WO2000031012A1 - Procede de fabrication d'acide allyloxy-carboxylique - Google Patents

Procede de fabrication d'acide allyloxy-carboxylique Download PDF

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Publication number
WO2000031012A1
WO2000031012A1 PCT/SE1999/002047 SE9902047W WO0031012A1 WO 2000031012 A1 WO2000031012 A1 WO 2000031012A1 SE 9902047 W SE9902047 W SE 9902047W WO 0031012 A1 WO0031012 A1 WO 0031012A1
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WIPO (PCT)
Prior art keywords
acid
allyloxy
propanediol
carboxylic acid
hydroxyalkyl
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PCT/SE1999/002047
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English (en)
Inventor
Bo Pettersson
Ulf Annby
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Perstorp Ab
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Priority to AU14365/00A priority Critical patent/AU1436500A/en
Publication of WO2000031012A1 publication Critical patent/WO2000031012A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules

Definitions

  • the present invention refers to a process for production of an allyloxy carboxylic acid.
  • the process comprises the step of reacting a lactone with at least one allyl halide in an alkaline medium at a charged molar ratio lactone to allyl halide of 1 to at least 1.
  • the present invention refers to an allyloxy carboxylic acid produced by said process and in yet a further aspect to the use of an allyloxy carboxylic acid, produced by said process, as component in oligomeric and polymeric compounds, for instance resins and binders.
  • allyl compounds are allyloxy alcohols and other allyl ethers of alcohols and epoxides, such as glycerol mono and diallyl ether, trimethylolpropane mono, di and triallyl ether, pentaerythritol allyl ethers and allyl glycidyl ethers.
  • a general procedure for production of polyalcohol allyl ethers is for example the Williamson method, which method includes reacting an alcoholic compound with an allyl halide, such as allyl chloride, in a caustic medium.
  • Some polyfunctional alcohols require, in order to obtain complete allylation, that obtained partially allylated ether is treated with sodium and subsequently reacted with an allyl halide, such as allyl bromide.
  • a further processes for preparation of allyl ethers of aliphatic, arylaliphatic and cycloaliphatic alcohols include reacting a diallyl ether with an alcohol in the presence of a mercury salt and a strong acid as for instance disclosed in US patents nos. 2,847,477 and 2,847,478. Further and alternative procedures for production of polyalcohol allyl ethers are disclosed in for instance US patents nos. 2,634,296 and 2,934,621.
  • Allyloxy alcohols such as glycerol mono and diallylether, trimethylolethane mono and diallylether, trimethylolpropane mono and diallylether, pentaerythritol mono, di and triallylether, are used as for instance alkyd and polyester components to impart oxygen and heat conversion as well as improved physical and chemical properties and resistance.
  • the application areas include coatings, laminates and moulded articles. Allyloxy alcohols normally reduce oxygen inhibition, thus increasing reaction speed and surface hardness.
  • the main use is in direct gloss paraffin-free unsaturated polyesters for wood coatings and development areas such as high solids and waterborne air-drying alkyds and radiation curing coatings, including waterbome and styrene-free systems.
  • allylethers of alcohols are to be found in acrylic thickeners, polyurethane elastomers and superabsorbants. Allyloxy alcohols and other allyl compounds as well as their application areas are thoroughly disclosed and discussed in a number of handbooks and chemical encyclopaedias including Kirk-Othmer "Encyclopedia of Chemical Technology", John Wiley & Sons Inc. 1978, Vol. 2, chapters "Allyl Compounds” pp. 97-108 and “Allyl Monomers and Polymers” pp 109-129. Allyloxy carboxylic acid are suitably used in the same or similar application areas as disclosed above for allyloxy alcohols as well as in areas such as carboxyl functional silicone derivatives, wherein SiH groups are reacted with olefmic unsaturation.
  • allyloxy carboxylic acids are presently rather insignificant compared to corresponding production and use of allyloxy alcohols.
  • allyl esters such as phthalates, carbonates and other carboxylates.
  • These esters are normally produced from di, tri and polyfunctional carboxylic acids such as phthalic, isophthalic, maleic, fumaric, succinic, citric and itaconic acid or anhydride by reaction with an allyl halide, such as allyl chloride, or allyl alcohol.
