Novel functionalized organopolysiloxane compound, its production method and use

Abstract

The present invention relates to novel functionalized organopolysiloxane compounds having a polysiloxane backbone, (meth)acrylic groups, and hydrophilic polyether groups. The invention further relates to a method for making said functionalized organopolysiloxanes and their use in making silicone gels, rubbers, coatings, and emulsions useful in a variety of applications, including cosmetics, personal care, medical, household care, textiles, electronics, coatings, construction, surfactants, defoamers, emulsifiers, and ophthalmic lens materials.

Description

[Technical Field]

[0001] The present invention relates to novel functionalized organopolysiloxane compounds. More specifically, the present invention relates to novel functionalized organopolysiloxane compounds with improved hydrophilicity that can be used as such or in the production of silicone gels, rubbers, coatings, and emulsions useful in a variety of applications, including cosmetics, personal care, medical care, household care, textiles, electronics, coatings, construction, surfactants, defoamers, and emulsifiers. Furthermore, the novel functionalized organopolysiloxane compounds of the present invention can be useful as ophthalmic lens materials. [Background technology]

[0002] Functionalized organopolysiloxane compounds have attracted considerable interest in many technical fields due to their unique properties. Among functionalized organopolysiloxanes, those that simultaneously possess non-polymerizable and polymerizable functional groups have been the focus of attention.

[0003] Prior art document US 4,259,467 discloses a polysiloxane compound containing hydrophilic side chains and terminally activated monounsaturated groups for free radical polymerization. Prior art document US 2014 / 0350278 A1 discloses a method for producing a polymerizable hybrid polysiloxane. The method involves reacting an organopolysiloxane having an average of three or more silicon hydride (SiH) groups per molecule, polyoxyethylene, and a catalyst. This process can produce a SiH-containing silicone-EO copolymer in which PEO is grafted onto the silicone chain. Prior art document US 2009 / 0234089 A1 discloses a hydrophilic polysiloxane macromonomer containing polyoxyethylene as a hydrophilic side chain in the polysiloxane main chain. Prior art document EP 3418319 A1 discloses a polysiloxane compound containing a polyoxyethylene group and a terminal (meth)acrylic group attached to the silicon atom by a bond containing an arylene group. Prior art document US2016 / 0311981A1 discloses a polysiloxane having polymerizable groups at both ends and a hydrophilic side chain having three hydroxyl groups and an alkyl group without an ether bond. Prior art document WO2022 / 141795A1 discloses a polysiloxane compound containing a polyoxyethylene group and one (meth)acrylic group only at the ends, not at the side chains. Summary of the Invention [Problem to be solved by the invention]

[0004] SUMMARY OF THE INVENTION An object of the present invention is to provide novel functionalized organopolysiloxane compounds having polyether side chains and (meth)acrylic end groups, and a method for preparing said novel functionalized organopolysiloxane compounds. [Means for solving the problem]

[0005] All these objectives are achieved, inter alia, by the following functionalized organopolysiloxanes: a units of formula (I): RSiO 1 / 2 - b unit of formula (II): R2R MET SiO 1 / 2 - c unit of formula (III): R2R PE SiO 1 / 2 - d unit of formula (IV): R2SiO 2 / 2 - e unit of formula (V): RR MET SiO 2 / 2 - f unit of formula (VI): RR PE SiO 2 / 2 In the formula, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, optionally substituted with one or more halogen atoms, preferably an alkyl group having 1 to 8 carbon atoms (such as methyl, ethyl, propyl or 3,3,3-trifluoropropyl group), a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms; R MET=

Chemical formula

Chemical formula

[0006] Another object of the present invention is a method for producing the functionalized organopolysiloxane disclosed above, comprising the following steps: 1) hydrosilylating an organohydrogenpolysiloxane compound with an alkenyl glycidyl ether and an alkenyl polyether, and 2) (meth)acrylating the epoxy functional groups of the glycidyl ether.

[0007] The present invention further relates to the use of said functionalized organopolysiloxanes in the production of silicone gels, rubbers, coatings and emulsions, which are useful in a variety of applications, including cosmetics, personal care, medical, house care, textiles, electronics, coatings, construction, surfactants, defoamers, emulsifiers, etc. The present invention further relates to the use of said functionalized organopolysiloxanes as such or in the production of ophthalmic lens materials. DETAILED DESCRIPTION OF THE INVENTION

[0008] Unless otherwise specified, the viscosity of the silicone compositions and their individual components described herein corresponds to the magnitude of the "Newtonian" dynamic viscosity at the indicated temperature, i.e., the dynamic viscosity measured in a manner known per se using a Haak rheometer at a shear rate gradient sufficiently low that the measured viscosity is independent of the shear rate gradient. For example, the viscosity can be measured using a Haak rheometer in a cone / plate 60 mm geometry, applying a sinusoidal stress of 1 Pa at 1 Hz.

