Novel functionalized organopolysiloxane compound, preparation method and application thereof

Abstract

The present invention relates to novel functionalized organopolysiloxane compounds having a polysiloxane backbone, a (meth) acrylic group and a hydrophilic polyether group. The invention also relates to a method for preparing said functionalized organopolysiloxanes and to the use thereof, which are used as such or for preparing silicone gels, rubbers, coatings and emulsions, which can be used in various applications such as cosmetics, personal care, medical treatment, home care, textiles, electronics, coatings, buildings, surfactants, antifoams, emulsifiers, ophthalmic lens materials.

Description

Technical Field

[0001] The present invention relates to novel functionalized organopolysiloxane compounds. More particularly, the present invention relates to novel functionalized organopolysiloxane compounds with improved hydrophilic properties, which can be used as such or in the preparation of silicone gels, rubbers, coatings, and emulsions, and are useful in various applications such as cosmetics, personal care, medical treatment, home care, textiles, electronics, coatings, construction, surfactants, defoamers, emulsifiers, and the like. Furthermore, the novel functionalized organopolysiloxane compounds of the present invention are useful as ophthalmic lens materials. Background Art

[0002] Functionalized organopolysiloxane compounds have attracted great attention in many technical fields due to their unique properties. Within the group of functionalized organopolysiloxanes, the focus is on compounds that contain both non-polymerizable and polymerizable functional groups.

[0003] Prior art document US 4,259,467 discloses polysiloxane compounds containing hydrophilic side chains and some free radical polymerizable monovalent unsaturated groups at the terminal positions. Prior art document US 2014 / 0350278 A1 discloses a method for preparing polymerizable hybrid polysiloxanes. The method comprises reacting an organopolysiloxane having an average of at least three silicon hydride (SiH) groups per molecule, polyoxyethylene, and a catalyst. The method enables the preparation of SiH-containing organosilicon-EO copolymers having PEO grafted onto the organosilicon chain. Prior art document US 2009 / 0234089 A1 discloses a hydrophilic polysiloxane macromonomer containing polyoxyethylene as a hydrophilic side chain in the polysiloxane backbone. Prior art document EP 3 418 319 A1 discloses a polysiloxane compound containing polyoxyethylene groups and terminal (meth)acrylic groups connected to silicon atoms via a linking moiety containing an arylene group. Prior art document US 2016 / 0311981 A1 discloses a polysiloxane having polymerizable groups at both terminal positions and hydrophilic side chains, wherein the hydrophilic side chains have alkyl groups having three hydroxyl groups and no ether bonds. Prior art document WO 2022 / 141795 A1 discloses a polysiloxane compound containing a polyoxyethylene group and a (meth)acrylic group only at the terminal position, but not as a side chain. Summary of the Invention

[0004] An object of the present invention is to provide novel functionalized organopolysiloxane compounds having polyether side chains and methacrylic terminal groups, and a process for preparing the novel functionalized organopolysiloxane compounds.

[0005] Summary of the Invention

[0006] All of these objects and others are achieved by the present invention, which is directed to functionalized organopolysiloxanes comprising:

[0007] -a formula (I): R3SiO 1 / 2 Unit

[0008] -b formula (II): R2R MET SiO 1 / 2 Unit

[0009] -c formula (III): R2R PE SiO 1 / 2 Unit

[0010] -d formula (IV): R2SiO 2 / 2 Unit

[0011] -e formula (V):RR MET SiO 2 / 2 Unit

[0012] -f formula (VI):RR PE SiO 2 / 2 Unit

[0013] in

[0014] R = a monovalent hydrocarbon radical having 1 to 12 carbon atoms, which is optionally substituted by one or more halogen atoms, preferably selected from an alkyl radical having 1 to 8 carbon atoms, such as a methyl, ethyl, propyl or 3,3,3-trifluoropropyl radical, a cycloalkyl radical having 3 to 8 carbon atoms and an aryl radical having 6 to 12 carbon atoms;

[0015]

[0016] where R 1 =-CH3 or -H, and p is a number such that 2≤p≤10;

[0017] R PE =-(CH2) m -O-(C2H4O) n -(C3H6O) o -R 2 , where R 2 =-H or a monovalent hydrocarbon radical having 1 to 4 carbon atoms, m is a number such that 2≤m≤10, n and o are zero or positive numbers such that 4≤(n+o)≤100, and;

[0018] 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.

