Functionalized QT-siloxane-based polymeric materials having low siloxane ring content and methods for preparing same

Abstract

The present invention relates to functionalized polymeric liquid polysiloxane materials containing non-organofunctional Q-type siloxane moieties and monoorganofunctional T-type siloxane moieties, and optionally triorganofunctional M-type siloxane moieties and / or diorganofunctional D-type siloxane moieties, characterized in that the polysiloxane materials have a specific degree of polymerization, contain a limited minority of four-membered Q2-type and / or Q3-type siloxane ring species relative to the total Q-type siloxane species, and are functionalized with specific groups. The present invention further relates to methods for producing the polymeric liquid polysiloxane materials and associated uses of the materials.

Description

[Technical field]

[0001] The present invention relates to a functionalized polymeric liquid polysiloxane material comprising non-organofunctional Q-type siloxane groups and monoorganofunctional T-type siloxane groups, and optionally triorganofunctional M-type siloxane groups and / or diorganofunctional D-type siloxane groups, the polysiloxane material having a specific degree of polymerization, a limited minor amount of four member ring-forming Q-type siloxane groups relative to the total Q-type siloxane species. 2 Type and / or Q 3 The present invention further relates to a method for producing the polymeric liquid polysiloxane material, as well as associated uses of the material. [Background technology]

[0002] In nanotechnology, organic / inorganic hybrid materials are obtained through a wide variety of preparation techniques. Sol-gel based techniques start with colloidal suspensions of molecular or oligomeric precursors, working for example in solution and causing the spontaneous formation of nanoparticle components. Sols are prepared in situ from olation and condensation reactions of oligomeric polyhydroxymetallates or by hydrolysis of alkoxysilanes in water-alcohol mixtures. When a low degree of condensation is desired, only small amounts of water reactants are used, which results in low molecular weight branched siloxane compounds. An example of such a preparation technique using acid-catalyzed hydrolysis in a non-diluted system (without solvent) is described in EP 1510520 A1. Generally, oligomers are obtained by hydrolysis of alkoxysilane monomers with such small amounts of water. Many of the single component compounds are commercially available; for example, in the case of Q-type tetraethoxysilane (TEOS), there are commercial oligomeric mixtures of ethyl silicate having a silicate content of 40% or even up to 50%, commonly referred to as Ethylsilicate 40, Ethylsilicate 50, or also known by brand names such as Dynasylan 40 or Dynasylan Silbond 50 (Evonik Industries).

[0003] Highly branched polyethoxysiloxanes (PEOS) are small molecular building blocks with typical molecular weights ranging from 500 to 50'000 Daltons, and sizes ranging from a few angstroms to single-digit nanometers. The word highly branched refers to compounds that are characterized by only a few linear species, but also contain siloxane rings to varying degrees. The preferred synthetic route is anhydrous or "non-hydrolytic" reaction conditions. This is because, in general, the preparation of highly branched siloxane polymers is much more versatile than the hydrolytic route mentioned above, since the condensation reaction can be controlled by the stoichiometric addition of the reactants, allowing better control over the final reaction product. Moreover, the synthesis can be carried out "neat", which means that there is no additional co-solvent, such as alcohol. As a result of a highly dendritic structure with a high degree of polymerization in the center and a low degree of linear chain branching at its periphery, PEOS exhibit lower melt viscosities and much greater solubility in themselves as well as in other organic solvents than their linear chain siloxane analogues.

[0004] Highly branched PEOS can be an attractive group of molecular precursors for building blocks of all kinds of hybrid molecules, which can be easily accessed by "non-hydrolytic" methods, e.g.: 1) Condensation of metal hydroxides obtained by reaction of metal alkoxides with alkali hydroxides (silanol route); 2) condensation of metal chlorides with metal alkoxides (chloride pathway); 3) Condensation of a single metal alkoxide with itself, with elimination of an ether; 4) condensation of the mixed acetoxy-alkoxy-metallate with itself, with elimination of the corresponding acetate ester (acetoxy route); or 5) Condensation of metal alkoxides by reaction with acetic anhydride in the presence of a suitable catalyst with elimination of the acetate ester (anhydride route) It is.

[0005] Method 2) is described in EP 0 728 793 A1, in which the preparation of highly branched polysiloxanes proceeds through the heterocondensation of chloro- and alkoxysilanes with alkyl halide elimination. The reaction is catalyzed by Ti, V and Zr-containing organometallic compounds.

