WO2004096965A1 - Tensioactifs insatures - Google Patents

Tensioactifs insatures Download PDF

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Publication number
WO2004096965A1
WO2004096965A1 PCT/GB2004/001820 GB2004001820W WO2004096965A1 WO 2004096965 A1 WO2004096965 A1 WO 2004096965A1 GB 2004001820 W GB2004001820 W GB 2004001820W WO 2004096965 A1 WO2004096965 A1 WO 2004096965A1
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Prior art keywords
group
carbon atoms
adduct
derived
composition
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PCT/GB2004/001820
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English (en)
Inventor
David Robert Edward Walker
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Huntsman International Llc
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Publication date
Priority claimed from GB0317881A external-priority patent/GB0317881D0/en
Priority claimed from GB0319339A external-priority patent/GB0319339D0/en
Priority claimed from GB0325525A external-priority patent/GB0325525D0/en
Application filed by Huntsman International Llc filed Critical Huntsman International Llc
Publication of WO2004096965A1 publication Critical patent/WO2004096965A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates generally to surfactants. More particularly, it relates to surfactants which contain at least one double bond in their molecular structure. Surfactants according to the present invention may be produced using terpene feedstocks.
  • Surfactants are generally recognized as being amphiphillic molecules that comprise a hydrophobic and a hydrophilic portion within the same molecule, and may be either synthetic or naturally-occurring.
  • Early synthetic surfactants were typically based on fatty acids obtained from natural glyceride oils or fats for a source of the hydrophobic part of the molecule which provided, exclusively, straight chain alkyl or alkenyl groups with an even number of carbon atoms. More recently, branched chain oxo alcohols, polypropylene oxide, and/or alkylbenzene groups of petrochemical origin have also been used as materials from which surfactants may be derived.
  • Some naturally-occurring surfactants include saponins in which the hydrophobic portion is a tri-terpenoid, such as a steroid, and the hydrophilic portion is a polyglycoside.
  • saponins in which the hydrophobic portion is a tri-terpenoid, such as a steroid, and the hydrophilic portion is a polyglycoside.
  • the amount of surfactants which are procurable therefrom are correspondingly limited.
  • the methods used to generate the hydrophilic portion of synthetic surfactants have been numerous and very diverse.
  • saponification of glycerides to give soaps hydrogenation of fatty acids to give fatty alcohols; amination or amidation to give amines, alkanolamides, amido amines or imidazolines; ethoxylation of alcohols, acids, amines or hydroxy esters, to give polyethoxylates; sulphation, sulphonation or phosphorylation of alcohols, ethoxylates, esters or hydrocarbons to give anionic surfactants; neutralisation or quaternisation of amines, amido amines or imidazolines to give cationic surfactants; carboxymethylation or carboxyethylation of amines, amido amines or imidazolines to give amphoteric or zwitterionic surfactants; oxidation of amines to give amine oxides; esterificaton of carboxylic acids with sucrose or sorbitan; and glycosylation of carboxylic acids to give polyg
  • One object of the present invention is to provide alternatives to the limited range of conventional hydrophobic feedstocks, which have chemical and biological activity capable of conferring, on the surfactants derived therefrom, enhanced surface activity, mildness, anti-microbial properties, self-preservation and favorable biodegradability and/or other functionalities in addition to their surface activity, in addition to being produced from renewable natural sources.
  • Terpenes may be notionally constructed from two or more isoprene units.
  • the hydrophobes of the present invention exhibit a range of biological activity, typically biocidal or biostatic, and often have characteristic aromas capable of attracting or repelling pests or enhancing the fragrance or flavour of a product.
  • Certain terpenes are known to possess conjugated double bonds, and therefore to be capable of undergoing Diels Alder addition reactions with dienophiles.
  • the resulting adducts when formed from a hydrophobic terpene and a dienophile, having a hydrophilic or hydrophilisable substituent, may be used as, or as intermediates in the preparation of, a new class of multifunctional surfactants .
