BR112020009700B1 - FUNCTIONALIZED POLYMERS, THEIR PREPARATION PROCESS, PERSONAL CARE FORMULATION AND USE OF AT LEAST ONE POLYMER - Google Patents

Abstract

The present invention relates to functionalized polymers, a process for producing the functionalized polymers and the use of the functionalized polymers, especially in the field of personal care.

Description

FIELD OF TECHNIQUE

[001] The invention relates to functionalized polymers, a process for producing functionalized polymers and the use of functionalized polymers, especially in the field of personal care.

PREVIOUS TECHNIQUE

[002] US2016250137 describes personal care compositions comprising an oil-in-water emulsion, at least one crystalline polymer with a C12-C22 side chain that contains at least one hydroxyl functional group, wherein the side-chain crystalline polymer has a crystalline melting point from 40 to 70 °C; and at least one active compound that interacts with the skin, wherein the active compound is incorporated into a crystalline matrix of the side-chain crystalline polymer, and wherein the active ingredient is released from the crystalline matrix at body temperatures, wherein the Personal care composition is devoid of sunscreen active ingredients.

[003] It is an objective of the invention to provide functionalized polymers with supreme properties in personal care applications.

DETAILED DESCRIPTION OF THE INVENTION

[004] It has been discovered that, surprisingly, the polymers according to claim 1 exhibit supreme properties in personal care applications.

[005] The present invention therefore provides special polymers, which are characterized in that the polymer has an average molecular weight in Mn number in the range of 2,000 to 9,000 g/mol.

[006] The invention further provides a process for producing polymers, as well as personal care formulations containing certain polymers.

[007] An advantage of the current invention is that the polymers lead to a more pleasant skin sensation.

[008] Another advantage of the current invention is that the polymers obtain a lot of water resistance in sunscreen formulations.

[009] An additional advantage of the current invention is that the polymers offer excellent compatibility with organic UV filters.

[010] An additional advantage of the current invention is that polymers are easier to formulate.

[011] An additional advantage of the current invention is that the polymers achieve good pigment dispersion.

[012] Additionally, the present invention leads to greater fragrance retention capacity in hair from personal care formulations.

[013] The polymers of the present invention, the process of the present invention, the preparations obtained with them and their use will now be described by way of example, without any intention of restricting the invention to those exemplary modalities. Where ranges, general formulas or classes of compounds are cited hereinafter, these may include not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds obtained by removing individual values (ranges) or compounds. Where documents are cited in the context of the present description, their contents may completely constitute part of the content of the description of the present invention.

[014] “Natural numbers”, as used in the present invention, do not include 0 (zero).

[015] Unless otherwise stated, all percentages (%) provided are percentages by weight.

[016] Unless otherwise stated, all ppm provided are ppm by weight.

[017] Viscosity values cited in the context of this invention should be understood as meaning, unless otherwise stated, dynamic viscosities that can be determined using methods familiar to those skilled in the art. The measurements cited here below were determined at a pressure of 101325 Pa, and a temperature of 23 °C, unless otherwise stated.

[018] A polymer comprising monomeric units of general formula (I) is claimed. general formula (I) with R1 = independently of each other selected from the group consisting of alkyl radicals and alkenyl radicals, which may be either branched or straight chain, unsubstituted or substituted, especially substituted by hydroxyl groups, R2 = independently each other selected from the group consisting of hydroxycarbyl radicals substituted by hydroxyl, preferably alkyl radicals, having 1 to 10, preferably 2 to 6, more preferably 2 to 4, carbon atoms, and R3 and R4 = independently of each other are selected from the group consisting of H and methyl, preferably H, with the monomeric units of general formula (I) constituting at least 90% by weight, preferably 95% by weight, of the total weight of the polymer, with at least 90% by weight of all R1 being selected from the group of alkyl and alkenyl radicals having 6 to 32, preferably 10 to 26, more preferably 12 to 22, carbon atoms, with the % by weight referring to the sum of all R1 present in the polymer, and with the weight ratio of the sum of all units carrying R2 to the sum of all units carrying R1 being in the range of 1:100 to 1:0.5, preferably 1:60 to 1:0.8, more preferably 1:30 to 1:1, characterized in that the polymer has an average molecular weight in Mn number in the range of 2,000 to 9,000, preferably 5,000 to 8,500, more preferably 6,000 to 8,000, g/mol.

[019] It is obvious from the above that R1, in the context of the present invention, does not include the groups defined by R2.

[020] The polymers according to the invention are copolymers, including random copolymers, graft copolymers and block copolymers.

[021] Preferably, the polymer according to the present invention consists of monomeric units of general formula (I).

[022] At least 90% by weight of all R1 can be mixtures, of course, and it is preferable that at least 90% by weight of all R1 contains a mixture of 0% by weight - 5% by weight cetyl, 40 % by weight - 55 % by weight stearyl, 1 % by weight - 15 % by weight arachidyl, 35 % by weight - 45 % by weight berenyl and 0 % by weight to 5 % by weight lignoceryl, the % by weight weight referring to the sum of all R1 present in the polymer.

[023] It is alternatively preferable that at least 90% by weight of all R1 contains a mixture of 0% by weight - 3% by weight myristyl, 40% by weight - 50% by weight cetyl, 40% by weight - 50 wt% stearyl and 0 wt% - 1 wt% arachidyl, the wt% referring to the sum of all R1 present in the polymer.

[024] At least 90% by weight of all R1 is preferably selected from the group of linear alkyl and alkenyl radicals with 12 to 22 carbon atoms, with stearyl and berenyl especially preferred.

[025] R2, independently of each other, is preferably selected from the group consisting of 2-hydroxy-ethyl, 2-hydroxy-propyl, 2-hydroxy-1-methylethyl, 4-hydroxy-butyl, 2-hydroxy- 3-phenoxypropyl and 2,3-dihydroxypropyl, with 2-hydroxyethyl being especially preferred.

[026] Preferably, the polymer according to the present invention is characterized in that the polymer has a melting point in the range of 41 °C to 69 °C, preferably 44 °C to 68 °C, more preferably 62 °C to 67 °C. °C.

