Biobased olefins in silicones

Abstract

The present invention relates to a process for producing a bio-based, alkyl-modified silicone polymer and its use in hygiene products and / or cosmetic products. According to the invention, the bio-based component is achieved by modification with bio-based olefins.

Description

[0001] The present invention relates to a process for producing a bio-based alkyl-modified silicone polymer and its use in hygiene products and / or cosmetic products. According to the invention, the bio-based component is achieved by using bio-based olefins in the silicone polymer production.

[0002] Silicones have a wide range of applications. They are heat-resistant, hydrophobic, dielectric, and generally considered physiologically compatible, which is why they are used for skin protection, cosmetic skincare, and in plastic surgery. Unlike mineral oils or vegetable oils, silicone polymers in particular are based on siloxane-based chain molecules as their basic structure. This is characterized by the periodically alternating arrangement of silicon and oxygen atoms with the general formula [R 1 R 2 SiO] nR groups are covalently bonded to the silicon atom. These R groups are organic, but can also be halogens and / or hydrogen atoms. Thus, in addition to the inorganic component, they also possess an organic component. However, these organo-modified silicones have a clear disadvantage: the modification of the R group is achieved using petrochemical-derived raw materials or is only possible to a limited extent from natural raw materials. However, there are requirements for consumer goods, such as cosmetic products, household care and cleaning products, as well as car care and cleaning products, that these products contain raw materials with a high natural content. This is also required by many labels and reflects the sustainability strategies of the UN and EU. In alkyl-modified silicone polymers, in particular, the R group consists of petrochemical-derived raw materials, such as olefins.

[0003] Conventional alkyl-modified silicones with an alkyl chain having a carbon number greater than or equal to 6 consist of petrochemical raw materials. Other product classes, such as alkoxylated silicones, contain only a small proportion of natural raw materials (<50%) due to their modification, or are adjusted to a proportion >50% by dilution with water, thereby losing quality.

[0004] Chieregato et al. reveal how short-chain olefins can be obtained from biomass (Chemicals and Fuels from Bio-Based Building Blocks, First Edition. Edited by Fabrizio Cavani, Stefania Albonetti, Francesco Basile, and Alessandro Gandini. 2016 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2016 by Wiley-VCH Verlag GmbH & Co. KGaA, pages 3-25).

[0005] Currently, there is no sustainable approach to producing these silicone polymers, especially alkyl-modified ones, with a high natural content.

[0006] Surprisingly, it was found that the use of naturally derived olefins in the synthesis of alkyl-modified silicone polymers is easily possible.

[0007] It should be clarified that the terms silicones, silicone polymers, siloxanes and siloxane polymers are synonymous and therefore do not limit the invention.

[0008] In a first embodiment, the problem underlying the invention is solved by a process for producing a bio-based alkyl-modified silicone polymer, comprising at least the following steps: a) Submission of at least one bio-based terminal olefin, b) Adding at least one siloxane polymer, c) Adding at least one transition metal catalyst, which is optionally dissolved in a solvent, d) Reaction of the mixture with stirring at a temperature of 65 °C to 130 °C, whereby the bio-based alkyl-modified silicone polymer is formed and the resulting alkyl-modified silicone polymer has a bio-based content of at least 45 wt.% based on the mass of the polymer, further defined according to the invention by the weight-average molar mass.

[0009] Surprisingly, it has been shown that bio-based alkyl-modified silicone polymers with a very high conversion of the siloxane polymer can be produced using the process according to the invention. The bio-based alkyl-modified silicone polymers obtained by the process according to the invention have a high bio-based content and are therefore better accepted by end customers, as the silicones are correspondingly more sustainable. The process according to the invention is thus characterized, among other things, by high energy and raw material efficiency, making it particularly sustainable.

[0010] By modifying a silicone framework with alkyl groups from natural raw materials, a higher bio-based content can be achieved than described in the literature. This modification is accomplished using an olefin with a carbon chain of C = 6 to 45.

