Functionalized polymers

Abstract

The present invention relates to functionalized polymers, methods of making functionalized polymers, and uses of functionalized polymers, especially in the field of personal care.

Description

Field of the invention

[0001] The present invention relates to a functionalized polymer, a method for preparing a functionalized polymer and the use of the functionalized polymer, especially in the field of personal care. State of the art

[0002] US2016250137 discloses a personal care composition comprising an oil-in-water emulsion, at least one C12-C22 side chain crystalline polymer, wherein the side chain crystalline polymer has a crystalline melting point of 35 to 70°C; and at least one skin-interacting active compound, wherein the active compound is incorporated into the crystalline matrix of the side chain crystalline polymer, and wherein the active ingredient is released from the crystalline matrix at body temperature, wherein the personal care composition is free of a sunscreen active.

[0003] It was an object of the present invention to provide a functionalized polymer having outstanding properties in personal care applications.

[0004] Invention Description

[0005] It was surprisingly found that the polymer according to claim 1 has outstanding properties in personal care applications.

[0006] The present invention thus provides a special polymer, which is characterized in that the polymer has a polydispersity index PDI of > 4.5.

[0007] The present invention further provides a method for preparing a polymer and personal care formulations containing certain polymers.

[0008] It is an advantage of the present invention that the polymer leads to a higher richness of the formulation.

[0009] It is a further advantage of the present invention that the polymer provides an excellent compatibility with organic UV filters.

[0010] It is a further advantage of the present invention that the polymer brings about an improved sensory and dry skin feel.

[0011] It is a further advantage of the present invention that the polymer forms an anti-malodour protective film.

[0012] The polymers of the present invention, the methods of the present invention, the preparations obtainable with these and their use are now described by way of example without intending to restrict the invention to these exemplary embodiments. If ranges, general formulae or classes of compounds are listed below, these shall not only include the respective ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds obtainable by removing individual values (ranges) or compounds. When documents are cited in the present specification, their content shall fully constitute part of the disclosure of the present invention.

[0013] As used in the present invention, "natural number" does not include 0 (zero).

[0014] All percentages (%) given are percent by weight, unless otherwise stated.

[0015] All ppm given are ppm by weight, unless otherwise stated.

[0016] Unless otherwise stated, the viscosity values listed in the present invention are to be understood as referring to the dynamic viscosity, which can be determined using methods familiar to the person skilled in the art. The measurement values listed below are determined at a pressure of 101325 Pa and a temperature of 23°C, unless otherwise stated.

[0017] A polymer is claimed, which comprises monomer units of the general formula (I)

[0018]

[0019] wherein

[0020] R 1 = independently of one another selected from the group consisting of alkyl and alkenyl, both of which can be branched or straight-chain, unsubstituted or substituted, preferably alkyl having 6 to 30, preferably 10 to 26, more preferably 12 to 24 carbon atoms,

[0021] R 2 = independently of one another selected from the group consisting of H and methyl, preferably H,

[0022] wherein the monomer units of the general formula (I) make up at least 90% by weight, preferably 95% by weight, of the total weight of the polymer,

[0023] characterized in that the polymer has a polydispersity index PDI of 4.5 to 20, preferably 4.6 to 15, more preferably 4.8 to 13.

[0024] The polymer according to the invention is a homopolymer and / or a copolymer, including random copolymers, graft copolymers and block copolymers, preferably a homopolymer.

[0025] The polymer according to the invention preferably consists of monomer units of the general formula (I).

[0026] Of course, at least 90% by weight of all R 1 may be a mixture, and preferably at least 90% by weight of all R 1 contains a mixture of 0% to 5% hexadecyl, 40% to 55% octadecyl, 1% to 15% eicosyl, 35% to 45% docosyl and 0% to 5% tetracosyl, these percentages by weight referring to all R1 The sum of all.

[0027] Or preferably, all R 1 At least 90% by weight of a mixture containing 0%–3% by weight tetradecyl, 40%–50% by weight hexadecyl, 40%–50% by weight octadecyl and 0%–1% by weight eicosyl, these weight percentages refer to all R present in the polymer. 1 The sum of all.

[0028] All R 1 At least 90% by weight is preferably selected from straight-chain alkyl and alkenyl groups having 12 to 22 carbon atoms, preferably alkyl, with octadecyl and docosyl being particularly preferred.

[0029] Preferably, the polymer according to the invention is characterized in that the polymer has a melting point in the range of 31°C to 75°C, preferably 35°C to 72°C, more preferably 40°C to 69°C.

[0030] Preferably, the polymer according to the invention is characterized in that it has a number-average molecular weight M in the range of 3,000 to 300,000, preferably 4,000 to 200,000, more preferably 5,000 to 100,000 g / mol. n .

[0031] Preferably, the polymer according to the invention is characterized in that it has a weight-average molecular weight M in the range of 13,500 to 6,000,000, preferably 18,000 to 3,000,000, more preferably 24,000 to 1,300,000 g / mol. w .

[0032] Preferably, the polymer according to the invention is characterized in that...

[0033] R 1 = Selected independently of octadecyl and / or docosyl groups,

[0034] R 2 =H.

[0035] The polymers of the present invention can be obtained in various ways. The polymers of the present invention are preferably obtained by the method of the present invention described below. Therefore, a method for preparing a polymer, preferably the polymer of the present invention, is claimed, comprising the following steps:

[0036] A) Provide 1 part by weight of monomer of general formula (II)

[0037]

[0038] in

[0039] R 1A = independently of one another selected from alkyl and alkenyl, both of which can be branched or straight-chain, unsubstituted or substituted, preferred hydrocarbons being alkyl groups having 6 to 30, preferably 10 to 26, more preferably 12 to 24 carbon atoms,

[0040] R 2A = independently of one another selected from H and methyl, preferably H,

[0041] B) adding at least one initiator to polymerize the monomers and to carry out the radical polymerization,

[0042] C) adding a further 1 to 15, preferably 2 to 10, more preferably 3 to 8 parts by weight of monomers of the general formula (II),

[0043] D) adding at least one initiator to polymerize the monomers and to carry out the radical polymerization, optionally

[0044] E) removing the excess monomers, and optionally,

[0045] F) purifying the resulting polymer.