[027] Preferably, the polymer according to the present invention is characterized in that the polymer has a weight-average molecular weight Mw in the range of 10,000 to 500,000, preferably 12,000 to 250,000, more preferably 15,000 to 150,000 g/mol.

[028] Preferably, the polymer according to the present invention is characterized in that the polymer has a ratio of weight-average molecular weight Mw to number-average molecular weight Mn in the range of 0.1 to 3.6, preferably 0.5 to 3.5, more preferably 2.3 to 3.3.

[029] Alternatively preferred, the polymer according to the present invention is characterized in that the polymer has a ratio of weight average molecular weight Mw to number average molecular weight Mn in the range of 8 to 100, preferably 10 to 80, more preferably 12 to 50.

[030] Preferably, the polymer according to the present invention is characterized by R1 = independently of each other selected from the group consisting of stearyl and berenyl, R2 = selected from the group consisting of 2-hydroxy-ethyl, 2-hydroxy-propyl, 2-hydroxy-1-methylethyl, 4-hydroxy-butyl, 2-hydroxy-3-phenoxypropyl and 2,3-dihydroxypropyl, with 2-hydroxy-ethyl being especially preferred, R3 and R4 = H.

[031] The polymers of the present invention are obtained in several ways. The polymers of the present invention are preferably obtained by the process of the present invention described below. Therefore, a process for preparing a polymer is claimed comprising the steps of A) providing a monomer (1) of general formula (II) and a monomer (2) of general formula (III) with R1A = independently of each other selected from the group consisting of alkyl radicals and alkenyl radicals, which may be either branched or straight chain, unsubstituted or substituted, especially substituted by hydroxyl groups, R2A = independently of each other selected from from the group consisting of hydroxycarbyl radicals substituted by hydroxyl, preferably alkyl radicals, having 1 to 10, preferably 2 to 6, more preferably 2 to 4, carbon atoms, R3A and R4A = independently of each other selected from the group that consists of H and methyl, preferably H, and with at least 90% by weight of all R1A are selected from the group of alkyl and alkenyl radicals having 6 to 32, preferably 10 to 26, more preferably 12 to 22, carbon atoms, with the weight % referring to the sum of all R1A present in the polymer, and a weight ratio of monomer (1) to monomer (2) in the range of 1:100 to 1:0.5, preferably 1:60 to 1: 0.8, more preferably 1:30 to 1:1, B) adding at least one initiator to polymerize the monomers and carry out a radical polymerization, optionally C) removing excess monomers and, optionally, D) purifying the polymer obtained , characterized in that the at least one initiator is added in an amount of 5 to 20,000 ppm, preferably 50 to 10,000 ppm, more preferably 100 to 5000 ppm, wherein the ppm refers to the total weight of the sum of all monomers (1 ) and (2) provided in step A) of the process.

[032] It is obvious from the above that R1A in the context of the present invention does not include the groups defined by R2A.

[033] R1A, preferably, is independently selected from the group consisting of alkyl radicals and unsubstituted alkenyl radicals.

[034] R2A independently of each other are preferably selected from the group consisting of 2-hydroxy-ethyl, 2-hydroxy-propyl, 2-hydroxy-1-methylethyl, 4-hydroxy-butyl, 2-hydroxy-3-phenoxypropyl and 2,3-dihydroxypropyl, with 2-hydroxyethyl being especially preferred.

[035] The initiator added in step B) of the process, according to the present invention, is an initiator that can be solid, liquid or dissolved in a solvent.

[036] The initiator added in step B) of the process, according to the present invention, is preferably selected from the group of 2,2'-azo-bis(2-methyl propionitrile), 2,2'-azodi( 2-methylbutyronitrile), 1,1'-azodi(hexahydrobenzonitrile), 4,4'-azo-bis(4-cyanovaleric acid), 2,2'-azo-bis(2,4-dimethyl valeronitrile), and 2,2'-azo-bis(2-cyclopropyl propionitrile), 2,2'-azo-bis(2-cyclobutyl propionitrile), 2,2'-azo-bis(2-cyclobutyl propionitrile), 2,2'- azo-bis(2,4-dimethyl valeronitrile), 1,1'-azo-bis(1-cycloheptanenitrile), 2,2'-azo-bis(methyleptilonitrile), 2,2'-azo-bis(2-cyclohexyl propionitrile), azo-bis-isobutyramidine 2HCl, phenyl-azo-triphenylmethane, 4-hydroxyphenyl-azo-triphenylmethane, peroxide and peroxy compounds such as benzoyl peroxide, tert-butyl peroxy pivalate, tert-amyl peroxypivalate, acetyl peroxide, propionyl peroxide , 2-isopropionyl peroxide, butyryl peroxide, diisobutyryl peroxide, dilauroyl peroxide, didecanoyl peroxide, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxineodecanoate, tert-butyl peroxydiethylacetate, tert-amyl peroxy-2-ethylexanoate, tert- amyl peroxy-2-ethylhexanoate, 2-methoxybenzoyl peroxide, cumyl peroxyneoheptanoate, tert-amyl peroxineodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyneoheptanoate, tert-amyl peroxyacetate, 4-benzylidenebutyryl peroxide, methyl phthaloyl peroxide, 1, 1-di(tert-amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxane, hydroperoxides such as isopropylcumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide , cumyl hydroperoxide, tert-Butyl hydroperoxide, tert-amyl hydroperoxide, carbonates such as diethyl peroxydicarbonate, tert-butylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-tert- butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dimyrysyl peroxydicarbonate, tert-amylperoxy 2-ethylhexyl carbonate, tert-butylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, ethyl tert-butyl peroxalate; benzyl (tert-butyl peroxy) oxalate; tertiary-butyl-N-(3-tolylperoxy) carbamate and persalt compounds, such as potassium persulfate and mixtures thereof, wherein 2,2'-azo-bis(2-methyl propionitrile), 2,2'-azodi (2-methylbutyronitrile), dilauroyl peroxide, cumyl peroxyneodecanoate, tert-amyl peroxy-2-ethylexanoate, tert-amyl peroxy-2-ethylexanoate are especially preferred.