  • An allyl halide may be converted to allyl alcohol and thus used to prepare esters.
  • Allyl ethers of hydroxyfunctional carboxylic acids such as mono and diallyl ethers of 2,2-dimethylolpropionic acid as disclosed in the Swedish patent no. 502 634, are usually produced by the Williamson method, or similar procedure, using protective chemistry for protection of the carboxylic group or groups.
  • Protective chemistry must be used in the production of allyl ethers of hydroxyfunctional carboxylic acids to avoid formation of allyl esters.
  • allyl compounds based on carboxylic acids include allyl hydroxy acids.
  • a method for preparation of ⁇ -allyl ⁇ -hydroxy acids is disclosed in "Palladium-catalyzed allylation of a-hydroxy acids" published in Recueil des Travaux Chimique des Pays-Bas, 111/3, March 1992, pages 129-137.
  • Mandelic and lactic acids are here converted into l,3-dioxolane-4-ones by treatment with acetone dimethyl acetate followed by deprotonation by treatment with allyl acetate and a catalytic amount of a palladium catalyst yielding allylated dioxolanone, which subsequently is hydrolysed to corresponding ⁇ -allyl ⁇ -hydroxy acid.
  • 3-allyloxypropionic acid produced from 3-allyloxypropionitrile and a lower alcohol in the presence of a catalyst and water is disclosed in Japanese Patent Application 61-93139.
  • Cyclisation of 3-allyloxy carboxylic acids by mixed Kolbe electrolysis into substituted tetrahydrofurans is disclosed by M. Huhtasaari et al in Angew. Chem. 1984, 96(12), pages 995-6.
  • Iodo lactonisation of unsaturated carboxylic acids, including allyloxy carboxylic acids, leading to 7 to 12-membered ring lactones is disclosed by B. Simonot et al in J. Org. Chem. 1994, 59, pages 5912-5919.
  • the present invention refers to a novel process for production of an allyloxy carboxylic acid.
  • the process comprises the step of reacting a lactone with at least one allyl halide in an alkaline medium, such as potassium and/or sodium hydroxide or other suitable alkali or alkaline earth metal hydroxide, at a charged molar ratio lactone to allyl halide of 1 to at least 1 , such as 1:1.1 to 1 :3 or 1:2.
  • the alkaline medium is present at a molar ratio allyl halide to alkaline medium of 1 to at least 1, preferably 1 to more than 1 or most preferably more than 2, such as 1 : 1.5 to 1:4 or 1 :3.
  • a suitable alkaline medium is to be found among for instance amines, such as tertiary amines, and alkali metal or alkaline earth metal hydroxide or carbonate, such as potassium and/or sodium hydroxide.
  • the reaction is in preferred embodiments carried out at a temperature of 60-150°C, such as 80-120°C or 90-110°C.
  • lactone distinguishes the internal mono, di or higher esters of hydroxycarboxylic acids from the cyclic esters of diols with dicarboxylic acids or carbonic acids.
  • the lactone is in preferred embodiments of the present invention ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -enantholactone or a derivative of such a lactone wherein one or more carbon atoms is/are alkanyl, cycloalkanyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl and/or aryl substituted, such as ⁇ -methyl, ⁇ -methyl, ⁇ , ⁇ -dimethyl and ⁇ -isopropyl propiolactone and similar or corresponding derivatives of said lactones.
  • Further lactones and derivatives thereof possible to employ according to the present invention may include compounds such as glycolide, ⁇ -methylene butyrol
  • Suitable allyl halides are in likewise preferred embodiments of the process of the present invention allyl chloride and/or allyl bromide.
  • the allyloxy carboxylic acid thus obtained is in preferred embodiments a linear or branched compound having 5 to 18 carbon atoms, such as a compound of formula
  • R is linear or branched alkanyl, or where applicable and possible alkenyl or alkynyl, having 2-12 carbon atoms.
  • Obtained allyloxy carboxylic acid is in especially preferred embodiments an allyloxy propanoic acid, an allyloxy butanoic acid, an allyloxy pentanoic acid, an allyloxy hexanoic acid, an allyloxy heptanoic acid, including where applicable alkanyl, alkenyl or alkynyl substituted derivatives of said acids.
