SE524569C2 - Process for the preparation of an allyloxycarboxylic acid, use of the allyoxycarboxylic acid prepared according to the process as component of oligomeric and polymeric binders, and 6-allyloxyhexanoic acid prepared according to the process - Google Patents

Abstract

A process for production of an allyloxy carboxylic acid. The process comprises reacting a lactone, such as beta -propiolactone, gamma -butyrolactone, delta -valerolactone, epsilon -caprolactone, zeta -enantholactone or a derivative thereof, 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 alkaline medium is in said process present at a molar ratio allyl halide to alkaline medium of 1 to at least 1 or preferably more than 1. In a further aspect, 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 the process as component in oligomeric and polymeric compounds, such as resins and binders.

Description

The production and use of allyloxycarboxylic acids is currently relatively small compared to the corresponding preparation and use of allyloxy alcohols. There is a great need for and after the practice of an expanded product range with allyloxycarboxylic acids and, to satisfy said need and demand, a simplified process for the production of allyloxycarboxylic acids.

Commonly manufactured and used allyl functional compounds based on acids include allyl esters, such as phthalates, carbonates and other carboxylates. These esters are normally made from di-, tri- and polyfurrctional carboxylic acids, such as phthalic, isophthalic, maleic, succinic, citric and itaconic acid, by reaction with an allyl halide, such as allyl chloride, or allyl alcohol.

An allyl halide can be converted to allyl alcohol and thereby used in the preparation of esters.

Allyl ethers of hydroxy-functional carboxylic acids, such as mono- and diallyl ethers of 2,2-dimethylolpropionic acid which are disclosed in Swedish patent no. 502 634, is usually prepared by the williarnson process or similar process, wherein protective chemistry is used to protect the carboxyl group or groups. Protective chemistry must be used in the preparation of allyl ethers of hydroxy-functional carboxylic acids to avoid the formation of allyl esters.

Additional allyl compounds based on carboxylic acids include allyl hydroxy acids. A process for the preparation of ot-allyl-α-hydroxy acids is disclosed in "Palladium-catalyzed allylation of ot-hydroxy acids" published in Recueil des T ravaux Chimique des Pays-Bas, III / 3, March 1992, pages 129-137. Mandelic and lactic acid are here converted to 1,3-dioxolan-4-ones by treatment with acetone dimethyl acetate followed by deprotonation by treatment with allyl acetate and a catalytic amount of a palladium catalyst to give allylated dioxolanones, which are then hydrolyzed to the corresponding ot-allyl or- hydroxy acid.

The present invention relates to allyloxycarboxylic acids prepared by reacting a lactone with at least one allyl halide in an alkaline medium, such as potassium and / or sodium hydroxide or other suitable salt of alkali metal or alkaline earth metal. The term lactone distinguishes the internal mono-, di- or higher esters of hydroxy-functional acids from cyclic esters of diols and carboxyl or carboxylic acids. In preferred embodiments of the present invention, the lactone is β-propiolactone, γ-butyrolactone, β-valerolactone, α-caprolactone,--enantolactone or a derivative of such a lactone wherein one or fl carbon atoms are alkanyl, cycloalkanyl, alkenyl, cycloalkenyl , alkynyl, cycloalkynyl and / or aryl substituted, such as ot-methyl, ß-methyl, ßß-dimethyl- and ß-isopropylpropiolactone and the like or corresponding derivatives of said lactones. Additional lactones and derivatives thereof which may be used in the present invention may include compounds such as glycolide, ot-methylenebutyrolactone, pantolactone, nepetalactone and gluconolactone. Suitable allyl halides are, in likewise preferred embodiments of the present invention, allyl chloride and / or allyl bromide. -CRO-CH2-CH = CH2 (Formula I) wherein R is linear or branched alkanyl, or where so is the applicator path and possibly alkenyl or alkynyl, having 2 to 12 carbon atoms. an allyloxypentanoic acid, an allyloxyhexanoic acid, an allyloxyheptanoic acid, including where applicable alkanyl, alkenyl or alkynyl substituted derivatives of said acids.