[0011] By incorporating side chains with a mass fraction of at least 51%, the silicone polymer meets the requirements, making it possible to produce formulations with a natural content greater than 50%. This provides a bio-based solution for the cosmetics and hygiene products industries, which previously could only be achieved using petrochemicals.

[0012] For the purposes of the present invention, unmodified siloxane polymers are understood to have the general formula (R 1 )3Si-[O-Si(R 2 )(R 3 )] n -O-Si(R 1 )3 where R 1 , R 2 and / or R 3 These are alkyl groups or hydrogen atoms. These are familiar to those skilled in the art, and according to the invention, it is possible to use all siloxane polymers in the process which have an alkyl group and / or at least one hydrogen atom.

[0013] R 1The alkane can thus be selected from linear and branched alkanes or hydrogen atoms, wherein the alkanes have a carbon number of C = 1 to 50, preferably a carbon number of C = 1 to 30, and particularly preferably a carbon number of C = 1 to 10. It is especially preferred that the carbon atoms be located at the ends of the siloxane polymer, i.e., as R. 1 , hydrogen, methyl, ethyl, isopropyl, propyl, butyl and / or isobutyl, even more preferably R 1 selected from methyl or hydrogen.

[0014] R 2 can be used with R 1The alkanes can be identical and can therefore be selected from linear and branched alkanes or hydrogen atoms, wherein the alkanes have a carbon number of C = 1 to 50, preferably a carbon number of C = 1 to 30, and particularly preferably a carbon number of C = 1 to 10. Hydrogen, methyl, ethyl, isopropyl, propyl, butyl and / or isobutyl are particularly preferred, and hydrogen or methyl are most preferred.

[0015] This also applies to R 3 , so R can also 3 with R 1 be identical. Thus, R can also be identical. 3The alkanes are selected from linear and branched alkanes or hydrogen atoms, wherein the alkanes have a carbon number of C = 1 to 50, preferably a carbon number of C = 1 to 30, and particularly preferably a carbon number of C = 1 to 10. Methyl, ethyl, isopropyl, propyl, butyl and / or isobutyl are most preferred, and hydrogen or methyl are most preferred.

[0016] The unmodified siloxane polymers used in the process according to the invention must not be selected in such a way that R 2 and R 3 They are identical if one of them is an alkane. However, they can be identical if R 2 and / or R 3 These are hydrogen atoms.

[0017] However, it is also possible that R 1 , R 2 and / or R 3 hydrogen atoms are, where the groups R 1 , R 2 and / or R 3 They can be different.

[0018] In a preferred embodiment of the unmodified siloxane polymer, R 3 a hydrogen atom, as well as R 1 and R 2 Alkane residues, as described above, with the general formula (R 1 )3Si-[O-Si(R 2 )(R 3 )] n -O-Si(R 1 )3, where R 1 and R 2 are the same or different.

[0019] According to the invention, a bio-based terminal olefin is understood to be a terminal olefin obtained from a natural source. The term terminal olefin used here refers to α-olefins that have at least one terminal, non-conjugated carbon-carbon double bond. This includes both linear and branched α-olefins. α-olefins may contain one or more carbon double bonds in addition to the terminal double bond, which are also known to those skilled in the art as dienes. Preferably, however, these are simple linear or branched α-olefins characterized by having only one double bond at the α-position.

[0020] The bio-based olefins used in the process according to the invention can be obtained from natural oils such as rapeseed oil, sunflower oil, avocado oil, or other natural oils. It is also possible to obtain the bio-based olefins from other natural substances, such as terpenes. It is also conceivable to obtain the bio-based olefins used in the invention from a bio-alcohol via dehydration. In particular, naturally derived alcohols that are converted to olefins via an elimination reaction can serve as a natural source. It is irrelevant how the olefins according to the invention are produced, as long as they are obtained from a natural source. Therefore, olefins that can be obtained from natural alcohols or bio-alcohols, especially fatty alcohols, are particularly suitable for the process according to the invention.According to the invention, a natural source is understood to mean that the olefins are obtained from renewable raw materials and, in particular, not from petrochemical sources. Bio-based olefins, within the meaning of the present invention, mean that the olefins contain at least 70% by weight, preferably at least 80% by weight, most preferably at least 90% by weight, and even more preferably at least 95% by weight of natural raw materials, based on the total mass of the respective olefin.