[0019] Another object of the present invention is a process for preparing the functionalized organopolysiloxanes disclosed above, wherein said process comprises the steps of: 1) hydrosilylation of an organohydrogenpolysiloxane compound with an alkenyl glycidyl ether and an alkenyl polyether, and 2) (meth)acrylation on the epoxy functional groups of the glycidyl ether.

[0020] The present invention further relates to the use of the functionalized organopolysiloxane, which can be used as is or in the preparation of silicone gels, rubbers, coatings, and emulsions, and can be used in various applications such as cosmetics, personal care, medical treatment, home care, textiles, electronics, coatings, construction, surfactants, defoamers, and emulsifiers. Furthermore, the present invention further relates to the use of the functionalized organopolysiloxane, which can be used as is or in the preparation of ophthalmic lens materials.

[0021] Detailed description of the invention

[0022] In the absence of other indications, the viscosity of the silicone compositions described herein and their individual components corresponds to 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 that is sufficiently low such that the measured viscosity is independent of the shear rate gradient. For example, the viscosity can be measured using a Haak rheometer with a 60 mm cone / plate geometry by applying a sinusoidal stress of 1 Pa at 1 Hz.

[0023] Unless otherwise stated, contents in % or ppm are by weight.

[0024] The present invention relates to functionalized organopolysiloxanes comprising:

[0025] -a formula (I): R3SiO 1 / 2 Unit

[0026] -b formula (II): R2R MET SiO 1 / 2 Unit

[0027] -c formula (III): R2R PE SiO 1 / 2 Unit

[0028] -d formula (IV): R2SiO 2 / 2 Unit

[0029] -e formula (V):RR MET SiO 2 / 2 Unit

[0030] -f formula (VI):RR PE SiO 2 / 2 Unit

[0031] in

[0032] R = a monovalent hydrocarbon radical having 1 to 12 carbon atoms, which is optionally substituted by one or more halogen atoms, preferably selected from an alkyl radical having 1 to 8 carbon atoms, such as a methyl, ethyl, propyl or 3,3,3-trifluoropropyl radical, a cycloalkyl radical having 3 to 8 carbon atoms and an aryl radical having 6 to 12 carbon atoms;

[0033]

[0034] where R 1 =-CH3 or -H, and p is a number such that 2≤p≤10;

[0035] R PE =-(CH2) m -O-(C2H4O) n -(C3H6O) o -R 2 , where R 2 =-H or a monovalent hydrocarbon radical having 1 to 4 carbon atoms, m is a number such that 2≤m≤10, n and o are zero or positive numbers such that 4≤(n+o)≤100, and;

[0036] 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.

[0037] It will be appreciated that in the above formulae (I) to (VI), if multiple R groups are present, they may be the same as or different from each other.

[0038] As defined above, R MET The group is a hydroxyl-containing (meth) acrylic group represented by formula (VII) or by formula (VIII). For the entire document, it should be understood that the (meth) acrylic group includes an acrylic group, a methacrylic group, or a mixture of the two. The groups represented by formula (VII) and by formula (VIII) are isomers that may be generated by the preparation steps. Depending on the selected synthesis route, R MET It can be a group of formula (VII), a group of formula (VIII) or a mixture of the two. In the case of a mixture, the group of formula (VII) can be the main group, typically greater than 75%. MET Within the definition of , p is a number such that 2≤p≤10, preferably 2≤p≤4, and more preferably p=3.

[0039] R as defined above PE The group contains a polyether structure and provides interesting hydrophilic properties for the functionalized organopolysiloxane according to the present invention. In R PE , m is a number such that 2 ≤ m ≤ 10, preferably 2 ≤ m ≤ 4, and more preferably m = 3. In R PE , n is the number of oxyethylene (OE) units, and o is the number of oxypropylene (OP) units. The (OE) and / or (OP) units form a polyether side chain. n and o are zero or numbers such that 4 ≤ (n + o) ≤ 100, preferably 5 ≤ (n + o) ≤ 30, and more preferably 6 ≤ (n + o) ≤ 20. According to one embodiment, o is zero, i.e., the R PE group contains only OE units. According to another embodiment, n is zero, i.e., the R PE group contains only OP units. According to another embodiment, both n and o are different from zero, i.e., the R PE group contains OE and OP units. In this case, the arrangement of the OE units and the OP units can be random, or can form blocks, or the random and block configurations can coexist.