The chemistry and properties of lactones and related compounds are described, for example, in the "Encyclopedia of Polymer Science and Technology", John Wiley & Sons Inc., 1969, vol. Ll, pp. 98-106 "Polymerization of Cyclic Esters and Lactones".

The present invention relates in a further aspect to a process for the synthesis of an allyloxycarboxylic acid. The process comprises reacting a lactone in an alkaline medium with at least one allyl halide at a charged molar ratio of lactone to allyl halide of 1 to at least 1, such as at a molar ratio of 1: 1, 1 to 1: 3 or 1: 2. The alkaline medium is present in a molar ratio of allyl halide to alkaline medium of 1 to at least 1, preferably 1 to more than 1 or more preferably more than 2, such as in a molar ratio of 1: 1, 5 to 1: 4 or 1: 3. A suitable alkaline medium is found among, for example, arnines, such as tertiary arnines, and hydroxides or carbonates of alkali metals or alkaline earth metals, such as potassium and / or sodium hydroxide. The reaction is carried out in preferred embodiments at a temperature of 60-150 ° C, such as 80-120 ° C or 90-110 ° C.

The lactone used in the process of the present invention is preferably β-propiolactone, γ-butyrolactone, β-valerolactone,--enantolactone or a derivative of such a lactone wherein one or more carbon atoms are alkanyl, cycloalkanyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl or aryl substituted, such as oL-methyl-, β-methyl, β-dimethyl and β-isopropylpropiolactone and similar derivatives of said lactones. Additional lactones and derivatives thereof which may be used in the process of the present invention may include compounds such as glycolide, ot-methylenebutyrolactone, pantolactone, nepetalactone and gluconolactone. Preferred allyl halides are allyl chloride and / or allyl bromide. 524 569 = The allyloxycarboxylic acid obtained in said process is in preferred embodiments a linear or branched compound having 5-18 carbon atoms, such as a compound of Formula I above. The resulting allyloxycarboxylic acid in particularly preferred embodiments is an allyloxypropanoic acid, an allyloxybutanoic acid, an allyloxypentanoic acid, an allyloxyhexanoic acid, an allyloxyheptanoic acid, including where applicable alkanyl, alkenyl or alkynyl diacid substituents.

The lactone is, in the most preferred embodiments of the process of the present invention, ε-caprolactone wherein the allyloxycarboxylic acid obtained is 6-allyloxyhexanoic acid.

The present invention relates in a further aspect to the use of an allyloxycarboxylic acid as above as a component in oligomeric and polymeric binders, such as common linear or branched esters and polyesters, dendritic or hyperbranched polyesters, star branched polyesters, polyol esters and polyol polyesters, silicone part derivatives and binder compositions.

Dendritic or hyperbranched polyesters are in preferred embodiments mono- or polydisperse macromolecules which are mainly of the type shown in and discussed in Swedish patents 468 771 and 503 342. Said dendritic or hyperbranched polyesters are consequently and preferably built from a core with at least one reactive hydroxyl or epoxide group to which core at least one dendron has been added. The dendron comprises at least one generation which is composed of at least one monomeric or polymeric branching chain extender, having at least two reactive hydroxyl groups and at least one reactive carboxyl group, optionally in combination with at least one extending chain extender having a reactive hydroxyl group and a reactive carboxyl group. The dendron is at least partially chain terminated by the addition of the allyloxycarboxylic acid, optionally in combination with at least one other chain stopper. The core of the dendritic or hyperbranching polyester is in preferred embodiments a mono-, di-, tri- or polyfurectional alcohol, such as a 5-alkyl-5-hydroxyalkyl-1,3-dioxane, a 5,5-di (hydroxyalkyl) -1 , 3-dioxane, and 2-alkyl-1,3-propanediol, and 2,2-dialkyl-1,3-propanediol, and 2-hydroxyalkyl-1,3-propanediol, and 2-alkyl-2-hydroxyalkyl- 1,3-propanediol, a 2,2-di (hydroxyalkyl) -1,3-propanediol, a 1,2,3-propanetriol or a dimer, trimer or polymer of any of the alcohols mentioned.