  • Desalted amphoteric and zwitterionic surfactants generally form L ⁇ -phase at higher concentrations, e.g. up to 80% or even higher, and are particularly preferred, where the objective is to supply the product in a pourable form at the highest convenient concentration.
  • electrolyte less concentrated and more mobile expanded
  • L ⁇ -phases can be obtained that are capable of indefinitely suspending particulate material.
  • Expanded L ⁇ -phases typically with repeat-spacing between 8 and 20, e.g. 10 to 15 nanometers, form when electrolyte is added to aqueous surfactants at concentrations just below those required to form a normal
  • L ⁇ -phase particularly to surfactants in the H-phase.
  • the H-phase also relates to surfactants in the H-phase.
  • the M- phase comprises surfactant molecules arranged to form cylindrical rods of indefinite length. It exhibits hexagonal symmetry and a distinctive texture under the polarising microscope. Typical H-phases have so high a viscosity that they appear to be curdy solids. H- phases near the lower concentration limit (the L x /H-phase boundary) may be pourable but have a very high viscosity and often a
  • Expanded L ⁇ -phases are described in more detail in EP O 530 708. In the absence of suspended matter they are translucent, unlike dispersed lamellar or spherulitic phases, which are usually opaque. They are optically anisotropic and have shear dependent viscosity.
  • Spherulitic phases comprise well-defined spheroidal bodies, usually referred to in the art as spherulites, in which surfactant bilayers are arranged as concentric shells.
  • the spherulites usually have a diameter in the range 0.1 to 15 microns and are dispersed in an aqueous phase in the manner of a classical emulsion, but interacting to form a structured system.
  • Spherulitic systems are described in more detail in EP O 151 884.
  • Fatty acid based amphoteric or zwitterionic surfactants do not readily form structured suspending systems, which has restricted their usefulness in liquid laundry detergents, despite their superior soil- removing power.
  • amphoteric or zwitterionic surfactants readily form
  • bilayers of surfactant are arranged with the hydrophobic part of the molecule on the interior and the hydrophilic part on the exterior of the bilayer (or vice versa).
  • the bilayers lie side by side, e.g. in a parallel or concentric configuration, sometimes separated
  • L ⁇ -phases also known as G-phases
  • G-phases can usually be
  • Such evidence may comprise first, second and
  • a number of surfactant blends are available as L ⁇ -phases at about 60 or
  • the present invention provides Diels Alder adducts, which are either surfactants having a hydrophobic portion and a hydrophilic portion, or intermediates in the preparation thereof, wherein the hydrophobic portion is derived from a hydrophobic terpene, which comprises two conjugated double bonds, or an isolated double conjugated with an allylic hydrogen atom, and which has from 10 to 30 carbon atoms per molecule, and wherein the hydrophilic portion: a) is derived from a dienophile, which comprises a double-bonded pair of carbon atoms and at least one adjacent activating group; and b) has at least one hydrophilic group, present in said dienophile prior to, or introduced during or after, the formation of the adduct.
  • surfactant material that is derived from a terpene- derived acid having a structure selected from the group consisting of:
  • R is selected from the group consisting of: hydrogen or methyl
  • said surfactant material is selected from the group consisting of: amphoacetates, betaines, amine oxides, alkoxylates, esters, amides, sugar esters, and simple metallic soaps such as the alkali metal, alkaline earth metal, and ammonium (alkyl-substituted or un-substituted) soaps.
  • FIG. 1 shows a comparison between surface tensions of conventional surfactants and those of the present invention.
  • FIG. 2 shows surface tension profiles of AAPB based on myrcene versus
  • Diels Alder adduct includes products of variations on the classical Diels Alder addition, such as the hetero variant, in which the dienophile is reacted with a compound, which comprises an ethylenic double bond conjugated with a non-ethylenic bond, such as a carbonyl group, or the ene reaction, in which the dienophile reacts with an isolated double bond, conjugated with an allylic hydrogen atom.
