil and isopropyl myristate, in which the mineral oil:soybean oil:isopropyl myristate weight ratio is 6:2:2.
Also suitable are fatty ester/fatty ester blends. A particularly preferred example of a blend of this type is a blend of isopropyl myristate and soybean oil, in which the isopropyl myristate:soybean oil weight ratio suitably ranges from 1:0.01 to 0.01:1, preferably from 1:0.1 to 0.1:1, most preferably from 2:1 to 1:2.
The total content of oily or fatty material in compositions of the invention suitably ranges from 1% to 25%, preferably from 5% to 15%, by total weight of oily or fatty material based on total weight of the composition.
(ii) Hair Styling Polymer
Hair styling polymers are well known articles of commerce and many such polymers are available commercially which contain moieties which render the polymers cationic, anionic, amphoteric or nonionic in nature. The polymers may be synthetic or naturally derived.
The amount of the polymer may range from 0.1 to 10%, preferably 0.5 to 6% by weight of the total composition.
Examples of anionic hair styling polymers are:
copolymers of vinyl acetate and crotonic acid;
terpolymers of vinyl acetate, crotonic acid and a vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid such as vinyl neodecanoate;
copolymers of methyl vinyl ether and maleic anhydride (molar ratio about 1:1) wherein such copolymers are 50% esterified with a saturated alcohol containing from 1 to 4 carbon atoms such as ethanol or butanol;
acrylic copolymers containing acrylic acid or methacrylic acid as the anionic radical-containing moiety with other monomers such as: esters of acrylic or methacrylic acid with one or more saturated alcohols having from 1 to 22 carbon atoms (such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, t-butyl acrylate, t-butyl methacrylate, n-butyl methacrylate, n-hexyl acrylate, noctyl acrylate, lauryl methacrylate and behenyl acrylate); glycols having from 1 to 6 carbon atoms (such as hydroxypropyl methacrylate and hydroxyethyl acrylate); styrene; vinyl caprolactam; vinyl acetate; acrylamide; alkyl acrylamides and methacrylamides having 1 to 8 carbon atoms in the alkyl group (such as methacrylamide, t-butyl acrylamide and n-octyl acrylamide); and other compatible unsaturated monomers.
The polymer may also contain grafted silicone, such as polydimethylsiloxane.
Specific examples of suitable anionic hair styling polymers are:
RESYN(copyright) 28-2930 available from National Starch (vinyl acetate/crotonic acid/vinyl neodecanoate copolymer);
ULTRAHOLD(copyright) 8 available from BASF (CTFA designation Acrylates/acrylamide copolymer);
the GANTREZ(copyright) ES series available from ISP Corporation esterified copolymers of methyl vinyl ether and maleic anhydride).
Other suitable anionic hair styling polymers include carboxylated polyurethanes Carboxylated polyurethane resins are linear, hydroxyl-terminated copolymers having pendant carboxyl groups. They may be ethoxylated and/or propoxylated at least at one terminal end. The carboxyl group can be a carboxylic acid group or an ester group, wherein the alkyl moiety of the ester group contains one to three carbon atoms. The carboxylated polyurethane resin can also be a copolymer of polyvinylpyrrolidone and polyurethane, having a CTFA designation PVP/polycarbamyl polyglycol ester. Suitable carboxylated polyurethane resins are disclosed in EP 0 619 111 A1 and U.S. Pat. No. 5,000,955. Other suitable hydrophilic polyurethanes are disclosed in U.S. Pat. Nos. 3,822,238; 4,156,066; 4,156,067; 4,255,550; and 4,743,673.
Amphoteric polymers which can contain cationic groups derived from monomers such as t-butyl aminoethyl methacrylate as well as carboxyl groups derived from monomers such as acrylic acid or methacrylic acid can also be used in the present invention. One specific example of an amphoteric hair styling polymer is Amphomer(copyright) (Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer) sold by the National Starch and Chemical Corporation.
Examples of nonionic hair styling polymers are homopolymers of N-vinylpyrrolidone and copolymers of N-vinylpyrrolidone with compatible nonionic monomers such as vinyl acetate. Nonionic polymers containing N-vinylpyrrolidone in various weight average molecular weights are available commercially from ISP Corporationxe2x80x94specific examples of such materials are homopolymers of N-vinylpyrrolidone having an average molecular weight of about 630,000 sold under the name PVP K-90 and are homopolymers of N-vinylpyrrolidone having an average molecular weight of about 1,000,000 sold under the name of PVP K-120.
Other suitable nonionic hair styling polymers are cross-linked silicone resins or gums. Specific examples include rigid silicone polymers such as those described in EP-A-240 350 and cross-linked silicone gums such as those described in WO 96/31188.
Examples of cationic hair styling polymers are copolymers of amino-functional acrylate monomers such as lower alkyl aminoalkyl acrylate, or methacrylate monomers such as dimethylaminoethyl methacrylate, with compatible monomers such as N-vinylpyrrolidone, vinyl caprolactam, alkyl methacrylates (such as methyl methacrylate and ethyl methacrylate) and alkyl acrylates (such as ethyl acrylate and n-butyl acrylate).
Specific examples of suitable cationic polymers are:
copolymers of N-vinylpyrrolidone and dimethylaminoethyl methacrylate, available from ISP Corporation as Copolymer 845, Copolymer 937 and Copolymer 958;
copolymers of N-vinylpyrrolidone and dimethylaminopropylacrylamide or methacrylamide, available from ISP Corporation as Styleze(copyright) CC10;
copolymers of N-vinylpyrrolidine and dimethylaminoethyl methacrylate;
copolymers of vinylcaprolactam, N-vinylpyrrolidone and dimethylaminoethylmethacrylate;
Polyquaternium-4 (a copolymer of diallyldimonium chloride and hydroxyethylcellulose);
Polyquaternium-11 (formed by the reaction of diethyl sulphate and a copolymer of vinyl pyrrolidone and dimethyl aminoethylmethacrylate), available from ISP as Gafquat(copyright) 734, 755 and 755N, and from BASF as Luviquat(copyright)PQ11;
Polyquaternium-16 (formed from methylvinylimidazolium chloride and vinylpyrrolidone), available from BASF as Luviquat(copyright) 370, FC 550, FC 905 and HM-552;
Polyquaternium-46 (prepared by the reaction of vinylcaprolactam and vinylpyrrolidone with methylvinylimidazolium methosulphate), available from BASF as Luviquat(copyright)Hold.
Examples of suitable naturally derived polymers include shellac, alginates, gelatins, pectins, starch, cellulose derivatives and chitosan or salts and derivatives thereof. Commercially available examples include Kytamer(copyright) (ex Amerchol) and Amaze(copyright) (ex National Starch).
With certain of the above-described polymers it may be necessary to neutralise some acidic groups to promote solubility/dispersibility. Examples of suitable neutralising agents include 2-amino-2-methyl-1,3-propanediol (AMPD); 2-amino-2-ethyl-1,3-propanediol (AEPD); 2-amino-2-methyl-1-propanol (AMP); 2-amino-1-butanol (AB); monoethanolamine (MEA); diethanolamine (DEA); triethanolamine (TEA); monoisopropanolamine (MIPA); diisopropanol-amine (DIPA); triisopropanolamine (TIPA); and dimethyl stearamine (DMS). A long chain amine neutralising agent such as stearamidopropyl dimethylamine or lauramidopropyl dimethylamine may be employed, as is described in U.S. Pat. No. 4,874,604. Also suitable are inorganic neutralisers, examples of which include sodium hydroxide, potassium hydroxide and borax. Mixtures of any of the above neutralising agents may be used. Amounts of the neutralising agents will range from about 0.001 to about 10% by weight of the total composition.
Cationic hair styling polymers, such as Polyquaternium-11 and in particular Polyquaternium-16, are the preferred hair styling polymers in compositions of the invention.
(iii) Oily/Fatty Material:Hair Styling Polymer Ratios
The oily or fatty material (i) and the hair styling polymer (ii) are generally incorporated into compositions of the invention in a weight ratio (calculated on the basis of total oily/fatty material to total hair styling polymer in the composition) ranging from 1:1 to 30:1, preferably from 3:1 to 15:1, most preferably from 8:3 to 12:1.
(iv) Water
Compositions of the present invention will also include water, preferably distilled or deionised, as a solvent or carrier for the hair styling polymer and other components. Water will typically be present in amounts ranging from 30% to 98%, preferably from 60% to 95% by weight based on total weight.
Alcohol may optionally be employed as a co-solvent in compositions of the invention. A suitable alcohol is an aliphatic straight or branched chain monohydric alcohol having 2 to about 4 carbon atoms. Isopropanol and especially ethanol are preferred. A suitable level for the alcohol is up to 20%, preferably from 5% to 15%, by weight based on total weight.
(v) Product Form and Optional Ingredients
Compositions of the invention may suitably be in aerosol form or non-aerosol form. A particularly preferred product form is an aerosol hair styling mousse. Aerosol hair styling mousse compositions are emitted from the aerosol container as a foam which is then typically worked through the hair with fingers or a hair styling tool and either left on the hair or rinsed out.