The core is in further preferred embodiments suitably an adduct 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 the dendritic or hyperbranched polyester is preferably 2,2-dimethylolpropionic acid, own-bis (hydroxymethyl) butyric acid, a, a, oc-tris (hydroxymethyl) acetic acid, a, or-bis (hydroxymethyl) -valeric acid, or, or- bis (hydroxy) propionic acid, 3,5-dihydroxybenzoic acid, oaß-dihydroxypropionic acid, heptonic acid, citric acid, tartaric acid, dihydroxynalonic acid or gluconic acid and the optional extender chain extender is hydroxyacetic acid, hydroxyvaleric acid, hydroxypropionic acid, propionic acid or 524,569 ε-caprolactone. An optional chain stopper, in addition to the allyloxycarboxylic acid, is preferably from the group consisting of monofunctional carboxylic acids or, where applicable, anhydrides thereof, glycidyl esters of monofunctional carboxylic acids, glycidyl ethers of monofunctional alcohols, carboxylic acid or carboxyl functional is applicable, anhydrides thereof and adducts between at least one allyloxy alcohol and at least one mono-, di-, tri- or polyfunctional carboxylic acid.

A star-branched polyester as above is preferably made up of a core with at least three reactive hydroxyl or carboxyl groups to which core at least three branches have been added. The branches comprise at least one generation composed of monomeric or polymeric chain extenders having a reactive hydroxyl group and a reactive carboxyl group. At least one of the branches is chain-terminated by the addition of the allyloxycarboxylic acid and at least one branch is optionally chain-terminated by the addition of at least one other chain stopper. Said core in preferred embodiments is a mono-, di-, tri- or polyfunctional alcohol, such as a 5-alkyl-5-hydroxyalkyl-1,3-dioxane, a 5,5-di (hydroxyalkyl) -1,3-dioxane , and 2-alkyl-1,3-propanediol, and 2,2-dialkyl-1,3-propanediol, and 2-hydroxyalkyl-1β-propanediol, and 2-alkyl-2-hydroxyalkyl-1,3-propanediol, a 2,2-di (hydroxyalkyl) -1,3-propanediol, a 1,2,3-propanetriol or a dimer, trimer or polymer of any of the alcohols mentioned.

The core may in further preferred embodiments suitably be an adduct 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 in the star-branched polyester is preferably a monohydroximonocarboxylic acid, such as hydroxyacetic acid, hydroxyvaleric acid, hydroxypropionic acid, hydroxypivalic acid or a lactone, such as glycolide, β-valerolactone, β-propiolactone, γ-butyrolactone and / or β-butyrolactone. Additional teachable chain extenders are alkyl substituted derivatives of said acids and lactones. An optional chain stopper, in addition to the allyloxycarboxylic acid, is preferably from the group consisting of monofunctional carboxylic acids or, where applicable, anhydrides thereof, glycidyl esters of monofunctional carboxylic acids, glycidyl ethers of monofunctional alcohols or carboxylic acid, tricarboxylic function is 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 as above is preferably composed of an alcohol having at least one reactive hydroxyl group to which the hydroxyl group allyloxycarboxylic acid has been added, optionally in combination with at least one other carboxylic acid, such as a monofunctional carboxylic acid having 1 to 24 carbon atoms. The alcohol in preferred embodiments is a mono-, di-, tri- or polyfunctional alcohol, such as an S-alkyl-S-hydroxyalkyl-1,3-dioxane, a 5,5-di (hydroxyalkyl) -1,3-dioxane, and Z-alkyl-1β-propanediol, and 2,2-dialkyl-1β-propanediol, and 2-hydroxyalkyl-1,3-propanediol, and 2-alkyl-2-hydroxyalkyl-1β-propanediol, and 2,2-di (hydroxy-524 569 j: = ~ j: = = alkyl) -1,3-propanediol, a 1,2,3-propanetriol or a dirner, trimer or polymer of any of said alcohols. The core in further preferred embodiments may suitably be an adduct of proximal alcohols, dimers, trimers or polymers and at least one alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and / or phenylethylene oxide.