[0046] R 1A preferred independently of one another selected from unsubstituted alkyl and alkenyl, more preferred alkyl groups having 6 to 30, preferably 10 to 26, more preferably 12 to 24 carbon atoms.

[0047] R 1A more preferred independently of one another selected from straight-chain alkyl and alkenyl groups having 12 to 22 carbon atoms, preferably alkyl groups, of which octadecyl and docosyl are particularly preferred.

[0048] The process according to the application is preferably a process for preparing polymers having a polydispersity index PDI of greater than 4.5.

[0049] The initiators added in steps B) and D) of the process according to the application can be initiators which are solid, liquid or dissolved in a solvent.

[0050] The same or different initiators can be added in steps B) and D) of the process according to the application.

[0051] Mixtures of initiators can be added in steps B) and / or D) of the process according to the application without restricting the scope of the application.

[0052] The initiator added in steps B) and D) of the method according to the invention is preferably selected from 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(hexahydrobenzyl nitrile), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2,4-dimethylpentanitrile), and 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2-cyclobutylpropionitrile), Nitriles), 2,2'-azobis(2-cyclobutylpropionitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), 1,1'-azobis(1-cycloheptanenitrile), 2,2'-azobis(methylheptanenitrile), 2,2'-azobis(2-cyclohexylpropionitrile), azobisisobutyramidine 2HCl, phenyl-azo-triphenylmethane, 4-hydroxyphenyl-azo-triphenylmethane, peroxides and peroxides, such as benzoyl peroxide, peroxide tert-butyl peroxypentanoate, tert-pentyl peroxypentanoate, acetyl peroxy, propionyl peroxy, 2-isopropionyl peroxy, butyryl peroxy, diisobutyryl peroxy, dilauryl peroxy, didecyl peroxy, cumyl peroxyneodecanate, 1,1,3,3-tetramethylbutyl peroxyneodecanate, tert-butyl peroxydiethylacetate, tert-pentyl peroxy-2-ethylhexanoate, tert-pentyl peroxy-2-ethylhexanoate, 2-methoxy peroxy Benzoyl, cumyl peroxyheptanyl peroxide, tert-amyl peroxyheptanyl peroxide, tert-butyl peroxyheptanyl peroxide, tert-amyl peroxyacetate, 4-benzylbutyryl peroxide, methyl phthaloyl peroxide, 1,1-di(tert-amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, hydroperoxides, such as dicumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, carbonates such as diethyl peroxycarbonate, tert-butylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, di-sec-butyl peroxycarbonate, diisopropyl peroxycarbonate, di(4-tert-butylcyclohexyl)peroxy dicarbonate, di(2-ethylhexyl)peroxy dicarbonate, di(hexadecyl)peroxy dicarbonate, di(myristyl)peroxy dicarbonate, tert-amylperoxy 2-ethylhexyl carbonate, tert-butylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, ethyl tert-butylperoxy oxalate; benzyl(tert-butyl peroxy)oxalate; tert-butyl-N-(3-methylphenylperoxy)carbamate and peracid salt compounds such as potassium persulfate and mixtures thereof,

[0053] Among these, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), dilauryl peroxide, cumyl peroxynonanoate, tert-amylperoxy-2-ethylhexanoate are particularly preferred.

[0054] The process step B) and / or process step D) in the process according to the application is preferably characterized in that the at least one initiator is added in an amount of 50 to 100,000 ppm, preferably 500 to 50,000 ppm, more preferably 2,000 to 25,000 ppm, per process step B) and / or D), wherein ppm each refer to the total weight of all monomers provided in process step A) (for the initiator added in step B)) and / or process step C) (for the initiator added in step D)).

[0055] The process step B) and / or D), preferably only B), in the process according to the application is preferably characterized in that the addition of the at least one initiator to polymerize the monomers is performed in at least two portions, while the free radical polymerization is performed after each portion of the initiator is added.

[0056] Method step B) and / or D) in the process according to the present application is carried out in neat or in a solvent, preferably in neat. The amount of solvent can vary from 1 to 95 wt.-%, preferably from 2 to 50 wt.-%, more preferably from 3 to 40 wt.-%, with wt.-% referring to the total weight of all monomers provided in method step A).

[0057] Possible solvents can be, but are not limited to: alcohols, such as methanol, ethanol, isopropanol, butanol, hexanol, tert-butanol, isoamyl alcohol, ethylene glycol, hexylene glycol, propylene glycol, butylene glycol, butyl diglycol, glycerol, ketones, such as methyl ethyl ketone, methyl butyl ketone, acetone, esters, such as methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, hexyl acetate, isooctyl acetate, methoxypropyl acetate, acids, such as formic acid, acetic acid, propionic acid, ethers, such as diethyl ether, dibutyl ether, tert-butyl methyl ether, petroleum ether, tetrahydrofuran, dioxane, polyethers, carbonates, such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, nitriles, such as benzonitrile, acetonitrile, toluene, xylene, ionic liquids, water, organic oils, such as and mixtures thereof.

[0058] In method step A) and / or C), preferably A) and C), of the process according to the present application, at least one chain transfer agent can be added, preferably in an amount such that the weight ratio of the initiator added in method step B) and / or D) to the chain transfer agent added in step A) (for the initiator added in step B)) and / or C) (for the initiator added in step D)), respectively, is in the range of 1 :5 to 1 :0.01, preferably 1 :1 to 1 :0.02, more preferably 1 :0.5 to 1 :0.05.