[0021] Furthermore, according to the invention, a transition metal catalyst is used in the process, which is optionally dissolved in a solvent. All hydrosilylation catalysts are suitable as a transition metal catalyst according to the invention. Those skilled in the art will know how to select them accordingly. The metals of the transition metal catalyst according to the invention are particularly preferably selected from the group consisting of platinum, iridium, rhodium, ruthenium, and / or iron, preferably selected from a platinum complex, and most preferably selected from platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solutions. Other alternatives include catalysts based on di-m-chlorobis(1,2-η)-cyclohexene, platinum(II) chloride, dichloro(1,5-cyclooctadiene)platinum, cis-bis-(benzonitrile)-dichloroplatinum, and hexachloroplatinic acid. According to the invention, the catalyst can also be used in a solvent in the process.The solvent is selected from known polymerization catalyst solvents, such as 1,3-divinyltetramethyldisiloxane (“Karstedt solution”), propanol, butyldiglycol and / or ethylene, allyl polyether, or allyl alcohols. However, it is also possible to carry out the reaction using solvent-free catalysts.

[0022] The process according to the invention thus provides a bio-based, alkyl-modified silicone polymer characterized in that it contains at least 50% by weight of bio-based material based on the mass of the polymer. This makes it possible to supply silicones with a high bio-based content to the cosmetics and hygiene products industries, which previously only had access to petrochemical-derived silicones.

[0023] Preferred embodiments of the inventive process for the production of bio-based alkyl-modified silicone polymers and their use are described below, wherein all features can be combined in any way and do not restrict the inventive process and its use in any way.

[0024] In a preferred embodiment, the method can be characterized in that the at least one unmodified siloxane polymer comprises at least one unit of the form-[Si(CH3)HO] n - with n = 1 to 100, preferably n = 25 to 90, most preferably n = 50 to 80. Thus, in this preferred embodiment, the unmodified siloxane polymer with the general formula (R 1 )3Si-[O-Si(R 2 )(R 3 )] n -O-Si(R 1 )3 also as (R 1 )3Si-[O-Si(CH3)(H)] 0-100 -O-Si(R 1 )3 are described, where R 2= CH3 and R 3 = H is. Furthermore, in this preferred embodiment, R can 1 = CH3, C2H5 or C3H7.

[0025] In addition, in this preferred embodiment, the at least one unmodified siloxane polymer can include a further unit of the form -[Si(CH3)2O] m -with m = 1 to 300, preferably m = 20 to 200, most preferably m = 50 to 150. Thus, in this preferred embodiment, the unmodified siloxane polymer with the general formula (R 1 )3Si-[O-Si(R 2 )(R 3 )] n -O-Si(R 1 )3 also as (R 1 )3Si-[O-Si(CH3)(H)] 0-100 -[OSi(CH3)2] 1-300 -O-Si(R 1 )3 can be described. Furthermore, in this preferred embodiment, R 1 = CH3, C2H5 or C3H7, even more preferred R 1 = CH3 or H.

[0026] In a further preferred embodiment, the bio-based terminal olefin in the process can have a carbon number of C = 6 to 45, preferably C = 9 to 30, most preferably C = 10 to 25, and even more preferably C = 11 to 20. The carbons can be either linear or branched. Preferably, only linear olefins are used. According to the invention, the olefin is a terminal olefin. This means that the double bond is located at the α-carbon atom, although further double bonds in the olefin are also possible.