[0006] Method 3) has not been extensively studied but is expected to allow the condensation of various transition metal oxides following the pioneering work of Bradley et al. on the alkoxy rearrangement mechanism (J. Chem. Soc., 1958, pp. 99-101).

[0007] Method 4) generally uses acetoxysilanes, which are quite costly. WO00 / 40640A1 describes the preparation of lightly branched organosilicon compounds through acetoxy derivatization starting from dimethylsiloxane prepolymers that have been crosslinked using trifunctional silanes. WO00 / 40640A1 describes the utility of the traditional acetoxy route when only a few condensation bonds need to be made, i.e., when linking monomeric components to oligomeric / polymeric components to produce larger macromolecules. This can be done, for example, by refluxing silanol-terminated prepolymers in the presence of an alkoxy-terminated crosslinker and acetic acid, or directly with an acetoxy-terminated crosslinker (e.g., triacetoxysilane) at elevated temperature under reflux.

[0008] Method 5) has been published by Moeller et al. (e.g. Macromolecules 2006, 39, 1701-1708) and is a more advanced technique for preparing polyalkylmetallates (PAMs) in terms of scalability, process safety and ease of implementation compared to methods 1) to 4). WO2004 / 058859A1 describes the preparation of single-component PAMs using an anhydride route.

[0009] WO2019 / 234062A1 discloses a method for producing a core-shell PEOS core with an organofunctional silane shell material. WO2019 / 234062A1 describes the preparation of a highly branched ethyl silicate "core" by non-hydrolytic acetic anhydride condensation chemistry followed by grafting of a shell, the shell being preferentially made from a selection of organofunctional T-type trialkoxysilanes in a second temporally separate step to create the building blocks of a hybrid organofunctional core-shell molecule. Both steps are preferably carried out in the presence of a tetraalkoxy titanate recombinant catalyst.

[0010] PCT / EP2020 / 075890 describes highly branched polyalkoxysiloxane materials containing Q and M, D and / or T type functional groups within the same polymer. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] EP1510520A1 [Patent Document 2] EP0728793A1 [Patent Document 3] WO00 / 40640A1 [Patent Document 4] WO2004 / 058859A1 [Patent Document 5] WO2019 / 234062A1 [Patent Document 6] PCT / EP2020 / 075890 [Patent Document 7] EP1576035B1 [Non-patent literature]

[0012] [Non-Patent Document 1] J.Chem.Soc., 1958, pp. 99-101 [Non-Patent Document 2] Macromolecules 2006, 39, pp. 1701-1708 [Non-Patent Document 3] Nanoscale, 2010, pp. 2,829~843 [Non-Patent Document 4] Nanoscale, 2011, pp. 3, 5120~5125 [Non-Patent Document 5] Macromol.Chem.Phys.2003, 204(7), pp. 1014-1026 [Non-Patent Document 6] Doklady Chem., vol. 349, 1996, pp. 190-19 Summary of the Invention [Problem to be solved by the invention]

[0013] It is an object of the present invention to provide improved functionalized organofunctional highly branched polyalkoxysiloxane materials containing Q and T, and optionally M and D type functionalities within the same polymer, methods for producing same, and various uses thereof. [Means for solving the problem]