  • the lactone is ⁇ -caprolactone, whereby obtained allyloxy carboxylic acid is 6-allyloxy hexanoic acid.
  • lactones and related compounds are disclosed in for instance "Encyclopedia of Polymer Science and Technology", John Wiley & Sons Inc., 1969, Vol. 11, pp 98-106 "Polymerisation of Cyclic Esters and Lactones” .
  • the present invention refers to an allyloxy carboxylic acid, especially produced by the process as disclosed above.
  • Said allyloxy carboxylic acid is in preferred embodiments an allyloxy propanoic acid, an allyloxy butanoic acid, an allyloxy pentanoic acid, an allyloxy hexanoic acid, an allyloxy heptanoic acid or an alkanyl, alkenyl or alkynyl substituted species of any of said allyloxy carboxylic acids.
  • the allyloxy carboxylic acid is in especially preferred embodiments is 6-allyloxy hexanoic acid produced from ⁇ -caprolactone and at least one allyl halide, such as allyl chloride or bromide.
  • the present invention refers to the use of an allyloxy carboxylic acid, as disclosed above, as component in oligomeric and polymeric compounds, such as ordinary linear or branched esters and polyesters, dendritic or hyperbranched polyesters, starbranched esters and polyesters, polyol esters and polyesters, silicone derivatives, phenolic resins, cement additives, such as concrete admixtures, and similar compositions.
  • Oligomeric and polymeric is here understood as having two or more monomer units.
  • Esters or polyesters are built up from ester units or ester units in combination with ether units and are suitably and optionally triglyceride or fatty acid modified.
  • Dendritic or hyperbranched polyesters are mono or polydisperse macromolecules of the type disclosed and discussed in the for instance Swedish patents 468 771 and 503 342. Said dendritic or hyperbranched polyester is preferably built up from a core derived from a compound having at least one reactive hydroxyl, epoxide, carboxyl or anhydride group to which core at least one dendron or branching chain extender is added.
  • the dendron comprises at least one generation built up from at least one monomeric or polymeric branching chain extender derived from a compound having at least three reactive groups of which at least one, preferably at least two, is a hydroxyl group and at least one is a carboxyl group, optionally in combination with at least one spacing chain extender derived from a compound having two reactive groups being one hydroxyl and one carboxyl group.
  • the hyperbranched or dendritic polyester is at least partially chain terminated by addition of said allyloxy carboxylic acid, optionally in combination with at least one other chain stopper.
  • the core of said dendritic or hyperbranched polyester is preferably derived from a mono, di, tri or polyfunctional alcohol, such as a 5-alkyl-5-hydroxyalkyl- -1,3-dioxane, a 5,5-dihydroxyalkyl-l,3-dioxane, a 2-alkyl-l,3-propanediol, a 2,2-dialkyl-l,3-propanediol, a 2-hydroxyalkyl-l,3-propanediol, a 2-alkyl-2-hydroxyalkyl- -1,3-propanediol, a 2,2-di(hydroxyalkyl)-l,3-propanediol, a 1,2,3-propanetriol or a dimer, trimer or polymer of any of said alcohols.
  • a mono, di, tri or polyfunctional alcohol such as a 5-alkyl-5-hydroxyalkyl- -1,3-di
  • the core is also suitably an adduct of any of said alcohols, dimers, trimers or polymers and at least one alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide and/or phenylethylene oxide.
  • the branching chain extender of said dendritic or hyperbranched polyester is preferably derived from 2,2-dimethylolpropionic acid, ⁇ , ⁇ -bis(hydroxymethyl)butyric acid, ⁇ , ⁇ , ⁇ -tris(hydroxymethyl)acetic acid, ⁇ , ⁇ -bis(hydroxymethyl)valeric acid, ⁇ , ⁇ -bis(hydroxy)propionic acid, 3,5-dihydroxybenzoic acid, ⁇ , ⁇ -dihydroxypropionic acid, heptonic acid, citric acid, tartaric acid, dihydroxymaloic acid or gluconic acid and the optional spacing chain extender is suitably derived from hydroxyacetic acid, hydroxyvaleric acid, hydroxypropionic acid, hydroxypivalic acid, glycolide, ⁇
  • An optional, and to the allyloxy carboxylic acid additional, chain stopper is preferably selected from the group consisting of mono functional carboxylic acids or, where applicable, anhydrides thereof, glycidyl esters of monofunctional carboxylic acids, glycidyl ethers of monofunctional alcohols, carboxyfunctional esters of di, tri or polyfunctional carboxylic acids or, where applicable, anhydrides thereof, and adducts between at least one allyloxy alcohol and at least one mono, di, tri or polyfunctional carboxylic acid.