[0027] In a further preferred embodiment, the bio-based terminal olefin is characterized in that it has at least one ester group, one carboxylic acid group, and / or one hydroxyl group. This means that a bio-based olefin according to the invention has either three of these groups, two of these three groups, or only one of these groups. This is explained in more detail below: If the bio-based terminal olefin has only one of these groups, this group is preferentially positioned at the opposite end relative to the terminal double bond of the olefin, such that the olefin is in the form R 4 -(CH2) n -CHCH2 is present, where n is selected from n = 6 to 45, preferably n = 9 to 30, most preferably n = 10 to 25, even more preferably n = 11 to 20 and R 4 the functional group is selected from an ester, carboxylic acid, or hydroxyl group. If the bio-based terminal olefin has two of these groups, one of these groups is preferably positioned at the other end with respect to the terminal double bond of the olefin and one in the alkyl chain, such that the olefin is in the form R 4 -(CH2) m -(CHR 5 )-(CH2) o -CHCH2 is present, whereby m and o are chosen from natural numbers such that their sum is a natural number n as defined above, and R 4 and R 5 an ester, carboxylic acid, or hydroxyl group. R 4 and R 5 be the same or different. If the bio-based terminal olefin has three of these groups, one of these groups is preferably positioned at the other end with respect to the terminal double bond of the olefin and two in the alkyl chain, such that the olefin is in the form R 4 -(CH2) m -(CHR 5 )-(CH2) o -(CHR 6 )- (CH2) p -CHCH2 is present, whereby m, o and p are chosen from natural numbers such that their sum is a natural number n as defined above, and R 4 , R 5 and R 6 an ester, carboxylic acid, or hydroxyl group. R 4 , R 5 and R6 be the same or different. The ester group gives this the form of R (4 / 5 / 6) = R 7 -OC-O- on where R 7 The choice is made from methyl, ethyl, isopropyl, propyl, butyl, or isobutyl. In all these embodiments, the carboxylic acid group has the form R (1 / 2 / 3) = HOOC and the hydroxyl group form R (1 / 2 / 3) = HO- up.

[0028] In a further preferred embodiment, the bio-based terminal olefin is characterized in that it has no further functional groups. Functional groups are understood to be halogens, carboxylic acids, esters, ethers, hydroxyl groups, and other functional groups familiar to those skilled in the art. This means that the olefin either has the form (CH2) n-CHCH2 or one of the forms shown above. This means that the bio-based terminal olefin according to the invention is a “pure” terminal olefin of the form (CH2) n -CHCH2 is or R 4 -(CH2) n -CHCH2, R 4 -(CH2) m -(CHR 5 )-(CH2) o -CHCH2, or also R 4 -(CH2) m -(CHR 5 )-(CH2) o -(CHR 6 )-(CH2) p -CHCH2, wherein these disclosed forms of the olefin do not have any additional groups. Thus, all preferred embodiments are disclosed and are not inconsistent with each other.

[0029] As previously described, the bio-based terminal olefin is obtained from a natural source or natural raw materials. Natural fatty alcohols are preferably used for the synthesis of the olefin. These natural fatty alcohols can be obtained directly from natural sources, such as beeswax, and converted to the corresponding olefin via an elimination reaction. It is also possible to obtain the fatty alcohols from fatty acids derived from natural oils. In this case, the fatty acid can be reduced to the corresponding alcohol and then eliminated to obtain the desired olefin.

[0030] In a preferred embodiment according to the inventive process, the bio-based content of the resulting bio-based alkyl-modified silicone polymer is 60 wt.% to 98 wt.%, preferably 80 wt.% to 95 wt.%, based on the mass of the polymer. For the purposes of this invention, "bio-based" means that the content is derived from a natural source, as described above. The bio-based content of the final siloxane polymer is achieved by incorporating the bio-based terminal olefins into the silicone polymer, thus creating a bio-based alkyl-modified silicone polymer. The bio-based content can therefore be controlled by modifying the functionality of the unmodified siloxane polymers. An increased proportion of terminal bio-based olefins corresponds to an increase in the bio-based content of the final product.