[037] Step B) of the process, in the process according to the present invention, is conducted in pure form or in a solvent, preferably in solvent. The amount of solvent can vary from 1 to 95%, preferably from 5 to 50%, more preferably from 10 to 40%, where the weight percentage refers to the total weight of the sum of all monomers (1) and (2 ) provided in step A) of the process.

[038] Possible solvents may be, but are not limited to: alcohols of the type methanol, ethanol, isopropanol, butanol, hexanol, tert-butanol, isoamyl alcohol, glycol, hexylene glycol, propylene glycol, butyl glycol, butyldiglycol, glycerin, ketones such as ethylmethyl ketone , methylbutyl ketone, acetone, methyl acetate-type ester, ethyl acetate, isopropylacetate, propyl acetate, butyl acetate, hexyl acetate, isooctyl acetate, methoxypropylacetate, acids such as formic acid, acetic acid, propionic acid, ether such as diethyl ether, dibutyl ether, tert-butyl methyl ether , petroleum ether, tetrahydrofuran, dioxane, polyethers, carbonates such as ethylenecarbonate, propylenecarbonate, dimethylcarbonate, diethylcarbonate, dipropylcarbonate, nitriles such as benzonitrile, acetonitrile, toluene, xylene, ionic liquids, water, organic oils such as TEGOSOFT®, types and mixtures thereof.

[039] In process step B, in the process according to the present invention, at least one chain transfer agent may be present, preferably in an amount such that the weight ratio of the initiator added in process step B and chain transfer agent is in the range of 1:20 to 1:0.1, preferably 1:10 to 1:1.

[040] The chain transfer agent preferably present in step B of the process, in the process according to the present invention, is selected from at least one of the group of tetrachloromethane, bromotrichloromethane, Isooctyl 3-mercaptopropionate, 4-methylbenzenethiol, tert-nonyl mercaptan, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 4,4-thiobisbenzenethiol, trimethylolpropane tris(3-mercaptopropionate), 1,8-dimercapto-3,6-dioxaoctane, n-dodecanethiol , ethyl mercaptan, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptohexanol, mercaptooctanol, propanethiol, dithiothreitol, cysteine, homocysteine, glutathione, tert-dodecanethiol, thioglycolic acid, dimercaptosuccinic acid, 2,3-dimercapto-1-propanesulfonic acid, acetylcysteine and thiophenol.

[041] In an alternative process, according to the present invention, no chain transfer agent is present in the process.

[042] Step B of the process, in the process according to the present invention, is preferably conducted at a temperature of 10 °C to 250 °C, preferably of 20 °C to 200 °C and more preferably of 60 °C to 180°C.

[043] Process step B, in the process according to the present invention, is preferably conducted at a pressure of 0.5 to 20 bar, more preferably 1 to 5 bar, and even more preferably at atmospheric pressure.

[044] Step B of the process, in the process according to the present invention, is preferably conducted at a pH of 3 to 10, more preferably 4 to 9, and even more preferably 5 to 8.

[045] Step B of the process, in the process according to the present invention, can preferably be conducted not only in daylight, but also in the absence of light, and is preferably conducted in the absence of light.

[046] Step C) of the process, in the process according to the present invention, has the purpose of removing excess monomers. Therefore, step C) in the process according to the present invention is a search step, with the addition of more initiator after the completion of step B of the process, in order to remove excess monomer. The additional initiator is preferably applied in concentrations of 0.01% to 5%, preferably 0.1 to 2.5%, more preferably 0.2% to 2%, wherein the weight percentage refers to the total weight of the sum of all monomers (1) and (2) provided in step A) of the process.

[047] Process step D) in the process according to the present invention may be water vapor distillation. Here, some water is applied to the solution in order to remove excess monomers from the reaction. The amount of water added can vary from 0.1 to 20%, preferably 0.5 to 10%, more preferably 1% to 5%, wherein the weight percentage refers to the total weight of the sum of all monomers (1 ) and (2) provided in step A) of the process.

[048] Additional cleaning steps D) in the process according to the present invention may be an extraction with water and/or organic solvents, a distillation with or without vacuum, and/or recrystallization with water and/or organic solvents .

[049] Either a search step or a water vapor distillation can both be applied in step C) of the process).

[050] An additional subject matter of the present invention is a polymer obtained by the process of the present invention. The polymer obtained by this process is preferably characterized by having an average molecular weight in Mn number in the range of 2,000 to 9,000 g/mol.

[051] An additional subject matter of the present invention is a personal care formulation containing at least one polymer of the present invention, or at least one polymer obtained by the process of the present invention.

[052] Furthermore, the formulations according to the invention may comprise at least one additional component selected from the group of emollients, emulsifiers, thickeners/viscosity regulators/stabilizers, UV photoprotective filters, antioxidants, hydrotropes (or polyols) , solids and fillers, film formers, pearlescent additives, deodorant and antiperspirant active ingredients, insect repellents, self-tanning agents, preservatives, conditioners, perfumes, dyes, odor absorbers, cosmetic active ingredients, care additives, excessively fatty agents , solid particles, solvents, in which perfumes, solid particles and/or photoprotective UV filters, especially organic filters, are preferably comprised.

[053] The solid particles preferably comprised are characterized by having an average particle size d50 of 0.1 to 1,000 μm.

[054] The average particle size d50 is preferably determined by scattering light in a laser beam with a Malvern Mastersizer 2000. The determination is carried out using dry measurement. Each time 20 to 40 g of powder is fed using a Scirocco dry powder feeder. Particle flow is controlled by operating the vibrating tray at a 70% feed rate. The dispersed air pressure is set to be 3 bar. Each measurement is accompanied by a background measurement (10 seconds / 10,000 single measurements). Sample measurement time is 5 seconds (5,000 single measurements). The refractive index as well as the blue light value are fixed to be 1.52. The evaluation is carried out using Mie theory.

[055] The substances that can be used as exemplary representatives of the individual groups, to be comprised in the formulation according to the invention, are known to those skilled in the art and can be found, for example, in the German application DE 102008001788.4. This patent application is incorporated herein by reference, and thus forms part of the specification.