[0014] In a first aspect, the present invention provides a method for producing a method for treating a cancer cell comprising the steps of: (i) [ka] a non-organofunctional Q-type siloxane group selected from the group consisting of: (ii) Optionally, in some cases [ka] A triorganofunctional M selected from the group consisting of 1 type siloxane group; (iii) Optionally, in some cases [ka] and a diorganofunctional D-type siloxane group selected from the group consisting of (iv) [ka] The present invention relates to a polymeric liquid polysiloxane material comprising or consisting of monoorganofunctional T-type siloxane groups selected from the group consisting of: In the above formula, [ka] represents a covalent siloxane bond to a silicon atom of another Q, M, D and / or T type group as defined in (i), (ii), (iii) and / or (iv); R 1 is methyl, ethyl, propyl, -P(=O)(OR 1’ )(OH), -P(OR 1’ )2, -P(=O)(OH)2, optionally selected from the group consisting of methyl and ethyl; R 1’ is selected from methyl, ethyl, propyl, and butyl; R 2 , R 3 and R 4 are each independently selected from the group consisting of methyl, ethyl, phenyl, cyclohexyl, vinyl, and cyclopentadienyl; R 5 is R 5U and R 5S selected from the group consisting of; R 5U is methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, linear, branched or cyclic C 5~16 Alkyl residues, optionally linear or branched, such as hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H,2H,2H-perfluoro)octyl, (1H,1H,2H,2H-perfluoro)dodecyl, (1H,1H,2H,2H-perfluoro)hexadecyl, vinyl, phenyl, cyclohexyl, cyclopentadienyl, cyclopentyl, [ka] and -LZ, Where: R 6 is methyl, ethyl, n-butyl, linear or branched C 5~14 Alkyl residues, optionally -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 11 CH3 and -(CH2) 13 CH3; n is an integer selected from the group consisting of 1, 2, 3, 4 and 5; L is an aliphatic linking group selected from the group consisting of -CH-, -CHCH-, -CHCHCH-, -CH-, -CH-CH-, and -CH-CH-CH-CH-; Z is Cl, Br, I, -OH, -SH, [ka] is a group selected from the group consisting of Where: R 7 is independently selected from the group consisting of methyl, ethyl, and n-butyl; R 5S teeth, [ka] and -L'-Y; Where: m is an integer selected from the group consisting of 1, 2, 3, and 4; R 8 are -Cl, -Br, -I, -F, -CN, -SCN, -N3, -NO2, -OH, -SO2OR 1’ and -OC(=O)R 12 selected from the group consisting of; R 9 -Cl, -Br, -I, -F, -CN, -COOH, -COOR 1’phenyl, o-, m- and p-vinylphenyl; R 9’ -COOH and -COOR 1’ selected from the group consisting of; L' is an aliphatic linker selected from the group consisting of -CH2-, -CH2CH2-, and -CH2CH2CH2-; and Y is [ka] [ka] is a group selected from the group consisting of Where: X is absent, -(NH)- or -O-; R 10 teeth, [ka] [ka] selected from the group consisting of; R 11 is R 8 , -XR 1’ and R 12c selected from the group consisting of; R 12 is R 12a , R 12b and R 12c selected from the group consisting of; Where: R 12a is a linear or branched, substituted or unsubstituted C 1~18 Alkyl, C 2~18 Alkenyl and C 2~18 alkynyl; R 12b teeth, - linear or branched, substituted or unsubstituted alkyl ethers, alkenyl ethers, alkynyl ethers, optionally substituted or unsubstituted poly(ethylene oxide), poly(propylene oxide) and polytetrahydrofuran with a molecular weight of up to 5000 g / mol; - unsubstituted polydimethylsiloxanes and polydivinylsiloxanes, and - selected from the group consisting of polysaccharides and oligosaccharides with a molecular weight of up to 5000 g / mol, optionally poly-D-glucose, oligo-D-glucose, chitosan, deacetylated oligochitin, oligo-beta-D-galactopyranuronic acid, polyalginic acid, oligoalginic acid, polyamylose, oligoamylose, polygalactose and oligogalactose; and R 12c teeth, - amino acids, oligopeptides and polypeptides with a molecular weight of up to 5000 g / mol, optionally oligopeptides and polypeptides made of naturally occurring amino acids with a molecular weight of up to 5000 g / mol; and - C 12~24 Fatty acids, optionally naturally occurring C 12~24 Fatty acids, optionally naturally occurring unsaturated fatty acids, optionally having 1 to 3 double bonds, naturally occurring C 12~24 selected from the group consisting of unsaturated fatty acids, optionally epoxidized fatty acids, optionally epoxidized castor oil, soybean oil, sunflower oil, optionally ring-opened epoxidized fatty acid based polyols, optionally natural oil based polyols (NOP), optionally castor oil, soybean oil or sunflower oil triglycerides; However, R 5S but [ka] provided that it is not; Where: Degree of polymerization of Q-type alkoxy end groups DP Q型is in the range of 1.3 to 2.7; Degree of polymerization of D-type alkoxy-terminated siloxane groups DP D型 is in the range of 1.0 to 1.9; Degree of polymerization DP of T-type alkoxy-terminated siloxane groups T型 is in the range of 1.1 to 2.7; the total content of triorganofunctional M-type siloxane groups (iii) in the polysiloxane material is 15 mol %, optionally not more than 10 mol %, optionally not more than 5 mol %; the total content of diorganofunctional D-type siloxane moieties (iii) in the polysiloxane material does not exceed 5, 10, 20, 30, 35 or 50 mol %; the material has a viscosity in the range of 10 to 100,000 cP, optionally about 25 to 50,000 cP, optionally 10 to 1,000 cP; the material contains less than 5, 2.5, 2, 1.5, 1 or 0.5 mol % silanol groups (Si-OH); the atomic ratio of T species to Q species in said material is in the range of 0.01:1 to 1:1; All R in the material 5 At least 1 mol %, optionally at least 3 mol %, optionally at least 5 mol %, optionally at least 7 mol % of the groups are R 5S It is based on And it is characterized by the following: - the polysiloxane material contains less than 45 mol%, optionally less than 37 mol%, optionally less than 30 mol% or less than 25 mol% of four-membered Q-type siloxane species combined; 2r Type and Q 3s,d and / or - Polysiloxane material, all Q 3 Less than 70 mol %, optionally less than 63 mol %, optionally less than 56 mol % or less than 50 mol % of the 4-membered Q 3s,3d and / or - the polysiloxane material contains less than 4.5 mol %, optionally less than 4.0 mol %, optionally less than 3.5 mol % or less than 3.0 mol % of double four-membered Q siloxane species relative to the total Q siloxane species; 3d and / or - Polysiloxane material, all Q 3 less than 25 mol %, optionally less than 20 mol %, optionally less than 17 mol %, or less than 14 mol % of double four-membered Q 3d The siloxane ring species include those of the type: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Double four membered siloxane ring species and Q 2r , Q 3s , and Q 3d The term is further explained below.