[0031] The structure of the bio-based alkyl-modified silicone polymer obtained according to the invention can thus be described by the fact that the residues in (R 1 )3Si-[O-Si(R 2 )(R 3 )] n -O-Si(R 1 )3 of the unmodified siloxane polymer used, R 2 and / or R 3 , can be substituted by the bio-based terminal olefin if the substituted residues R 2 and / or R 3 Hydrogen are involved. This process involves hydrosilylation, in which, under the influence of a catalyst, a silane is added to the double bond of the α-carbon atom of a bio-based olefin.

[0032] In a further preferred embodiment, the process in step d) is carried out at a temperature of 70 °C to 120 °C, particularly preferably from 75 °C to 115 °C, most preferably from 80 °C to 110 °C.

[0033] In a further preferred embodiment, the process is characterized in that the siloxane polymer is almost completely converted. In this preferred embodiment, almost complete conversion means that the free hydrogens of the siloxane polymer, i.e., silanes of the form Si-H, are converted and consequently these groups have undergone a reaction with the bio-based olefin according to the invention. This conversion can be determined by the content of the SiH groups. In this preferred embodiment, complete conversion corresponds to a conversion of at least 85%, preferably at least 90%, even more preferably at least 95%, or most preferably at least 99%, based on the amount of substance of the siloxane polymer used.

[0034] In a further preferred embodiment, the process is characterized in that the sequence of steps a), b), c), and d) according to the invention is carried out as follows. However, steps a) and b) can be interchanged as long as the input component is at the reaction temperature. This ensures an efficient process with a high conversion rate. It should be clarified here that other process steps can be incorporated between the steps and are not excluded.

[0035] Furthermore, the invention also discloses the use of a bio-based alkyl-modified silicone polymer, preferably obtained by a process according to the present invention, as an excipient in cosmetic or hygiene products. Possible uses according to the invention are explained in more detail below: Bio-based, alkyl-modified silicone polymers obtained according to the invention can be used as emollients in cosmetic and personal care products. The modification allows for control of the skin feel, depending on the alkyl chain distribution. Additionally, this product class offers further benefits such as texture control, improved spreading and distribution behavior, reduced stickiness, enhanced water repellency, pigment dispersion, film-forming properties, and solubilizing effects, thus enabling a wide range of applications. The products are also ideally suited for use in polishes or wax formulations for the care of hard surfaces and leather. The modification allows for the creation of a distinctive feel, the necessary water repellency, and glossy effects.

[0036] A combination of amino or quaternary nitrogen groups and bio-based alkyl-modified silicone polymers obtained according to the invention can be used as conditioning agents and emulsifiers in hair care and cleaning products, improving combability, smoothness, and feel. Furthermore, the products achieve color and heat protection due to the bio-based alkyl-modified silicone polymer obtained according to the invention. When used in cleaning and care products for household, laundry, and automotive applications, the products produce a glossy effect, water repellency, and can improve the feel of the hair.

[0037] A combination of amido-amino groups (reaction of amino groups and glucone-delta-lactone) and bio-based, alkyl-modified silicone polymers obtained according to the invention can be used as a PEG-free silicone emulsifier for W / O, O / W, Si / W, and W / Si formulations in cosmetic and personal care products. In addition to their emulsifying function, these products offer further benefits such as pigment dispersion, improved texture, and reduced stickiness. Furthermore, these types of polymers are suitable as conditioning agents in hair care and cleaning products. The modification is characterized by a unique feel and improved dry combability. Other areas of application include polishes, fabric softeners, and cleaning agents.

[0038] The moderate hydrophobicity of the polymers makes them particularly well-suited for fabric softeners and floor care / cleaning products, as the former requires hydrophilicity while the latter only needs moisture protection. Furthermore, the products can enhance the intensity of fragrances and provide longer-lasting freshness.

[0039] A combination of polyethers or polyglycols and bio-based alkyl-modified silicone polymers obtained according to the invention can be used as a silicone emulsifier / surfactant for W / O, O / W, Si / W and W / Si in cosmetic and personal care products. In addition to the emulsifier function, these products also offer additional effects such as pigment dispersion, texture improvement, reduction of stickiness, and can support the cleaning effect as a mild surfactant.