[056] With regard to the additional optional components and the quantities of these components used, reference is expressly made to the relevant manuals known to those skilled in the art, for example, K. Schrader, “Grundlagen und Rezepturen der Kosmetika [Fundamentals and Formulations of Cosmetics ]”, 2nd edition, pages 329 to 341, Hüthig Buch Verlag Heidelberg.

[057] The quantities of the respective additives depend on the intended use.

[058] Typical guide formulations for the respective applications are known in the prior art and are contained, for example, in the manufacturers' brochures of the respective base materials and active ingredients. These existing formulations can generally be adopted unchanged. If required, however, the desired modifications can be accepted without complication, through simple experiments, for the purposes of adaptation and optimization.

[059] It is also immediately claimed to use at least one polymer of the present invention, or at least one polymer obtained by the process of the present invention, to form a film on a surface, especially skin and/or hair.

[060] It is also immediately claimed to use at least one polymer of the present invention, or at least one polymer obtained by the process of the present invention, to maintain a fragrance on a surface, especially skin and/or hair.

[061] It is also immediately claimed to use at least one polymer of the present invention, or at least one polymer obtained by the process of the present invention, to provide a dry skin sensation to formulations, especially emulsions.

[062] The use of at least one polymer of the present invention, or at least one polymer obtained by the process of the present invention, for the dispersion of solid pigments is also immediately claimed. Solid pigments are those preferably included in the formulation according to the present invention.

[063] Two or more polymers according to the invention can be used together.

[064] The examples adduced hereinafter describe the present invention by way of example, without any intention that the invention, the scope of which is evident from the full description and claims, is restricted to the embodiments specified in the examples.

EXAMPLES DETERMINATION OF MOLECULAR WEIGHT BY GEL PERMEATION CHROMATOGRAPHY (GPC):

[065] GPC can be used to enable the identification of the molecular weight of the polymer.

[066] The sample was prepared by making a 10 mg/mL solution that uses tetrahydrofuran as the diluent. The sample preparation was placed in the oven at 54°C for ten minutes, then on a pulse action shaker for 60 minutes to aid dissolution. Upon visual inspection, the sample appeared to be completely dissolved in the diluent. The prepared sample was analyzed using two PolyPore 300 x 7.5 mm columns (manufactured by Agilent Technologies), a Waters 2695 chromatographic system, tetrahydrofuran mobile phase, and refractive index detection. The sample was filtered through 0.45 um nylon filters before injection into liquid chromatography.

[067] The standards used for calibration are EasiVial narrow polystyrene (PS) standards from Agilent Technologies. Narrow polystyrene standards ranging from 2,520,000 to 162 Daltons were used for calibration. The system uses a PSS SECcurity 1260 RI detector. The PS calibration curve is used to determine molecular weight averages. The recording of diagrams and the determination of different molecular weights is carried out by the Win GPC Unichrom 8.1 software.

DETERMINATION OF THE MELTING POINT BY DSC:

[068] This method describes a generalized procedure for determining the melting temperatures of polymers by differential scanning calorimetry (DSC). The method was based on ASTM E7941 and ASTM D 34182. DSC calibration is performed in accordance with ASTM E 9672.

CHEMICALS:

[069] Berrenyl acrylate (abcr) Stearyl acrylate (abcr) Hexadecyl methacrylate (abcr) 2-hydroxyethyl acrylate (BASF) 4-hydroxybutyl acrylate (BASF) Mercaptoethanol (abcr) Isopropyl alcohol (Aldrich) 2,2'-Azodi(2- methylbutyronitrile) (AMBN) (Akzo Nobel) Dilauroyl peroxide (Akzo Nobel) Deionized water EXAMPLE 1:

[070] 175 g of berrenyl acrylate, 25 g of 2-hydroxyethyl acrylate and 0.4 g of AMBN were added in 60 minutes at 80 ° C, in a four-necked flask filled with 40 g of isopropanol, equipped with a stirrer. KPG blade, an internal thermometer, two funnels with tap, reflux condenser and an extension for two more necks, in agitation, after oxygen is removed from the system through nitrogen purge for about 20 minutes. The mixture was stirred at 80 °C for another 3 hours. Subsequently, the solvent was removed by vacuum distillation (<100 mbar), followed by the addition of 1 g of dilauroyl peroxide and reaction for 60 minutes at 110 °C. This step was repeated. The batch is then cooled to 90°C and a dose of deionized water is introduced and thoroughly mixed. The water is finally removed by vacuum distillation. Mn = 7,300 g/mol, Mw = 21,000, Mw/Mn = 2.8 Tm = 65 °C EXAMPLE 2:

[071] 155 g of stearyl acrylate, 45 g of 2-hydroxyethyl acrylate and 0.4 g of AMBN were added in 90 minutes at 80 ° C, in a four-necked flask filled with 50 g of isopropanol, equipped with a stirrer. KPG blade, an internal thermometer, two funnels with tap, reflux condenser and an extension for two more necks, in agitation, after oxygen is removed from the system through nitrogen purge for about 20 minutes. The mixture was stirred at 80 °C for another 3 hours. Subsequently, the solvent was removed by vacuum distillation (<100 mbar), followed by the addition of 1g of dilauroyl peroxide and reaction for 60 minutes at 125 °C. This step was repeated. The batch is then cooled to 90°C and a dose of deionized water is introduced and thoroughly mixed. The water is finally removed by vacuum distillation. Mn = 7,500 g/mol, Mw = 19,000, Mw/Mn = 2.6 Tm = 49 °C EXAMPLE 3:

[072] 135 g of Berrenyl acrylate, 65 g of 2-hydroxyethyl acrylate and 0.4 g of AMBN were added in 90 minutes at 80 ° C, in a four-necked flask filled with 50 g of isopropanol, equipped with a stirrer. KPG blade, an internal thermometer, two funnels with tap, reflux condenser and an extension for two more necks, in agitation, after oxygen is removed from the system through nitrogen purge for about 20 minutes. The mixture was stirred at 80 °C for another 3 hours. Subsequently, the solvent was removed by vacuum distillation (<100 mbar), followed by the addition of dilauroyl peroxide and reaction for 60 minutes at 125 °C. This step was repeated. The batch is then cooled to 90 °C and a dose of deionized water is introduced. The water is removed by vacuum distillation. Mn = 7,800 g/mol, Mw = 23,000, Mw/Mn = 3.1 Tm = 63 °C EXAMPLE 4:

[073] 135 g of Berrenyl acrylate, 65 g of 4-hydroxybutyl acrylate and 0.4 g of AMBN were added in 90 minutes at 80 ° C, in a four-neck flask filled with 50 g of isopropanol, equipped with a stirrer. KPG blade, an internal thermometer, two funnels with tap, reflux condenser and an extension for two more necks, in agitation, after oxygen is removed from the system through nitrogen purge for about 20 minutes. The mixture was stirred at 80 °C for another 3 hours. Subsequently, the solvent was removed by vacuum distillation (<100 mbar), followed by the addition of dilauroyl peroxide and reaction for 60 minutes at 125 °C. This step was repeated. The batch is then cooled to 90 °C and a dose of deionized water is introduced. The water is removed by vacuum distillation. Mn = 8,100 g/mol, Mw = 25,000, Mw/Mn = 3.2 Tm = 62 °C EXAMPLE 5:

[074] 155 g of Hexadecyl methacrylate, 45 g of 2-hydroxyethyl methacrylate and 0.4 g of AMBN were added in 90 minutes at 80 ° C, in a four-neck flask filled with 50 g of isopropanol, equipped with a stirrer. KPG blade, an internal thermometer, two funnels with tap, reflux condenser and an extension for two more necks, in agitation, after oxygen is removed from the system through nitrogen purge for about 20 minutes. The mixture was stirred at 80 °C for another 3 hours. Subsequently, the solvent was removed by vacuum distillation (<100 mbar), followed by the addition of dilauroyl peroxide and reaction for 60 minutes at 125 °C. This step was repeated. The batch is then cooled to 90 °C and a dose of deionized water is introduced. The water is removed by vacuum distillation. Mn = 7,400 g/mol, Mw = 18,000, Mw/Mn = 2.9 Tm = 25 °C COMPARATIVE EXAMPLE:

[075] This example corresponds to US2016250137. To a resin boiler, equipped with an overhead stirrer and condenser, 16 g of stearyl acrylate, 4 g of hydroxyethyl acrylate and 0.07 g of mercaptoethanol were added. The mixture in the resin boiler was heated to 110 °C, and oxygen was removed from the system by means of nitrogen purging for about 30 minutes, followed by the addition of 0.35 g of t-amylperoxy 2-ethylhexanoate. After allowing sufficient time for any initial exotherm to subside, 64 g of stearyl acrylate, 16 g of hydroxyethyl acrylate, 0.28 g of mercaptoethanol, and 1.38 g of were pumped into the reaction vessel for 60 to 90 minutes. The polymer mixture continued to react naturally for another 60 minutes, followed by the addition of 0.7 g of t-butylperoxybenzoate and reaction for 60 minutes. The mixture was then placed under reduced pressure for 60 minutes to remove volatile residues. Mn = 51,000 g/mol Mw = 220,000 Mw/Mn = 3.5 Tm = 48 °C

[076] All concentrations in the application examples are provided in percentage by weight. Common homogenization processes known to those skilled in the art were used to produce the emulsions. Emulsions, therefore, were typically produced by heating the oil phase and water phase to 70-75 °C. Subsequently, both the oil phase was stirred in the water, and the oil phase and water phase were combined without stirring. The mixture was then homogenized using a suitable homogenizer (e.g. Ultraturrax) for about 1-2 minutes. The stabilizing polymers (e.g. carbomers) are preferably stirred in the emulsion as an oil suspension at temperatures of 50-60 °C. The mixture is then briefly homogenized. The addition of further ingredients (e.g. preservatives, active ingredients) was preferably carried out at 40 °C. If the formulations were preserved with organic acids, the pH of the emulsions was adjusted to about 5. If the formulations contained water-soluble organic sunscreens, the pH of the emulsions was adjusted to about 6.5-7.0. APPLICATION EXAMPLE 1: SENSORY EVALUATION OF COSMETIC FORMULATIONS CONTAINING ORGANIC POLYMER ACCORDING TO THE CURRENT INVENTION, COMPARED TO ORGANIC POLYMERS NOT ACCORDING TO THE CURRENT INVENTION

[077] It was observed that organic polymers functionalized with hydroxyl, according to the current invention, present advantages in relation to sensation on the skin. To illustrate the effect, oil-in-water (O/W) sun care emulsions according to the following table were prepared on a 200 g scale. An organic polymer-free carrier formulation was prepared for reference. Another film-forming organic polymer, based on alternative chemistry (VP/eicosene copolymer), was also used as a representative organic polymer based on the prior art.

[078] The skin feel of the emulsions was evaluated by the panel test

[079] In comparison, the vehicle formulation (formulation 1) was rated as the oiliest, least waxy and most slippery formulation (average rating 5.0). This feeling of oily, slippery skin was somewhat reduced when VP/eicosene copolymer was added (average rating 3.7). Likewise, with organic polymer according to comparative example the skin sensation was additionally improved (average rating 2.3). However, when organic polymers according to example 1 and 2 were used, the skin feeling was particularly accepted as dry (average rating 1.2 and 1.8).

[080] This experiment clearly showed that organic polymers according to the invention have more pronounced “dry feeling” properties, which make them more ideally suited for sun care applications, among others. APPLICATION EXAMPLE 2: WATER RESISTANCE TESTING OF COSMETIC FORMULATIONS CONTAINING ORGANIC POLYMER ACCORDING TO THE CURRENT INVENTION COMPARED TO ORGANIC POLYMERS NOT ACCORDING TO THE CURRENT INVENTION

[081] It was observed that hydroxyl-functionalized organic polymers, according to the current invention, present better film-forming properties, compared to non-inventive organic polymers. To illustrate the effect, oil-in-water (O/W) sun care emulsions according to the following table were prepared on a 200 g scale. An organic polymer-free carrier formulation was prepared for reference.