Aerosol-form compositions of the invention will include an aerosol propellant (v) which serves to expel the other materials from the container, and forms the mousse character in mousse compositions. The aerosol propellant included in styling compositions of the present invention can be any liquefiable gas conventionally used for aerosol containers. Examples of suitable propellants include dimethyl ether and hydrocarbon propellants such as propane, n-butane and isobutane. The propellants may be used singly or admixed. Water insoluble propellants, especially hydrocarbons, are preferred because they form emulsion droplets on agitation and create suitable mousse foam densities.
The amount of the propellant used is governed by normal factors well known in the aerosol art. For mousses the level of propellant is generally up to 30%, preferably from 2% to 30%, most preferably from 3% to 15% by weight based on total weight of the composition. If a propellant such as dimethyl ether includes a vapour pressure suppressant (e.g. trichloroethane or dichloromethane), for weight percentage calculations, the amount of suppressant is included as part of the propellant.
Aerosol hair styling mousses will typically also include one or more surfactants in a total amount ranging from 0.01% to 5%, preferably from 0.01% to 1%, most preferably from 0.02% to 0.8% by weight based on total weight.
Surfactants are generally classified as nonionic, anionic, cationic, amphoteric or zwitterionic according to their ionic behaviour in aqueous solution.
Examples of nonionic surfactants are condensation products of aliphatic (C8-C18) primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 3 to 30 ethylene oxide groups. Other suitable nonionics include esters of sorbitol, esters of sorbitan anhydrides, esters of propylene glycol, fatty acid esters of polyethylene glycol, fatty acid esters of polypropylene glycol, ethoxylated esters and polyoxyethylene fatty ether phosphates.
Examples of anionic surfactants are the alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, Nalkoyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, and alpha-olefin sulphonates, especially their sodium, magnesium ammonium and mono-, di- and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether phosphates and alkyl ether carboxylates may contain from one to 10 ethylene oxide or propylene oxide units per molecule, and preferably contain 2 to 3 ethylene oxide units per molecule.
Examples of cationic surfactants are cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride, tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, tallowtrimethylammonium chloride, cocotrimethylammonium chloride, (and the corresponding hydroxides thereof), and those materials having the CTFA designations Quaternium-5, Quaternium-31 and Quaternium-18.
Examples of amphoteric and zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkylamphoglycinates alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms.
Preferred surfactants for use in aerosol hair styling mousses according to the invention are nonionic surfactants such as polysorbate 20, polysorbate 80, ethoxylated nonylphenol, steareth-20, cetosteareth-20, steareth-30, cetosteareth-30, steareth-50, cetosteareth-50, and mixtures thereof. Surfactants selected from anionic, cationic, amphoteric and zwitterionic surfactants may suitably be used in conjunction with any of the above nonionic surfactants, to improve, for example, foaming power and/or foam stability.
The method of preparing aerosol hair styling mousse compositions according to the invention follows conventional aerosol filling procedures. The composition ingredients (not including the propellant) are charged into a suitable pressurisable container which is sealed and then charged with the propellant according to conventional techniques.
Compositions of the invention may also take a non-foaming product form, such as a hair styling cream, leave-on conditioner or gel.
Such a cream, leave-on conditioner or gel will typically include a structurant or thickener, typically at a level of from 0.1% to 10%, preferably 0.5% to 3% by weight based on total weight.
Examples of suitable structurants or thickeners are polymeric thickeners such as carboxyvinyl polymers. A carboxyvinyl polymer is an interpolymer of a monomeric mixture comprising a monomeric olefinically unsaturated carboxylic acid, and from about 0.01% to about 10% by weight of the total monomers of a polyether of a polyhydric alcohol. Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air. Suitably the molecular weight of the carboxyvinyl polymer is at least 750,000, preferably at least 1,250,000, most preferably at least 3,000,000. Preferred carboxyvinyl polymers are copolymers of acrylic acid cross-linked with polyallylsucrose as described in U.S. Pat. No. 2,798,053. These polymers are provided by B.F. Goodrich Company as, for example, CARBOPOL 934, 940, 941 and 980. Other materials that can also be used as structurants or thickeners include those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g. methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose), guar gum, sodium alginate, gum arabic, xanthan gum, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. It is also possible to use inorganic thickeners such as bentonite or laponite clays.
(vi) Further Optional Ingredients
Compositions of this invention may contain any other ingredient normally used in hair treatment formulations. These other ingredients may include, viscosity modifiers, preservatives, colouring agents, polyols such as glycerine and polypropylene glycol, chelating agents such as EDTA, antioxidants such as vitamin E acetate, fragrances, antimicrobials and sunscreens. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally these optional ingredients are included individually at a level of up to about 5% by weight of the total composition.
The invention is further illustrated by way of the following Examples, in which all percentages are by weight based on total weight unless otherwise stated.

Abstract: The compositions have improved strength and durability of hair hold and superior sensory feel.

Unilever Home and Personal Care USA, division of Conopco, Inc.


A catalyst composition that is the combination of or the reaction product of ingredients comprising an iron-containing compound, an organomagnesium compound, and an xcex1-acylphosphonate diester.

This invention relates to an iron-based catalyst composition for preparing high-vinyl conjugated diene polymers.
High-vinyl polybutadiene, also called 1,2-polybutadiene, is typically characterized by having greater than about 60% of its monomeric units in the 1,2-(vinyl) configuration. Two forms of commercially useful high-vinyl polybutadiene include syndiotactic 1,2-polybutadiene and atactic 1,2-polybutadiene.
Syndiotactic 1,2-polybutadiene has a stereoregular structure in which the side-chain vinyl groups are located alternately on the opposite sides in relation to the polymeric main chain. Due to its stereoregular structure, syndiotactic 1,2-polybutadiene is a crystalline thermoplastic resin and has a melting temperature within the range of about 80xc2x0 C. to about 215xc2x0 C., depending on the 1,2-linkage content and syndiotacticity. For processability reasons, it is generally desirable for syndiotactic 1,2-polybutadiene to have a melting temperature of less than about 190xc2x0 C.
Syndiotactic 1,2-polybutadiene uniquely exhibits the properties of both plastics and rubber, and therefore it has many uses. For example, films, fibers, and various molded articles can be made from syndiotactic 1,2-polybutadiene. It can also be blended into and co-cured with natural or synthetic rubbers in order to improve the properties thereof. Various transition metal catalyst systems based on cobalt, titanium, vanadium, chromium, and molybdenum for preparing syndiotactic 1,2-polybutadiene have been reported. The majority of these catalyst systems, however, have no practical utility because they have low catalytic activity or poor stereoselectivity, and in some cases they produce low molecular weight polymers or partially crosslinked polymers unsuitable for commercial use.
Atactic 1,2-polybutadiene has a stereoirregular structure in which the side-chain vinyl groups are located randomly on the opposite sides in relation to the polymeric main chain. Due to its stereoirregular structure, atactic 1,2-polybutadiene is an amorphous rubbery elastomer and is typically characterized by having a glass transition temperature from about xe2x88x9250xc2x0 C. to about 0xc2x0 C. without a readily detectable melting temperature. Atactic 1,2-polybutadiene is utilized in a variety of applications. For example, atactic 1,2-polybutadiene is useful in tire tread compositions because it provides a good balance of traction and rolling resistance.
Atactic 1,2-polybutadiene is commonly produced by anionic polymerization utilizing alkyllithium initiators which are modified with Lewis base modifiers such as chelating diamines, ethers, tertiary amines, acetals, ketals, and compounds of similar structures. The vinyl content of polybutadiene prepared utilizing these Lewis base modifiers decreases drastically as the polymerization temperature is increased. For this reason, it is difficult to prepare atactic 1,2-polybutadiene at high polymerization temperatures utilizing Lewis base modifiers. However, since high polymerization temperatures generally promote a higher polymerization rate, it is often desirable to utilize moderately high temperatures in commercial polymerizations in order to maximize productivity as well as to reduce the production cost.
Because syndiotactic 1,2-polybutadiene and atactic 1,2-polybutadiene are useful products and the catalysts known heretofore in the art have many shortcomings, it would be advantageous to develop new and significantly improved catalyst compositions that have high catalytic activity and stereoselectivity for polymerizing 1,3-butadiene into syndiotactic 1,2-polybutadiene or atactic 1,2-polybutadiene.
In general the present invention provides a catalyst composition that is the combination of or the reaction product of ingredients comprising an iron-containing compound, an organomagnesium compound, and an xcex1-acylphosphonate diester.
The present invention also includes a catalyst composition formed by a process comprising the step of combining an iron-containing compound, an organomagnesium compound, and an xcex1-acylphosphonate diester.
The present invention further provides process for forming conjugated diene polymers comprising the step of polymerizing conjugated diene monomers in the presence of a catalytically effective amount of a catalyst composition formed by combining an iron-containing compound, an organomagnesium compound, and an xcex1-acylphosphonate diester.
Advantageously, the catalyst composition of the present invention has very high catalytic activity and stereoselectivity for polymerizing conjugated diene monomers such as 1,3-butadiene. This activity and selectivity, among other advantages, allows conjugated diene polymers such as syndiotactic 1,2-polybutadiene and atactic 1,2-polybutadiene to be produced in high yields with low catalyst levels after relatively short polymerization times. In addition, the iron-containing compounds that are utilized in the catalyst composition of this invention are generally stable, inexpensive, relatively innocuous, and readily available. Further, the catalyst composition of this invention has high catalytic activity in a wide variety of solvents including the environmentally-preferred nonhalogenated solvents such as aliphatic and cycloaliphatic hydrocarbons. Furthermore, this catalyst composition is operational over a wide range of polymerization temperatures. Still further, the performance characteristics of the catalyst composition can be readily controlled by changing the steric and electronic characteristics of the organic substituents of the xcex1-acylphosphonate diester.