[0040] The concept of the present invention is explained in more detail with the following exemplary embodiments, which do not limit the subject matter of the invention to these.

[0041] As is known to those skilled in the art, the amount of reactive SiH functionalities of the polysiloxane used is given in mol / kg. The allyl content of the olefin used is characterized by a theoretically calculated iodine number (IN).

[0042] As is also known to those skilled in the art, the reaction conversion is determined by the gas-volumetric displacement of a saturated aqueous potassium chloride solution upon contact of the polysiloxane with a butanolic 10% (based on the mass fraction of the salt) potassium hydroxide solution.

[0043] All polymeric materials obtained were analyzed using the weight-average (M) method. w ) molar mass characterized by gel permeation chromatography (Infinity 1260, Agilent).

[0044] Materials obtained in this way, solid at 22 °C, were characterized via their melting point using dynamic differential thermal analysis (DIN EN ISO 11357-1:2016, EN ISO 11357-2:2020, EN ISO 11357-3:2018) (DSC 204 F1 PH ASC Phoenix). ® , Netzsch Gerätebau GmbH, additionally equipped with an intracooler from Huber, T start = -75 °C, T ende = 200 °C, ΔT = 10 K min -1 ).

[0045] Materials obtained in this way, which were liquid at 22 °C, were additionally characterized by rotational viscometry (60 rpm, 22 °C, attachment L2, HAAKE™ Viscotester™ C, Thermo Scientific™) in addition to determining the melting point via kinematic viscosity.

[0046] Production of the bio-based alkyl-modified silicone polymer: Example 1: Conversion of a bio-based C10-C18 terminal olefin (IZ=113)

[0047] In a 250 mL reaction vessel, 140 g of the C10-C18 olefin were placed and heated to 100 °C with stirring. After reaching the required temperature, 30.0 g of a hydrogen siloxane of the middle formula was added with continuous stirring: (CH3)3Si-[O-Si(CH3)(H)] 60-80 -O-Si(CH3)3,

[0048] characterized by a hydrogen content of 16.1 mol / kg and a calculated molecular weight of 3800-5000 Da, added within 75 minutes and mixed with 0.0453 g of a dilute Karstedt solution in Dowanol DPM ®(Dipropylene glycol methyl ether, Dow Chemical, USA) was added to the reaction mixture to achieve a Pt content of 8 ppm. The reaction progress was monitored by gas volumetric SiH determination. After 12 h, an SiH content of <90 ppm was determined, thus defining the reaction as complete. This corresponds to a conversion of 99.4% of the siloxane polymer. The product obtained is solid to waxy at 22 °C. A melting point of 34 °C was measured, and a weight-average molar mass of M was determined. w = 28000 Determined. Example 2: Conversion of a bio-based C10-C18 terminal olefin (IZ=113)

[0049] In a 250 mL reaction vessel, 127 g of the C10-C18 olefin were placed and heated to 80 °C with stirring. After reaching the required temperature, 70.0 g of a hydrogen siloxane of the middle formula was added with continuous stirring: (CH3)3Si-[O-Si(CH3) 15-30 (H)] 15-30 -O-Si(CH3)3, characterized by a valence of 7.04 mol / kg and a calculated molecular weight of 2200-4200 Da, dosed within 60 minutes and mixed with 0.0504 g of a Karstedt solution in the solvent Dowanol DPM ® (Dow Chemical, USA) was adjusted to achieve a Pt content of 8 ppm in the reaction mixture. After complete addition of the hydrogen siloxane, the temperature was increased to 110 °C. The reaction progress was monitored by gas volumetric SiH determination. After 5 h, an SiH content of <25 ppm was determined, thus defining the reaction as complete. This corresponds to a conversion of 99.6% of the siloxane polymer. The product obtained is liquid at 22 °C and clear to yellowish. A dynamic viscosity of 143 mPas and a melting point of 13.9 °C were measured, along with a weight-average molar mass of M. w = 11600 Da determined. Example 3: Implementation of a bio-based terminal olefin with ester functionalization (IZ=138)