[0059] The chain transfer agent preferably added in method step A) and / or C), preferably A) and C), of the process according to the present application is selected from at least one of the following: tetrachloromethane, bromotrichloromethane, 3-mercapto propyl isooctyl ester, 4-methylbenzenethiol, tert-nonyl mercaptan, pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercapto propionate), 4,4'-thiobisbenzenethiol, trimethylolpropane tri(3-mercaptopropionate), 1,8-dimercapto-3,6-dioxaoctane, n-dodecanethiol, ethanethiol, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptohexanol, mercaptooctanol, propanethiol, dithiothreitol, cysteine, homocysteine, glutathione, tert-dodecanethiol, mercaptoacetic acid, dimercaptosuccinic acid, 2,3-dimercapto-1 -propanesulfonic acid, acetylcysteine and benzenethiol.

[0060] In an alternative process according to the present application, no chain transfer agent is present in the process.

[0061] Method steps B) and D) in the process according to the present application are preferably carried out at a temperature of from 10°C to 250°C, preferably from 20°C to 200°C, and more preferably from 60°C to 180°C.

[0062] Method steps B) and D) in the process according to the present application are preferably carried out at a pressure of from 0.5 to 20 bar, more preferably from 1 to 5 bar, and again more preferably at atmospheric pressure.

[0063] Method steps B) and D) in the process according to the present application are preferably carried out at a pH of from 3 to 10, more preferably from 4 to 9, and again more preferably from 5 to 8.

[0064] Method steps B) and D) in the process according to the present application are preferably not only carried out in daylight, but also in the absence of light, and preferably in the absence of light.

[0065] Method step E) in the process according to the present application serves to remove excess monomers.

[0066] When step E) in the process according to the present application is a chasing step, this is a preferred process according to the present application. It is therefore preferred that step E) in the process according to the present application comprises the addition of further initiator after the completion of method step D) to remove excess monomers. The further initiator is preferably applied in a concentration of from 0.01 wt.-% to 5 wt.-%, preferably from 0.1 wt.-% to 2.5 wt.-%, more preferably from 0.2 wt.-% to 2 wt.-%, wherein wt.-% refers to the total weight of all monomers provided in method steps A) and C). The addition of further initiator in step E) in the process according to the present application is preferably repeated up to four times, preferably twice, more preferably once. The initiator added in step E) of the present application is selected from the same initiators applicable in steps B) and D) according to the present application, with the same preference hierarchy. The reaction conditions in process E) of the present application are also selected from the same conditions applicable in steps B) and D) according to the present application, with the same preference hierarchy.

[0067] The further purification step F) in the process according to the present application can be selected from extraction with water and / or organic solvents, distillation under vacuum or without vacuum, and / or recrystallization from water and / or organic solvents.

[0068] Step F) in the process according to the present application preferably comprises steam distillation. Here, some water is applied to the reaction mixture to remove excess monomers, unwanted by-products, decomposed initiator and / or solvent from the reaction. The amount of water added can vary from 0.1 wt.-% to 20 wt.-%, preferably from 0.5 wt.-% to 10 wt.-%, more preferably from 1 wt.-% to 5 wt.-%, wherein wt.-% refers to the total weight of all monomers provided in method steps A) and C).

[0069] It is preferred that step E) is included in the process according to the application, more preferably steps E) and F).

[0070] In the preferred process according to the application, the monomers of the general formula (II) make up at least 90% by weight, preferably 95% by weight, of all polymerisable monomers present in the overall process.

[0071] A further subject matter of the present application is a polymer obtainable by the process according to the application. The polymer obtainable by this process is preferably characterised in that it has a polydispersity index PDI of greater than 4.5.

[0072] A further subject matter of the present application is a personal care formulation which contains at least one polymer according to the application or at least one polymer obtainable by the process according to the application.

[0073] Furthermore, the formulation according to the application can comprise at least one additional component selected from

[0074] emollients,

[0075] emulsifiers,

[0076] thickeners / viscosity regulators / stabilisers,

[0077] UV light protection filters,

[0078] antioxidants,

[0079] hydrotropes (or polyols),

[0080] solids and fillers,

[0081] film formers,

[0082] pearlescent additives,

[0083] deodorising and antiperspirant active ingredients,

[0084] repellents,

[0085] self-tanning agents,

[0086] preservatives,

[0087] conditioning agents,

[0088] perfumes,

[0089] dyes,

[0090] odour absorbers,

[0091] cosmetic active ingredients,

[0092] care additives,

[0093] richening agents,

[0094] solid particles,

[0095] solvents,

[0096] Preferably, the formulations comprise fragrances, solid particles and / or UV light protection filters, in particular organic filters.

[0097] The solid particles which are preferably contained are characterized by having an average particle size d50 of 0.1 to 1000 pm.

[0098] The average particle size d50 is preferably determined by light scattering in a laser beam using a Malvern Mastersizer 2000. The determination is carried out using dry method measurement. A Scirocco dry powder feeder is used to feed in 20 to 40 grams of powder per time. The particle flow is controlled so that the vibrating tray is operated at a feed rate of 70%. The dispersion gas pressure is adjusted to 3 bar. Each measurement is accompanied by a measurement of the background (10 seconds / 10,000 single measurements). The measurement time for the sample is 5 seconds (5,000 single measurements). The refractive index as well as the blue light value are fixed at 1.52. The evaluation is carried out using the Mie theory.

[0099] Substances which are exemplary representatives of the individual classes which can be contained in the formulations according to the application are known to the person skilled in the art and can be found, for example, in the German application DE 102008001788.4. This patent application is hereby incorporated by reference and thus forms part of the present disclosure.

[0100] With regard to further optional components and the amounts of these components used, explicit reference is made to the relevant handbooks known to the person skilled in the art, for example K. Schrader, "Grundlagen und Rezepturen der Kosmetika [Fundamentals and Formulations of Cosmetics]", 2nd edition, pages 329 to 341, Hϋthig Buch Verlag Heidelberg.

[0101] The amounts of the individual additives depend on the intended use.

[0102] Typical guideline formulations for the individual applications are known from the prior art and are contained, for example, in the manufacturer's brochures of the individual base materials and active ingredients. These existing formulations can generally be employed as they are. If desired, however, in order to adapt and optimize, the required modifications can be made with the aid of simple experiments and without great complexity.