[0009] Unless otherwise specified, % or ppm contents are by weight.

[0010] The object of the present invention is the following functionalized organopolysiloxanes: a units of formula (I): RSiO 1 / 2 b units of formula (II): R2R MET SiO 1 / 2 c units of formula (III): R2R PE SiO 1 / 2 - d unit of formula (IV): R2SiO 2 / 2 - e unit of formula (V): RR MET SiO 2 / 2 - f unit of formula (VI): RR PE SiO 2 / 2 In the formula, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, optionally substituted with one or more halogen atoms, preferably an alkyl group having 1 to 8 carbon atoms (such as methyl, ethyl, propyl or 3,3,3-trifluoropropyl group), a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms; R MET=

Chemical formula

Chemical formula

[0011] It is understood that in the above formulas (I) to (VI), when a plurality of R groups are present, they may be the same as or different from each other.

[0012] R as defined above MET The group is a hydroxy-containing (meth)acrylic group represented by formula (VII) or formula (VIII). Throughout this specification, it should be understood that a (meth)acrylic group includes an acrylic group, a methacrylic group, or a mixture of the two. The groups represented by formula (VII) and formula (VIII) are isomers that may result from the manufacturing process. Depending on the synthetic route chosen, R MET R can be a group of formula (VII), a group of formula (VIII), or a mixture of both. In the case of a mixture, the groups of formula (VII) will predominate, typically accounting for 75% or more. MET In the definition, p is a number that satisfies 2≦p≦10, preferably 2≦p≦4, and more preferably p=3.

[0013] R as defined above PE The group contains a polyether structure, which confers interesting hydrophilic properties to the functionalized organopolysiloxanes according to the present invention. PE In the definition of R, m is a number that satisfies 2≦m≦10, preferably 2≦m≦4, and more preferably m=3. PE In the definition of (R), n is the number of oxyethylene (OE) units, and o is the number of oxypropylene (OP) units, (OE) and / or (OP) units forming a polyether side chain. n and o are 0 or 4≦(n+o)≦100, preferably 5≦(n+o)≦30, and more preferably 6≦(n+o)≦20. In one embodiment, o is 0, i.e., R PE In another embodiment, n is 0, i.e., R PE In another embodiment, n and o are both different from 0, i.e., R PE The group contains both OE and OP units, in which case the OE and OP units may be arranged randomly, in blocks, or in both random and block arrangements.

[0014] The functionalized organopolysiloxane according to the present invention contains at least units of formulas (I) to (VI), and the number of each unit is defined by numbers a to f respectively. According to the present invention, a, b, c, d, e, and f are numbers such that 0 ≦ a < 2, 0 < b ≦ 2, 0 ≦ c < 2, 10 ≦ d ≦ 500, 0 ≦ e ≦ 100, 1 ≦ f ≦ 100, and (a + b + c) = 2.

[0015] In the definition of the functionalized organopolysiloxane, a is the number of units of formula (I). a is a number such that 0 ≦ a < 2. Preferably 0 ≦ a ≦ 1. More preferably, 0 ≦ a ≦ 0.5. In one embodiment, a is 0, that is, the functionalized organopolysiloxane does not contain or substantially does not contain units of formula (I). However, it is possible that units of formula (I) remain in trace amounts or insignificant amounts.

[0016] In the definition of the functionalized organopolysiloxane, b is the number of units of formula (II). b is a number such that 0 < b ≦ 2. Preferably 0.5 ≦ b ≦ 2. More preferably 1 ≦ b ≦ 2.

[0017] In the definition of the functionalized organopolysiloxane, c is the number of units of formula (III). c is a number such that 0 ≦ c < 2. Preferably, 0 ≦ c ≦ 1.5. More preferably, 0.3 ≦ c ≦ 1. In one embodiment, c is 0, that is, the functionalized organopolysiloxane can not contain or substantially not contain units of formula (III). According to another embodiment, c is different from 0. In one embodiment, b + c is greater than 1, preferably 1 < (b + c) ≦ 2, more preferably 1.5 ≦ (b + c) ≦ 2, still more preferably 1.7 ≦ (b + c) ≦ 2. Preferably b > c, that is, the terminal siloxy unit (R with a functional group) of formula (II) is more than the terminal siloxy unit (R with a functional group) of formula (III). Preferably b / (b + c) > 0.5, more preferably b / (b + c) > 0.55. MET The terminal siloxy unit having a functional group PE The terminal siloxy unit having a functional group

[0018] In the definition of the functionalized organopolysiloxane, d is the number of units of formula (IV). d is a number that satisfies 10≦d≦500. Preferably, 10≦d≦200. More preferably, 20≦d≦100.