Further preferred embodiments include the use of the allyloxycarboxylic acid in carboxylfurictional silicone derivatives, wherein the SiH group, for example in the presence of a catalyst, is reacted with oleic unsaturation, such as allyl groups, in oligomeric or polymeric carboxyl-functional superabsorbents and as a polymer copolymer of emulsion.

The allyloxycarboxylic acid which is used as a component of the above binder is in various preferred embodiments an allyloxypropanoic acid, an allyloxybutanoic acid, an allyloxypentanoic acid, an allyloxyhexanoic acid, an allyloxyheptanoic acid or an alkanyl, alkenyl or alkynyl subunit or alkynyl subunit. The allyloxycarboxylic acid in the most preferred embodiments is 6-allyloxyhexanoic acid.

It is believed, without further explanation, that one skilled in the art may, by the foregoing description, fully practice the present invention. The following preferred embodiments are therefore intended to be illustrative only, without in any way limiting the remaining record.

Examples 1-7 relate to the synthesis of allyloxycarboxylic acids from a lactone and an allyl halide, especially the synthesis of 6-allyloxyhexanoic acid by reaction with allyl bromide in the alkaline medium potassium hydroxide. Examples 2-4 relate to the use of the 6-allyloxyhexanoic acid as the polyester component.

EXAMPLE 1 4.7 moles of ε-caprolactone, 12.8 moles of allyl bromide, 18.5 moles of potassium hydroxide (85% aq) and 8000 ml of toluene were mixed (mechanical stirring) in a reaction flask. The reaction mixture was heated to reflux (z 97 ° C) and kept at reflux (97-100 ° C) for 10 hours. The reaction mixture was now cooled to room temperature. 12000 ml of water were added and the mixture was separated into an organic and an aqueous phase. The aqueous phase was collected and acidified to pH z 2 with SM hydrochloric acid and extracted with a total of 2500 ml of ethyl ether. The ether phase obtained from the extraction was washed with water, dried over sodium sulfate and evaporated on a roller evaporator. . nn n nn nnn n n n n n n n n n n n n n n n n n n n n n n nn nnvn nnnnnnn 702 g of 6-allyloxy hexanoic could e f s filtration collected as a yellowish oily liquid.

The product was determined by 1 H-NMR to be said allyloxycarboxylic acid. Furthermore, the acid number of the obtained 6-allyloxyhexanoic acid was very close to the theoretical acid number for the approximate acid.

Theoretical acid number, mg KOH / g: 324 Analyzed acid number, mg KOI-I / g: 327 Allyloxycarboxylic acids such as β-allyloxypropanoic acid, 4-allyloxybutanoic acid and 5-allyloxypentanoic acid were prepared in a similar manner from β-propiolactol and γ-butyrone. However, the reaction conditions were adjusted to the general properties and reactivity of the reactants and media.

The reaction mechanism can be further demonstrated by the reaction scheme simplified below, wherein ε-caprolactone is reacted with allyl chloride in the presence of an excess of sodium hydroxide to give 6-allyloxyhexanoic acid.

\ / C (š / HHH Excess 0 | | | N OH ll: çck / cfg + c |: = cc |: -ci _-f ___> Nao-c- (cngs-o-cnz-crhcnz + Naci CC 1- 1 H Åh fi h OO H + || ll NaO-C_ (CH2) 5-O-CH2-CH = CH2 _ - _> l-10-C- (CHgk-O-CHg-CH = CH2 EXAMPLE 2 A hyperbranched polyester was prepared from a core 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-allyloxyhexanoic acid prepared in Example 1.

Step 1: 308.9 g pentaerythritol pentaethoxylate (Polyol PP 50 "", Perstorp Polyols, Sweden), 460.5 g 2,2-dimethylolpropionic acid (Bis-MPAT ", Perstorp Polyols, Sweden) and 0.46 g sulfuric acid (96 wt. -%) was charged to a 4-necked reaction flask equipped with a stirrer, pressure gauge, condenser and primer.The temperature was raised to 120 ° C, at which temperature the 2,2-dimethylolpropionic acid began to melt and esterification water was formed.The temperature was now raised for 20 minutes to 140 ° C. C, whereby a transparent solution was obtained, after which a vacuum of 30-50 mm Hg was applied.