  • Tepene refers to the naturally occurring oligomers of isoprene and their derivatives, or their nature-identical synthetic counterparts. The terpene is preferably a mono-, sesque-, or diterpene, and is desirably a hydrocarbon. However the term “terpene” as used herein includes hydrophobic terpenoids having one or more carbonyl groups and monohydroxy terpenols. A preferred terpene for use as the diene is
  • myrcene examples include -terpinene, citral (hetero variant of a
  • the dienophile selected preferably has from 2 to 10 carbon atoms per molecule.
  • the activating group(s) may comprise a hydrophilic group, such as a carboxyl, carboxylic anhydride, hydroxymethyl, sulphonyl or phosphonyl group.
  • the activating group may comprise, for example, a carbonyl, carboxylic ester, halogen, aryl, aminomethyl, cyano or nitro group.
  • Typical examples include acrylic acid, methyl aery late, polyethyleneglycol acrylate, glyceryl monoacrylate, methacrylic acid, methyl methacrylate, maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid, crotonic acid, isocrotonic acid, aconitic acid, itaconic acid, angelic acid, tiglic acid, vinylphosphonic acid, vinyl sulphonic acid, vinyl chloride, styrene, styrene sulphonic acid, allyl alcohol, allyl amine and acrolein.
  • the reaction may be carried out in the conventional manner for Diels Alder additions by heating the reaction mixture, in substantially stoichiometric proportions, optionally in a suitable organic solvent, e.g. petroleum, limonene, or an aromatic solvent such as benzene or toluene, if required for fluidity.
  • a Diels Alder catalyst e.g. a Lewis acid such as aluminium chloride may be employed, however we have found that un-catalysed reactions may give better coloured end products, especially in processes, which involve the subsequent amidation of the adduct.
  • the reaction temperature is preferably greater than 50° C, more preferably greater than 70°C, even more preferably greater than 90°C, more preferably still, greater than 100° C, most preferably greater than 120 °C, provided that it does not exceed the decomposition temperature of the product. Depending on stability of the product and reactivity of the reaction mixture, higher temperatures, greater than 130°C may sometimes be preferred. Temperatures will preferably be less than 250 °C more preferably less than 200°C, even more preferably less than 180°C, most preferably less than 160°C.
  • the elevated temperature is maintained for a sufficient time to obtain an acceptable yield of the adduct.
  • the time required depends on the reactivity of the particular reagents, the temperature, the stability of the product and commercial considerations (e.g. the value of the product against the cost of prolonging the heating step) , however, typically, it is greater than 30 minutes, preferably greater than one hour, more preferably greater than two hours, but is preferably less than twenty four hours, more preferably less than fifteen hours, and more preferably still less than ten hours.
  • the adducts of the invention are typically ring compounds, which comprise a mixture of para and meta isomers, with the activating group either in, or perpendicular to the plane of the ring, respectively.
  • the mixture may be used as such, but we do not exclude separating the isomers.
  • the product may be used as a surfactant in its own right.
  • these groups are anionic groups, such as carboxyl, sulphonyl or phosphonyl
  • the product may require neutralisation with a suitable base to form a salt, such as the sodium, potassium, ammonium, ethanolamine or isopropylamine salt.
  • the adduct may be used as an intermediate in the preparation of the surfactant product, by treating it with any of the conventional processes used for generating the hydrophilic portion of a surfactant, such as those listed above.
  • a carboxylate group may be esterified with sorbitan or sucrose, glycosylated or ethoxylated to provide a non-ionic surfactant. It may be amidated, e.g. with an alkanolamine to form an alkanolamide, with a diamine, to form an amido amine, or with diethylenetriamine to form an imidazoline, which may in turn be quaternised, e.g. with hydrochloric acid or dimethyl sulphate to form a cationic surfactant, or carboxymethylated with chloracetic acid to form an amphoacetate.
  • adducts of this invention may be converted into novel members of any of the surfactant groups currently available commercially, and the invention includes all such derivatives.
  • carboxylic acid intermediates of the invention especially those obtained by the reaction of an unsaturated carboxylic acid, such as acrylic acid,
  • the same products may be obtained by reacting the terpene with a pre-ethoxylated acrylic, or other unsaturated, acid. These products exhibit particularly good biocidal properties.