[0040] 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 the numbers a to f respectively. According to the present invention, a, b, c, d, e, and f are numbers such that for the following: 0 ≤ a < 2; 0 < b ≤ 2; 0 ≤ c < 2; 10 ≤ d ≤ 500; 0 ≤ e ≤ 100; 1 ≤ f ≤​​​​​​​​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. According to one embodiment, c is zero, i.e. the functionalized organopolysiloxane may be free of or substantially free of units of formula (III). According to another embodiment, c is different from zero. According to one embodiment, b+c is strictly greater than 1, preferably, 1<(b+c)≤2, more preferably, 1.5≤(b+c)≤2, even more preferably, 1.7≤(b+c)≤2. Preferably, b>c, i.e. the units of formula (II) present (having R MET The terminal silyloxy unit of the functional group) is larger than the unit of formula (III) (having R PE Preferably, b / (b+c)>0.5, more preferably, b / (b+c)>0.55.

[0044] In the definition of the functionalized organopolysiloxane, d is the number of units of formula (IV). d is a number such that 10≤d≤500. Preferably, 10≤d≤200. More preferably, 20≤d≤100.

[0045] In the definition of the functionalized organopolysiloxane, e is the number of units of formula (V). e is a number such that 0 ≤ e ≤ 100. Preferably, 0 ≤ e ≤ 10. More preferably, 0.1 ≤ e ≤ 5. According to one embodiment, e is zero, i.e., the functionalized organopolysiloxane may be free or substantially free of units of formula (V). According to another embodiment, e is different from zero.

[0046] In the definition of the functionalized organopolysiloxane, f is the number of units of formula (VI). f is a number such that 1≤f≤100. Preferably, 1≤f≤50. More preferably, 1≤f≤20.

[0047] According to one embodiment, the functionalized organopolysiloxane is such that, preferably, 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.

[0048] According to one embodiment, a may be 0, ie the functionalized organopolysiloxane according to the invention may be substantially free of siloxy units of formula (I).The functionalized organopolysiloxane according to this embodiment advantageously comprises no non-reactive ends.

[0049] According to another embodiment, a and c may both be 0, i.e., the functionalized organopolysiloxane according to the present invention may be substantially free of siloxy units of formula (I) and siloxy units of formula (III). The functionalized organopolysiloxane according to this embodiment advantageously comprises only (meth)acrylic groups as terminal ends.

[0050] According to another embodiment, both c and e can 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 only in terminal positions and the polyether groups are only pendant groups within the chain.

[0051] The content of polyether groups in the functionalized organopolysiloxane has an impact on the hydrophilic properties of the polymer. One way to define the polyether group content is to calculate the ratio between the weight of the polyether chains and the total weight of the polymer. According to one embodiment, the functionalized organopolysiloxane according to the present invention has a polyether group content of 10% to 70% by weight, preferably 30% to 50% by weight (weight of polyether groups relative to the total weight of the polymer).

[0052] Preferably, the functionalized organopolysiloxane according to the present invention is a linear organopolysiloxane. Therefore, it preferably contains no or essentially no compounds of the formula RSiO 3 / 2 Siloxy units of formula SiO 4 / 2 The siloxy units (commonly referred to as T units) are siloxy units.

[0053] The functionalized organopolysiloxane according to the present invention may have a dynamic viscosity at 25° C. of 100 to 50,000 mPa.s, preferably 500 to 10,000 mPa.s, and more preferably 500 to 5,000 mPa.s. The functionalized organopolysiloxane according to the present invention may preferably be referred to as organopolysiloxane oil.

[0054] It will be clear to those skilled in the art that the structure of the functionalized organopolysiloxane according to the present invention, as defined above, is a statistical structure. The arrangement of the siloxy units may be random or may form blocks, or both random and block configurations may coexist. Furthermore, the number of siloxy units per unit, a to f, within the functionalized organopolysiloxane is an average value, thus providing the average structure of the functionalized organopolysiloxane. As is generally known to those skilled in the art, this average structure can be determined by means of NMR analysis.