[0103] The use of at least one polymer according to the application or at least one polymer obtainable by the process according to the application for forming a film on a surface, in particular on the skin and / or the hair, is also claimed herein.

[0104] Also claimed herein is the use of at least one polymer of the present application or at least one polymer obtainable by the process of the present application for retaining fragrance on a surface, especially skin and / or hair.

[0105] Also claimed herein is the use of at least one polymer of the present application or at least one polymer obtainable by the process of the present application for imparting a dry skin feel to a formulation, especially an emulsion.

[0106] Also claimed herein is the use of at least one polymer of the present application or at least one polymer obtainable by the process of the present application for dispersing solid pigments. Solid pigments are those which are preferably contained in a formulation according to the present application.

[0107] Two or more polymers according to the present application can be used together.

[0108] The examples cited below illustrate the present application and are not intended to limit the application to the embodiments specified in the examples, the scope of the application being apparent from the entire specification and claims. BRIEF DESCRIPTION OF DRAWINGS

[0110] Figure 1 : Grey scale image for analysing clarity of oil gel

[0111] Figure 2 : Bubble corrected image for quantification Figure 1 of the oil gel. Examples

[0112] Molecular weight determination by gel permeation chromatography (GPC):

[0113] The GPC measurement for determining the polydispersity PDI, which is the quotient of the weight average molecular weight Mw and the number average molecular weight Mn, was performed under the following measurement conditions:

[0114] The sample was prepared by making a 10 mg / mL solution using tetrahydrofuran as diluent. The sample preparation was placed in an oven at 54 °C for 10 minutes and then on a wrist action shaker for 60 minutes to aid dissolution. On visual inspection, the sample appeared to be completely dissolved in the diluent. The prepared sample was analysed using two 300 x 7.5 mm polypore columns (manufactured by Agilent Technologies), a Waters 2695 chromatographic system, tetrahydrofuran mobile phase and refractive index detection. The sample was filtered through a 0.45 μιη nylon filter prior to injection into the liquid chromatograph.

[0115] The calibration standards used were EasiVial narrow distribution polystyrene (PS) standards from Agilent Technologies. Narrow distribution polystyrene standards from 2.520.000 to 162 Dalton were used for calibration. The system uses a PSS SECcurity 1260 RI detector. The PS calibration curve was used to determine the molecular weight average. The recording of the chart and the determination of the different molecular weights were performed by Win GPC Unichrom 8.1 software.

[0116] Melting point determination by DSC:

[0117] This method describes the general procedure for determining the melting temperature of a polymer by differential scanning calorimetry (DSC). The method is based on ASTM E7941 and ASTM D 34182. The calibration of the DSC is performed according to ASTM E 9672.

[0118] Chemicals:

[0119] Docosyl acrylate (abcr)

[0120] Octadecyl acrylate (abcr)

[0121] 2-Mercaptoethanol (Aldrich)

[0122] Isopropanol (Aldrich)

[0123] Tert-butyl peroxy-3,5,5-trimethylhexanoate (Akzo Nobel)

[0124] Tert-amyl peroxy-2-ethylhexanoate (Akzo Nobel)

[0125] Example 1:

[0126] After removing oxygen from the system by purging with nitrogen for approximately 20 minutes, 4 grams of isopropanol and 16 grams of octadecyl acrylate were placed in a four necked flask equipped with a KPG paddle stirrer, internal thermometer, two dropping funnels, a reflux condenser and extensions for the other two necks and heated to 80°C under stirring. 0.27 grams of tert-amyl peroxy-2-ethylhexanoate dissolved in 0.75 grams of isopropanol were added and stirred for another 30 minutes. Thereafter 64 grams of octadecyl acrylate and 1.1 grams of tert-amyl peroxy-2-ethylhexanoate dissolved in 3 grams of isopropanol were added within 60 minutes and stirred for another 3 hours at 80°C. The temperature was raised to 125°C and the residual solvent distilled off. Finally, 0.4 grams of tert-butyl peroxy-3,5,5-trimethylhexanoate were added within 15 minutes and stirred for 60 minutes at 125°C. This procedure was repeated once.

[0127] Mn = 11000 g / mol, Mw = 76000 g / mol, PDI = 6.9

[0128] Tm = 49 °C

[0129] Example 2:

[0130] After removal of oxygen from the system by purging with nitrogen for about 20 minutes, 122 grams of octadecyl acrylate and 0.2 grams of 2-mercaptoethanol were placed in a four necked flask equipped with a KPG paddle stirrer, internal thermometer, two dropping funnels, a reflux condenser and extensions for the other two necks under stirring and heated to 100 °C. 0.29 grams of t-amyl peroxy-2-ethylhexanoate was added within 5 minutes and stirred for additional 60 minutes at 125 °C. Thereafter 1.8 grams of t-amyl peroxy-2-ethylhexanoate was added within 25 minutes and stirred for 5 minutes. Then 487 grams of octadecyl acrylate, 0.8 grams of 2-mercaptoethanol and 8.6 grams of t-amyl peroxy-2-ethylhexanoate were added within 90 minutes and stirred for additional 30 minutes at 125 °C. Finally, 3 grams of t-butyl peroxy-3,5,5-trimethylhexanoate was added within 15 minutes and stirred for 60 minutes at 125 °C. This procedure was repeated twice.