The catalyst composition is formed by combining (a) an iron-containing compound, (b) an organomagnesium compound, and (c) an xcex1-acylphosphonate diester. In addition to the three catalyst ingredients (a), (b), and (c), other organometallic compounds or Lewis bases can also be added, if desired.
Various iron-containing compounds or mixtures thereof can be employed as ingredient (a). Iron-containing compounds that are soluble in a hydrocarbon solvent such as aromatic hydrocarbons, aliphatic hydrocarbons, or cycloaliphatic hydrocarbons are advantageously employed. Hydrocarbon-insoluble iron-containing compounds, however, can be suspended in the polymerization medium to form the catalytically active species and are therefore also useful.
The iron atom in the iron-containing compounds can be in various oxidation states including but not limited to the 0, +2, +3, and +4 oxidation states. Divalent iron compounds (also called ferrous compounds), wherein the iron atom is in the +2 oxidation state, and trivalent iron compounds (also called ferric compounds), wherein the iron atom is in the +3 oxidation state, are generally preferred. Suitable iron-containing compounds include, but are not limited to, iron carboxylates, iron organophosphates, iron organophosphonates, iron organophosphinates, iron carbamates, iron dithiocarbamates, iron xanthates, iron xcex2-diketonates, iron alkoxides or aryloxides, iron halides, iron pseudo-halides, iron oxyhalides, and organoiron compounds.
Suitable iron carboxylates include iron(II) formate, iron(III) formate, iron(II) acetate, iron(III) acetate, iron(II) acrylate, iron(III) acrylate, iron(II) methacrylate, iron(III) methacrylate, iron(II) valerate, iron(III) valerate, iron(II) gluconate, iron(III) gluconate, iron(II) citrate, iron(III) citrate, iron(II) fumarate, iron(III) fumarate, iron(II) lactate, iron(III) lactate, iron(II) maleate, iron(III) maleate, iron(II) oxalate, iron(III) oxalate, iron(II) 2-ethylhexanoate, iron(III) 2-ethylhexanoate, iron(II) neodecanoate, iron(III) neodecanoate, iron(II) naphthenate, iron(III) naphthenate, iron(II) stearate, iron(III) stearate, iron(II) oleate, iron(III) oleate, iron(II) benzoate, iron(III) benzoate, iron(II) picolinate, and iron(III) picolinate.
Suitable iron organophosphates include iron(II) dibutyl phosphate, iron(III) dibutyl phosphate, iron(II) dipentyl phosphate, iron(III) dipentyl phosphate, iron(II) dihexyl phosphate, iron(III) dihexyl phosphate, iron(II) diheptyl phosphate, iron(III) diheptyl phosphate, iron(II) dioctyl phosphate, iron(III) dioctyl phosphate, iron(II) bis(1-methylheptyl) phosphate, iron(III) bis(1-methylheptyl) phosphate, iron(II) bis(2-ethylhexyl) phosphate, iron(III) bis(2-ethylhexyl) phosphate, iron(II) didecyl phosphate, iron(III) didecyl phosphate, iron(II) didodecyl phosphate, iron(III) didodecyl phosphate, iron(II) dioctadecyl phosphate, iron(III) dioctadecyl phosphate, iron(II) dioleyl phosphate, iron(III) dioleyl phosphate, iron(II) diphenyl phosphate, iron(III) diphenyl phosphate, iron(II) bis(p-nonylphenyl) phosphate, iron(III) bis(p-nonylphenyl) phosphate, iron(II) butyl (2-ethylhexyl) phosphate, iron(III) butyl (2-ethylhexyl) phosphate, iron(II) (1-methylheptyl) (2-ethylhexyl) phosphate, iron(III) (1-methylheptyl) (2-ethylhexyl) phosphate, iron(II) (2-ethylhexyl) (p-nonylphenyl) phosphate, and iron(III) (2-ethylhexyl) (p-nonylphenyl) phosphate.
Suitable iron organophosphonates include iron(II) butyl phosphonate, iron(III) butyl phosphonate, iron(II) pentyl phosphonate, iron(III) pentyl phosphonate, iron(II) hexyl phosphonate, iron(III) hexyl phosphonate, iron(II) heptyl phosphonate, iron(III) heptyl phosphonate, iron(II) octyl phosphonate, iron(III) octyl phosphonate, iron(II) (1-methylheptyl) phosphonate, iron(III) (1-methylheptyl) phosphonate, iron(II) (2-ethylhexyl) phosphonate, iron(III) (2-ethylhexyl) phosphonate, iron(II) decyl phosphonate, iron(III) decyl phosphonate, iron(II) dodecyl phosphonate, iron(III) dodecyl phosphonate, iron(II) octadecyl phosphonate, iron(III) octadecyl phosphonate, iron(II) oleyl phosphonate, iron(III) oleyl phosphonate, iron(II) phenyl phosphonate, iron(III) phenyl phosphonate, iron(II) (p-nonylphenyl) phosphonate, iron(III) (p-nonylphenyl) phosphonate, iron(II) butyl butylphosphonate, iron(III) butyl butylphosphonate, iron(II) pentyl pentylphosphonate, iron(II) pentyl pentylphosphonate, iron(II) hexyl hexylphosphonate, iron(III) hexyl hexylphosphonate, iron(II) heptyl heptylphosphonate, iron(III) heptyl heptylphosphonate, iron(II) octyl octylphosphonate, iron(III) octyl octylphosphonate, iron(II) (1-methylheptyl) (1-methylheptyl)phosphonate, iron(III) (1-methylheptyl) (1-methylheptyl)phosphonate, iron(II) (2-ethylhexyl) (2-ethylhexyl)phosphonate, iron(III) (2-ethylhexyl) (2-ethylhexyl)phosphonate, iron(II) decyl decylphosphonate, iron(III) decyl decylphosphonate, iron(II) dodecyl dodecylphosphonate, iron(III) dodecyl dodecylphosphonate, iron(II) octadecyl octadecylphosphonate, iron(III) octadecyl octadecylphosphonate, iron(II) oleyl oleylphosphonate, iron(III) oleyl oleylphosphonate, iron(II) phenyl phenylphosphonate, iron(III) phenyl phenylphosphonate, iron(II) (p-nonylphenyl) (p-nonylphenyl)phosphonate, iron(III) (p-nonylphenyl) (p-nonylphenyl)phosphonate, iron(II) butyl (2-ethylhexyl)phosphonate, iron(III) butyl (2-ethylhexyl)phosphonate, iron(II) (2-ethylhexyl) butylphosphonate, iron(III) (2-ethylhexyl) butylphosphonate, iron(II) (1-methylheptyl) (2-ethylhexyl)phosphonate, iron(III) (1-methylheptyl) (2-ethylhexyl)phosphonate, iron(II) (2-ethylhexyl) (1-methylheptyl)phosphonate, iron(III) (2-ethylhexyl) (1-methylheptyl)phosphonate, iron(II) (2-ethylhexyl) (p-nonylphenyl)phosphonate, iron(III) (2-ethylhexyl) (p-nonylphenyl)phosphonate, iron(II) (p-nonylphenyl) (2-ethylhexyl)phosphonate, and iron(III) (p-nonylphenyl) (2-ethylhexyl) phosphonate. Suitable iron organophosphinates include iron(II) butylphosphinate, iron(III) butylphosphinate, iron(II) pentylphosphinate, iron(III) pentylphosphinate, iron(II) hexylphosphinate, iron(III) hexylphosphinate, iron(II) heptylphosphinate, iron(III) heptylphosphinate, iron(II) octylphosphinate, iron(III) octylphosphinate, iron(II) (1-methylheptyl)phosphinate, iron(III) (1-methylheptyl)phosphinate, iron(II) (2-ethylhexyl) phosphinate, iron(III) (2 -ethylhexyl) phosphinate, iron(II) decylphosphinate, iron(III) decylphosphinate, iron(II) dodecylphosphinate, iron(III) dodecylphosphinate, iron(II) octadecylphosphinate, iron(III) octadecylphosphinate, iron(II) oleylphosphinate, iron(III) oleylphosphinate, iron(II) phenylphosphinate, iron(III) phenylphosphinate, iron(II) (p-nonylphenyl)phosphinate, iron(III) (p-nonylphenyl)phosphinate, iron(II) dibutylphosphinate, iron(III) dibutylphosphinate, iron(II) dipentylphosphinate, iron(III) dipentylphosphinate, iron(II ) dihexylphosphinate, iron(III) dihexylphosphinate, iron(II) diheptylphosphinate, iron(III) diheptylphosphinate, iron(II) dioctylphosphinate, iron(III) dioctylphosphinate, iron(II) bis (1-methylheptyl) phosphinate, iron (III) bis (1-methylheptyl) phosphinate, iron (II) bis (2-ethylhexyl) phosphinate, iron (III) bis (2-ethylhexyl) phosphinate, iron (II) didecylphosphinate, iron(III) didecylphosphinate, iron(II) didodecylphosphinate, iron(III) didodecylphosphinate, iron(II) dioctadecylphosphinate, iron(III) dioctadecylphosphinate, iron(II) dioleylphosphinate, iron(III) dioleylphosphinate, iron(II) diphenylphosphinate, iron(III) diphenylphosphinate, iron(II) bis(p-nonylphenyl)phosphinate, iron(III) bis(p-nonylphenyl)phosphinate, iron(II) butyl (2-ethylhexyl) phosphinate, iron (III) butyl (2-ethylhexyl) phosphinate, iron (II) (1-methylheptyl) (2-ethylhexyl)phosphinate, iron(III) (1-methylheptyl) (2-ethylhexyl)phosphinate, iron (II) (2-ethylhexyl) (p-nonylphenyl)phosphinate, and iron(III) (2-ethylhexyl)(p-nonylphenyl)phosphinate.