[0016] For example, the polymeric liquid polysiloxane material described herein in all its embodiments may be a core-shell structure, with the core consisting mainly of Q-type groups and the shell having a different composition from the shell consisting mainly of T-type groups, and optionally further including M and D-type groups. Herein, the core is also referred to as a "precursor (material)". Alternatively, the polymeric liquid material may also include a "core-only" material, meaning that there is no shell and that the Q and T-type moieties are essentially randomly distributed within the core. The term "core-shell" as used herein is generally understood in the art (see, for example, Nanoscale, 2010, 2, 829-843 or Nanoscale, 2011, 3, 5120-5125). With respect to the core-shell product, the interface between the core and the shell should be understood as a diffuse shell rather than a sharp boundary where the composition changes suddenly. The structure of this diffusion shell layer, in which the concentration of functional shell species varies over several bond lengths or angstroms, is a direct result of condensation chemistry, i.e., grafting of functional silane shells onto preformed polysiloxane cores. The outer branches of dendritic polysiloxane cores are highly permeable to small silane monomers and oligomers, so it is clear that the degree of shell grafting is highest at the periphery, but there is no clear cutoff. Nevertheless, the term core-shell is still applied because grafting at the center of the core is largely hindered by the average degree of bonding (number of bridging oxygen bonds (Si-O-Si bonds) per silicon center) at the center of the core being higher than at the core periphery, both for steric reasons and because of the reduced availability of reactive alkoxy groups. As a result, the term core-shell is used in reference to polymeric liquid materials in the sense of polysiloxane cores with diffusion shells as described herein.

[0017] R 5 When contains a silane group, the resulting moiety is called a "bipodal silane."

[0018] The polysiloxane materials described herein are preferably made of a four-membered ring, Q2r Type and / or Q 3s,d Due to the small number of siloxane ring species, they are highly dendritic, linear and liquid species.

[0019] For example, exemplary materials according to the present invention may contain Q, T, D and / or M type silane monomers (Q 0 , T 0 , D 0 , M 0 ) to Q n , T n , D n and M n (n≧1) moieties, e.g., in a smaller molar amount, in other words, its total siloxane molar content must be greater than the total molar content of silane monomers, excluding HMDSO, which may be present in any amount, either as a monomer or, e.g., as a solvent or co-solvent. Similarly, the material may optionally contain a significant fraction of smaller oligomers, e.g., mixtures of oligomers ranging from dimeric to pentameric polysiloxanes, optionally also featuring mixed QT and, optionally, QD linkage modes.

[0020] The materials of the present invention contain less than 5, 2.5, 2, 1.5, 1, or 0.5 mol % silanol groups (Si-OH), which is the OR of Q, T, or D type silanes. 1 This means that the group is, to this extent, an -OH group.