[0131] Mn = 9900 g / mol, Mw = 98000 g / mol, PDI = 9.9

[0132] Tm = 47.3 °C

[0133] Example 3:

[0134] After removal of oxygen from the system by purging with nitrogen for about 20 minutes, 122 grams of octadecyl acrylate and 0.2 grams of 2-mercaptoethanol were placed in a four necked flask equipped with a KPG paddle stirrer, internal thermometer, two dropping funnels, a reflux condenser and extensions for the other two necks under stirring and heated to 100 °C. 0.29 grams of t-amyl peroxy-2-ethylhexanoate was added within 5 minutes and stirred for additional 60 minutes at 125 °C. Thereafter 1.8 grams of t-amyl peroxy-2-ethylhexanoate was added within 25 minutes and stirred for 5 minutes. Then 487 grams of octadecyl acrylate, 0.8 grams of 2-mercaptoethanol and 8.6 grams of t-amyl peroxy-2-ethylhexanoate were added within 90 minutes and stirred for additional 30 minutes at 125 °C. Finally, 3 grams of t-butyl peroxy-3,5,5-trimethylhexanoate was added within 15 minutes and stirred for 60 minutes at 125 °C. This procedure was repeated twice.

[0135] Mn = 9500 g / mol, Mw = 89000 g / mol, PDI = 9.4

[0136] Tm = 64 °C

[0137] Comparative Example:

[0138] After removal of oxygen from the system by purging with nitrogen for about 20 minutes, 20 grams of isopropanol were placed in a four necked flask, equipped with a KPG paddle stirrer, internal thermometer, two dropping funnels, a reflux condenser and extensions for the two other necks, under stirring and heated to 80°C. 1.03 grams of t-amyl peroxy-2-ethylhexanoate, 60 grams of stearyl acrylate and 0.1 grams of 2-mercaptoethanol dissolved in 4.1 grams of isopropanol were added within 90 minutes and stirring was continued for another 3 hours. The temperature was raised to 125°C and the residual solvent was distilled off under vacuum assisted at 50 mbar. Thereafter, 0.3 grams of t-butyl peroxy-3,5,5-trimethylhexanoate were added and stirring was continued at 125°C for 60 minutes. This procedure was repeated again.

[0139] Mn = 4200 g / mol, Mw = 11000 g / mol, PDI = 2.6

[0140] Tm = 49°C

[0141] Application Example 1 : Higher richness of the formulations

[0142] It has been found that the functionalized polymers according to the present application have advantages in terms of skin feel. To illustrate this effect, oil-in-water (O / W) sunscreen emulsions according to the following table were prepared on a 200 gram scale. Formulations with non-functionalized polymers not according to the present application were prepared for comparison.

[0143]

[0144]

[0145] One month after preparation, the viscosity was determined with a Brookfield RV-DV I device, spindle 93, 10 rpm. All formulations showed similar viscosities in the range of 24-32 Pa-s and exhibited a pasty soft texture.

[0146] The emulsions were evaluated in terms of skin feel by a sensory panel test. 13 trained panelists applied 20 μΙ_ of each formulation on a defined test area of about 10 cm 2 on the volar forearm without knowing the composition of the formulations. The formulations were distributed within the test area by a circular motion with the fingers until complete absorption (or maximum 60 circles). The evaluation of the skin feel parameters was done during the distribution of the formulations on the skin.

[0147] The "richness" of a formulation is desirable in functional cosmetics, such as anti-aging applications, where the consumer associates a rich skin feel with anti-aging activity. Richness is not only presented by the viscosity of the formulation, but also by the behavior of the formulation upon application on the skin and the mechanical breakdown of the emulsion structure, best represented by skin feel parameters such as "spreadability" and "waxiness". The lower the spreadability and the higher the waxiness, the higher the perceived richness of the formulation.

[0148] The panelists were asked to grade the spreadability of the three formulations from 0 (very difficult to spread) to 10 (very easy to spread) and the waxiness from 0 (non-waxy) to 10 (very waxy). The scores from all panelists were averaged and the average ratings were subjected to a factor analysis (one-factor principal component analysis, varimax rotation) to extract the relative "richness" of the three formulations, which was obtained by normalization of the data on a scale of -1 to +1. In this way, a value of -1 corresponds to the lowest richness (relatively light; high spreadability and low waxiness), and a value of +1 corresponds to the highest richness (relatively low spreadability and high waxiness).

[0149]

[0150]

[0151] Surprisingly, it was found that the organic polymers according to the present application (Examples 1 and 2) have a more pronounced "richness" than the organic polymers which are not according to the present application (Comparative Examples), which makes them ideally especially suitable for anti-aging applications.

[0152] Application Example 2: Compatibility with organic UV filters (viscosity and clarity of the oil gels)

[0153] It has been found that the functionalized polymers according to the present application have an advantage in terms of UV filter compatibility. To exemplify the effect, oil gel systems with organic UV filters according to the following table were prepared on a 50 gram scale. Oil gels with functionalized polymers which are not according to the present application were prepared for comparison.

[0154]

[0155] The oil gels were prepared by mixing the ingredients and heating to 60-70°C until a clear solution was obtained. After cooling under gentle stirring, when the initial turbidity was observed, it was homogenized with an UltraTurrax at 20,500 rpm for 30 seconds. The mixture was immediately filled into glass bottles, left to crystallize without further stirring.

[0156] The high compatibility of the oil / UV filter and the organic polymer is indicated by the high viscosity and at the same time high clarity of the resulting oil gel. It is generally assumed that in this case the organic UV filter and the emollient are most effectively / uniformly embedded in the three-dimensional network formed by the organic polymer.

[0157] The viscosity of the oil gels was determined 1 week after preparation with a Brookfield RV-DV I device, spindle 96, 100 rpm.

[0158] The photos of the oil gels in glass bottles were taken under standardized conditions with the light source located behind the bottle.

[0159] The grey scale images were analyzed for clarity of the oil gels by image processing using ImageJ 1.51k (see Figure 1 ). The higher the clarity of the oil gel, the more background light is transmitted and the brighter the image. Therefore the image was converted to a black and white image by thresholding, exactly by removing all pixels with a grey value of 0-209 (converted to 0 = white) and converting all grey values of 210-255 to black (= 255). In case of incorporation of air bubbles as indicated by white circles in the resulting binary image, these were manually corrected by filling with the surrounding (black) pixel information (see Figure 2 ). In this way, the clarity of the oil gel can be quantified by the amount of black pixels, or more precisely, by the percentage of area covered by black pixels.