Suitable iron carbamates include iron(II) dimethylcarbamate, iron(III) dimethylcarbamate, iron(II) diethylcarbamate, iron(III) diethylcarbamate, iron(II) diisopropylcarbamate, iron(III) diisopropylcarbamate, iron(II) dibutylcarbamate, iron(III) dibutylcarbamate, iron(II) dibenzylcarbamate, and iron(III) dibenzylcarbamate.
Suitable iron dithiocarbamates include iron(II) dimethyldithiocarbamate, iron(III) dimethyldithiocarbamate, iron(II) diethyldithiocarbamate, iron(III) diethyldithiocarbamate, iron(II) diisopropyldithiocarbamate, iron(III) diisopropyldithiocarbamate, iron(II) dibutyldithiocarbamate, iron(III) dibutyldithiocarbamate, iron(II) dibenzyldithiocarbamate, and iron(III) dibenzyldithiocarbamate.
Suitable iron xanthates include iron(II) methylxanthate, iron(III) methylxanthate, iron(II) ethylxanthate, iron(III) ethylxanthate, iron(II) isopropylxanthate, iron(III) isopropylxanthate, iron(II) butylxanthate, iron(III) butylxanthate, iron(II) benzylxanthate, and iron(III) benzylxanthate.
Suitable iron xcex2-diketonates include iron(II) acetylacetonate, iron(III) acetylacetonate, iron(II) trifluoroacetylacetonate, iron(III) trifluoroacetylacetonate, iron(II) hexafluoroacetylacetonate, iron(III) hexafluoroacetylacetonate, iron(II) benzoylacetonate, iron(III) benzoylacetonate, iron(II) 2,2,6,6-tetramethyl-3,5-heptanedionate, and iron (III) 2,2,6, 6-tetramethyl-3,5-heptanedionate.
Suitable iron alkoxides or aryloxides include iron(II) methoxide, iron(III) methoxide, iron(II) ethoxide, iron(III) ethoxide, iron(II) isopropoxide, iron(III) isopropoxide, iron(II) 2-ethylhexoxide, iron(III) 2-ethylhexoxide, iron(II) phenoxide, iron(III) phenoxide, iron(II) nonylphenoxide, iron(III) nonylphenoxide, iron(II) naphthoxide, and iron(III) naphthoxide.
Suitable iron halides include iron(II) fluoride, iron(III) fluoride, iron(II) chloride, iron(III) chloride, iron(II) bromide, iron(III) bromide, and iron(II) iodide. Suitable iron pseudo-halides include iron(II) cyanide, iron(III) cyanide, iron(II) cyanate, iron(III) cyanate, iron(II) thiocyanate, iron(III) thiocyanate, iron(II) azide, iron(III) azide, and iron(III) ferrocyanide (also called Prussian blue). Suitable iron oxyhalides include iron(III) oxychloride and iron(III) oxybromide.
The term xe2x80x9corganoiron compoundxe2x80x9d refers to any iron compound containing at least one covalent iron-carbon bond. Suitable organoiron compounds include bis(cyclopentadienyl)iron(II) (also called ferrocene), bis(pentamethylcyclopentadienyl)iron(II) (also called decamethylferrocene), bis(pentadienyl)iron(II), bis(2,4-dimethylpentadienyl) iron(II), bis(allyl)dicarbonyliron(II), (cyclopentadienyl)(pentadienyl)iron(II), tetra(1-norbornyl)iron(IV), (trimethylenemethane)tricarbonyliron(II), bis(butadiene)carbonyliron(0), (butadiene)tricarbonyliron(0), and bis(cyclooctatetraene)iron (0).
Various organomagnesium compounds or mixtures thereof can be utilized as ingredient (b). As used herein, the term xe2x80x9corganomagnesium compoundxe2x80x9d refers to any magnesium compound containing at least one covalent magnesium-carbon bond. Organomagnesium compounds that are soluble in a hydrocarbon solvent are preferred.
A preferred class of organomagnesium compounds that can be utilized is represented by the general formula MgR12, where each R1, which may be the same or different, is a mono-valent organic group that is attached to the magnesium atom via a carbon atom. Preferably, each R1 is a hydrocarbyl group such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, with each group preferably containing from 1 carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to about 20 carbon atoms. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, boron, sulfur, and phosphorus atoms.
Specific examples of organomagnesium compounds that are represented by the general formula MgR12 include dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, di-n-butylmagnesium, di-sec-butylmagnesium, diisobutylmagnesium, di-t-butylmagnesium, di-n-hexylmagnesium, di-n-octylmagnesium, diphenylmagnesium, di-p-tolylmagnesium, and dibenzylmagnesium, and the like, and mixtures thereof. Commercial dibutylmagnesium is particularly useful due to its availability and its solubility in aliphatic and cycloaliphatic hydrocarbon solvents. Commercial dibutylmagnesium is actually an organometallic oligomer and is comprised of a mixture of n-butyl, sec-butyl, and n-octyl groups bonded to the magnesium atom.
Another preferred class of organomagnesium compounds is represented by the general formula R2MgX, where R2 is a mono-valent organic group that is attached to the magnesium atom via a carbon atom, and X is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group. Preferably, R2 is a hydrocarbyl group such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, with each group preferably containing from 1 carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to about 20 carbon atoms. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, boron, sulfur, and phosphorus atoms. Preferably, X is a carboxylate group, an alkoxide group, or an aryloxide group, with each group preferably containing 1 to 20 carbon atoms.
Suitable organomagnesium compounds that are represented by the general formula R2MgX include, but are not limited to, hydrocarbylmagnesium hydride, hydrocarbylmagnesium halide, hydrocarbylmagnesium carboxylate, hydrocarbylmagnesium alkoxide, hydrocarbylmagnesium aryloxide, and the like, and mixtures thereof.
Specific examples of organomagnesium compounds that are represented by the general formula R2MgX include methylmagnesium hydride, ethylmagnesium hydride, butylmagnesium hydride, hexylmagnesium hydride, phenylmagnesium hydride, benzylmagnesium hydride, methylmagnesium chloride, ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, butylmagnesium bromide, hexylmagnesium bromide, phenylmagnesium bromide, benzylmagnesium bromide, methylmagnesium hexanoate, ethylmagnesium hexanoate, butylmagnesium hexanoate, hexylmagnesium hexanoate, phenylmagnesium hexanoate, benzylmagnesium hexanoate, methylmagnesium ethoxide, ethylmagnesium ethoxide, butylmagnesium ethoxide, hexylmagnesium ethoxide, phenylmagnesium ethoxide, benzylmagnesium ethoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide, butylmagnesium phenoxide, hexylmagnesium phenoxide, phenylmagnesium phenoxide, benzylmagnesium phenoxide, and the like, and mixtures thereof.
Useful xcex1-acylphosphonate diesters that can be employed as ingredient (c) of the catalyst composition include acyclic xcex1-acylphosphonate diesters, cyclic xcex1-acylphosphonate diesters, and mixtures thereof. Acyclic xcex1-acylphosphonate diesters may be represented by the following structure:
where R3 is a hydrogen atom or a mono-valent organic group, and each R4, which may be the same or different, is a mono-valent organic group. Preferably, R3 and R4 are hydrocarbyl groups such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, with each group preferably containing from 1 carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to about 20 carbon atoms. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, boron, sulfur, and phosphorus atoms.
xcex1-Acylphosphonate diesters are known in the art and can be conveniently prepared by the Michaelis-Arbusov reactions of trihydrocarbyl phosphites with carboxylic acid halides or carboxylic acid anhydrides.
Suitable types of acyclic xcex1-acylphosphonate diesters include, but are not limited to, dihydrocarbyl formylphosphonates, dihydrocarbyl acetylphosphonates, dihydrocarbyl propionylphosphonates, dihydrocarbyl butyrylphosphonates, dihydrocarbyl isobutyrylphosphonates, dihydrocarbyl pivaloylphosphonates, dihydrocarbyl 2-ethylhexanoylphosphonates, dihydrocarbyl cyclohexanoylphosphonates, dihydrocarbyl acryloylphosphonates, dihydrocarbyl methacryloylphosphonates, dihydrocarbyl crotonylphosphonates, dihydrocarbyl benzoylphosphonates, dihydrocarbyl toluoylphosphonates, dihydrocarbyl anisoylphosphonates, and dihydrocarbyl naphthoylphosphonates. Mixtures of the above acyclic xcex1-acylphosphonate diesters may also be utilized.