  • Said dendron may be prefabricated and by reaction added to said core, or produced by repeated addition of branching and optional spacing chain extenders using a divergent or convergent process.
  • a starbranched polyester is preferably built up from a core derived from a compound having at least three reactive hydroxyl, epoxide, carboxyl or anhydride groups to which core at least three branches are added.
  • the branches comprises at least one generation built up from monomeric or polymeric chain extenders derived from compounds having one reactive hydroxyl group and one reactive carboxyl group. At least one of said branches is chain terminated by addition of said allyloxy carboxylic acid and at least one branch is optionally chain terminated by addition of at least one other chain stopper.
  • Said core is suitably derived from a mono, di, tri or polyfunctional alcohol, such as a 5-alkyl-5-hydroxyalkyl-l,3-dioxane, a 5,5-dihydroxyalkyl-l,3-dioxane, a 2-alkyl-l,3-propanediol, a 2,2-dialkyl-l,3-propanediol, a 2-hydroxyalkyl-l,3-propanediol, a 2-alkyl-2-hydroxyalkyl-l,3-propanediol, a
  • a mono, di, tri or polyfunctional alcohol such as a 5-alkyl-5-hydroxyalkyl-l,3-dioxane, a 5,5-dihydroxyalkyl-l,3-dioxane, a 2-alkyl-l,3-propanediol, a 2,2-dialkyl-l,3-propanedi
  • the core can furthermore be derived from an adduct of any of said alcohols, dimers, trimers or polymers and at least one alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide and/or phenylethylene oxide.
  • the chain extender of said starbranched polyester is preferably derived from a monohydroxy monocarboxylic acid, such as hydroxyacetic acid, hydroxyvaleric acid, hydroxypropionic acid, hydroxypivalic acid or a lactone such as glycolide, ⁇ -valerolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -caprolactone.
  • a monohydroxy monocarboxylic acid such as hydroxyacetic acid, hydroxyvaleric acid, hydroxypropionic acid, hydroxypivalic acid or a lactone such as glycolide, ⁇ -valerolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -caprolactone.
  • suitable chain extenders are derived from alkyl substituted derivatives of said acids and lactones.
  • An optional, and to the allyloxy carboxylic acid additional, chain stopper is preferably selected from the group consisting of monofunctional carboxylic acids or, where applicable, anhydrides thereof, glycidyl esters of monofunctional carboxylic acids, glycidyl ethers of monofunctional alcohols, carboxyfunctional esters of di, tri or polyfunctional carboxylic acids or, where applicable, anhydrides thereof, and adducts between at least one allyloxy alcohol and at least one mono, di, tri or polyfunctional carboxylic acid.
  • a polyol ester is preferably built up from an alcohol having at least one reactive hydroxyl group to which hydroxyl group said allyloxy carboxylic acid is added, optionally in combination with at least one other carboxylic acid, such as a monofunctional carboxylic acid having 1-24 carbon atoms.
  • the alcohol is suitably a mono, di, tri or polyfunctional alcohol, such as a 5-alkyl-5-hydroxyalkyl-l,3-dioxane, a 5,5-dihydroxyalkyl-l,3-dioxane, a 2-alkyl-l,3-propanediol, a 2,2-dialkyl-l,3-propanediol, a 2-hydroxyalkyl-l,3-propanediol, a 2-alkyl-2-hydroxyalkyl-l,3-propanediol, a 2,2-di(hydroxyalkyl)-l,3-propanediol, a 1,2,3-propanetriol or a dimer, trimer or polymer of any of said alcohols.