[0160] The results are summarized in the table below.

[0161] Oil gels A B C D Viscosity [Pa-s] 4.2 15 11 4.0 Image black pixel area % 10.1 33.2 18.3 7.86

[0162] Surprisingly, it was found that the higher the polydispersity index of the organic polymer, the higher the viscosity and clarity of the resulting oil gel. This means that a higher PDI leads to a better interaction in the complex mixture with the combination of cosmetic emollients (mixtures) and various organic UV filters. This experiment shows that the organic polymers according to the application are most compatible with organic UV filters, which makes them ideally suitable, inter alia, for sunscreen applications.

[0163] Application Example 3: Compatibility with organic UV filters (in vitro UVAPF / SPF of sunscreen formulations)

[0164] It has been found that the functionalized polymers according to the application have an advantage in terms of UV filter compatibility. To exemplify this effect, oil-in-water (O / W) sunscreen emulsions according to the table below were prepared on a 200 gram scale. Formulations with non-functionalized polymers according to the application were prepared for comparison.

[0165]

[0166]

[0167] 1mg / cm 2 The emulsion was applied to a roughened polymethyl methacrylate (PMMA) plate (7.0 x 3.5 cm, 2 μm roughness). The sample was dried at 30°C for 30 minutes on a plate (McG&Co.KG). SPF testing was performed using a Labsphere UV-2000S UV transmittance analyzer. UVAPF / SPF is the ratio between the in vitro UVA protection factor and the in vitro SPF, obtained experimentally. This value is an indicator of broadband UV protection, and the European Commission has recommended since 2006 that all sunscreen products have a UVAPF / SPF ≥ 0.33 (in vivo) to provide sufficient breadth. The absolute in vitro UVAPF / SPF does not necessarily match the absolute in vivo value, but in vitro testing is often used for screening purposes and comparing different film-forming agents before selecting candidates for time- and cost-intensive in vivo SPF testing. Therefore, the in vitro UVAPF / SPF should be optimized (as close to 0.33 as possible) and should not be negatively affected by the film-forming agent.

[0168] The results of the in vitro SPF test are summarized in the table below.

[0169] Formulation A (Example 1) B (Example 3) C (Comparative) UVAPF / SPF 0.20 0.25 0.14

[0170] Surprisingly, organic polymers with higher polydispersity indices also showed higher UVAPF / SPF values ​​in in vitro SPF tests.

[0171] This experiment demonstrates that, as shown by the optimized UVAPF / SPF value, the organic polymer according to the invention is most compatible in sunscreen formulations.

[0172] Application Example 4: Improved sensory experience and dry feel

[0173] The functionalized polymers according to the present invention have been found to have advantages in terms of skin feel. To illustrate this effect, an oil-in-water (O / W) sunscreen emulsion was prepared in a 200-gram scale according to the table below.

[0174] Formulations having functionalized polymers not according to the invention were prepared for comparison.

[0175]

[0176]

[0177] The skin feel of the emulsion was evaluated using a sensory panel test. Fourteen trained panel members, unaware of the formulation's composition, applied the emulsion to approximately 10 cm of the palmar forearm. 220 μL of each formulation was applied on a defined test area. The formulation was distributed by a circular motion with the fingers on the test area until complete absorption (or maximum 60 circles). The evaluation of the skin feel parameters was performed during the distribution of the formulation on the skin. In particular, the "dry feel" of the formulations was evaluated by the skin feel parameters: greasiness, absorption and slipperiness.

[0178] A dry feel is desirable in functional formulations, like sunscreen lotions, which tend to leave a greasy and slippery residue when containing organic UV filters and where the consumer. Therefore, in such systems, it is appreciated to have a fast absorption and leave a low greasiness and slipperiness.

[0179] The panelists were asked to grade the skin feel parameters of the three sunscreen formulations from Example 1 from 0 (attribute not noticeable) to 10 (attribute very noticeable).

[0180] The scores from all panelists were averaged and the average ratings were subjected to a factor analysis (one-factor principal component analysis, varimax rotation) to extract the relative "dryness" of the three formulations, which was obtained by a normalization of the data on a scale from -1 to +1. In this way, a value of -1 corresponds to the lowest dryness (relative greasiness and slipperiness, low absorption), a value of +1 corresponds to the highest dryness (very little greasiness and slipperiness, good absorption).

[0181]

[0182] Surprisingly, it was found that the organic polymers according to the present application have a more noticeable "dryness" than the organic polymers which are not according to the present application, which makes them ideally especially suitable for sunscreen applications.

[0183] Application Example 5: Protective film against cigarette smoke

[0184] It has been found that the functionalized polymers according to the present application have an advantage in protecting the skin from the odor caused by cigarette smoke. To exemplify this effect, oil-in-water (O / W) body care lotions according to the following table were prepared on a 200 gram scale. Formulations with functionalized polymers which are not according to the present application were prepared for comparison.

[0185]

[0186]

[0187] The protective effect of the emulsions was evaluated by sensory panel tests. Nine volunteers were recruited for the study. Each panel member applied one formulation on each volar forearm (first volunteer: formulations 1 and 2, second volunteer: formulations 3 and 1, third volunteer: formulations 2 and 3, and so on), in this way each formulation was tested on 6 forearms. The forearms were prepared by washing with a SLES solution (12% aqueous sodium laureth sulfate solution) for 30 seconds and air-drying for 5 minutes. 200 mg of each formulation was applied on the volar forearm (entire) on an area of approximately 100 cm 2 A frying pan (Tristar FR-6935) was filled with 2 liters of frying oil (Palmin) and adjusted to 170°C. 750 grams of Pommes Frites (Mc Cain, 1-2-3-Frites Original, equilibrated at room temperature) were fried for 10 minutes. During the frying process, each volunteer once put their two volar forearms under the evaporating vapors of the frying pan at a specified distance of approximately 50 cm for 30 seconds. The smell evaluation was performed by three trained professional sniffers after 5 minutes of the frying process, volunteers were treated subsequently. The olfactory evaluation was performed 5 minutes after the vapor treatment and the degree of rancid / fatty smell on the volar forearms was evaluated on a scale from 0 (not perceptible) to 5 (very pronounced). Perceptible differences between left and right forearm were rated by a difference of at least one value on the rating scale. The average rating score determined by the three professionals for each formulation is summarized in the following table:

[0188] Formulation A (Example 2) B (Example 3) C (Comparative) Odour rating score, average 2.61 3.00 2.72

[0189] Surprisingly it was found that the organic polymers according to the present application have the most pronounced protective properties against the attachment of malodors to the skin, which makes them ideally especially suitable for facial and body care applications with protective requirements.