  • the aforesaid carboxylic acid intermediates of the invention may be amidated, e.g. with 3-(dimethylamino) propylamine, using any of the conventional amidation methods to make, e.g.
  • amidation product may be carboxymethylated with sodium chloroacetate to provide a novel betaine, which combines a mildness characteristic of betaines with a microbicidal activity, contrasting with the usual behaviour of fatty acid derived betaines.
  • the latter are microbial growth promoters.
  • the amidation product may be oxidised, e.g. by reaction with hydrogen peroxide, to form a novel amine oxide.
  • Amphoteric or zwitterionic surfactants of the invention which have been prepared by carboxymethylation, normally contain about 20%, by weight based on the total weight of surfactant, of sodium chloride, formed as a by-product of the reaction between the amine or amidoamine precursor, and chloroacetic acid.
  • the salt can be removed or substantially reduced, either during or after preparation, for example by electrodialysis, e.g. as described in GB 1 525 692 or in EP 0 736 521, by membrane filtration, for example as described is EP 0 626 881, or, less preferably, by displacing metal ion e.g. using ion exchange or by solvent precipitation.
  • it is possible to prepare zwitterionic surfactants with low salt levels by carboxyethylating the precursor amine or amidoamine with acrylic acid.
  • Amphoteric or zwitterionic surfactants of the invention have also been observed to form spherulitic suspending systems, in the presence of sufficient electrolyte.
  • surfactants of this invention form L ⁇ -phases, vary according to the
  • the terpene derived surfactants of this invention form L ⁇ - phases more readily than their fatty acid analogues, and may be supplied as high active products.
  • Surfactants of the present invention have been found to exhibit useful secondary properties in addition to surface activity. These include biocidal or biostatic activity, or the ability to enhance or modify fragrances and flavours. They have also been found to exhibit improved surfactancy, and higher critical micelle concentrations, compared with their fatty acid-derived analogues.
  • the invention will be illustrated by the following examples, in which all proportions are by weight, based on the total weight of the composition, and all temperatures are in degrees centigrade, unless stated to the contrary.
  • the following examples shall be construed as exemplary of various embodiments of the present invention, and shall not be construed as being delimitive thereof in any way.
  • Example I was repeated, replacing the myrcene with ⁇ -terpinene in
  • the reaction temperature was raised to 150°C, and maintained for five hours.
  • the product had a sweet spicy aroma and a cloud point below 20° C.
  • Example I was repeated, replacing the acrylate with acrylic acid in the same molar proportions. The temperature was maintained at 130°C for three hours. The product was insoluble in deionised water, but is a valuable intermediate for the preparation of surfactants. It dissolves in dilute alkali, e.g. sodium hydroxide, to form a soap. It may be substituted for fatty acid in any of the known processes for converting the latter into surfactants.
  • alkali e.g. sodium hydroxide
  • the carboxylic acid of example III was amidated with 3-(dimethylamino) propylamine, to form the corresponding alkyl amido propylamine.
  • the adduct was refluxed at atmospheric pressure with a small stoichiomteric excess of the amine, and the product stripped, with further additions of amine to help remove water.
  • the amido propylamine was then carboxymethylated in aqueous solution by heating with an equimolar proportion of sodium chloracetate for 8 hours at 80°C, while maintaining the pH at 10. The pH was then raised to 11.5, and heating continued for a further 4 hours. The pH was finally adjusted to 5.
  • Example IV shows strong broad spectrum biocidal activity, whereas the fatty acid equivalent, even with added preservative, is a prompter of microbial growth.
  • Example IV The product of Example IV was concentrated to 60% by weight active, at which it formed a viscous, yellow oil. A drop of the latter on the slide of polarising microscope was observed. Initially a batonette texture, indicative of H-phase, was seen to develop rapidly, but after being allowed to dry by evaporation overnight, a typical texture indicative of
  • Example II The product of Example I was evaluated for activity against E. coli, following the procedure of Example VI.