Suitable dihydrocarbyl formylphosphonates include dimethyl formylphosphonate, diethyl formylphosphonate, di-n-propyl formylphosphonate diisopropyl formylphosphonate, di-n-butyl formylphosphonate, diisobutyl formylphosphonate, di-t-butyl formylphosphonate, bis(2,2,2-trifluoroethyl) formylphosphonate, bis (2,4-dimethyl-3-pentyl) formylphosphonate, bis(2-ethylhexyl) formylphosphonate, dineopentyl formylphosphonate, bis(cyclohexylmethyl) formylphosphonate, dibenzyl formylphosphonate, dicyclobutyl formylphosphonate, dicyclopentyl formylphosphonate, dicyclohexyl formylphosphonate, diphenyl formylphosphonate, ditolyl formylphosphonate, dinaphthyl formylphosphonate, dially formylphosphonate, dimethallyl forrnylphosphonate, and dicrotyl formylphosphonate.
Suitable dihydrocarbyl acetylphosphonates include dimethyl acetylphosphonate, diethyl acetylphosphonate, di-n-propyl acetylphosphonate diisopropyl acetylphosphonate, di-n-butyl acetylphosphonate, diisobutyl acetylphosphonate, di-t-butyl acetylphosphonate, bis (2,2,2-trifluoroethyl) acetylphosphonate, bis(2,4-dimethyl-3-pentyl) acetylphosphonate, bis(2-ethylhexyl) acetylphosphonate, dineopentyl acetylphosphonate, bis (cyclohexylmethyl) acetylphosphonate, dibenzyl acetylphosphonate, dicyclobutyl acetylphosphonate, dicyclopentyl acetylphosphonate, dicyclohexyl acetylphosphonate, diphenyl acetylphosphonate, ditolyl acetylphosphonate, dinaphthyl acetylphosphonate, dially acetylphosphonate, dimethallyl acetylphosphonate, and dicrotyl acetylphosphonate.
Suitable dihydrocarbyl propionylphosphonates include dimethyl propionylphosphonate, diethyl propionylphosphonate, di-n-propyl propionylphosphonate diisopropyl propionylphosphonate, di-n-butyl propionylphosphonate, diisobutyl propionylphosphonate, di-t-butyl propionylphosphonate, bis(2,2,2-trifluoroethyl) propionylphosphonate, bis(2,4-dimethyl-3-pentyl) propionylphosphonate, bis(2-ethylhexyl) propionylphosphonate, dineopentyl propionylphosphonate, bis(cyclohexylmethyl) propionylphosphonate, dibenzyl propionylphosphonate, dicyclobutyl propionylphosphonate, dicyclopentyl propionylphosphonate, dicyclohexyl propionylphosphonate, diphenyl propionylphosphonate, ditolyl propionylphosphonate, dinaphthyl propionylphosphonate, dially propionylphosphonate, dimethallyl propionylphosphonate, and dicrotyl propionylphosphonate.
Suitable dihydrocarbyl butyrylphosphonates include dimethyl butyrylphosphonate, diethyl butyrylphosphonate, di-n-propyl butyrylphosphonate diisopropyl butyrylphosphonate, di-n-butyl butyrylphosphonate, diisobutyl butyrylphosphonate, di-t-butyl butyrylphosphonate, bis (2,2,2-trifluoroethyl) butyrylphosphonate, bis(2,4-dimethyl-3-pentyl) butyrylphosphonate, bis(2-ethylhexyl) butyrylphosphonate, dineopentyl butyrylphosphonate, bis(cyclohexylmethyl) butyrylphosphonate, dibenzyl butyrylphosphonate, dicyclobutyl butyrylphosphonate, dicyclopentyl butyrylphosphonate, dicyclohexyl butyrylphosphonate, diphenyl butyrylphosphonate, ditolyl butyrylphosphonate, dinaphthyl butyrylphosphonate, dially butyrylphosphonate, dimethallyl butyrylphosphonate, and dicrotyl butyrylphosphonate.
Suitable dihydrocarbyl isobutyrylphosphonates include dimethyl isobutyrylphosphonate, diethyl isobutyrylphosphonate, di-n-propyl isobutyrylphosphonate diisopropyl isobutyrylphosphonate, di-n-butyl isobutyrylphosphonate, diisobutyl isobutyrylphosphonate, di-t-butyl isobutyrylphosphonate, bis(2,2,2-trifluoroethyl) isobutyrylphosphonate, bis(2,4-dimethyl-3-pentyl) isobutyrylphosphonate, bis(2-ethylhexyl) isobutyrylphosphonate, dineopentyl isobutyrylphosphonate, bis(cyclohexylmethyl) isobutyrylphosphonate, dibenzyl isobutyrylphosphonate, dicyclobutyl isobutyrylphosphonate, dicyclopentyl isobutyrylphosphonate, dicyclohexyl isobutyrylphosphonate, diphenyl isobutyrylphosphonate, ditolyl isobutyrylphosphonate, dinaphthyl isobutyrylphosphonate, dially isobutyrylphosphonate, dimethallyl isobutyrylphosphonate, and dicrotyl isobutyrylphosphonate.
Suitable dihydrocarbyl pivaloylphosphonates include dimethyl pivaloylphosphonate, diethyl pivaloylphosphonate, di-n-propyl pivaloylphosphonate diisopropyl pivaloylphosphonate, di-n-butyl pivaloylphosphonate, diisobutyl pivaloylphosphonate, di-t-butyl pivaloylphosphonate, bis(2,2,2-trifluoroethyl) pivaloylphosphonate, bis(2,4-dimethyl-3-pentyl) pivaloylphosphonate, bis(2-ethylhexyl) pivaloylphosphonate, dineopentyl pivaloylphosphonate, bis(cyclohexylmethyl) pivaloylphosphonate, dibenzyl pivaloylphosphonate, dicyclobutyl pivaloylphosphonate, dicyclopentyl pivaloylphosphonate, dicyclohexyl pivaloylphosphonate, diphenyl pivaloylphosphonate, ditolyl pivaloylphosphonate, dinaphthyl pivaloylphosphonate, dially pivaloylphosphonate, dimethallyl pivaloylphosphonate, and dicrotyl pivaloylphosphonate.
Suitable dihydrocarbyl 2-ethylhexanoylphosphonates include dimethyl 2-ethylhexanoylphosphonate, diethyl 2-ethylhexanoylphosphonate, di-n-propyl 2-ethylhexanoylphosphonate diisopropyl 2-ethylhexanoylphosphonate, di-n-butyl 2-ethylhexanoylphosphonate, diisobutyl 2-ethylhexanoylphosphonate, di-t-butyl 2-ethylhexanoylphosphonate, bis(2,2,2-trifluoroethyl) 2-ethylhexanoylphosphonate, bis(2,4-dimethyl-3-pentyl) 2-ethylhexanoylphosphonate, bis(2-ethylhexyl) 2-ethylhexanoylphosphonate, dineopentyl 2-ethylhexanoylphosphonate, bis(cyclohexylmethyl) 2-ethylhexanoylphosphonate, dibenzyl 2-ethylhexanoylphosphonate, dicyclobutyl 2-ethylhexanoylphosphonate, dicyclopentyl 2-ethylhexanoylphosphonate, dicyclohexyl 2-ethylhexanoylphosphonate, diphenyl 2-ethylhexanoylphosphonate, ditolyl 2-ethylhexanoylphosphonate, dinaphthyl 2-ethylhexanoylphosphonate, dially 2-ethylhexanoylphosphonate, dimethallyl 2-ethylhexanoylphosphonate, and dicrotyl 2-ethylhexanoylphosphonate.
Suitable dihydrocarbyl cyclohexanoylphosphonates include dimethyl cyclohexanoylphosphonate, diethyl cyclohexanoylphosphonate, di-n-propyl cyclohexanoylphosphonate diisopropyl cyclohexanoylphosphonate, di-n-butyl cyclohexanoylphosphonate, diisobutyl cyclohexanoylphosphonate, di-t-butyl cyclohexanoylphosphonate, bis(2,2,2-trifluoroethyl) cyclohexanoylphosphonate, bis(2 ,4-dimethyl-3-pentyl) cyclohexanoylphosphonate, bis(2-ethylhexyl) cyclohexanoylphosphonate, dineopentyl cyclohexanoylphosphonate, bis(cyclohexylmethyl) cyclohexanoylphosphonate, dibenzyl cyclohexanoylphosphonate, dicyclobutyl cyclohexanoylphosphonate, dicyclopentyl cyclohexanoylphosphonate, dicyclohexyl cyclohexanoylphosphonate, diphenyl cyclohexanoylphosphonate, ditolyl cyclohexanoylphosphonate, dinaphthyl cyclohexanoylphosphonate, dially cyclohexanoylphosphonate, dimethallyl cyclohexanoylphosphonate, and dicrotyl cyclohexanoylphosphonate.
Suitable dihydrocarbyl acryloylphosphonates include dimethyl acryloylphosphonate, diethyl acryloylphosphonate, di-n-propyl acryloylphosphonate diisopropyl acryloylphosphonate, di-n-butyl acryloylphosphonate, diisobutyl acryloylphosphonate, di-t-butyl acryloylphosphonate, bis(2,2,2-trifluoroethyl) acryloylphosphonate, bis(2,4-dimethyl-3-pentyl) acryloylphosphonate, bis(2-ethylhexyl) acryloylphosphonate, dineopentyl acryloylphosphonate, bis(cyclohexylmethyl) acryloylphosphonate, dibenzyl acryloylphosphonate, dicyclobutyl acryloylphosphonate, dicyclopentyl acryloylphosphonate, dicyclohexyl acryloylphosphonate, diphenyl acryloylphosphonate, ditolyl acryloylphosphonate, dinaphthyl acryloylphosphonate, dially acryloylphosphonate, dimethallyl acryloylphosphonate, and dicrotyl acryloylphosphonate.