[0190] Example formulations

[0191] The following formulation examples list "organic polymer" without further specification. All the following examples were formulated with the organic polymer (Example 1), the organic polymer (Example 2) and the organic polymer (Example 3) according to the examples of the present application; thus each formulation was prepared in three different embodiments.

[0192] Sunscreen spray SPF 30

[0193]

[0194]

[0195] Oil Release Sun Care Lotion SPF 50

[0196]

[0197]

[0198] Sun Care Spray SPF 30

[0199]

[0200] Clear Sun Care Spray SPF 25

[0201]

[0202] Light O / W Sun Care Lotion SPF 30

[0203]

[0204]

[0205] Dry Touch Hand Moisturizing Cream SPF 15

[0206]

[0207]

[0208] Anti-Aging BB Cream SPF 10

[0209]

[0210]

[0211] Moisturizing Care BB Cream SPF 15

[0212]

[0213]

[0214] Anhydrous Stick SPF 10

[0215]

[0216] O / W Sun Protect & Bronze SPF 20

[0217]

[0218]

[0219] Sun Protection Foam SPF 50

[0220]

[0221]

[0222] W / O Sun Protection Shake-Shake SPF 20

[0223]

[0224] Lightweight W / O Sun Protection Shake-Shake SPF 20

[0225]

[0226] W / O Organic Shake-Shake SPF 30 PA+++

[0227]

[0228]

[0229] Summer Paradise Cream SPF 30

[0230]

[0231]

[0232] On the go UV Protection Stick SPF 50

[0233]

[0234]

[0235] Transparent UV Protection Water Spray SPF 30

[0236]

[0237]

[0238] Sunscreen SPF 25

[0239]

[0240] Inorganic water-resistant O / W sunscreen SPF 20

[0241]

[0242]

[0243] Feel the sun spray SPF 50

[0244]

[0245]

[0246] Sun Protection Stick

[0247]

[0248]

[0249] W / O quick-breaking cream SPF 15

[0250]

[0251] Fun in the Sun SPF 30 spray

[0252]

[0253] Cationic sun screen SPF 10

[0254]

[0255]

[0256] W / O sunscreen emulsion SPF 8, water-resistant

[0257]

[0258] Cationic sun screen SPF 20, water-resistant

[0259]

[0260] Cationic Sun Screen SPF 15, water resistant

[0261]

[0262]

[0263] Cationic Sun Screen SPF 25

[0264]

[0265] Everyday Sunshine Cream SPF 15

[0266]

[0267]

[0268] High Sun Protection Lotion O / W SPF 50

[0269]

[0270]

[0271] Icy O / W Sunscreen Lotion SPF 25

[0272]

[0273]

[0274] Low Viscosity W / O Sunscreen Lotion SPF 25 PA+++

[0275]

[0276] O / W Sunscreen Gel SPF 30 PA+++

[0277]

[0278]

[0279] Sun care Aqua Gel SPF 50, PA+++

[0280]

[0281]

[0282] High Protection O / W Sunscreen SPF 50 PA+++

[0283]

[0284]

[0285] Transparent Sun Stick SPF 50, PA++++

[0286]

[0287]

[0288] Sunscreen SPF 15

[0289]

[0290]

[0291] Sunscreen Spray SPF 30

[0292]

[0293] Anhydrous Stick

[0294]

[0295]

[0296] AP / Deo Stick

[0297]

[0298] AP / Deo Roll-On

[0299]

[0300] Deo Roll-On, PEG-Free, ACH-Free

[0301]

[0302]

[0303] O / W AP / Deo Roll-On

[0304]

[0305]

[0306] AP / Deo Roll-On, PEG-Free and ACH-Free

[0307]

[0308] AP / De bars

[0309]

[0310] W / O foundation

[0311]

[0312]

[0313] Color cosmetic foundation

[0314]

[0315]

[0316] Cooling after sun gel

[0317]

[0318]

[0319] W / O emulsion

[0320]

[0321] W / O cream

[0322]

[0323]

[0324] Anti-aging day care

[0325]

[0326]

[0327] W / O emulsion

[0328]

[0329] Skin replenishing serum

[0330]

[0331]

[0332] Dual-action wrinkle serum

[0333]

[0334] Lip filler color lipstick

[0335]

[0336] Lip filler lipstick

[0337]

[0338]

[0339] W / O emulsion

[0340]

[0341] O / W cream

[0342]

[0343]

[0344] After shave lotion

[0345]

[0346] W / O emulsion

[0347]

[0348] W / O emulsion

[0349]

[0350] Retinol cream

[0351]

[0352] Anti-aging moisturizer

[0353]

[0354]

[0355] Shaving cream

[0356]

[0357] Sprayable hair gel, PEG-free

[0358]

[0359]

[0360] Strong Hold Styling Gel

[0361]

[0362] Leave-In Conditioner Foam

[0363]

[0364] Leave-In Conditioner Spray

[0365]

Claims

1. A polymer comprising monomeric units of the general formula (I) ###0001### wherein wherein the monomeric units of the general formula (I) constitute at least 90 wt.-% of the total weight of the polymer, R 1 = independently of one another selected from linear alkyl groups having 6 to 30 carbon atoms, R 2 = independently of one another selected from H and methyl, the monomeric units of the general formula (I) constitute at least 95 wt.-% of the total weight of the polymer. characterized in that The polymer has a polydispersity index PDI of 6.9 to 20, and the polymer has a number average molecular weight M n .