[0055] The functionalized organopolysiloxane according to the present invention can be prepared 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-step process comprising 1) hydrosilylation of an organohydrogenpolysiloxane compound with an alkenyl glycidyl ether and an alkenyl polyether, and 2) (meth)acrylation on the epoxy functional groups of the glycidyl ether.

[0056] More particularly, the functionalized organopolysiloxane according to the invention can be obtained starting from an organohydrogenpolysiloxane compound comprising:

[0057] -a formula (I): R3SiO 1 / 2 Unit

[0058] -(b+c) formula (IX): R2HSiO 1 / 2 Unit

[0059] -d formula (IV): R2SiO 2 / 2 Unit

[0060] -(e+f) formula (X):RHSiO 2 / 2 Unit,

[0061] wherein R, a, b, c, d, e and f are as defined above.

[0062] The organohydrogenpolysiloxane compound can be purchased from an organosilicon manufacturer or produced according to a general method known to those skilled in the art.

[0063] In the first step, the organohydrogenpolysiloxane compound can be reacted with an alkenyl glycidyl ether and an alkenyl polyether via a hydrosilylation reaction, wherein the alkenyl glycidyl ether is selected from and mixtures thereof, wherein p is as defined above; and

[0064] The alkenyl polyether is selected from 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.

[0065] The alkenyl glycidyl ether is preferably allyl glycidyl ether.

[0066] The alkenyl polyether is preferably of the formula CH2=CH-CH2-O-(C2H4O)n -(C3H6O) o -R 2 Allyl polyether, wherein R 2 , n and o are as defined above.

[0067] The reaction with the alkenyl glycidyl ether and with the alkenyl polyether can be carried out simultaneously or sequentially. According to one embodiment, the reaction can be carried out sequentially by first reacting the organohydrogenpolysiloxane compound with the alkenyl glycidyl ether and then adding the alkenyl polyether.

[0068] The temperature of the hydrosilylation in the presence of a hydrosilylation catalyst may be 0°C to 150°C, preferably 20°C to 100°C.

[0069] The hydrosilylation catalyst may be chosen, in particular, from platinum and rhodium compounds, but may also be chosen from silicon compounds, such as those described in patent applications WO 2015 / 004396 and WO 2015 / 004397; germanium compounds, such as those described in patent application WO 2016 / 075414; or nickel, cobalt, or iron complexes, such as those described in patent applications WO 2016 / 071651, WO 2016 / 071652, and WO 2016 / 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, complexes of platinum and organic products described in US Pat. Nos. 3,159,601, 3,159,602, and 3,220,972 and European Patents EP 0057459, 0188978, and 0190530, or complexes of platinum and vinylated organosiloxanes described in US Pat. Nos. 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.

[0070] The amount of the 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.

[0071] Preferably, the amount of alkenyl glycidyl ether and alkenyl polyether is such that the reaction is carried out with an excess of alkenyl glycidyl ether and alkenyl polyether for one molar equivalent of SiH groups in the organohydrogenpolysiloxane compound. When the hydrosilylation reaction is complete, vacuum is typically used to distill off or strip off excess unreacted alkenyl glycidyl ether and / or alkenyl polyether and optionally non-reactive organosilicon volatiles.

[0072] At the end of the hydrosilylation step 1) an intermediate functionalized organopolysiloxane compound is obtained. Said intermediate compound is similar to the functionalized organopolysiloxane according to the invention in that it comprises:

[0073] -a formula (I): R3SiO 1 / 2 Unit

[0074] -c formula (III): R2R PE SiO 1 / 2 Unit

[0075] -d formula (IV): R2SiO 2 / 2 Unit

[0076] -f formula (VI):RR PE SiO 2 / 2 Unit,

[0077] However, the siloxy units of formula (II) and (V) are replaced by:

[0078] -b formula (XI): R2R EPOX SiO 1 / 2 Unit

[0079] -e formula (XII):RR EPOX SiO 2 / 2 Unit

[0080] Among them, R PE , a, b, c, d, e and f are as defined above, and

[0081] where p is as defined above.

[0082] The second step of the process for obtaining the functionalized organopolysiloxanes according to the invention comprises (meth)acrylation on the epoxy functions of the glycidyl ether.(Meth)acrylation via epoxy ring opening is a reaction frequently described in the literature.