Suitable dihydrocarbyl methacryloylphosphonates include dimethyl methacryloylphosphonate, diethyl methacryloylphosphonate, di-n-propyl methacryloylphosphonate diisopropyl methacryloylphosphonate, di-n-butyl methacryloylphosphonate, diisobutyl methacryloylphosphonate, di-t-butyl methacryloylphosphonate, bis(2,2,2-trifluoroethyl) methacryloylphosphonate, bis(2,4-dimethyl-3-pentyl) methacryloylphosphonate, bis(2-ethylhexyl) methacryloylphosphonate, dineopentyl methacryloylphosphonate, bis(cyclohexylmethyl) methacryloylphosphonate, dibenzyl methacryloylphosphonate, dicyclobutyl methacryloylphosphonate, dicyclopentyl methacryloylphosphonate, dicyclohexyl methacryloylphosphonate, diphenyl methacryloylphosphonate, ditolyl methacryloylphosphonate, dinaphthyl methacryloylphosphonate, dially methacryloylphosphonate, dimethallyl methacryloylphosphonate, and dicrotyl methacryloylphosphonate.
Suitable dihydrocarbyl crotonylphosphonates include dimethyl crotonylphosphonate, diethyl crotonylphosphonate, di-n-propyl crotonylphosphonate diisopropyl crotonylphosphonate, di-n-butyl crotonylphosphonate, diisobutyl crotonylphosphonate, di-t-butyl crotonylphosphonate, bis(2,2,2-trifluoroethyl) crotonylphosphonate, bis(2,4-dimethyl-3-pentyl) crotonylphosphonate, bis(2-ethylhexyl) crotonylphosphonate, dineopentyl crotonylphosphonate, bis(cyclohexylmethyl) crotonylphosphonate, dibenzyl crotonylphosphonate, dicyclobutyl crotonylphosphonate, dicyclopentyl crotonylphosphonate, dicyclohexyl crotonylphosphonate, diphenyl crotonylphosphonate, ditolyl crotonylphosphonate, dinaphthyl crotonylphosphonate, dially crotonylphosphonate, dimethallyl crotonylphosphonate, and dicrotyl crotonylphosphonate.
Suitable dihydrocarbyl benzoylphosphonates include dimethyl benzoylphosphonate, diethyl benzoylphosphonate, di-n-propyl benzoylphosphonate disopropyl benzoylphosphonate, di-n-butyl benzoylphosphonate, diisobutyl benzoylphosphonate, di-t-butyl benzoylphosphonate, bis(2,2,2-trifluoroethyl) benzoylphosphonate, bis(2,4-dimethyl-3-pentyl) benzoylphosphonate, bis(2-ethylhexyl) benzoylphosphonate, dineopentyl benzoylphosphonate, bis(cyclohexylmethyl) benzoylphosphonate, dibenzyl benzoylphosphonate, dicyclobutyl benzoylphosphonate, dicyclopentyl benzoylphosphonate, dicyclohexyl benzoylphosphonate, diphenyl benzoylphosphonate, ditolyl benzoylphosphonate, dinaphthyl benzoylphosphonate, dially benzoylphosphonate, dimethallyl benzoylphosphonate, and dicrotyl benzoylphosphonate.
Suitable dihydrocarbyl toluoylphosphonates include dimethyl toluoylphosphonate, diethyl toluoylphosphonate, di-n-propyl toluoylphosphonate diisopropyl toluoylphosphonate, di-n-butyl toluoylphosphonate, diisobutyl toluoylphosphonate, di-t-butyl toluoylphosphonate, bis(2,2,2-trifluoroethyl) toluoylphosphonate, bis(2,4-dimethyl-3-pentyl) toluoylphosphonate, bis(2-ethylhexyl) toluoylphosphonate, dineopentyl toluoylphosphonate, bis(cyclohexylmethyl) toluoylphosphonate, dibenzyl toluoylphosphonate, dicyclobutyl toluoylphosphonate, dicyclopentyl toluoylphosphonate, dicyclohexyl toluoylphosphonate, diphenyl toluoylphosphonate, ditolyl toluoylphosphonate, dinaphthyl toluoylphosphonate, dially toluoylphosphonate, dimethallyl toluoylphosphonate, and dicrotyl toluoylphosphonate.
Suitable dihydrocarbyl anisoylphosphonates include dimethyl anisoylphosphonate, diethyl anisoylphosphonate, di-n-propyl anisoylphosphonate diisopropyl anisoylphosphonate, di-n-butyl anisoylphosphonate, diisobutyl anisoylphosphonate, di-t-butyl anisoylphosphonate, bis(2,2,2-trifluoroethyl) anisoylphosphonate, bis(2,4-dimethyl-3-pentyl) anisoylphosphonate, bis(2-ethylhexyl) anisoylphosphonate, dineopentyl anisoylphosphonate, bis(cyclohexylmethyl) anisoylphosphonate, dibenzyl anisoylphosphonate, dicyclobutyl anisoylphosphonate, dicyclopentyl anisoylphosphonate, dicyclohexyl anisoylphosphonate, diphenyl anisoylphosphonate, ditolyl anisoylphosphonate, dinaphthyl anisoylphosphonate, dially anisoylphosphonate, dimethallyl anisoylphosphonate, and dicrotyl anisoylphosphonate.
Suitable dihydrocarbyl naphthoylphosphonates include dimethyl naphthoylphosphonate, diethyl naphthoylphosphonate, di-n-propyl naphthoylphosphonate diisopropyl naphthoylphosphonate, di-n-butyl naphthoylphosphonate, diisobutyl naphthoylphosphonate, di-t-butyl naphthoylphosphonate, bis(2,2,2-trifluoroethyl) naphthoylphosphonate, bis(2,4-dimethyl-3-pentyl) naphthoylphosphonate, bis(2-ethylhexyl) naphthoylphosphonate, dineopentyl naphthoylphosphonate, bis(cyclohexylmethyl) naphthoylphosphonate, dibenzyl naphthoylphosphonate, dicyclobutyl naphthoylphosphonate, dicyclopentyl naphthoylphosphonate, dicyclohexyl naphthoylphosphonate, diphenyl naphthoylphosphonate, ditolyl naphthoylphosphonate, dinaphthyl naphthoylphosphonate, dially naphthoylphosphonate, dimethallyl naphthoylphosphonate, and dicrotyl naphthoylphosphonate.
Cyclic xcex1-acylphosphonate diesters contain a ring structure that is formed by a divalent organic group bridging the two oxygen atoms that are singly-bonded to the phosphorus atom. These cyclic xcex1-acylphosphonate diesters may be represented by the following structure:
where R3 is the same as defined above, and R5 is a divalent organic group. Preferably, R3 is a hydrocarbyl groups such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, with each group preferably containing from 1 carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to about 20 carbon atoms. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, boron, sulfur, and phosphorus atoms. Preferably, R5 is a hydrocarbylene group such as, but not limited to, alkylene, substituted alkylene, cycloalkylene, substituted cycloalkylene, alkenylene, substituted alkenylene, cycloalkenylene, substituted cycloalkenylene, arylene, and substituted arylene groups, with each group preferably containing from 1 carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to about 20 carbon atoms. These hydrocarbylene groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, boron, sulfur, and phosphorus atoms.
Suitable types of cyclic xcex1-acylphosphonate diesters include, but are not limited to, hydrocarbylene formylphosphonates, hydrocarbylene acetylphosphonates, hydrocarbylene propionylphosphonates, hydrocarbylene butyrylphosphonates, hydrocarbylene isobutyrylphosphonates, hydrocarbylene pivaloylphosphonates, hydrocarbylene 2-ethylhexanoylphosphonates, hydrocarbylene cyclohexanoylphosphonates, hydrocarbylene acryloylphosphonates, hydrocarbylene methacryloylphosphonates, hydrocarbylene crotonylphosphonates, hydrocarbylene benzoylphosphonates, hydrocarbylene toluoylphosphonates, hydrocarbylene anisoylphosphonates, and hydrocarbylene naphthoylphosphonates. Mixtures of the above cyclic xcex1-acylphosphonate diesters may also be utilized.
Suitable hydrocarbylene formylphosphonates include 2-oxo-2-formyl-5-butyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-formyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-formyl-1,3,2-dioxaphosphorinane, 2-oxo-2-formyl-4-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-formyl-5-ethyl-5-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-formyl-5,5-diethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-fonnyl-5-methyl-5-propyl-1,3,2-dioxaphosphorinane, 2-oxo-2-formyl-4-isopropyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-formyl-4,6-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-formyl-4-propyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-formyl-4-methyl-1,3,2-dioxaphospholane, 2-oxo-2-formyl-4,5-dimethyl-1,3,2-dioxaphospholane, 2-oxo-2-formyl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, 2-oxo-2-formyl-4,5-benzo-1,3,2-dioxaphospholane, 2-oxo-2-formyl-4,5-(3xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-formyl-4,5-(4xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-formyl-4,5-(4xe2x80x2-tert-butylbenzo)-1,3,2-dioxaphospholane, and 2-oxo-2-formyl-4,5-naphthalo-1,3,2-dioxaphospholane.