[0021] It has been surprisingly discovered that the materials described herein can be prepared without the need for any active condensation reactants, such as acetic anhydride, for example, by using the rearrangement catalysts described herein. M, D and / or T type silanes are reacted with Q type precursors or core materials in a nucleophilic substitution / condensation ("rearrangement") reaction. Without wishing to be bound by theory, one of the driving forces for this substitution reaction (also called "grafting") is the high molecular weight of the four-membered Q in the Q type precursor materials used to prepare the polysiloxane materials described herein. 2r Type and / or Q 3s,d It is believed that this arises from ring strain of the type siloxane ring species. The release of ring tension in the Q-type core material is sufficient to efficiently add, i.e., graft, M, D and / or T-type silanes to the Q-type core material without the need for additional chemical reactants, such as acetic anhydride, and essentially no recombinant catalyst is required as defined herein, even though the reaction time may be significantly extended. Exemplary structural formulas (represented in 2D) of such core materials are shown in Figure 1, where selected exemplary R 1 A population of alkoxy ligands is seen depending on the relatively large amount of monomeric or oligomeric Q-type starting material used in the preparation of each precursor.

[0022] Further, similar structural exemplary representations of materials described herein are shown in FIG. 2, again for the general case having various organofunctional T, D and M groups, and also for the specific case having three non-identical T-type functional groups.

[0023] [ka]

[0024] The term "four-membered" ring or polysiloxane ring or Q-type ring species referred to herein always refers to all Q rings contained in the material that are part of the four-membered polysiloxane ring structure.2r and Q 3s,d Two representative examples of such typical arrangements of groups in a four-member ring structure, single and double, are shown in the formula above. Q 2r The ring group occurs in both "single" and "double" ring structures, with each Q 2r Two siloxane bonds and two alkoxy groups (-OR 1 ) substituents. In the example of a single four-member siloxane ring on the left, 2r Ring type (circle) and "one" Q 3s Only ring species (squares) are possible. In the second example shown to the right, a siloxane ring formed of two linked four members (a bicyclic structure), Q 2r Ring type (circle) and "one ring" Q 3s In addition to the seed (square), there is a "double-ring" Q located at the bridge connecting the two rings. 3d Seeds (rectangles, dashed lines) are also possible. 3d Note that in the species, all siloxane bonds are part of a two-ring network. 3s The wavy lines on the oxygen atoms attached to the groups indicate any other possible Q n , T n , D n Or M n It should also be noted that the siloxane bond to the group (n≧1) is depicted. In the above examples of typical configurations, the groups are of type Q, however, it should be further understood that these are merely examples to aid in the understanding of one of ordinary skill in the art, and in fact, they are not limited to type Q groups. Indeed, it is within the scope of the present disclosure that the presence of type T and / or D groups in such four member polysiloxane ring structures is fully anticipated.

[0025] As used herein, Q in a siloxane ring structure formed by any four members 2 The species is "Q 2r " in the single ring structure and the double ring structure. 3 " species are "Q 3s " and "Q3d "

[0026] For quantification purposes, there are various indices that can be used to define or qualify the polysiloxane ring species formed by the four members mentioned above. The first is the ratio of Q to the total Q species in the material. 2r and Q 3s,d It should be defined as the total number of ring species:

[0027]

number

[0028] The second index is the total Q 3 Q for species 3s,d It should be defined as the total number of ring species:

[0029]

number

[0030] The third index is the Q ratio for the total Q species in the material. 3d It should be defined as the total number of ring species:

[0031]

number

[0032] The fourth index is the total Q 3 Q for species 3d It should be defined as the total number of ring species:

[0033]

number

[0034] All mol% numbers given herein are by way of example only and are not intended to be limiting unless otherwise specified. 29It is defined by the sum of all D, M or T type silicon atoms divided by the sum of all silicon atoms in the material as measured by Si-NMR. The variable A is the spectral peak area as further defined below.

[0035] The four members of Q form the total Q type siloxane species. 2 Type and / or Q 3 The mol% of the siloxane ring species is as demonstrated in the examples below. 29 The polysiloxane materials described herein contain less than the specified mol% of the total Q-type siloxane species, which are formed of four members (Q 2r &Q 3s,d ) and / or (Q 2r ) and / or (Q 3s single) and / or (Q 3d This means that the material contains less than the specified mol% of four-membered Q 2r Chemical species of siloxane rings, less than the specified mol%, formed by four members Q 3s,d The chemical species of the siloxane ring and / or the Q formed by four members, less than the specified mol% 2r Type and Q 3s,d For all embodiments described herein, the four-membered Q 3s,d The chemical species of the siloxane ring is Q 3s,d type siloxane species, in which case one Q 3s,d The siloxanes are part of one or two four member ring systems.