[0019] In the definition of the functionalized organopolysiloxane, e is the number of units of formula (V). e is a number satisfying the relationship 0≦e≦100. Preferably, e≦10. More preferably, e≦5.

[0020] In one embodiment, e is 0, i.e., the functionalized organopolysiloxane can be free or substantially free of units of formula (V). In another embodiment, e is different from 0.

[0021] In the definition of the functionalized organopolysiloxane, f is the number of units of formula (VI). f is a number satisfying 1≦f≦100. Preferably, f is 1≦f≦50. More preferably, f is 1≦f≦20.

[0022] According to one embodiment, the functionalized organopolysiloxane preferably has a range of 0≦a≦1; 0.5≦b≦2; 0≦c≦1.5; 10≦d≦200; 0≦e≦10 and 1≦f≦50, and more preferably has a range of 0≦a≦0.5; 1≦b≦2; 0.3≦c≦1; 20≦d≦100; 0.1≦e≦5 and 1≦f≦20.

[0023] According to one embodiment, a can be 0, i.e., the functionalized organopolysiloxane according to the present invention can be substantially free of siloxy units of formula (I). Preferably, the functionalized organopolysiloxane according to this embodiment does not include non-reactive end groups.

[0024] According to another embodiment, a and c can both be 0, i.e., the functionalized organopolysiloxane according to the present invention can be substantially free of siloxy units of formula (I) and siloxy units of formula (III). Advantageously, the functionalized organopolysiloxane according to this embodiment comprises only (meth)acrylic groups as end groups.

[0025] According to another embodiment, c and e can both be 0, i.e., the functionalized organopolysiloxane according to the present invention can be substantially free of siloxy units of formula (III) and siloxy units of formula (V). The functionalized organopolysiloxane according to this embodiment can be advantageous because the (meth)acrylic groups are present only in terminal positions and the polyether groups are present only as pendant groups within the chain.

[0026] The content of polyether groups in the functionalized organopolysiloxane affects the hydrophilicity of the polymer. One way to define the content of polyether groups is to calculate the ratio of the weight of the polyether chain to the total weight of the polymer. According to one embodiment, the content of polyether groups in the functionalized organopolysiloxane according to the present invention is 10% to 70% by weight, preferably 30% to 50% by weight (weight of polyether groups to total weight of the polymer).

[0027] Preferably, the functionalized organopolysiloxane according to the present invention is a linear organopolysiloxane, and therefore has the formula RSiO 3 / 2 where the symbol R is as defined above and is commonly referred to as T unit, and siloxy units of the formula SiO 4 / 2 It is preferred that the siloxy group be free or substantially free of siloxy units (commonly referred to as T units).

[0028] The functionalized organopolysiloxane according to the present invention has a dynamic viscosity at 25° C. of 100 mPa·s to 50,000 mPa·s, preferably 500 mPa·s to 10,000 mPa·s, and more preferably 500 mPa·s to 5,000 mPa·s. The functionalized organopolysiloxane according to the present invention is preferably called an organopolysiloxane oil.

[0029] It will be clear to those skilled in the art that the structure of the functionalized organopolysiloxane of the present invention is a statistical structure, as defined above. The arrangement of the siloxy units may be random or block, or a random structure and a block structure may coexist. Furthermore, the numbers a to f of each siloxy unit in the functionalized organopolysiloxane are average values, and therefore represent the average structure of the functionalized organopolysiloxane. Such average structures can be determined by NMR analysis, as is well known to those skilled in the art.

[0030] The functionalized organopolysiloxane according to the present invention can be produced by any method known to those skilled in the art. According to one embodiment, the functionalized organopolysiloxane according to the present invention can be obtained by a two-stage process, which comprises: 1) hydrosilylation of an organohydrogenpolysiloxane compound with an alkenyl glycidyl ether and an alkenyl polyether; and 2) (meth)acrylation of the epoxy functional group of the glycidyl ether.

[0031] More specifically, the functionalized organopolysiloxane according to the present invention can be obtained from an organohydrogenpolysiloxane compound comprising the following components: a units of formula (I): RSiO 1 / 2 (b+c) units of formula (IX): R2HSiO 1 / 2 d units of formula (IV): RSiO 2 / 2 -(e+f) unit of formula (X): RHSiO 2 / 2 where R, a, b, c, d, e and f are as defined above.