[0050] 153 g of the olefin were placed in a 250 mL reaction vessel and heated to 100 °C with stirring. After reaching the required temperature, 40 g of a hydrogen siloxane of the middle formula was added with continuous stirring: (CH3)3Si-[O-Si(CH3)(H)] 60-80 -O-Si(CH3)3, characterized by a valence of 16.1 mol / kg and a calculated molecular weight of 3800-5000 Da, dosed within 60 minutes and mixed with 0.0515 g of a Karstedt solution in the solvent Dowanol DPM ®(Dow Chemical, USA) was adjusted to a Pt content of 8 ppm in the reaction mixture. The reaction progress was monitored by gas volumetric SiH determination. After 5 h, an SiH content of <70 ppm was determined, and the reaction was thus defined as complete. This corresponds to a conversion of 99.6% of the siloxane polymer. The product obtained is liquid at 22 °C and clear to yellowish. A dynamic viscosity of 385 mPas and a melting point of -22 °C were measured, and a weight-average molar mass of M was determined. w = 11200. Determined. Example 4: Conversion of a bio-based C8-C14 terminal olefin (IZ=181)

[0051] 114 g of the olefin were placed in a 250 mL reaction vessel and heated to 80 °C with stirring. After reaching the required temperature, 100 g of a hydrogen siloxane of the middle formula was added with continuous stirring: (CH3)3Si-[O-Si(CH3) 15-30 (H)] 15-30-O-Si(CH3)3, characterized by a valence of 7.04 mol / kg and a calculated molecular weight of 2200-4200 Da, dosed within 60 minutes and mixed with 0.0568 g of a Karstedt solution in the solvent Dowanol DPM ® (Dow Chemical, USA) was adjusted to achieve a Pt content of 8 ppm in the reaction mixture. After complete addition of the hydrogen siloxane, the temperature was increased to 110 °C. The reaction progress was monitored by gas volumetric SiH determination. After 6 h, an SiH content of <20 ppm was determined, thus defining the reaction as complete. This corresponds to a conversion of 99.6% of the siloxane polymer. The product obtained is liquid at 22 °C and is clear and yellowish. A dynamic viscosity of 66 mPas and a melting point of -57 °C were measured, along with a weight-mean molar mass of M. w = 7900 Determined.

[0052] Formulation of a moisturizing day cream: B phase ingredient Bio-based origin% vol. Petrochemical origin in vol. A Isopropyl myristate 2,00 2,00 almond oil 0,85 0,85 silicone polymer 6,00 - silicone polymer - 6,00 Caprylic / Capric Triglyceride 11,00 11,00 Cetearly-glucoside 2,00 2,00 Tocopherol acetate 0,25 0,25 Fragrance 0,10 0,10 B Glycerin 10,00 10,00 Trisodium citrate 0,50 0,50 Sodium benzoate 0,30 0,30 Water Remaining quantity up to 100 Remaining quantity up to 100 Quantity of petrochemical raw materials* <1 5,4 Natural origin content of the formulation according to ISO 16128-1** > 99,3 >93,7 * Figures in vol.% ** Percentage figure Production:

[0053] The components of phase A were heated together in a container to 65 °C and stirred. The components of phase B were heated together in a container to 85 °C and stirred. Subsequently, phase B was imulsified into phase A and then cooled to 20 °C while stirring. Calculation for classification according to ISO 16128-1:

[0054] Silicone polymer according to Example 1 modified with the bio-based terminal olefin C = 16: In MW Amount in wt.% Fossil component 1154 6 Mineral content 138 1 Organic share 17100 93 In total 18392 100

[0055] Thus, the silicone polymer according to the invention had a bio-content of 93%, whereas petrochemical silicone polymers have no bio-content.