[0036] The atomic ratio of T to Q species in this material is 0 , T 1 , T 2 , and T 3 ) silicon atoms and all Q-type species (Q 0 , Q 1 , Q 2 , Q 3 , and Q 4) is the ratio between silicon atoms.

[0037] The polymeric liquid polysiloxane materials described herein are 5S are functionalized, i.e., all R 5 At least 1 mol%, optionally at least 3 mol%, optionally at least 5 mol%, optionally at least 7 mol% of the moiety are R 5S R 5S is considered to be a functionalized group. 5S The functionalization of R 5S was functionalized (i.e., used for reconstitution grafting, previously R 5S Functionalized T 0 Either T-type silane or siloxane moieties (which are T-type oligomer precursors) can be introduced into the polysiloxane material, for example by selection to the extent defined herein, or alternatively to a lesser extent, i.e., less than 1 mol %, to produce a polysiloxane material. The T-type siloxane or silane moieties in the material corresponding to those disclosed herein are represented by R 5S does not contain or (R 5 R 5S If the T-type siloxane group does not contain R on the already grafted T-type siloxane moiety, 5U or by functionalizing R 5S R 5S By further grafting functionalized T-type silane or oligomer, R 5S It can be functionalized. 5U The functionalization of the R groups can be carried out by known chemical methods and are described in connection with the present method. 5S It should be noted that functionalization, as described herein, is a specific form of functionalization, while the general term "organofunctional silane or siloxane" refers to a silane / siloxane that generally has an organic group bonded directly to its silicon atom.

[0038] Optionally, in some cases, for all aspects and embodiments described herein, all R 5 0 mol% of the group is R 5S It is based on

[0039] R of grafted T-type siloxane 5U If the group is functionalized, R 5U and R 2 , R 3 , R 4 Cases in which some or similar reactivity between the substituents can be expected, or even no difference in chemical selectivity, are within the scope of the present invention. 2 , R 3 and / or R 4 When R is selected from phenyl and vinyl, 5U In contrast, R 2 , R 3 , and / or R 4 Some of the groups are functionalized, for example 5 to 95 mol %, or for example 25 to 90 mol %. 2 , R 3 , and / or R 4 Functionalization of the groups can result in the following exemplary chemical groups: [ka]

[0040] R 2 , R 3 , R 4 and R 5 The functionalization of can be determined by known spectroscopic means, for example by nuclear magnetic resonance spectroscopy, e.g. 1 H-, 13 C-, and optionally 15 N or 33 S or 31P-NMR can identify and quantify, and optionally isotopically enriched for analytical verification of these functionalization reactions. Specifically, during these types of organic reactions, such as addition or substitution or radical reactions, proton and carbon signals shift in NMR response due to changes in electronic structure and structural environment and the resulting effect on magnetic coupling. Typically, signals from protons or groups of protons or carbons disappear when such organic reactions occur, and new peaks additionally appear on the upfield or downfield side of the spectrum, depending on how the functionalization reaction affects the magnetic coupling of the species of interest. Thus, both the disappearance of old chemical signals and the appearance of new signals can be quantitatively tracked with NMR spectroscopy. Quantitative reaction monitoring of organic reactions is common general knowledge and does not require further explanation.

[0041] As used herein, the term "unsubstituted" means replaced only with hydrogen. As used herein, the term "substituted" means that any one or more hydrogens on the specified atom or group are independently replaced with an atom other than hydrogen, optionally with a halogen, optionally with fluorine, chlorine, bromine, iodine, thiol, carboxyl, acrylate, cyano, nitro, alkyl (optionally C1-C 10 ), aryl (optionally phenyl, benzyl or benzoyl), alkoxy groups, sulfonyl groups, tertiary or quaternary amines, or by a selection from the indicated substituents, provided that the normal valence of the designated atom is not exceeded and that the substitution results in a stable compound, i.e., a compound that can be isolated and characterized using conventional means. Optionally, the substitution is at the beta or omega position of the hydrocarbon chain (R 5SWhen the attachment of the substituent is through an alpha position, it occurs on the opposite terminal hydrocarbon) or, optionally, on the beta or gamma position of the hydrocarbon chain (the carbon next to or next to the carbon to which the substituent is attached). In the case of unsaturated hydrocarbons, the substitution optionally occurs at the beta or omega position of the hydrocarbon chain, or, optionally, on a carbon that is part of a double or triple bond, or on a carbon immediately adjacent thereto.