[0032] The organohydrogenpolysiloxane compounds can be purchased from silicone manufacturers or prepared according to common methods known to those skilled in the art.

[0033] In a first step, an organohydrogenpolysiloxane compound can be reacted with an alkenyl glycidyl ether and an alkenyl polyether via a hydrosilylation reaction, the alkenyl glycidyl ether being [ka] [ka] and mixtures thereof, wherein p is as defined above; The alkenyl polyether is CH2=CH-O-(C2H4O) n -(C3H6O) o -R 2 , CH2=CH-(CH2) m-2 -O-(C2H4O) n -(C3H6O) o -R 2 and mixtures thereof, wherein R 2 , n, o and m are as defined above.

[0034] The alkenyl glycidyl ether is preferably allyl glycidyl ether.

[0035] The alkenyl polyether preferably has the formula CH2=CH-CH2-O-(C2H4O) n -(C3H6O) o -R 2 where R 2 , n and o are as defined above.

[0036] The reaction with the alkenyl glycidyl ether and alkenyl polyether can be carried out simultaneously or sequentially. According to one embodiment, the reaction is carried out sequentially by first reacting the organohydrogenpolysiloxane compound with the alkenyl glycidyl ether and then adding the alkenyl polyether.

[0037] The hydrosilylation temperature can be set to 0°C to 150°C, preferably 20°C to 100°C, in the presence of a hydrosilylation catalyst.

[0038] The hydrosilylation catalyst can be selected from platinum compounds and rhodium compounds, in particular, but also from silicone compounds such as those described in patent applications WO2015 / 004396 and WO2015 / 004397, germanium compounds such as those described in patent applications WO2016 / 075414, or nickel, cobalt, or iron complexes such as those described in patent applications WO2016 / 071651, WO2016 / 071652, and WO2016 / 071654. The catalyst is preferably a compound derived from at least one metal belonging to the platinum group. These catalysts are well known. In particular, platinum and organic compound complexes as described in US Patents 3,159,601, 3,159,602, and 3,220,972, and European Patents EP 0,057,459, EP 0,188,978, and EP 0,190,530, or platinum and vinylated organosiloxane complexes as described in US Patents 3,419,593, 3,715,334, 3,377,432, and 3,814,730, can be used.Preferably, the hydrosilylation catalyst is a platinum-derived compound.Preferably, the hydrosilylation catalyst is a Karstedt platinum catalyst.

[0039] The amount of hydrosilylation catalyst may preferably range from 2 ppm to 400 ppm, preferably from 5 ppm to 200 ppm, calculated as the weight of platinum metal relative to the total weight of the reaction medium.

[0040] Preferably, the alkenyl glycidyl ether and alkenyl polyether are present in an amount such that the reaction is carried out with an excess of alkenyl glycidyl ether and alkenyl polyether per mole equivalent of SiH groups in the organohydrogenpolysiloxane compound. Once the hydrosilylation reaction is complete, excess unreacted alkenyl glycidyl ether and / or alkenyl polyether, and optionally non-reactive silicone volatiles, can be distilled or removed, typically using a vacuum.

[0041] At the end of the hydrosilylation step 1), an intermediate functionalized organopolysiloxane compound is obtained, which is similar to the functionalized organopolysiloxane of the present invention in that it contains the following components: a units of formula (I): RSiO 1 / 2 c units of formula (III): R2R PE SiO 1 / 2 d units of formula (IV): RSiO 2 / 2 - f unit of formula (VI): RR PE SiO 2 / 2、 provided that the siloxy groups of formulas (II) and (V) are replaced with: b unit of formula (XI): R2R EPOX SiO 1 / 2 e unit of formula (XII): RR EPOX SiO 2 / 2 where R, R PE , a, b, c, d, e and f are as defined above; R EPOX = [ka] p is as defined above.

[0042] The second step of the process for obtaining functionalized organopolysiloxanes according to the invention involves (meth)acrylation of the epoxy groups of the glycidyl ethers. (Meth)acrylation by ring-opening of the epoxy groups is a reaction that has been frequently described in the literature.