2. The polymer of claim 1, wherein R 1 = are independently from each other selected from alkyl having 10 to 26 carbon atoms.

3. The polymer according to claim 1 or 2, characterized in that, R 1 = are independently from each other selected from alkyl groups having 12 to 24 carbon atoms.

4. The polymer according to claim 1 or 2, characterized in that, R 2 = are independently from each other selected from H.

5. The polymer according to claim 1 or 2, characterized in that The polymer has a polydispersity index PDI of 6.9 to 15.

6. The polymer according to claim 1 or 2, characterized in that The polymer has a polydispersity index PDI of 6.9 to 13.

7. The polymer according to claim 1 or 2, characterized in that The polymer has a melting point in the range of 31 °C to 75 °C.

8. The polymer according to claim 1 or 2, characterized in that All R 1 are at least 90% by weight selected from linear alkyl groups having 12 to 22 carbon atoms.

9. The polymer of claim 1, wherein All R are C18H37 1 at least 90% by weight of R are selected from octadecyl and docosyl.

10. The polymer according to claim 1 or 2, characterized in that The polymer has a melting point in the range of 35 °C to 72 °C.

11. The polymer according to claim 1 or 2, characterized in that The polymer has a melting point in the range of 40 °C to 69 °C.

12. The polymer according to claim 1 or 2, characterized in that 14. A process for the preparation of a polymer according to any one of claims 1 to 13, which process comprises the following steps:

13. The polymer according to claim 1 or 2, characterized by The polymer has a weight average molecular weight M in the range of 34,500 to 1,300,000 g / mol w . A) providing 1 parts by weight of monomers of the general formula (II) ###0002### wherein B) adding at least one initiator to polymerize the monomers and to perform a free radical polymerization, C) adding further 1 to 15 parts by weight of monomers of the general formula (II), R 1A = independently of one another selected from linear alkyl groups having 6 to 30 carbon atoms, R 2A = independently of one another selected from H and methyl, D) adding at least one initiator to polymerize the monomers and to perform a free radical polymerization, optionally E) removing the excess monomers, and optionally, F) purifying the resulting polymer. In step C) further 2 to 10 parts by weight of monomers of the general formula (II) are added. In step C) further 3 to 8 parts by weight of monomers of the general formula (II) are added.

15. The method of claim 14, wherein, R 1A = are independently from each other selected from alkyl having 10 to 26 carbon atoms.

16. The method of claim 14, wherein, R 1A = are independently from each other selected from alkyl groups having 12 to 24 carbon atoms.

17. The method of claim 14, wherein, R 2A = are independently from each other selected from H.

18. The method of claim 14, wherein, ​ 19. The method of claim 14, wherein, ​ 20. The method of claim 14, wherein The initiator is selected from the group consisting of 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1 '-azobis(hexahydrobenzene nitrile), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2-cyclobutylpropionitrile), 2,2'-azobis(2-cyclobutylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1 '-azobis(1 -cycloheptanenitrile), 2,2'-azobis(methylheptanonitrile), 2,2'-azobis(2-cyclohexylpropionitrile), azobis-isobutyramide dihydrochloride, phenyl-azo-triphenylmethane, 4-hydroxyphenyl-azo-triphenylmethane, benzoyl peroxide, t-butyl peroxypivalate, t-amyl peroxypivalate, acetyl peroxide, propionyl peroxide, 2-isopropionyl peroxide, butyryl peroxide, diisobutyryl peroxide, dilauryl peroxide, dicaprylyl peroxide, cumyl phenylperoxy pivalate, 1,1,3,3-tetramethylbutyl peroxy pivalate, t-butyl diethyl peroxide, t-amyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, 2-methoxybenzoyl peroxide, cumyl phenylperoxy neohexanoate, t-amyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl peroxy neohexanoate, t-amyl peroxy acetate, 4-benzylidenebutyryl peroxide, methylphthalyl peroxide, 1,1 -di(t-amylperoxy)cyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, dicumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumyl hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, diethyl peroxydicarbonate, isopropyl t-butyl peroxy carbonate, 2-ethylhexyl t-butyl peroxy carbonate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di(hexadecyl) peroxydicarbonate, di(myristyl) peroxydicarbonate, 2-ethylhexyl t-amyl peroxy carbonate, isopropyl t-butyl peroxy carbonate, 2-ethylhexyl t-butyl peroxy carbonate, ethyl t-butyl peroxy oxalate; (t-butylperoxy) benzyl oxalate; t-butyl-N-(3-methylphenylperoxy) carbamate; potassium persulfate and mixtures thereof.

21. The method of claim 14, wherein In process step B) and / or D) the addition of the at least one initiator is carried out in at least two portions to polymerize the monomers, while after each portion of initiator is added a free radical polymerization is carried out.

22. The method of claim 14, wherein In process step A) and / or C) at least one chain transfer agent is added.

23. Polymer obtained according to the process of any one of claims 14 to 22.

24. A personal care formulation containing at least one polymer according to any one of claims 1 to 14 or 23.

25. Use of at least one polymer according to any one of claims 1 to 14 or 23 or a formulation according to claim 24 for forming a film on a surface.

26. Use according to claim 25, characterized in that The surface is skin and / or hair.

27. Use of at least one polymer according to any one of claims 1 to 14 or 23 or a formulation according to claim 24 for imparting a dry skin feel to a formulation.

28. Use according to claim 27, characterized in that The formulation is an emulsion.

29. Use of at least one polymer according to any one of claims 1 to 14 or 23 or a formulation according to claim 24 for retaining a fragrance on a surface.

30. Use according to claim 29, characterized in that The surface is skin and / or hair.

31. Use of at least one polymer according to any one of claims 1 to 14 or 23 or a formulation according to claim 24 for dispersing a solid pigment.

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