[0083] It is known that organopolysiloxanes containing meth(acrylate) functional groups can be obtained industrially by reacting an epoxy-functional organopolysiloxane with (meth)acrylic acid in the presence of a chromium-based catalyst. This reaction is described, for example, in the article "Synthesis and characterization of a vinylester resin with an oligo(dimethy 1siloxane) backbone" by Rao et al., Makromol. Chem., Rapid Commun. 7, 703-707 (1986), in which an organopolysiloxane containing chain-terminal epoxy functional groups is reacted with methacrylic acid in the presence of chromium diisopropylsalicylate to form an α,ω-bis(methacrylate)-substituted organopolysiloxane. US Pat. 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 is carried out in a solvent that is a mixture of n-butanol and methyl isobutyl ketone. Hydroquinone is 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, but in the absence of alcohol.

[0084] Other types of catalysts are known to catalyze the reaction between epoxy-functionalized organopolysiloxanes and (meth)acrylic acid. For example, US Pat. Nos. 4,293,678, 4,558,082, 4,777,233, and 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 exemplified as catalysts for this reaction. More recently, US Pat. No. 10,738,217 describes the use of iron complexes in oxidation state (III) as catalysts.

[0085] The (meth)acrylation step can be carried out using any method known to those skilled in the art. Typically, the intermediate functionalized organopolysiloxane compound according to this reaction can be reacted with acrylic acid or methacrylic acid, or a mixture of the two, at a temperature of 25°C to 130°C, preferably 50°C to 130°C, and even more preferably 70°C to 125°C, in the presence of a suitable catalyst, preferably a chromium-based catalyst. This reaction can be carried out using at least one mole, preferably one to ten moles, of (meth)acrylic acid for each mole of epoxy groups in the intermediate functionalized organopolysiloxane compound. To prevent gelation of the reactive groups, polymerization inhibitors such as methoxyphenol, phenothiazine, hydroquinone, or tert-butylcatechol can be used.

[0086] The functionalized organopolysiloxanes according to the invention are obtained at the end of the (meth)acrylation step 2).

[0087] Preferably, an additional purification step can be performed between step 1) and step 2), or after step 2), or after both.

[0088] According to one embodiment, the method for preparing the functionalized organopolysiloxane according to the present invention may include a purification step 1′ between the hydrosilylation step 1) and the (meth)acrylation step 2). This purification step 1′) may be carried out by any method known to those skilled in the art, for example by precipitation with an organic solvent such as acetone, filtration and washing, extraction in a suitable solvent, dialysis, reverse osmosis or ultrafiltration, or any combination of these methods. With the aid of this purification step, the intermediate functionalized organopolysiloxane compound according to the present invention can be obtained in pure form, for example in the form of a concentrated solution that is free of, or at least substantially free of, starting materials and / or secondary products formed during the hydrosilylation step. This purification step can be repeated, for example, two to ten times. Alternatively, the purification step can be carried out continuously until a selected purity is reached. The selected purity can, in principle, be as high as desired.

[0089] According to another embodiment, the process for preparing the functionalized organopolysiloxane according to the invention may comprise a purification step 2′) after the (meth)acrylation step 2). Typically, the purification step 2′) may consist of a devolatilization step that allows the solvent and excess (meth)acrylic acid (if present) to be evaporated. The solvent may optionally be recycled. The devolatilization step may be carried out according to any method known to those skilled in the art, for example by distillation under reduced pressure at a suitable temperature. A further filtration step may also be carried out.

[0090] The functionalized organopolysiloxanes according to the invention can be highly beneficial for several technical fields.

[0091] Compared to the prior art document US 2009 / 0234089A1, the functionalized organopolysiloxanes according to the present invention differ at least in the link between the polysiloxane backbone and the (meth)acrylic groups: whereas US 2009 / 0234089A1 provides an propylene bond, optionally with several polyoxyethylene groups (m-(C2H4O)-groups, where m in US 2009 / 0234089A1 is from 0 to 10), the functionalized organopolysiloxanes according to the present invention comprise a (meth)acrylic acid monoester containing hydroxyl groups in the ortho position. Without wishing to be bound by any theory, it is believed that the presence of hydroxyl groups ortho to the (meth)acrylic group provides improved properties, such as improved hydrophilicity.