Suitable hydrocarbylene acetylphosphonates include 2-oxo-2-acetyl-5-butyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-4-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-5-ethyl-5-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-5,5-diethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-5-methyl-5-propyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-4-isopropyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-4,6-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-4-propyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acetyl-4-methyl- 1,3,2-dioxaphospholane, 2-oxo-2-acetyl-4,5-dimethyl- 1,3,2-dioxaphospholane, 2-oxo-2-acetyl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, 2-oxo-2-acetyl-4,5-benzo-1,3,2-dioxaphospholane, 2-oxo-2-acetyl-4,5-(3xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-acetyl-4,5-(4xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-acetyl-4,5- (4xe2x80x2-tert-butylbenzo) -1,3,2-dioxaphospholane, and 2-oxo-2-acetyl-4,5-naphthalo-1,3,2-dioxaphospholane.
Suitable hydrocarbylene isobutyrylphosphonates include 2-oxo-2-isobutyryl-5-butyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-4-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-5-ethyl-5-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-5,5-diethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-5-methyl-5-propyl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-4-isopropyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-4,6-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-4-propyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-isobutyryl-4-methyl-1,3,2-dioxaphospholane, 2-oxo-2-isobutyryl-4,5-dimethyl-1,3,2-dioxaphospholane, 2-oxo-2-isobutyryl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, 2-oxo-2-isobutyryl-4,5-benzo-1,3,2-dioxaphospholane, 2-oxo-2-isobutyryl-4,5-(3xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-isobutyryl-4,5-(4xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-isobutyryl-4,5-(4xe2x80x2-tert-butylbenzo)-1,3,2-dioxaphospholane, and 2-oxo-2-isobutyryl-4,5-naphthalo-1,3,2-dioxaphospholane. Suitable hydrocarbylene pivaloylphosphonates include 2-oxo-2-pivaloyl-5-butyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-4-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-5-ethyl-5-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-5,5-diethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-5-methyl-5-propyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-4-isopropyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-4,6-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-4-propyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-pivaloyl-4-methyl-1,3,2-dioxaphospholane, 2-oxo-2-pivaloyl-4,5-dimethyl-1,3,2-dioxaphospholane, 2-oxo-2-pivaloyl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, 2-oxo-2-pivaloyl-4,5-benzo-1,3,2-dioxaphospholane, 2-oxo-2-pivaloyl-4,5-(3xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-pivaloyl-4,5-(4xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-pivaloyl-4,5-(4xe2x80x2-tert-butylbenzo)-1,3,2-dioxaphospholane, and 2-oxo-2-pivaloyl-4,5-naphthalo-1,3,2-dioxaphospholane.
Suitable hydrocarbylene cyclohexanoylphosphonates include 2-oxo-2-cyclohexanoyl-5-butyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-4-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-5-ethyl-5-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-5,5-diethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-5-methyl-5-propyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-4-isopropyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-4,6-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-4-propyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-cyclohexanoyl-4-methyl-1,3,2-dioxaphospholane, 2-oxo-2-cyclohexanoyl-4,5-dimethyl-1,3,2-dioxaphospholane, 2-oxo-2-cyclohexanoyl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, 2-oxo-2-cyclohexanoyl-4,5-benzo-1,3,2-dioxaphospholane, 2-oxo-2-cyclohexanoyl-4,5-(3xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-cyclohexanoyl-4,5-(4xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-cyclohexanoyl-4,5-(4xe2x80x2-tertbutylbenzo)-1,3,2-dioxaphospholane, and 2-oxo-2-cyclohexanoyl-4,5-naphthalo-1,3,2-dioxaphospholane.
Suitable hydrocarbylene acryloylphosphonates include 2-oxo-2-acryloyl-5-butyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-4-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-5-ethyl-5-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-5,5-diethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-5-methyl-5-propyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-4-isopropyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-4,6-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-4-propyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-acryloyl-4-methyl-1,3,2-dioxaphospholane, 2-oxo-2-acryloyl-4,5-dimethyl-1,3,2-dioxaphospholane, 2-oxo-2-acryloyl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, 2-oxo-2-acryloyl-4,5-benzo-1,3,2-dioxaphospholane, 2-oxo-2-acryloyl-4,5-(3xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-acryloyl-4,5-(4xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-acryloyl-4,5-(4xe2x80x2-tert-butylbenzo)-1,3,2-dioxaphospholane, and 2-oxo-2-acryloyl-4,5-naphthalo-1,3,2-dioxaphospholane.
Suitable hydrocarbylene benzoylphosphonates include 2-oxo-2-benzoyl-5-butyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-4-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-5-ethyl-5-methyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-5,5-diethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-5-methyl-5-propyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-4-isopropyl-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-4,6-dimethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-4-propyl-5-ethyl-1,3,2-dioxaphosphorinane, 2-oxo-2-benzoyl-4-methyl-1,3,2-dioxaphospholane, 2-oxo-2-benzoyl-4,5-dimethyl-1,3,2-dioxaphospholane, 2-oxo-2-benzoyl-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane, 2-oxo-2-benzoyl-4,5-benzo-1,3,2-dioxaphospholane, 2-oxo-2-benzoyl-4,5-(3xe2x80x2-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-benzoyl-4,5-(4-methylbenzo)-1,3,2-dioxaphospholane, 2-oxo-2-benzoyl-4,5-(4xe2x80x2-tert-butylbenzo)-1,3,2-dioxaphospholane, and 2-oxo-2-benzoyl-4,5-naphthalo-1,3,2-dioxaphospholane.
The catalyst composition of this invention has very high catalytic activity over a wide range of catalyst concentrations and catalyst ingredient ratios. The polymers having the most desirable properties, however, are obtained within a narrower range of catalyst concentrations and catalyst ingredient ratios. Further, the three catalyst ingredients (a), (b), and (c) may interact to form an active catalyst species. Accordingly, the optimum concentration for any one catalyst ingredient is dependent upon the concentrations of the other catalyst ingredients. The molar ratio of the organomagnesium compound to the iron-containing compound (Mg/Fe) can be varied from about 1:1 to about 50:1, more preferably from about 2:1 to about 30:1, and even more preferably from about 3:1 to about 20:1. The molar ratio of the xcex1-acylphosphonate diester to the iron-containing compound (P/Fe) can be varied from about 0.5:1 to about 50:1, more preferably from about 1:1 to about 25:1, and even more preferably from about 2:1 to about 10:1.
The catalyst composition is formed by combining or mixing the three catalyst ingredients (a), (b), and (c). Although an active catalyst species is believed to result from this combination, the degree of interaction or reaction between the various ingredients or components is not known with any great degree of certainty. Therefore, the term xe2x80x9ccatalyst compositionxe2x80x9d has been employed to encompass a simple mixture of the ingredients, a complex of the various ingredients that is caused by physical or chemical forces of attraction, a chemical reaction product of the ingredients, or a combination of the foregoing.
The catalyst composition can be formed by using one of the following methods:
First, the catalyst composition may be formed in situ by adding the three catalyst ingredients to a solution containing monomer and solvent, or simply bulk monomer, in either a stepwise or simultaneous manner. When adding the catalyst ingredients in a stepwise manner, the sequence in which the catalyst ingredients are added is not critical. Preferably, however, the organomagnesium compound is added first, followed by the iron-containing compound, and then followed by the xcex1-acylphosphonate diester.
Second, the three catalyst ingredients may be pre-mixed outside the polymerization system at an appropriate temperature, which is generally from about xe2x88x9220xc2x0 C. to about 80xc2x0 C., and the resulting catalyst composition is then added to the monomer solution.
Third, the catalyst composition may be pre-formed in the presence of conjugated diene monomer. That is, the three catalyst ingredients are pre-mixed in the presence of a small amount of conjugated diene monomer at an appropriate temperature, which is generally from about xe2x88x9220xc2x0 C. to about 80xc2x0 C. The amount of conjugated diene monomer that is used for pre-forming the catalyst can range from about 1 to about 500 moles per mole of the iron-containing compound, more preferably from about 5 to about 250 moles per mole of the iron-containing compound, and even more preferably from about 10 to about 100 moles per mole of the iron-containing compound. The resulting catalyst composition is then added to the remainder of the conjugated diene monomer that is to be polymerized.
Fourth, the catalyst composition may be formed by using a two-stage procedure. The first stage involves reacting the iron-containing compound with the organomagnesium compound in the presence of a small amount of conjugated diene monomer at an appropriate temperature, which is generally from about xe2x88x9220xc2x0 C. to about 80xc2x0 C. In the second stage, the foregoing reaction mixture and the xcex1-acylphosphonate diester are charged in either a stepwise or simultaneous manner to the remainder of the conjugated diene monomer that is to be polymerized.
Fifth, an alternative two-stage procedure may also be employed. An iron-ligand complex is first formed by pre-combining the iron-containing compound with the xcex1-acylphosphonate diester. Once formed, this iron-ligand complex is then combined with the organomagnesium compound to form the active catalyst species. The iron-ligand complex can be formed separately or in the presence of the conjugated diene monomer that is to be polymerized. This complexation reaction can be conducted at any convenient temperature at normal pressure, but for an increased rate of reaction, it is preferable to perform this reaction at room temperature or above. The time required for the formation of the iron-ligand complex is usually within the range of about 10 minutes to about 2 hours after mixing the iron-containing compound with the xcex1-acylphosphonate diester. The temperature and time used for the formation of the iron-ligand complex will depend upon several variables including the particular starting materials and the solvent employed. Once formed, the iron-ligand complex can be used without isolation from the complexation reaction mixture. If desired, however, the iron-ligand complex may be isolated from the complexation reaction mixture before use.