[0043] It is known that organopolysiloxanes containing meth(acrylate) functional groups can be industrially obtained by reacting an epoxy-functionalized organopolysiloxane with (meth)acrylic acid in the presence of a chromium-based catalyst. This reaction is described, for example, in the paper "Synthesis and Characterization of Vinyl Ester Resins Having an Oligo(dimethylsiloxane) Backbone" by Rao et al. (Makromol. Chem., Rapid Commun. 7, 703-707 (1986)), in which an organopolysiloxane containing epoxy functional groups at the chain end is reacted with methacrylic acid in the presence of chromium diisopropyl salicylate to form an α,ω-bis(methacrylate)-substituted organopolysiloxane. U.S. Patent No. 6,548,568 also teaches the preparation of organopolysiloxanes containing acrylate functional groups by reacting an organopolysiloxane containing epoxy functional groups with acrylic acid in the presence of chromium(III) acetate. The reaction was carried out in a mixed solvent of n-butanol and methyl isobutyl ketone. Hydroquinone was added as a polymerization inhibitor for (meth)acrylic acid. More recently, US 10,829,597 describes the use of chromium complexes in oxidation state (III) as catalysts in the absence of alcohol.

[0044] Other types of catalysts are known to catalyze the reaction between epoxy-functionalized organopolysiloxanes and (meth)acrylic acid. For example, US Patents US 4,293,678, US 4,558,082, US 4,777,233, and US 4,908,274 disclose the use of organic catalysts such as amines (e.g., tributylamine, trimethylamine, benzyldimethylamine), tetramethylguanidine, tetramethylurea, sulfonic acids (e.g., p-toluenesulfonic acid and methanesulfonic acid), trifluoroacetic acid, or morpholine and its derivatives. For example, cyclic diamines such as 1,4-diazabicyclo(2,2,2)octane are widely used as catalysts for this reaction. More recently, US Patent No. 10,738,217 describes the use of iron complexes in oxidation state (III) as catalysts.

[0045] Any method known to those skilled in the art can be used to carry out the (meth)acrylation step. Typically, the resulting intermediate functionalized organopolysiloxane compound can be reacted with acrylic acid, methacrylic acid, or a mixture of the two in the presence of a suitable catalyst, preferably a chromium-based catalyst, at temperatures between 25°C and 130°C, preferably between 50°C and 130°C, and more preferably between 70°C and 125°C. The reaction can be carried out using at least 1 mole, preferably 1 to 10 moles, of (meth)acrylic acid per mole of epoxy groups in the intermediate functionalized organopolysiloxane compound. To prevent gelation of the reactive groups, a polymerization inhibitor, such as methoxyphenol, phenothiazine, hydroquinone, or tert-butylpyrocatechol, can be used.

[0046] The functionalized organopolysiloxanes according to the invention are obtained at the end of the (meth)acrylation step 2).

[0047] Preferably, an additional purification step can be carried out between step 1) and step 2) or after step 2), or both.

[0048] According to one embodiment, the method for producing a functionalized organopolysiloxane according to the present invention can include a purification step 1′) between the hydrosilylation step 1) and the (meth)acrylation step 2). Purification step 1′) can be carried out by any method known to those skilled in the art, such as precipitation with an organic solvent such as acetone, filtration and washing, extraction with a suitable solvent, dialysis, reverse osmosis, or ultrafiltration, or any combination of these methods. This purification step allows the intermediate functionalized organopolysiloxane compound according to the present invention to be obtained in a pure form, for example, in the form of a concentrated solution that is free, or at least substantially free, of starting materials and / or secondary products formed during the hydrosilylation step. The purification step can be repeated, for example, from two to ten times. Alternatively, the purification step can be carried out continuously until the selected purity is reached. The selected purity can, in principle, be as high as desired.

[0049] According to another embodiment, the method for producing a functionalized organopolysiloxane according to the present invention can include a purification step 2') after the (meth)acrylation step 2). Typically, the purification step 2') comprises a devolatilization step, which allows the solvent and, if present, excess (meth)acrylic acid to be removed by evaporation. The solvent can be recycled if necessary. The devolatilization step can be carried out by any method known to those skilled in the art, for example, by distillation at an appropriate temperature under reduced pressure. A further filtration step can also be carried out.

[0050] The functionalized organopolysiloxanes according to the invention can be of great interest in several technical fields.

[0051] Compared to prior art document US 2009 / 0234089 A1, the functionalized organopolysiloxanes of the present invention differ at least in the bond between the polysiloxane backbone and the (meth)acrylic group: whereas US 2009 / 0234089 A1 shows a propylene bond, optionally with a small number of polyoxyethylene groups (m -(CHO)- groups, where m is 0 to 10 in US 2009 / 0234089 A1), the functionalized organopolysiloxanes of the present invention contain (meth)acrylic acid monoesters containing vicinal hydroxyl groups. Without wishing to be bound by any theory, it is believed that the presence of vicinal hydroxyl groups to the (meth)acrylic group provides improved properties, such as improved hydrophilicity.