  • the alcohol can also be an adducts of any of said alcohols, dimers, trimers or polymers and at least one alkylene oxide, such as ethylene oxide, propylene oxide, butylene
  • allyloxy carboxylic acid includes its use in carboxyl functional silicone derivatives, wherein SiH groups, for instance in the presence of a catalyst, are reacted with olefmic unsaturation, such as allyl groups, in oligomeric or polymeric carboxyl functional superabsorbants, and as copolymer in emulsion polymerisation of polymeric binders.
  • Said oligomeric or polymeric compound can advantageously also be a polyolefine, such as polyethylene, polypropylene, polystyren or polyacrylate, comprising said allyloxy carboxylic acid as co-monomer.
  • the allyloxy carboxylic synthesised by the process of the present invention and used as component in above disclosed compounds is in various preferred embodiments an allyloxy propanoic acid, an allyloxy butanoic acid, an allyloxy pentanoic acid, an allyloxy hexanoic acid, an allyloxy heptanoic acid or an alkanyl, alkenyl or alkynyl substituted derivative thereof.
  • the allyloxy carboxylic acid is in the most preferred embodiments 6-allyloxy hexanoic acid.
  • Example 1 refers to the synthesis of allyloxy carboxylic acids from a lactone and an allyl halide, especially synthesis of 6-allyloxy hexanoic acid by reaction with allyl bromide in the alkaline medium potassium hydroxide.
  • Examples 2-4 refer to the use of said 6-allyloxy hexanoic acid as polyester component.
  • Allyoxy carboxylic acids such as 3-allyloxy propanoic acid, 4-allyloxy butanoic acid and 5-allyloxy pentanoic acid are prepared similarly from ⁇ -propiolactone, ⁇ -butyrolactone and ⁇ -valerolactone.
  • the reaction conditions are, however, adjusted to the general properties and reactivity of included reactants and media.
  • the reaction mechanism can be disclosed by below simplified reaction scheme, wherein ⁇ -caprolactone is reacted with allyl chloride in the presence of excess sodium hydroxide, whereby 6-allyloxy hexanoic acid is yielded
  • a hyperbranched polyester was prepared from a core molecule consisting of ethoxylated pentaerythritol and a branching chain extender consisting of 2,2-dimethylolpropionic acid.
  • the polyester was chain terminated with propionic acid and 6-allyloxy hexanoic acid prepared in Example 1.
  • Step 1 308.9 g of pentaerythritol pentaethoxylate (Polyol PP 50, Perstorp Polyols, Sweden), 460.5 g of 2,2-dimethylolpropionic acid (Bis-MPA, Perstorp Polyols, Sweden) and 0.46 g of sulphuric acid (96%-w/w) were charged in a 4-necked reaction flask equipped with stirrer, pressure gauge, cooler and receiver. The temperature was raised to 120°C, at which temperature 2,2-dimethylolpropionic acid began to melt and esterification water was formed. The temperature was now during 20 minutes raised to 140°C, giving a transparent solution, whereby a vacuum of 30-50 mm Hg was applied.
  • Polyol PP 50 Perstorp Polyols, Sweden
  • 2,2-dimethylolpropionic acid Bis-MPA, Perstorp Polyols, Sweden
  • sulphuric acid 96%-w/w
  • the reaction was, under stirring, allowed to continue for 4 hours, after which time the acid value was determined to be 7.0 mg KOH/g. 460.5 g of 2,2-dimethylolpropionic acid and 0.7 g of sulphuric acid (96%-w/w) were now during 15 minutes added to the reaction mixture. A vacuum of 30-50 mm Hg was applied when charged 2,2-dimethylolpropionic acid was dissolved. The reaction was now allowed to continue for a further 4 hours giving a final acid value of « 10 mg KOH/g.
  • Step 2 1185.1 g of the hyperbranched polyester obtained in Step 1, 399.9 g of propionic acid and 75 g of xylene were charged in a 4-necked reaction flask provided with a stirrer, nitrogen inlet, a Dean-Stark receiver and a cooler. The reaction mixture was during 25 minutes heated to 130°C, whereby water began to evaporate. The reaction was allowed to continue at this temperature for 360 minutes until an acid value of 11-12 mg KOH/g was obtained. Xylene was now removed by applying full vacuum during « 20 minutes.