When a solution of the catalyst composition or one or more of the catalyst ingredients is prepared outside the polymerization system as set forth in the foregoing methods, an organic solvent or carrier is preferably employed. The organic solvent may serve to dissolve the catalyst composition or ingredients, or the solvent may simply serve as a carrier in which the catalyst composition or ingredients may be suspended. It is normally desirable to select an organic solvent that is inert with respect to the catalyst composition. Useful solvents include hydrocarbon solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, and cycloaliphatic hydrocarbons. Non-limiting examples of aromatic hydrocarbon solvents include benzene, toluene, xylenes, ethylbenzene, diethylbenzene, mesitylene, and the like. Non-limiting examples of aliphatic hydrocarbon solvents include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexanes, isopentanes, isooctanes, 2,2-dimethylbutane, petroleum ether, kerosene, petroleum spirits, mineral spirits, and the like. And, non-limiting examples of cycloaliphatic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and the like. Commercial mixtures of the above hydrocarbons may also be used. For environmental reasons, aliphatic and cycloaliphatic solvents are highly preferred.
The catalyst composition exhibits very high catalytic activity for the polymerization of conjugated diene monomers. Specific examples of conjugated diene monomers that can be polymerized include, but are not limited to, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1 ,3-butadiene, 2-methyl- 1,3-pentadiene, 3-methyl- 1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene. Mixtures of two or more conjugated dienes may also be utilized in copolymerization. The preferred conjugated diene monomers are 1,3-butadiene, isoprene, 1,3-pentadiene, and 1,3-hexadiene. The most preferred conjugated diene monomer is 1,3-butadiene. A preferred embodiment of this invention is directed toward the polymerization of 1,3-butadiene into syndiotactic 1,2-polybutadiene or atactic 1,2-polybutadiene.
The production of conjugated diene polymers is accomplished by polymerizing conjugated diene monomers in the presence of a catalytically effective amount of the foregoing catalyst composition. The total catalyst concentration to be employed in the polymerization mass depends on the interplay of various factors such as the purity of the catalyst ingredients, the polymerization temperature, the polymerization rate and conversion desired, and many other factors. Accordingly, a specific total catalyst concentration cannot be definitively set forth except to say that catalytically effective amounts of the respective catalyst ingredients should be used. Generally, the amount of the iron-containing compound used can be varied from about 0.01 to about 2 mmol per 100 g of conjugated diene monomer, more preferably from about 0.02 to about 1.0 mmol per 100 g of conjugated monomer, and even more preferably from about 0.05 to about 0.5 mmol per 100 g of conjugated diene monomer.
The polymerization of conjugated diene monomers is preferably carried out in an organic solvent as the diluent. Accordingly, a solution polymerization system may be employed in which both the monomer to be polymerized and the polymer formed are soluble in the polymerization medium. Alternatively, a precipitation polymerization system may be employed by choosing a solvent in which the polymer formed is insoluble. In both cases, an amount of organic solvent in addition to the amount of organic solvent that may be used in preparing the catalyst composition is usually added to the polymerization system. The additional organic solvent may be the same as or different from the organic solvent used in preparing the catalyst composition. It is normally desirable to select an organic solvent that is inert with respect to the catalyst composition employed to catalyze the polymerization. Exemplary hydrocarbon solvents have been set forth above. When a solvent is employed, the concentration of the conjugated monomer to be polymerized is not limited to a special range. Preferably, however, the concentration of the 1,3-butadiene monomer present in the polymerization medium at the beginning of the polymerization should be in a range of from about 3% to about 80% by weight, more preferably from about 5% to about 50% by weight, and even more preferably from about 10% to about 30% by weight.
The polymerization of conjugated diene monomers may also be carried out by means of bulk polymerization, which refers to a polymerization environment where no solvents are employed. The bulk polymerization can be conducted either in a condensed liquid phase or in a gas phase.
In performing the polymerization of conjugated diene monomers, a molecular weight regulator may be employed to control the molecular weight of the polymer to be produced. As a result, the scope of the polymerization system can be expanded in such a manner that it can be used for the production of conjugated diene polymers having a wide range of molecular weights. Suitable types of molecular weight regulators that can be utilized include, but are not limited to, xcex1-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene; accumulated diolefins such as allene and 1,2-butadiene; nonconjugated diolefins such as 1,6-octadiene, 5-methyl-1,4-hexadiene, 1,5-cyclooctadiene, 3,7-dimethyl-1,6-octadiene, 1,4-cyclohexadiene, 4-vinylcyclohexene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,2-divinylcyclohexane, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, and 1,2,4-trivinylcyclohexane; acetylenes such as acetylene, methylacetylene, and vinylacetylene; and mixtures thereof. The amount of the molecular weight regulator used, expressed in parts per hundred parts by weight of the conjugated diene monomer (phm), is from about 0.01 to about 10 phm, preferably from about 0.02 to about 2 phm, and more preferably from about 0.05 to about 1 phm.
The molecular weight of the polymer to be produced can also be effectively controlled by conducting the polymerization of conjugated diene monomers in the presence of hydrogen gas. In this case, the partial pressure of hydrogen gas is preferably from about 0.01 to about 50 atmospheres.
The polymerization of conjugated diene monomers may be carried out as a batch process, a continuous process, or a semi-continuous process. In the semi-continuous process, monomer is intermittently charged as needed to replace that monomer already polymerized. In any case, the polymerization is preferably conducted under anaerobic conditions by using an inert protective gas such as nitrogen, argon or helium, with moderate to vigorous agitation. The polymerization temperature may vary widely from a low temperature, such as xe2x88x9210xc2x0 C. or below, to a high temperature such as 100xc2x0 C. or above, with a preferred temperature range being from about 20xc2x0 C. to about 90xc2x0 C. The heat of polymerization may be removed by external cooling, cooling by evaporation of the monomer or the solvent, or a combination of the two methods. Although the polymerization pressure employed may vary widely, a preferred pressure range is from about 1 atmosphere to about 10 atmospheres.
Once a desired conversion is achieved, the polymerization can be stopped by adding a polymerization terminator that inactivates the catalyst. Typically, the terminator employed is a protic compound, which includes, but is not limited to, an alcohol, a carboxylic acid, an inorganic acid, water, or a mixture thereof. An antioxidant such as 2,6-di-tert-butyl-4-methylphenol may be added along with, before or after the addition of the terminator. The amount of the antioxidant employed is usually in the range of 0.2% to 1% by weight of the polymer product. When the polymerization has been stopped, the polymer can be recovered from the polymerization mixture by utilizing conventional procedures of desolventization and drying. For instance, the polymer may be isolated from the polymerization mixture by coagulation of the polymerization mixture with an alcohol such as methanol, ethanol, or isopropanol, followed by filtration, or by steam distillation of the solvent and the unreacted monomer, followed by filtration. The isolated polymer is then dried to remove residual amounts of solvent and water. Alternatively, the polymer may be isolated from the polymerization mixture by directly drum drying the polymerization cement.
Advantageously, the iron-based catalyst composition can be manipulated to vary the characteristics of the resulting conjugated diene polymer. For example, in a preferred embodiment of this invention where 1,3-butadiene is polymerized into polybutadiene, the characteristics of the resulting polybutadiene can be controlled by varying the molar ratio of the organomagnesium compound to the iron-containing compound. Namely, when the molar ratio of the organomagnesium compound to the iron-containing compound is relatively low (e.g., 6:1 or less), atactic 1,2-polybutadiene is formed. On the other hand, when the molar ratio of the organomagnesium compound to the iron-containing compound is relatively high (e.g., 8:1 or more), syndiotactic 1,2-polybutadiene is formed. Further, by selecting an intermediate molar ratio of the organomagnesium compound to the iron-containing compound (e.g., 7:1), it is also possible to prepare a blend of syndiotactic 1,2-polybutadiene and atactic 1,2-polybutadiene.
The conjugated diene polymers produced with the catalyst composition of this invention have many uses. For example, the atactic 1,2-polybutadiene can be utilized in rubber compositions that are used to manufacture tire treads having the optimum balance of traction, wear, and rolling resistance. The syndiotactic 1,2-polybutadiene can be blended into and co-cured with various natural or synthetic rubbers in order to improve the properties thereof. For example, the syndiotactic 1,2-polybutadiene can be incorporated into elastomers in order to improve the green strength of those elastomers, particularly in tires. The supporting or reinforcing carcass of tires is particularly prone to distortion during tire building and curing procedures. For this reason, the incorporation of the syndiotactic 1,2-polybutadiene into rubber compositions that are utilized in the supporting carcass of tires has particular utility in preventing or minimizing this distortion. In addition, the incorporation of the syndiotactic 1,2-polybutadiene into tire tread compositions can reduce the heat build-up and improve the tear and wear resistance of tire treads. The syndiotactic 1,2-polybutadiene is also useful in the manufacture of films and packaging materials and in many molding applications.

Iron-based catalyst for producing high-vinyl polybutadiene