[0052] Furthermore, (meth)acrylate functional groups can react via radical processes under actinic and / or thermal activation according to a polyaddition polymerization mechanism.

[0053] Due to the enhanced hydrophilic properties of the combination of hydrophilic polyether chains in addition to hydrophobic silicone chains, the functionalized organopolysiloxanes of the present invention can be used as is or in the production of silicone gels, rubbers, coatings and emulsions, and are useful in a variety of applications, including cosmetics, personal care, medical, household care, textiles, electronics, coatings, construction, surfactants, defoamers, emulsifiers, etc.

[0054] In cosmetics and personal care, the functionalized organopolysiloxanes according to the present invention are suitable as ingredients or additives in cosmetic products such as hair sprays, creams, lotions, gels, hair conditioners, hair setting compositions and the like.

[0055] Functionalized organopolysiloxanes are also suitable as release agents and coatings for textiles, paper, wood, plastics, sheets, metals, etc. They can also be used as adhesion promoters, or as lubricants and wetting agents in paints and varnishes.

[0056] The use of silicone coatings to form release coatings (non-stick coatings) on the surface of substrates is well known in the art. Silicone release coatings are typically prepared as follows: a silicone composition is applied to a substrate in an industrial coating device equipped with rollers operating at very high speeds. The silicone composition applied to the substrate cures to form a solid silicone release coating. The resulting coated substrate is also called a silicone liner. This silicone liner is particularly suitable for lamination with adhesives, since the silicone release coating facilitates the removal of adhesives reversibly adhered to the substrate. Therefore, these silicone liners can be used in adhesive labels, strips including envelopes, graphic arts, and medical and healthcare applications. Silicone compositions used to form release coatings are typically cured (crosslinked) under radiation, particularly UV or visible radiation emitted from doped or undoped mercury lamps or LEDs (light-emitting diodes).

[0057] The present invention relates to the use of the functionalized organopolysiloxanes described herein for the manufacture of silicone coatings that can be used as release coatings on substrates. The present invention also relates to a method for preparing a coating on a substrate, comprising the steps of applying to the substrate a silicone composition comprising the functionalized organopolysiloxanes described herein and curing the composition. The present invention also relates to the coated substrates obtained by this method.

[0058] Further areas of use include in the construction sector as an additive in cementitious and non-cementitious systems and for the protection of structures, in particular in the production of weatherproof coatings and sealants.

[0059] Furthermore, the functionalized organopolysiloxanes of the present invention are particularly suitable as hydrophilizing softeners for textiles. Synthetic fibers (such as polyester, polyamide, and polyolefin fibers) are often unable to absorb water or sweat due to their extremely hydrophobic nature. This characteristic, which is extremely unpleasant for the wearer of such fabrics, can be completely eliminated by treating textile fibers or fabrics with the hydrophilic organofunctional silicone copolymers of the present invention. This makes the fibers hydrophilic, allowing them to absorb sweat and providing a pleasant, soft feel. The functionalized organopolysiloxanes are also suitable as wrinkle-resistant agents in the textile field.

[0060] The functionalized organopolysiloxane according to the present invention is particularly suitable as an ophthalmic lens material. In the present invention, the term "ophthalmic lens" typically refers to any lens worn in the anterior segment of the eye for purposes such as vision correction, examination, and treatment, and preferably includes intraocular lenses, corneal lenses, and contact lenses. The present invention further relates to an ophthalmic lens material containing the functionalized organopolysiloxane disclosed above, and to an ophthalmic lens, particularly a contact lens, containing the material.

[0061] Various embodiments of the present invention may be better understood with reference to the following examples, which are provided for illustrative purposes and are not intended to limit the invention to the examples described herein. [Example]

[0062] raw materials -Poly(methylhydrogen)(dimethyl)siloxane (α / ω) with SiH groups in the chain and at the chain ends -Allyl glycidyl ether (AGE) (Thermoscientific / 99% or more) -Allyl polyether POLYGLYKOL A500 (manufactured by Clariant) - Karstedt catalyst: platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Pt content: 10 wt.%) -Methacrylic acid (Sigma Aldrich) Chromium (III) acetate (MinsChem) Cr content: 22% by weight -4-Methylpentan-2-one (MIBK) (VWR / GPRRECTAPUR) -Butanol (VWR / NORMAPUR) -4-Methoxyphenol (MEHQ) (Solvay) -Ethanol (VWR / SUPELCO)

[0063] Step 1: [(CH 3 ) 3 SiO 1 / 2 ] 0.3 [(CH 3 ) 2 R EPOXY SiO 1 / 2 ] 1 [(CH 3 ) 2 R PEG11 SiO 1 / 2 ] 0.7 [(CH 3 ) 2 SiO 2 / 2 ] 29 [(CH 3 )R EPOXY SiO 2 / 2]1 [(CH 3 )R PEG11 SiO 2 / 2 ] 6 Preparation of In a 500 mL stirred reactor under a nitrogen atmosphere, the following were combined: 125 g (α / ω) of poly(methylhydrogen)(dimethyl)siloxane with SiH groups in the chain and at the chain ends (SiH group content 9.38% by weight, i.e. 321.3 mmol of SiH groups per 100 g of polysiloxane), and - 10.96 g (0.096 mol) of allyl glycidyl ether (AGE).