[0092] Alternatively, the (meth)acrylate functional groups can react according to a polyaddition polymerization mechanism by free radical processes under actinic and / or thermal activation.

[0093] Due to the combination of hydrophilic polyether chains in addition to hydrophobic silicone chains and due to improved hydrophilic properties, the functionalized organopolysiloxane according to the present invention can be used as is or for preparing silicone gels, rubbers, coatings and emulsions, and can be used in various applications such as cosmetics, personal care, medical care, home care, textiles, electronics, coatings, construction, surfactants, defoamers, emulsifiers, etc.

[0094] In cosmetics and personal care, the functionalized organopolysiloxanes according to the invention are suitable as ingredients or additives for cosmetics, such as hair sprays, creams, lotions, gels, conditioners or hair styling compositions.

[0095] These functionalized organopolysiloxanes are also suitable as release agents and coating materials. They are also suitable for coating textiles, paper, wood, plastics, sheets, and metals. They can be used as adhesion promoters or as lubricants and wetting agents for paints and varnishes.

[0096] The use of silicone coatings to produce release coatings (non-stick coatings) on the surface of substrate materials is well known in the art. The preparation of silicone release coatings is generally carried out as follows: a silicone composition is applied to a substrate in an industrial coating device comprising a roller operating at very high speeds. Once applied to the substrate, the silicone composition is cured to form a solid silicone release coating. The resulting coated substrate is also referred to as a silicone liner. Such silicone linings can be particularly well laminated with adhesives because the silicone release coating facilitates the removal of adhesive materials that are reversibly bonded to these substrates. These silicone linings can therefore be used in the following areas: self-adhesive labels, envelopes containing adhesive strips, graphic arts, medical care and health care applications. The silicone composition used to form the release coating is generally cured (crosslinked) under radiation, particularly under UV or visible radiation emitted by doped or undoped mercury vapor lamps or LEDs (light emitting diodes).

[0097] The present invention relates to the use of a functionalized organopolysiloxane as described herein for preparing an organosilicon coating that can be used as a release coating on a substrate. The present invention also relates to a method for preparing a coating on a substrate, comprising the steps of applying an organosilicon composition comprising a functionalized organopolysiloxane as described herein to a substrate; and curing the composition. The present invention also relates to a coated substrate obtainable by this method.

[0098] Further areas of use are in the construction sector as additives in cement-containing and cement-free systems and for protecting structures, in particular for producing weather-resistant coatings or sealing compounds.

[0099] Furthermore, the functionalized organopolysiloxanes according to the present invention are particularly suitable as hydrophilic softeners for textiles. Synthetically produced fibers (e.g., polyester, polyamide, or polyolefin fibers) are typically so hydrophobic that they cannot absorb water or sweat. This highly unpleasant property for the wearer of such textiles can be completely eliminated by treating the textile fibers or textiles with the hydrophilic organofunctional organosilicon copolymers according to the present invention. The textiles thereby become hydrophilic and can absorb sweat, and they also acquire a pleasantly soft hand. The functionalized organopolysiloxanes are also suitable as anti-wrinkle agents in the textile industry.

[0100] Furthermore, the functionalized organopolysiloxanes according to the present invention are particularly suitable as ophthalmic lens materials. In the present invention, the term "ophthalmic lens" typically refers to any lens that is fitted to the anterior segment of the eye for purposes such as vision correction, testing, and treatment, and preferably includes intraocular lenses, corneal lenses, and contact lenses. The present invention also relates to ophthalmic lens materials comprising the functionalized organopolysiloxanes disclosed above, as well as ophthalmic lenses, particularly contact lenses, comprising such materials. DETAILED DESCRIPTION

[0101] Various embodiments of the present invention may be better understood by reference to the following examples which are provided by way of illustration.The present invention is not limited to the examples given herein.