[082] Two μL/cm2 of emulsion were applied to the skin in vitro (VITRO-SKIN®, IMS Inc.) and left until dry. A sun protection factor (SPF) water resistance test was performed. First, in vitro skin SPF was determined using a Labsphere UV-1000 ultraviolet transmittance analyzer. The in vitro skin was then immersed in a water bath. The water was stirred using a hot plate and magnetic stir bar for 80 minutes at 300 rpm and 40 °C. The skin was removed from the water bath, allowed to dry, and the SPF was determined again. The percentage loss of SPF (SPF after water immersion compared to SPF before water immersion) is summarized in the following table.

[083] Interestingly, the emulsion with organic polymer according to comparative example (formulation 4) showed a greater reduction in the SPF value after immersion in water, compared to the emulsion with organic polymer according to example 1 and 2 (

[084] Although the molecular weight of organic polymer according to the comparative example is greater, the loss of SPF is also greater. This indicates weaker film-forming properties, which may be due to a weaker interaction of organic polymer according to the comparative example with organic UV filters, than organic polymers according to the invention. APPLICATION EXAMPLE 3: SUN PROTECTION FACTOR (SPF) TESTING OF COSMETIC FORMULATIONS CONTAINING ORGANIC POLYMER IN ACCORDANCE WITH THE CURRENT INVENTION, COMPARED TO ORGANIC POLYMERS NOT IN ACCORDANCE WITH THE CURRENT INVENTION

[085] It is observed that hydroxyl-functionalized organic polymers, according to the current invention, show better compatibility with organic UV filters, compared to non-inventive organic polymers. To illustrate the effect, oil-in-water (O/W) sun care emulsions according to the following table were prepared on a 200 g scale. An organic polymer-free carrier formulation was prepared for reference. Another film-forming organic polymer, based on alternative chemistry (VP/eicosene copolymer), was used as a common reference and representative of the organic polymer based on the prior art.

[086] One mg/cm2 of emulsion was applied to polymethylmethacrylate (PMMA) plates (7.0 x 3.5 cm, roughness 2 μm, Schonberg GmbH & Co. KG) and left until dry. A sun protection factor (SPF) test was conducted using a Labsphere UV-2000S ultraviolet transmittance analyzer. The SPF efficiency (SPF / % of sunscreen used) of the individual formulations is summarized in the following table.

[087] The carrier formulation (formulation 1) yielded an SPF efficiency of 2.0, which increased if organic polymer was used, which may have contributed mainly to the interaction of organic polymer with organic UV filter. The commonly used reference VP/eicosene copolymer (formulation 5) increased the SPF efficiency to 2.3, which was identical to the effect of the organic polymer, according to comparative example (formulation 4). Interestingly, emulsions with organic polymer, according to example 1 and 2 (formulations 2 and 3), increased the SPF efficiency beyond 2.6 and 2.5, respectively. This effect indicates an even stronger interaction of organic polymer according to the current invention with organic UV filters, compared to non-inventive organic polymers. APPLICATION EXAMPLE 4: PROCESSING OF COSMETIC FORMULATIONS CONTAINING ORGANIC POLYMER ACCORDING TO THE CURRENT INVENTION COMPARED TO ORGANIC POLYMERS NOT ACCORDING TO THE CURRENT INVENTION

[088] It was observed that hydroxyl-functionalized organic polymers, according to the current invention, present advantages with regard to processing in cosmetic emulsions compared to non-inventive organic polymers. To illustrate the effect, water-in-oil (W/O) emulsions according to the following table were prepared on a 200 g scale. Phase A was heated to 80-90°C and phase B (hot/cold processing [h/c]: room temperature, hot/hot processing [h/h]: 80°C) was added for 120 seconds to the A, under stirring, using a dual-stage pulse countercurrent stirrer at 500 rpm. The mixture is pre-homogenized for one minute at 1,500 rpm, before cooling in a water bath to 40 °C, followed by the addition of phase C. Final homogenization is conducted below 30 °C for 120 seconds at 1,500 rpm.

[089] A carrier formulation without organic polymer, and using increasing amounts of cosmetic waxes alternatively, was prepared for reference as a “standard procedure”. W/O emulsion

[090] Observations during the processing of W/O emulsions containing organic polymer according to the current invention (formulation 2, 3) and non-inventive organic polymer (formulation 4), all compared to the “standard procedure” (formulation 1), are observed in table a. follow:

[091] Interestingly, the final emulsion with organic polymer according to comparative example (formulation 4) was not formed under hot/hot processing conditions, although the melting point temperature/crystallization of organic polymer according to comparative example and example 2 is similar (48 ° C, 49 ° C), and only the melting point of organic polymer according to example 1 is higher (65 ° C). Also under hot/cold processing conditions, the addition of the water phase to the oil phase was delayed during the processing of the formulation containing organic polymer, according to a comparative example.

[092] This application example clearly shows that the properties of organic polymers, according to the current invention, present advantages with respect to processing into W/O cosmetic emulsions, compared to non-inventive organic polymers. APPLICATION EXAMPLE 5: PIGMENT DISPERSION IN COSMETIC FORMULATIONS CONTAINING ORGANIC POLYMER ACCORDING TO THE CURRENT INVENTION, COMPARED TO ORGANIC POLYMERS NOT ACCORDING TO THE CURRENT INVENTION

[093] It was observed that organic polymers functionalized with hydroxyl, according to the current invention, present advantages in relation to pigment dispersion. To illustrate the effect, water-in-oil (W/O) colored cosmetic emulsions, according to the following table, were prepared on a 200 g scale. An organic polymer-free carrier formulation was prepared for reference.

[094] The color of the emulsions was evaluated using a Dr. Lange Micro Color LMG140 colorimeter and laboratory color space. The combination of white, yellow, red and black pigments yields a colored skin emulsion, which is typical for foundations. Better pigment dispersion provides a more intense color, indicated by increased color component 'a' (red), which is summarized in the following table.