[0064] The temperature was raised to 40° C. 34.6 mg of Karstedt catalyst solution were added and the reaction medium was stirred.

[0065] Thereafter, the temperature was raised to 75°C, and 209.6 g of allyl polyether A500 was added.

[0066] At the end of the reaction, the reaction medium was distilled under vacuum (T=90° C., P=1 mBar).

[0067] The product was purified by dialysis and finally distilled.

[0068] 1H NMR confirmed the absence of reactant and solvent residues. The epoxy group content (0.228 mol / kg) was determined by potentiometric titration.

[0069] Step 2: [(CH 3 ) 3 SiO 1 / 2 ] 0.3 [(CH 3 ) 2 R MET SiO 1 / 2 ] 1 [(CH 3 ) 2 R PEG11 SiO 1 / 2 ] 0.7 [(CH 3 ) 2 SiO 2 / 2 ] 29 [(CH 3 )R MET SiO 2 / 2]1 [(CH 3 )R PEG11 SiO 2 / 2 ] 6 Preparation of In a 150 mL stirred reactor, the following were combined: 50 g of the intermediate organopolysiloxane obtained in step 1; - 1.96 g of methacrylic acid; - 0.013 g of chromium (III) acetate; - MEHQ 0.06 g; -MIBK + butanol 5.78g.

[0070] The reaction was carried out at 115°C. After the conversion of the epoxy groups was complete, the mixture was devolatilized. The methacrylate functionality content was determined by 1H-NMR.

[0071] Applicable tests: Base silicone = acrylate-functionalized organopolysiloxane with a viscosity of approximately 1000 mPa·s Catalyst = TPOL (ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate) PEG12 Dimethicone = Polyoxyethylene functionalized organopolysiloxane with a viscosity of 200-800 mPa·s Functionalized organopolysiloxane 1 = general formula [(CH3)3SiO 1 / 2 ] 0.3 [(CH3)2R MET SiO 1 / 2 ]1[(CH3)2R PEG11 SiO 1 / 2 ] 0.7 [(CH3)2SiO 2 / 2 ] 90 [(CH3)R MET SiO 2 / 2]1 [(CH3)R PEG11 SiO 2 / 2 ]6, which was prepared by a method similar to that disclosed above.

[0072] The silicone coating composition was prepared by mixing the components shown in Table 1 below. The values ​​are expressed in weight percent. The resulting composition was applied to a PET substrate (application amount: 6 g / m 2 ), undoped and cured under a mercury lamp. The performance of the coated substrates was evaluated as follows:

[0073] [Table 1]

[0074] The slipperiness at low speed (0.3 m / min) was evaluated using a dynamometer. The coefficients of friction Ks (static friction coefficient) and Kd (kinetic friction coefficient) were measured in accordance with ISO 8295. Ks was calculated from the initial peak value of sled tension, and Kd was calculated from the average value of sled tension over a specified sliding distance.

[0075] High speed slipperiness was assessed manually by sliding a gloved hand very quickly across the surface.

[0076] Antistatic: Antistatic properties were evaluated by rubbing a PET film coated sample with a glove 10 times and then measuring the static electricity. After 10 more rubs, the measurement was repeated. The static electricity was measured (in kV) at a distance of 10 cm using a Fraser 715 capacitance meter.

[0077] The release performance was evaluated based on the FINAT3 test method, which measures the release force of adhesive tape Tesa 7475 peeled from a silicone surface at 0.3 m / min. A measured release force of less than 10 cN / 25 mm is considered to be very good for release coating applications.

[0078] When compared with the control composition A, the addition of 5 wt. % of the functionalized organopolysiloxane according to the present invention (composition C) does not reduce the release performance in the application of release coatings. The composition before coating is transparent. Composition C has the advantage of exhibiting excellent antistatic and abrasion resistance to silicone coatings. This technical effect is superior to that achieved when the comparable silicone polyether compound (composition B) is added.