  • the ethoxylate gave a 61% reduction in the viability of E coli, compared to only 4% by a C ⁇ 2- ⁇ 4 fatty alcohol ethoxylate.
  • Example II The product of Example II was evaluated for activity against E. coli,
  • Example III was repeated without catalyst. On heating tol05° C, the mixture exothermed to 178° C. After cooling to 140° C, the product was aged for 1 hour.. The adduct was obtained in good yield. The isomer ratio was 50/50.
  • Example IV was repeated using the adduct of Example X in place of that of Example III. A cream coloured product of substantially improved colour was obtained.
  • a terpene which is preferably selected from the group consisting of: myrcene and alpha terpinene, is reacted with acrylic acid to form an adduct acid material according to the following formula:
  • the adduct acid product from the reaction in (I ) may be subsequently employed in place of a conventional carboxylic acid (having hydrocarbon chain lengths (Cio to C 20 ) and branched or linear character recognized by those skilled in the detergent arts as being useful for producing detersive materials including soaps and the like) in forming various types of detergents known to those skilled in the art which include without limitation: betaines, amine oxides, amphoacetates, alkoxylates, amides and esters.
  • reaction of the adduct acid from reaction (I) with dimethylaminopropylamine yields an amide having a dimethylamino end cap which can be subsequently quaternized with chloroacetic acid or its sodium salt, using means well known in the art, to provide alkylamidopropylbetames which are heretofore unknown, and which possess the properties descried in this specification, which make these materials high value added multi-functional detersive agents.
  • DMAPA dimethylaminopropylamine
  • Another embodiment of the present invention involves the reaction of alpha-terpinene with acrylic acid to yield an adduct acid, according to the reaction:
  • alkylamidopropyl amine oxides which are prepared by first treating the acid produced in reaction (III) with a diamine such as DMAPA, and then subsequently oxidizing the amine so formed with a peroxide, such as hydrogen peroxide, under conditions known to those skilled in the art as being useful for producing amine oxides, which yields:
  • the acid adducts produced in reactions (I) and (III) may be used as starting materials for the preparation of the sucrose and sorbitan esters shown in (VII) , (VIII), (IX), and (X) below.
  • RO is an alkylene oxide selected from the group consisting of: ethylene oxide, propylene oxide, and butylene oxide, including mixtures of any two or more of the foregoing, in random and block co-polymer fashion, wherein n may be any integral value between 1 and 50, preferably between 3 and 30, and more preferably still between about 3 and 20, and including mixtures of materials having different values of n.
  • the acid adducts from structures (I) and (III) above may also be employed to produce amphoacetates according to the following methods.
  • To make an imidazoline base intermediate 300 grams (1.44 moles) of the adduct acid from reaction (I) above is combined with 151.5g (1.46 moles) of aminoethylethanolamine (AEEA) .
  • AEEA aminoethylethanolamine
  • the temperature is slowly ramped up to 185 °C and vacuum slowly increased from 240 mbar absolute to 20 mbar absolute over the course of about five hours.
  • the reactor contents are cooled and a second charge of 37.5g (0.36 moles) AEEA is added.
  • the reactor is re-heated to 185°C at 90 mbar absolute and maintained at this temperature for a further 6 hours, after which time the vacuum is increased over 5 hours to 10 mbar absolute. At this stage, the contents of the reactor are cooled and offloaded.
  • a second quantity of 98.7 grams of 47 % (wt.) aqueous NaOH is charged into the addition funnel and slowly added to the flask so as to maintain the pH of the flask in the range of 9.5 to 11.2 over the course of about 24 hours.
  • the flask contents are cooled and sampled for analysis. Analysis showed 53 ppm monochloroacetate remaining.
  • the pH is adjusted to 8.6 with concentrated aqueous HC1.
  • the total solids content was determined to be 41.85%, and the NaCl content was 9.4%.