  • Step 3 990.6 g of the partially chain terminated hyperbranched polyester obtained in Step 2, 606.3 g of 6-allyloxy hexanoic acid obtained in Example 1, 128 g hexane, 3.2 g of/?-toloune sulphonic acid, 1.6 g of hydroquinone (10% in ethanol) and 1.6 g calcium hydroxide were charged in a 4-necked reaction flask provided with a stirrer, nitrogen inlet, a Dean-Stark receiver and a cooler. The reaction mixture was during 45 minutes heated to 110°C, whereby water began to evaporate. The reaction was allowed to continue for 17 hours until an acid value of 13-14 mg KOH/g was obtained. The temperature was during the reaction allowed to gradually increase until a temperature of 120°C was obtained after « 8 hours. Finally, heptane was removed by applying full vacuum during « 35 minutes.
  • a hyperbranched polyester was prepared from a core molecule consisting of ethoxylated pentaerythritol and a branching chain extender consisting of 2,2-dimethylolpropionic acid.
  • the polyester was chain terminated with caprylic/capric acid and 6-allyloxy hexanoic acid prepared in Example 1.
  • Step 1 Step 1 of Example 2 was repeated without differences.
  • Step 2 830.0 g of the of the hyperbranched polyester obtained in Step 1, 677.7 g of a mixture of caprylic and capric acid, 2.0 g of calcium hydroxide and 75 g of xylene were charged in a 4-necked reaction flask equipped with stirrer, nitrogen inlet, cooler and water trap (Dean-Stark). The reaction mixture was during 50 minutes heated to 170°C, whereby esterification water began to evaporate. The temperature was now during 120 minutes raised from 170°C to 210°C, giving a temperature gradient of 0.3°C/minute. The esterification was allowed to continue under stirring for 510 minutes until an acid value of ⁇ 6 mg KOH/g was obtained.
  • Step 3 of Example 2 was repeated with the difference that 990.6 g of the partially chain terminated hyperbranched polyester obtained in Step 2 of the present Example was used instead of 990.6 g of the partially chain terminated hyperbranched polyester obtained in Step 2 of Example 2.
  • the final acid value was determined to be 13.9 mg KOH/g.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de fabrication d'acide allyloxy-carboxylique. Le procédé consiste à faire réagir un lactone tel que β-propiolactone, η-butyrolactone, δ-valérolactone, ε-caprolactone, z-énantholactone ou leur dérivé avec au moins un halogénure d'allyle dans un milieu alcalin, avec un taux molaire chargé lactone / halogénure d'allyle 1 à 1 ou plus. Dans ce procédé, le milieu alcalin est présent avec un taux molaire de l'halogénure d'allyle par rapport au milieu alcalin d'1 à 1 ou, de préférence, plus. Dans un autre aspect, la présente invention concerne un acide allyloxy-carboxylique produit par ce procédé. Elle concerne aussi l'utilisation de l'acide allyloxy-carboxylique produit par ce procédé en tant que composant de composés oligomères et polymères tels que résines et liants.
PCT/SE1999/002047 1998-11-20 1999-11-17 Procede de fabrication d'acide allyloxy-carboxylique WO2000031012A1 (fr)

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AU14365/00A AU1436500A (en) 1998-11-20 1999-11-17 Process for production of an allyloxy carboxylic acid

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SE9803965A SE524569C2 (sv) 1998-11-20 1998-11-20 Förfarande för framställning av en allyloxikarboxylsyra, användning av allyoxikarboxylsyran framställd enligt förfarandet som komponent i oligomera och polymera bindemedel samt 6-allyloxihexansyra framställd enligt förfarandet
SE9803965-4 1998-11-20

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN107353414A (zh) * 2017-08-04 2017-11-17 苏州大学 超支化聚己内酯及其制备方法
CN116396015A (zh) * 2022-12-02 2023-07-07 佛山市顺德区和乐商品混凝土有限公司 一种抗裂混凝土及其制备方法

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WO1996012754A1 (fr) * 1994-10-24 1996-05-02 Perstorp Ab Macromolecule a ramification importante du type polyester
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