The reaction was allowed to proceed with stirring for 4 hours, after which the acid number was determined to be 7.0 e.u. | n n n n n n. s - e ~ -. ... . -. v. . . u .- '7. ». - _. . . - ». - v. .now. -. . e. ... . . -. s e .i n ... »-. . . . . . u u H u .. mg KOH / g. 460.5 g of 2,2-dimethylolpropionic acid and 0.7 g of sulfuric acid (96% by weight) were now charged to the reaction mixture over 15 minutes. A vacuum of 30-50 mm Hg was applied when charged 2,2-dimethylolpropionic acid dissolved. The reaction is now continued for a further 4 hours using a final acid number of 10 mg KOH / g was obtained.

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 to a 4-necked reaction flask equipped with stirrer, nitrogen supply, Dean-Stark publisher and condenser. The reaction mixture was heated to 130 ° C for 25 minutes at which time water began to evaporate. The reaction is continued for 360 minutes at this temperature until an acid value of 11-12 mg KOH / g is obtained. Xylene was driven off by applying full vacuum for z 20 minutes.

Step 3: 990.6 g of the partially chain-terminated hyperbranched polyester obtained in Step 2, 606.3 g of 6-allyloxyhexanoic acid obtained in Example 1, 128 g of heptane, 3.2 g of p-toluenesulfonic acid, 1.6 g of hydroquinone (10% in ethanol) and 1.6 g of calcium hydroxide were charged to a 4-necked reaction flask equipped with a stirrer, nitrogen gasifier, Dean-Stark publisher and condenser. The reaction mixture was heated to 10 ° C for 45 minutes at which time water began to evaporate. The reaction is continued for 17 hours until an acid value of 13-14 mg KOH / g is obtained. The temperature under ck during the reaction gradually rises until a temperature of 120 ° C is obtained after z 8 hours. Finally, the heptane was removed by applying full vacuum for z 35 minutes.

The final acid number was determined to be 13.6 mg KOH / g.

The obtained allyl-functional polyester had a viscosity of 4900 mPas at 23 ° C, which is very and positively low in relation to its high molecular weight.

EXAMPLE 3 A hyperbranched polyester was prepared from a core 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-allyloxyhexanoic acid prepared in Example 1.

Step 1: Step 1 of Example 2 was repeated without differences.

Step 2: 830.0 g of the hyper-branched polyester obtained in Step 1, 667.7 g of caprylic and capric acid, 2.0 g of calcium hydroxide and 75 g of xylene were charged to a 4-necked reaction flask equipped with stirrer, nitrogen supply, condenser and water trap. (Dean-Stark). The reaction mixture was heated to 170 ° C for 50 minutes at which time esterification water began to evaporate. The temperature was now raised for 120 minutes from 170 ° C to 210 ° C, giving a temperature gradient of 524,569 0.3 ° C / minute. The esterification vid and stirring is continued for 510 minutes until an acid value of <6 mg KOH / g is obtained. The xylene was removed by a 20 minute vacuum evaporation.

Step 3: 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 number was determined to be 13.9 mg KOH / g.

EXAMPLE 4 Chain termination of a hydroxyl-functional polyester by addition of 6-allyloxyhexanoic acid obtained in Example 1. 100 g of a polyester having a hydroxyl number of 205 mg KOH / g, 610 g of 6-allyloxyhexanoic acid obtained in Example 1, 130 g hexane, 3.5 g of p-toluenesulfonic acid, 1.6 g of hydroquinone (10% in ethanol) and 1.6 g of calcium hydroxide were charged to a 4-necked reaction flask equipped with a stirrer, nitrogen supply, Dean-Stark publisher and condenser. The reaction mixture was heated to 110 ° C for 60 minutes, at which time water began to evaporate. The temperature was raised slowly to 120 ° C during the reaction. The reaction is continued until an acid value of 13-14 mg KOH / g is obtained.

Finally, heptane was removed by applying full vacuum for z 30 minutes.