[0102] Example

[0103] raw material :

[0104] - Poly(methylhydrogen)(dimethyl)siloxane having SiH groups in the chain and at the chain ends (α / ω)

[0105] -Allyl glycidyl ether (AGE) (from Thermo scientific / 99%+)

[0106] -Allyl polyether POLYGLYKOL A500 (from Clariant)

[0107] -Karstedt catalyst: platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Pt content: 10 wt%)

[0108] -Methacrylic acid (from Sigma Aldrich)

[0109] - Chromium(III) acetate (from MinsChem). Cr content: 22 wt.%

[0110] -4-Methylpentan-2-one (MIBK) (from VWR / GPR RECTAPUR)

[0111] -Butanol (from VWR / NORMAPUR)

[0112] -4-Methoxyphenol (MEHQ) (from Solvay)

[0113] -Ethanol (from VWR / SUPELCO)

[0114] Step 1: [(CH3)3SiO 1 / 2 ] 0.3 [(CH3)2R EPOXY SiO 1 / 2 ]1[(CH3)2R PEG11 SiO 1 / 2 ] 0.7 [(CH3) 2SiO 2 / 2 ] 29 [(CH3)R EPOXY SiO 2 / 2 ]1[(CH3)R PEG11 SiO 2 / 2 Preparation of 6

[0115] Under nitrogen, in a 500 mL stirred reactor, mix:

[0116] 125 g of poly(methylhydrogen)(dimethyl)siloxane having SiH groups in the chain and at the chain ends (α / ω), containing 9.38% by weight of SiH groups (ie 321.3 mmol of SiH groups for 100 g of polysiloxane), and

[0117] - 10.96 g of allyl glycidyl ether (AGE) (0.096 mol).

[0118] The temperature was raised to 40° C. 34.6 mg of Karstedt's catalyst solution were added, and the reaction medium was stirred.

[0119] The temperature was then raised to 75° C. 209.6 g of allyl polyether A500 were added.

[0120] At the end of the reaction, the reaction medium was distilled under vacuum (T=90° C., P=1 mbar).

[0121] The product is purified by dialysis and finally distilled.

[0122] The absence of any reactant or solvent residues was confirmed by 1H NMR. The epoxy group content (0.228 mol / kg) was determined by potentiometric titration.

[0123] Step 2: [(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 ] 29 [(CH3)R MET SiO 2 / 2 ]1[(CH3)R PEG11 SiO 2 / 2 Preparation of 6

[0124] In a 150 mL stirred reactor, combine:

[0125] - 50 g of the intermediate organopolysiloxane obtained in step 1;

[0126] - 1.96 g of methacrylic acid;

[0127] - 0.013 g of chromium(III) acetate;

[0128] -0.06 g of MEHQ;

[0129] - 5.78 g of MIBK + butanol.

[0130] The reaction was carried out at 115° C. When the conversion of the epoxy groups was complete, the mixture was devolatilized. The methacrylate functional group content was determined by 1H-NMR.

[0131] Application testing:

[0132] Base silicone = organopolysiloxane functionalized with acrylate groups with a viscosity of approximately 1000 mPa.s

[0133] Catalyst = TPOL (ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate)

[0134] PEG 12 dimethicone = organopolysiloxane functionalized with polyoxyethylene groups with a viscosity of 200-800 mPa·s

[0135] 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 compound.

[0136] The silicone coating composition was prepared by mixing the components disclosed in Table 1 below. The figures are expressed in wt %. The composition thus obtained was coated on a PET substrate (coating weight: 6 g / m 2 ) and then cured by an undoped mercury vapor lamp. Evaluation of the properties of the coated substrates:

[0137] [Table 1]

[0138] Silicone coating composition: A B C Basic silicone 95％ 90％ 90％ catalyst 5％ 5％ 5％ PEG 12 dimethicone 5％ Functionalized organopolysiloxane 1 5％ performance: The visual appearance of the composition clear turbid clear Ks 0.55 0.44 0.33 Kd 0.57 0.49 0.41 Smoothness at high speeds Not smooth Slightly smooth Very smooth Antistatic performance (kV) 0.60-0.80 0.20-0.40 0.11-0.15 Release performance (cN / 25mm) <10 <10 <10

[0139] The slipperiness at low speed (0.3 m / min) was evaluated using a dynamometer. The coefficients of friction, Ks (static friction coefficient) and Kd (dynamic friction coefficient), were measured according to ISO 8295. Ks was calculated from the initial peak value of the tensile force on the slider, while Kd was calculated from the average value of the tensile force on the slider during a specified sliding distance.

[0140] Sliding properties at high speeds were assessed manually by sliding the hand in the glove very quickly over the surface.