Claims

1. Functionalized organopolysiloxanes, including: a unit of formula (I): R 3 SiO 1 / 2 b units of formula (II): R 2 R MET SiO 1 / 2 - c unit of formula (III): R 2 R PE SiO 1 / 2 d units of formula (IV): R 2 SiO 2 / 2 - e unit of formula (V): RR MET SiO 2 / 2 f units of formula (VI): RR PE SiO 2 / 2 During the ceremony, R=a monovalent hydrocarbon group having 1 to 12 carbon atoms, optionally substituted with one or more halogen atoms, preferably selected from alkyl groups having 1 to 8 carbon atoms (such as methyl, ethyl, propyl, or 3,3,3-trifluoropropyl groups), cycloalkyl groups having 3 to 8 carbon atoms, and aryl groups having 6 to 12 carbon atoms; R MET= 【Chemistry 1】 (VII) or 【Chemistry 2】 (VIII) wherein R 1 =-CH 3 or -H, where p is a number satisfying 2≦p≦10; R PE =-(CH 2 ) m -O-(C 2 H 4 O) n -(C 3 H 6 O) o -R 2 and R 2 = -H or a monovalent hydrocarbon group having 1 to 4 carbon atoms, m is a number satisfying 2≦m≦10, and n and o are 0 or positive numbers satisfying 4≦(n+o)≦100; a, b, c, d, e, and f are numbers such that 0≦a<2, 0<b≦2, 0≦c<2, 10≦d≦500, 0≦e≦100, 1≦f≦100, and (a+b+c)=2.

2. R MET is a mixture of groups of formula (VII) and groups of formula (VIII), with the group of formula (VII) being preferably the predominant group, more preferably R MET 2. The functionalized organopolysiloxane of claim 1, wherein at least 75% of the groups are groups of formula (VII).

3. 3. The functionalized organopolysiloxane according to claim 1, wherein the functionalized organopolysiloxane satisfies 0≦a≦1, 0.5≦b≦2, 0≦c≦1.5, 10≦d≦200, 0≦e≦10, and 1≦f≦50, and more preferably 0≦a≦0.5, 1≦b≦2, 0.3≦c≦1, 20≦d≦100, 0.1≦e≦5, and 1≦f≦20.

4. 4. The functionalized organopolysiloxane of any one of claims 1 to 3, wherein the functionalized organopolysiloxane is free or substantially free of siloxy units of formula (I), preferably a is 0.

5. 4. The functionalized organopolysiloxane of claim 1, wherein the functionalized organopolysiloxane is free or substantially free of siloxy units of formula (I) and siloxy units of formula (III), and preferably a and c are both 0.

6. 6. The functionalized organopolysiloxane of any one of claims 1 to 5, wherein the functionalized organopolysiloxane is free or substantially free of siloxy units of formula (III) and siloxy units of formula (V), and preferably c and e are both 0.

7. 7. The functionalized organopolysiloxane according to claim 1, wherein the content of polyether groups in the functionalized organopolysiloxane according to the invention is from 10% to 70% by weight, preferably from 30% to 50% by weight (weight of polyether groups relative to the total weight of the polymer).

8. 8. A method for producing the functionalized organopolysiloxane of claim 1, comprising the steps of: 1) hydrosilylation of an organohydrogenpolysiloxane compound with an alkenyl glycidyl ether and an alkenyl polyether; and 2) (meth)acrylation of the epoxy functional groups of the glycidyl ether.

9. 9. The method of claim 8, wherein the method further comprises a purification step 1') between the hydrosilylation step 1) and the (meth)acrylation step 2).

10. 10. The method according to claim 9, wherein the purification step 1') is carried out by precipitation with an organic solvent such as acetone, filtration and washing, extraction with a suitable solvent, dialysis, reverse osmosis or ultrafiltration, or any combination of these methods.

11. The method according to any one of claims 8 to 10, wherein the method further comprises a purification step 2') after the (meth)acrylation step 2).

12. 12. The method according to claim 11, wherein the purification step 2') consists of a devolatilization step.

13. The use of the functionalized organopolysiloxane of any one of claims 1 to 7 in a variety of applications, including cosmetics, personal care, medical, house care, textiles, electronics, coatings, construction, surfactants, defoamers, emulsifiers, or in the production of silicone gels, rubbers, coatings, and emulsions useful for such applications.

14. 8. Use of the functionalized organopolysiloxane according to any one of claims 1 to 7 as an ophthalmic lens material or in the manufacture of an ophthalmic lens material.

15. Use of the functionalized organopolysiloxane of any one of claims 1 to 7 in the manufacture of a silicone coating that can be used as a release coating on a substrate.

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