Claims (1)

A process for the preparation of an allyloxycarboxylic acid characterized in that the process comprises reaction in an alkaline medium between a lactone and at least one allyl halide at a charged molar ratio of lactone to allyl halide of 1 to at least 1, wherein the the alkaline medium is present at a molar ratio of allyl halide to alkaline medium of 1 to at least 1. Process according to claim 1, characterized in that the molar ratio of lactone to allyl halide is between 1: 1.2 and 1: 3, such as 1: 2. Process according to claim 1 or 2, characterized in that the alkaline medium comprises at least one hydroxide of at least one alkali metal or alkaline earth metal. Process according to claim 3, characterized in that said alkali metal is potassium and / or sodium. Process according to any one of claims 1-4, characterized in that a molar-containing allyl halide to alkaline medium of 1: 1.5 to 1: 4, such as 1: 3. Process according to any one of claims 1-5, characterized in that the reaction takes place at a temperature of 60-150 ° C, such as 80-120 ° C or 90-110 ° C. Process according to any one of claims 1-6, characterized in that the allyl halide is allyl chloride and / or allyl bromide. Process according to any one of claims 1-7, characterized in that the lactone is a β-propiolactone, a γ-butyrolactone, an β-valerolactone, an ε-caprolactone or a--enantolactone. Process according to any one of claims 1-7, characterized in that the lactone is a β-propiolactone, a γ-butyrolactone, an β-valerolactone, an β-caprolactone or a--enantolactone in which one or fl your carbon atoms have alkanyl- , alkenyl and / or alkynyl substituted, such as α-methylpropiolactone, β-methylpropiolactone, β-dimethylpropiolactone or β-isopropylpropiolactone. Process according to any one of claims 1-9, characterized in that the allyloxycarboxylic acid produced is an allyloxypropanoic acid, an allyloxybutyric acid, an allyloxypentanoic acid, an allyloxyhexanoic acid or an allyloxyheptanoic acid. Process according to any one of claims 1-9, characterized in that the allyloxycarboxylic acid produced is an allyloxypropanoic acid, an allyloxybutanoic acid, a, 12. is. 14. 15. 16. 17. 18. 19. 524 569 11 allyloxypentanoic acid, an allyloxyhexanoic acid or an allyloxyheptanoic acid in which one or more carbon atoms have been alkanyl, alkenyl and / or alkynyl substituted. Process according to any one of claims 1-11, characterized in that the lactone is ε-caprolactone, the allyloxycarboxylic acid produced being δ-allyloxyhexanoic acid. Use of an allyloxycarboxylic acid prepared according to any one of claims 1 to 12, wherein the allyloxycarboxylic acid is a component in the preparation of oligomeric and polymeric binders. Use according to claim 13, wherein the binder is an ester or polyester composed of one or more ester units, optionally in combination with one or two ether units. Use according to claim 14, wherein said ester or said polyester is triglyceride and / or fatty acid modified. Use according to any one of claims 13-15, wherein said polyester is a dendritic or hyperiorbranched polyester composed of a core with at least one reactive hydroxyl or epoxide group to which core at least one dendron has been added, which dendron is at least partially chain terminated by addition of the allyloxycarboxylic acid. Use according to claim 16, wherein the core is a mono-, di-, tri- or polyfunctional alcohol such as an S-alkyl-S-hydroxyalkyl-1,3-dioxane, a 5,5-di (hydroxyalkyl) -1,3- dioxane, and Z-alkyl-1β-propanediol, and 2,2-dialkyl-1,3-propanediol, and Z-hydroxyalkyl-1β-propanediol, and Z-alkyl-Z-hydroxyalkyl-1β-propanediol, and 2, 2-di (hydroxyalkyl) -1,1-propanediol or a 1,2,3-propanetriol. Use according to claim 16, wherein the core is a dimer, trimer or polymer of a mono-, di-, tri- or polyfunctional alcohol such as an S-alkyl-S-hydroxyalkyl-1β-dioxane, a 5,5-di (hydroxyalkyl) -1,3-dioxane, and 2-alkyl-1,3-propanediol, and 2,2-dialkyl-1,3-propanediol, and 2-hydroxyalkyl-1,3-propanediol, and Z-alkyl-Z- hydroxyalkyl-1β-propanediol, a 2,2-di (hydroxyalkyl) -1β-propanediol or a 1,2,3-propanetriol. Use according to claim 16, wherein the core is an adduct between a mono-, di-, tri- or polyfunctional alcohol such as an S-alkyl-S-hydroxyalkyl-1,3-dioxane, a 5,5-di (hydroxyalkyl) -1 , 3-dioxane, and 2-alkyl-1,3-propanediol, and 2,2-dialkyl-1,3-propanediol, and Z-hydroxyalkyl-1β-propanediol, and Z-alkyl-Z-hydroxyalkyl-1 , 3-propanediol, a 2,2-di (hydroxyalkyl) -1,3-propanediol, a 1,2,3-propanetriol or a dirner, trimer or polymer of said alcohol and at least one alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide and / or phenylethylene oxide. Use according to any one of claims 16-19, wherein the dendron comprises at least one generation composed of at least one monomeric or polymeric branching chain extender, with at least two reactive hydroxyl groups and at least one reactive carboxyl group, optionally in combination with at least one extending chain extender having a reactive hydroxyl group and a reactive carboxyl group. Use according to claim 20, wherein the branching chain extender is ZJ-dimethylolpropionic acid, α, ot-bis (hydroxymethyl) butyric acid, ot, ot, ot-tris (hydroxymethyl) -acetic acid, ot, cx-bis (hydroxynethyl) valeric acid, ot, oL -bis (hydroxy) propionic acid, 3,5-dihydroxybenzoic acid, β-dihydroxypropionic acid, heptonic acid, citric acid, tartaric acid, dihydroximalonic acid or gluconic acid. Use according to claim 16, wherein the optional extender chain extender is hydroxyacetic acid, hydroxyvaleric acid, hydroxypropionic acid, hydroxypivalic acid, glycolide, γ-butyrolactone, β-propiolactone or ε-caprolactone. Use according to any one of claims 16-22, wherein the dendritic or hyperiorbranched polyester is at least partially chain terminated by the addition of at least one monofunctional carboxylic acid or anhydride, at least one glycidyl ester of a monofunctional carboxylic acid, at least one glycidyl ether of a mono-monofunctional monofunctional di-, tri- or polyfunctional carboxylic acid or anhydride and / or at least one adduct between at least one allyloxy alcohol and at least one mono-, di-, tri- or poly-functional carboxylic acid. Use according to 1 fl of 14, wherein said polyester is a star-branched polyester built from a core with at least three reactive hydroxyl or epoxide groups to which core at least three branches have been added, which branches comprise at least one generation built of monomeric or polymeric chain extenders with a reactive hydroxyl group and a reactive carboxyl group, wherein at least one branch is chain terminated by the addition of the allyloxycarboxylic acid. Use according to claim 24, wherein the core is a mono-, di-, tri- or polyfunctional alcohol such as a 5-alkyl-5-hydroxyalkyl-1,3-dioxane, a 5,5-di (hydroxyalkyl) -1,3- dioxane, and Z-alkyl-1β-propanediol, and 2,2-dialkyl-1,3-propanediol, and Z-hydroxyalkyl-1β- -propanediol, and Z-alkyl-Z-hydroxyalkyl-1,3-propanediol, and 2,2-di (hydroxyalkyl) -1-β-propanediol or a 1,2,3-propanethiol. Use according to claim 24, wherein the core is a dimer, timer or polymer of a mono-, di-, tri- or polyfunctional alcohol such as an S-alkyl-S-hydroxyalkyl-1,3-dioxane, a 5,5-di ( hydroxyalkyl) -1,3-dioxane, and Z-alkyl-1β-propanediol, and 2,2-dialkyl-1,3- 27. 