  • amphoacetates exist in two forms, as mono and di-carboxylated products, as shown in the following two structures:
  • surfactant materials include: amphoacetates, betaines, amine oxides, alkoxylates, esters, amides, sugar esters, and simple metallic soaps such as the alkali metal, alkaline earth metal, and ammonium (alkyl-substituted or un-substituted)

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des composés d'addition dérivés par le biais d'un procédé de Diels-Alder, lesquels composés d'addition comprennent une partie hydrophobe et une partie hydrophile, laquelle partie hydrophobe est dérivée d'un terpène hydrophobe qui comprend d'une part deux liaisons doubles conjuguées ou une liaison conjuguée double isolée et un atome d'hydrogène allylique et d'autre part entre 10 et 30 atomes de carbone, laquelle partie hydrophile : a) est dérivée d'un diénophile qui comprend une paire d'atomes de carbone à liaison double et au moins un groupe d'activation adjacent ; et b) comprend au moins un groupe hydrophile préalablement présent dans le diénophile ou introduit pendant ou après la formation du composé d'addition. Les composés d'addition sont utilisés pour préparer divers types de tensioactifs connus des initiés pour être productibles à partir d'acides gras conventionnels.
PCT/GB2004/001820 2003-04-29 2004-04-29 Tensioactifs insatures WO2004096965A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
GB0309668.2 2003-04-29
GB0309668 2003-04-29
GB0317881A GB0317881D0 (en) 2003-07-31 2003-07-31 Novel surfactants
GB0317881.1 2003-07-31
GB0319339.8 2003-08-16
GB0319339A GB0319339D0 (en) 2003-08-16 2003-08-16 Novel surfactants
GB0325525A GB0325525D0 (en) 2003-11-01 2003-11-01 Novel surfactants
GB0325525.4 2003-11-01

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WO2004096965A1 true WO2004096965A1 (fr) 2004-11-11

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012103156A1 (fr) * 2011-01-25 2012-08-02 Amyris, Inc. Tensioactifs
WO2013028307A1 (fr) * 2011-08-24 2013-02-28 Amyris, Inc. Dérivés de terpènes hydrocarbonés
WO2013148842A1 (fr) * 2012-03-27 2013-10-03 Stepan Company Tensio-actifs et solvants contenant des adduits de diels-alder
US9181393B2 (en) 2011-08-17 2015-11-10 Dow Global Technologies, Llc Biorenewable biodegradable surfactants
US10472463B2 (en) 2014-06-20 2019-11-12 Dsm Ip Assets B.V. Resin, composition and use

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54103846A (en) * 1978-01-31 1979-08-15 Hisamitsu Pharmaceut Co Inc Production of cyclohexenecarboxylic acid derivative, intermediate for anti-allergic drug and surfactant
US4709084A (en) * 1985-09-23 1987-11-24 Union Camp Corporation Terpene-based ester tackifiers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54103846A (en) * 1978-01-31 1979-08-15 Hisamitsu Pharmaceut Co Inc Production of cyclohexenecarboxylic acid derivative, intermediate for anti-allergic drug and surfactant
US4709084A (en) * 1985-09-23 1987-11-24 Union Camp Corporation Terpene-based ester tackifiers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 0031, no. 23 (C - 061) 16 October 1979 (1979-10-16) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012103156A1 (fr) * 2011-01-25 2012-08-02 Amyris, Inc. Tensioactifs
US9181393B2 (en) 2011-08-17 2015-11-10 Dow Global Technologies, Llc Biorenewable biodegradable surfactants
WO2013028307A1 (fr) * 2011-08-24 2013-02-28 Amyris, Inc. Dérivés de terpènes hydrocarbonés
WO2013148842A1 (fr) * 2012-03-27 2013-10-03 Stepan Company Tensio-actifs et solvants contenant des adduits de diels-alder
EP2831139A4 (fr) * 2012-03-27 2015-10-28 Stepan Co Tensio-actifs et solvants contenant des adduits de diels-alder
US10472463B2 (en) 2014-06-20 2019-11-12 Dsm Ip Assets B.V. Resin, composition and use

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