[095] When the organic polymer according to comparative example was used (formulation 4), the red color component increased compared to the vehicle formulation (Δa= 1.6), indicating slightly increased pigment distribution in the oil phase. However, when the organic polymer according to example 1 and 2 was used (formulations 2 and 3), the difference in color was greater (ΔE=3.3 and 2.8), indicating even better distribution of the organo-modified pigments in the oil phase. This experiment shows that organic polymers, according to the current invention, are better at achieving even more pigment distribution, which makes them ideally suited for color cosmetic applications, among others. APPLICATION EXAMPLE 6: FRAGRANCE OIL RETENTION TEST OF COSMETIC FORMULATIONS CONTAINING ORGANIC POLYMER ACCORDING TO THE CURRENT INVENTION, COMPARED TO ORGANIC POLYMERS NOT ACCORDING TO THE CURRENT INVENTION

[096] It is observed that hydroxyl-functionalized organic polymers, according to the current invention, present better fragrance properties, compared to non-inventive organic polymers. To illustrate the effect, conditioning formulations according to the following table were prepared on a 200 g scale. An organic polymer-free carrier formulation was prepared for reference.

[097] The fragrance retention test was performed using standardized human hair braids (4 g, Caucasian hair, Kerling Int., Germany). The hair braids have been pre-treated by bleaching. Bleaching powder (e.g. "Blondor Special", Wella) and hydrogen peroxide (e.g. "Welloxyd 9%", Wella) were mixed into a paste (weight ratio powder : hydrogen peroxide = 2 : 3 ). The paste was applied to the hair braids with a brush. After exposure time of 30 minutes at room temperature, the hair braids were washed in running water at approximately 37 °C for two minutes. Subsequently, the hair braids were washed with a shampoo (12% sodium lauryl sulfate in water, 3% sodium chloride; 0.25 g shampoo/g hair) for one minute, and then washed for one minute. The procedure was repeated once. After the second washing step, the hair braids were washed for two minutes. Pre-damaged hair was equilibrated overnight at 50% relative humidity and 22°C. Before application of the test formulation, the hair braid was soaked by flowing water at approximately 37 °C. Water was squeezed between the fingers, then the conditioner formulation was applied (0.1 g/g of hair) and gently rubbed into the hair. After a dwell time of one minute, the hair braid was washed under a stream of water for one minute. The treated hair was equilibrated for 12 hours at 50% relative humidity and 22°C.

[098] Paired hair braids were provided in a blind and random manner to a collective of twelve trained participants, such that each combination of pairs (hair braids treated with formulation 1 and 2, 1 and 3, 1 and 4, 2 and 3, 2 and 4, 3 and 4) was evaluated twice. Participants were asked to differentiate between hair braids with the highest fragrance intensity (rating 1) from the lowest intensity (rating 2). A rating of 1.5 was assigned to both hair braids in case no difference was observed. Average ratings are summarized in the table below.

[099] When the hair braid was evaluated with vehicle (formulation 1), an average rating of 1.92 was obtained, which corresponds to the lowest preference. When the organic polymer according to the comparative example was used (formulation 4), the preference was slightly higher (rating 1.67), indicating better fragrance retention. However, when the organic polymer according to example 1 and 2 was used (formulations 2 and 3), the preference was higher (rating 1.17 and 1.25), indicating even better retention of fragrance oil in the hair. This effect may be due to better solubilization of fragrance in the formulation and therefore better hair coverage, or due to better interaction of hair, fragrance oil and organic polymer, resulting in better fragrance retention in the hair. EXAMPLE FORMULATIONS AP/Stick Deodorant AP/roll-on deodorant Roll-on deodorant, PEG-free, ACH-free SPF 30 sunscreen spray Oil Release Sun Protection Lotion SPF 50 Sun protection spray SPF 30 Cooling after sun gel Light O/W Sun Care Lotion A/O basis Moisturizing cream for dry touch hands Formulation of colored cosmetics Anti-aging BB cream SPF 15 Moisturizing BB cream SPF 15 W/O emulsion Cream A/O Anhydrous stick Daily anti-aging care AP/Deodorant stick W/O emulsion Skin revitalizing serum Double action wrinkle serum Lip filler lipstick W/O emulsion O/A & Bronze sunscreen O/W Cream Colored lip filler lipstick After shave lotion W/O emulsion W/O emulsion Retinol Cream Anti-aging moisturizer Sun protection foam SPF 50 Shaving cream PEG-free AP/Deodorant Lotion Sun protection A/O Shake-Shake

Claims (15)