28. 29. 30. 31. 32. 524 569 13 -propanediol, and 2- hydroxyalkyl-1,3-propanediol, a Z-alkyl-Z-hydroxyalkyl-1β-propanediol, a 2,2-di (hydroxyalkyl) -1,3-propanediol or a 1,2,3-propanetriol. Use according to claim 24, wherein the core is an adduct between a mono-, di-, tri- or poly-functional alcohol such as an S-alkyl-S-hydroxyalkyl-1,3-dioxane, a 5,5-di (hydroxyalkyl) -1 , 3-dioxane, and Z-alkyl-1β-propanediol, and 2,2-dialkyl-1,3--propanediol, and Z-hydroxyalkyl-1,3-propanediol, and Z-alkyl-Z-hydroxyalkyl-1β -propanediol, a 2,2-di (hydroxyalkyl) -1,3-propanediol, a 1,2,3-propanethiol or a dimer, trimer or polyurea of said alcohol and at least one alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide and / or phenylethylene oxide. Use according to any one of claims 24-27, wherein the chain extender is hydroxyacetic acid, hydroxyvaleric acid, hydroxypropionic acid, hydroxypivalic acid, glycolide, γ-butyrolactone, β-propiolactone, ε-caprolactone. Use according to any one of claims 24-28, wherein at least one branch of the star-branched polyester is chain terminated by the addition of at least one monofunctional carboxylic acid or anhydride, at least one glycidyl ester of a mono-functional carboxylic acid, at least one glycidyl ether of a mono-functional alcohol and at least one carboxyl-functional di-, tri- or polyfunctional carboxylic acid or anhydride and / or at least one adduct between at least one allyloxy alcohol and at least one mono-, di-, tri- or polyfunctional carboxylic acid. Use according to claim 13, wherein said ester or polyester is an ester or polyester composed of an alcohol having at least one reactive hydroxyl group to which the hydroxyl group allyloxycarboxylic acid has been added, optionally in combination with at least one other carboxylic acid. Use according to claim 30, wherein the alcohol is a mono-, di-, tri- or polyfunctional alcohol such as a 5-alkyl-5-hydroxyalkyl-1,3-dioxane, a 5,5-di (hydroxyalkyl) -1,3- dioxane, and Z-alkyl-1β-propanediol, and 2,2-dialkyl-1,3-propanediol, and 2-hydroxyalkyl-1,3--propanediol, and 2-alkyl-2-hydroxyalkyl-1,3-propanediol , a 2,2-di (hydroxyalkyl) -1-propanediol or a 1,2,3-propanetriol. Use according to claim 30, wherein the alcohol is a dimer, trimer or polymer of a mono-, di-, tri- or polyfunctional alcohol such as a 5-alkyl-5-hydroxyalkyl-1,3-dioxane, a 5,5-di ( hydroxyalkyl) -1,3-dioxane, and Z-alkyl-LB-propanediol, and 2,2-dialkyl-1,3-propanediol, and Z-hydroxyalkyl-1,3-propanediol, and Z-alkyl-Z-hydroxyalkyl 1,3-propanediol, a 2,2-di (hydroxyalkyl) -1β-propanediol or a 1,2,3-propanetriol. Use according to claim 30, wherein the alcohol is an adduct between a mono-, di-, tri- or polymeric alcohol such as an S-alkyl-S-hydroxyalkyl-1,3- dioxane, and 5,5-di (hydroxyalkyl) -1,3-dioxane, and Z-alkyl-1β-propanediol, and 2,2-dialkyl-1,3-propanediol, and Z-hydroxyalkyl-1β-propanediol, a Z-alkyl-Z-hydroxyalkyl--1,3-propanediol, a 2,2-di (hydroxyalkyl) -1,3-propanediol, a 1,2,3-propanetriol or a dimer, trimer or polymer of said alcohol and at least one alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide and / or phenylethylene oxide. Use according to claim 13, wherein the binder is a carboxyl-functional silicone derivative. Use according to claim 13, wherein the binder is a carboxyl functional superabsorbent. Use according to claim 13, wherein the allyloxycarboxylic acid is a copolymer in emulsion polymerization of a polymeric binder. Allyloxycarboxylic acid is characterized in that the allyloxycarboxylic acid is a 6-allyloxyhexanoic acid prepared by the process according to any one of claims 1-7, wherein the lactone is an α-caprolactone.