[0141] Antistatic properties: The antistatic properties were evaluated by measuring the electrostatic charge on the coated sample of PET film after 10 rubbings with a glove. The measurement was repeated a second time after 10 new rubbings. The charge (value in kV) was measured at 10 cm using a Fraser 715 electrometer.

[0142] Release performance was evaluated according to the FINAT 3 test method, which measures the release force of a Tesa 7475 adhesive tape peeled off from a silicone surface at 0.3 m / min. When the measured release force is below 10 cN / 25 mm, the release performance is considered very good for release coating applications.

[0143] When compared to control composition A, the addition of 5 wt.% of the functionalized organopolysiloxane of the present invention (composition C) did not reduce release performance in release coating applications. The composition was clear before coating. Advantageously, composition C exhibited good antistatic and friction-reducing properties for silicone coatings. Its technical performance was superior to that of the comparative silicone polyether compound (composition B).

Claims

1. A functionalized organopolysiloxane comprising: -a formula (I): R3SiO 1 / 2 Unit -b formula (II): R2R MET SiO 1 / 2 Unit -c formula (III): R2R PE SiO 1 / 2 Unit -d formula (IV): R2SiO 2 / 2 Unit -e formula (V):RR MET SiO 2 / 2 Unit -f formula (VI):RR PE SiO 2 / 2 Unit in R = a monovalent hydrocarbon radical having 1 to 12 carbon atoms, which is optionally substituted by one or more halogen atoms, preferably selected from an alkyl radical having 1 to 8 carbon atoms, such as a methyl, ethyl, propyl or 3,3,3-trifluoropropyl radical, a cycloalkyl radical having 3 to 8 carbon atoms and an aryl radical having 6 to 12 carbon atoms; where R 1 =-CH3 or -H, and p is a number such that 2≤p≤10; R PE =-(CH2) m -O-(C2H4O) n -(C3H6O) o -R 2 , where R 2 =-H or a monovalent hydrocarbon radical having 1 to 4 carbon atoms, m is a number such that 2≤m≤10, n and o are zero or positive numbers such that 4≤(n+o)≤100, and; 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. The functionalized organopolysiloxane according to claim 1, wherein R MET It is a mixture of a group of formula (VII) and a group of formula (VIII), wherein the group of formula (VII) is preferably the main group, and more preferably more than 75% of R MET The group is a group of formula (VII).

3. The functionalized organopolysiloxane according to claim 1 or claim 2, wherein the functionalized organopolysiloxane is such that 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. The functionalized organopolysiloxane according to any one of claims 1 to 3, wherein the functionalized organopolysiloxane is free or substantially free of siloxy units of formula (I), and preferably, a is zero.

5. The functionalized organopolysiloxane according to any one of claims 1 to 3, 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 zero.

6. The functionalized organopolysiloxane according to 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 zero.

7. The functionalized organopolysiloxane according to any one of claims 1 to 6, wherein the content of polyether groups of the functionalized organopolysiloxane according to the invention is 10% to 70% by weight, preferably 30% to 50% by weight (weight of polyether groups relative to the total weight of the polymer).

8. A method for preparing a functionalized organopolysiloxane according to any one of claims 1 to 7, wherein the method comprises the following steps: 1) hydrosilylation of an organohydrogenpolysiloxane compound with an alkenyl glycidyl ether and an alkenyl polyether, and 2) (meth)acrylation on the epoxy functional group of the glycidyl ether.

9. The process according to claim 8, wherein the process additionally comprises a purification step 1') between the hydrosilylation step 1) and the (meth)acrylation step 2).

10. The process 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 in a suitable solvent, dialysis, reverse osmosis or ultrafiltration, or any combination of these methods.

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

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

13. Use of the functionalized organopolysiloxane according to any one of claims 1 to 7, wherein the functionalized organopolysiloxane is used as such or for preparing silicone gels, rubbers, coatings and emulsions, and can be used in various applications such as cosmetics, personal care, medical treatment, home care, textiles, electronics, coatings, construction, surfactants, defoamers, and emulsifiers.

14. Use of the functionalized organopolysiloxane according to any one of claims 1 to 7 as such or for the preparation of an ophthalmic lens material.

15. Use of a functionalized organopolysiloxane according to any one of claims 1 to 7 for producing an organosilicon coating which can be used as a release coating on a substrate.

Images