1. Polymer comprising the monomeric units of the general formula (I) R3 R4 with R1 = independently of each other selected from the group consisting of alkyl radicals and alkenyl radicals, which may be either branched or straight chain, unsubstituted or substituted, especially substituted by hydroxyl groups, R2 = independently of each other selected from from the group consisting of hydroxycarbyl radicals substituted by hydroxyl, preferably alkyl radicals, having 1 to 10, preferably 2 to 6, more preferably 2 to 4, carbon atoms, R3 and R4 = independently of each other selected from the group that consists of H and methyl, preferably H, and with the monomeric units of general formula (I) constituting at least 90% by weight, preferably 95% by weight, of the total weight of the polymer, with at least 90% by weight of all R1 selected from the group of alkyl and alkenyl radicals with 6 to 32, preferably 10 to 26, more preferably 12 to 22, carbon atoms, with the weight % referring to the sum of all R1 present in the polymer, and with the ratio of weight of the sum of all units carrying R2 to the sum of all units carrying R1 being in the range of 1:100 to 1:0.5, preferably 1:60 to 1:0.8, more preferably 1:30 to 1:1, characterized in that the polymer has an average molecular weight in Mn number in the range of 2,000 to 9,000, preferably 5,000 to 8,500, more preferably 7,000 to 8,000 g/mol. 2. Polymer according to claim 1, characterized in that the polymer has a melting point in the range of 41 °C to 69 °C, preferably 44 °C to 68 °C, more preferably 62 °C to 67 °C. 3. Polymer according to claim 1 or 2, characterized in that the polymer has a ratio of weight-average molecular weight Mw to number-average molecular weight Mn in the range of 0.1 to 3.6, preferably 0.5 to 3 .5, more preferably 2.3 to 3.3. 4. Polymer according to any one of the preceding claims, characterized by R1 = independently selected from the group consisting of stearyl and berenyl, R2 = 2-Hydroxyethyl, R3 and R4 = H. 5. Process for preparing a polymer comprising the steps of: A) providing a monomer (1) of general formula (II) and a monomer (2) of general formula (III) R1A general formula (II) with R1A = independently of each other selected from the group consisting of alkyl radicals and alkenyl radicals, which may be either branched or straight chain, unsubstituted or substituted, especially substituted by hydroxyl groups, R2A = independently of each other selected from from the group consisting of hydroxycarbyl radicals substituted by hydroxyl, preferably alkyl radicals, having 1 to 10, preferably 2 to 6, more preferably 2 to 4, carbon atoms, R3A and R4A = independently of each other selected from the group that consists of H and methyl, preferably H, and with at least 90% by weight of all R1A selected from the group of alkyl and alkenyl radicals having 6 to 32, preferably 10 to 26, more preferably 12 to 22, carbon atoms, with the % by weight referring to the sum of all R1A present in the polymer, and a weight ratio of polymer (1) to polymer (2) in the range of 1:100 to 1:0.5, preferably 1:60 to 1:0.8, more preferably 1:30 to 1:1, B) addition of at least one initiator to polymerize the monomers and carry out a radical polymerization, optionally C) removal of excess monomers, and, optionally, D) purification of the polymer obtained, characterized by the initiator be added in an amount of 5 to 20,000 ppm, preferably 50 to 10,000 ppm, more preferably 100 to 5,000 ppm, wherein the ppm refers to the total weight of the sum of all monomers (1) and (2) provided in the stage A) of the process. 6. Process according to claim 5, characterized in that the initiator is selected from the group of 2,2'-azo-bis(2-methyl propionitrile), 2,2'-azodi(2-methylbutyronitrile), 1 ,1'-azodi(hexahydrobenzonitrile), 4,4'-azo-bis(4-cyanovaleric acid), 2,2'-azo-bis(2,4-dimethyl valeronitrile), and 2,2'-azo -bis(2-cyclopropyl propionitrile), 2,2'-azo-bis(2-cyclobutyl propionitrile), 2,2'-azo-bis(2-cyclobutyl propionitrile), 2,2'-azo-bis (2, 4-dimethyl valeronitrile), 1,1'-azo-bis(1-cycloheptanenitrile), 2,2'-azo-bis(methyleptilonitrile), 2,2'-azo-bis(2-cyclohexyl propionitrile), azo-bis - isobutyramidine 2HCl, phenyl-azo-triphenylmethane, 4-hydroxyphenyl-azo-triphenylmethane, peroxide and peroxy compounds, such as benzoyl peroxide, tert-butyl peroxy pivalate, tert-amyl peroxypivalate, acetyl peroxide, propionyl peroxide, 2-isopropionyl peroxide, butyryl peroxide, diisobutyryl peroxide, dilauroyl peroxide, didecanoyl peroxide, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, tert-butyl peroxydiethylacetate, tert-amyl peroxy-2-ethylexanoate, tert-amyl peroxy-2-ethylexanoate , 2-methoxybenzoyl peroxide, cumyl peroxyneheptanoate, tert-amyl peroxineodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyneheptanoate, tert-amyl peroxyacetate, butyryl 4-benzylideneperoxide, methyl phtoloyl peroxide, 1,1-di(tert - amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, hydroperoxides such as isopropylcumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumyl hydroperoxide, tert. -Butyl hydroperoxide, tert-amyl hydroperoxide, carbonates such as diethyl peroxydicarbonate, tert-butylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dimyrysyl peroxydicarbonate, tert-amylperoxy 2-ethylhexyl carbonate, tert-butylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, ethyl tert-butyl peroxalate; benzyl (tert-butyl peroxy) oxalate; tertiary-butyl-N-(3-tolylperoxy) carbamate and persalt compounds, such as potassium persulfate and mixtures thereof. 7. Process according to claim 5 or 6, characterized in that, in step B), at least one chain transfer agent is present, preferably in an amount such that the weight ratio of the added initiator and the transfer agent chain is in the range of 1 : 20 to 1 : 0.1, preferably 1 : 10 to 1 : 1. 8. Process according to claim 7, characterized in that the chain transfer agent is selected from at least one of the group of tetrachloromethane, bromotrichloromethane, isooctyl 3-mercaptopropionate, 4-methylbenzenethiol, tert-nonyl mercaptan, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 4,4'-thiobisbenzenethiol, trimethylolpropane tris(3-mercaptopropionate), 1,8-dimercapto-3,6-dioxaoctane, n-dodecanethiol, ethyl mercaptan, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptohexanol, mercaptooctanol, propanethiol, dithiothreitol, cysteine, homocysteine, glutathione, tert-dodecanethiol, thioglycolic acid, Dimercaptosuccinic acid, 2,3-Dimercapto-1-propanesulfonic acid, acetylcysteine and thiophenol. 9. Process according to claim 5 or 6, characterized in that no chain transfer agent is present in the process. 10. Polymer, characterized in that it is obtained by the process according to any one of claims 5 to 8. 11. Personal care formulation, characterized in that it contains at least one polymer according to any one of claims 1 to 4 or 10. 12. Use of at least one polymer according to any one of claims 1 to 4 or 10, or a formulation according to claim 11, characterized in that it is to form a film on a surface, especially skin and/or hair. 13. Use of at least one polymer according to any one of claims 1 to 4 or 10, or a formulation according to claim 11, characterized in that it is for maintaining a fragrance on a surface, especially skin and/or hair. 14. Use of at least one polymer according to any one of claims 1 to 4 or 10, or a formulation according to claim 11, characterized in that it is to provide a dry skin sensation to the formulations, especially emulsions. 15. Use of at least one polymer according to any one of claims 1 to 4 or 10, or a formulation according to claim 11, characterized in that it is for dispersing solid pigments.