[0056] Formulation of a conditioner for hair care: C phase ingredient Bio-based origin% vol. Petrochemical origin in vol. A Water Remaining quantity to 100.00 Remaining quantity to 100.00 B Cetearyl alcohol 5,00 5,00 Behentrimonium chloride 85% 3,00 3,00 Cetyl esters 1,00 1,00 Jojoba oil 0,50 0,50 coconut oil 0,50 0,50 silicone polymer 2,50 - silicone polymer - 2,50 C Sodium benzoate and potassium sorbate 0,75 0,75 Lactic acid 80% At pH 3.7 - 4.5 At pH 3.7 - 4.5 Tocopherol acetate 0,15 0,15 Fragrance 0,10 0,10 Quantity of petrochemical raw materials* <3 <3 Natural origin content of the formulation according to ISO 16128-1** >99 >97 * Figures in vol.% ** Percentage and mineral origin taken into account Production:

[0057] The components of phase B were heated together in a container to 85 °C and stirred together. Phase A was heated to 85 °C.

[0058] Phase B was then imulsified into Phase A and subsequently cooled to 40 °C while stirring, the ingredients of Phase C were added, and the pH was adjusted using lactic acid. Calculation for classification according to ISO 16128-1:

[0059] Silicone polymer according to example 2 modified with the bio-based terminal olefin C = 14-16: In MW Amount in wt.% Fossil component 930 13 Mineral content 1744 24 Organic share 4500 63 In total 7174 100

[0060] Thus, the silicone polymer according to the invention had a bio-content of 63%, whereas petrochemical silicone polymers have no bio-content.

[0061] It has been found that the bio-based silicone polymers according to the invention can be used without any problems. This allows both compliance with guidelines and increased consumer acceptance. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited non-patent literature

[0000] Chemicals and Fuels from Bio-Based Building Blocks, First Edition. Edited by Fabrizio Cavani, Stefania Albonetti, Francesco Basile, and Alessandro Gandini.2016Wiley-VCH Verlag GmbH & Co. KGaA. Published 2016 by Wiley-VCH Verlag GmbH & Co. KGaA, page 3-25

[0004] DIN EN ISO 11357-1:2016

[0044] EN ISO 11357-2:2020

[0044] EN ISO 11357-3:2018

[0044]

Claims

[1] Method for producing a bio-based alkyl-modified silicone polymer comprising at least the following steps: a) Submission of at least one bio-based terminal olefin, b) Adding at least one unmodified siloxane polymer, c) Adding at least one transition metal catalyst, which is optionally dissolved in a solvent, d) Reaction of the mixture with stirring at a temperature of 65 °C to 130 °C, whereby the alkyl-modified silicone polymer is formed and the resulting alkyl-modified silicone polymer has a bio-based content of at least 45 wt.% based on the mass of the polymer. [2] Method according to claim 1 characterized by , that at least one unmodified siloxane polymer contains at least one unit of the form - [Si(CH3)HO] n - with n= 1 to 100. [3] Method according to claim 2 characterized by, that at least one siloxane polymer is another unit of the form -[Si(CH3)2O] m - with m = 1 to 300. [4] Method according to at least one of claims 1 to 3 characterized by , that at least one bio-based terminal olefin has a carbon number of 5 to 25, preferably 6 to 20, most preferably 10 to 18. [5] Method according to at least one of claims 1 to 4 characterized by that at least one bio-based terminal olefin has at least one ester, one carboxylic acid and / or one hydroxyl group. [6] Method according to at least one of claims 1 to 5 characterized by that at least one bio-based terminal olefin has no further additional functional groups. [7] Method according to at least one of claims 1 to 6 characterized bythat the obtained alkyl-modified silicone polymer has at least a bio-based content of 60 wt.% to 98 wt.%, preferably 80 wt.% to 95 wt.% based on the mass of the polymer. [8] Method according to at least one of claims 1 to 7 characterized by that at least one bio-based terminal olefin was obtained from a natural source of fatty alcohols, in particular from fatty alcohols with a chain length of C = 6 to 45. [9] Use of an alkyl-modified silicone polymer, in particular obtained by a process according to at least one of claims 1 to 7, as an excipient in cosmetic and / or hygiene products.