[0042] In the context of the present invention, it is understood that the preceding terms, such as "linear or branched", "substituted or unsubstituted", indicate that each one of the following terms should be interpreted as modified by said preceding term. For example, the scope of the term "linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl, carbocycle" includes linear or branched, substituted or unsubstituted alkyl; linear or branched, substituted or unsubstituted alkenyl; linear or branched, substituted or unsubstituted alkynyl; linear or branched, substituted or unsubstituted alkylidene; and linear or branched, substituted or unsubstituted carbocycle. For example, "C 1~18 Alkyl, C 2~18 Alkenyl, and C 2~18 The term "alkynyl" refers to a group of compounds having 1 or 2 to 18 carbons and an alkyl, alkenyl, or alkynyl functional group.

[0043] The term "alkyl" refers to a saturated, straight or branched chain hydrocarbon group containing the indicated number of carbons, e.g., straight or branched chain "(C 1~18 )Alkyl" refers to a hydrocarbon group having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 2,2-dimethylbutyl, and the like.

[0044] Where an alkyl chain is characterized by a name that allows for linear or branched isomers, all linear or branched isomers are encompassed by that name, for example, "butyl" encompasses n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0045] The term "alkenyl" refers to an at least partially unsaturated, substituted or unsubstituted, straight or branched chain hydrocarbon group having the indicated number of carbon atoms, e.g., "(C 2~18 )Alkenyl" refers to a hydrocarbon group having 2 to 18 carbon atoms, such as an ethenyl (vinyl), propenyl (allyl), isopropenyl, butenyl, isoprenyl, or hex-2-enyl group, or a hydrocarbon group containing a methylene chain interrupted by one double bond, such as found in monounsaturated fatty acids, or a hydrocarbon group containing a polyene interrupted by methylene, such as found in polyunsaturated fatty acids, containing two or more of the structural units -[CH=CH-CH2]- below.

[0046] The term "alkynyl" refers to an at least partially unsaturated, substituted or unsubstituted, straight or branched chain hydrocarbon group, which may have, for example, from 2 to 18 carbon atoms, such as an ethynyl, propynyl, butynyl, acetylenyl, or propargyl group.

[0047] The expression "alkyl ether" refers to a saturated or unsaturated, linear or branched hydrocarbon group with a number of atoms resulting in a molecular weight of up to 5000 g / mol. An alkyl ether group as used herein should be understood to mean any linear or branched, substituted or unsubstituted alkyl chain that contains an oxygen atom as an ether motif, i.e., an oxygen bonded by two methylene groups. Exemplary alkyl ethers are polyethylene glycol (PEG), poly(propylene oxide), polypropylene glycol (PPG), and polytetrahydrofuran chains. The ether residue is bonded to the formulae shown in the present invention through the oxygen atom of the ether residue. Optionally, in some cases, when the ether residue is substituted at a carbon atom with a nucleophilic substituent, such as an amine or a thiol, the ether residue can be bonded to the formulae shown in the present invention through the nucleophilic substituent.

[0048] As used herein, phrases defining the limits of a length range, such as "1 to 5" or "(C 1~5 ) means any integer from 1 to 5, i.e., 1, 2, 3, 4, and 5. In other words, any range defined by two integers explicitly recited is meant to include and disclose any integers defining said limits, as well as any integers subsumed within said range.

[0049] The scope of the present invention includes analogs of the above-mentioned and claimed compounds characterized in that hydrogen attached to one or more carbons, optionally attached to one or more aromatic carbons, is replaced by a halogen atom, e.g., F, Cl or Br, optionally and optionally F.

[0050] When a residue or group described herein is characterized as having two further residues of the same name, e.g. R 10 but [ka] If, then each of these further residues (in this example R 12 ) is the residue shown herein (in this example R 12 ) may be selected independently from the definitions of

[0051] Those skilled in the art will recognize that R 5S R to form 1’ , R 8 , R 9 , R 9’ , L', Y, X, R 10 , R 11 , and R 12 It is understood that any combination of R must result in a stable compound, i.e., a compound that can be isolated and characterized using conventional means. Those skilled in the art will appreciate that in a polymeric liquid material, any combination of R 1’ , R 8 , R 9 , R 9’ , L', Y, X, R 10 , R 11 , and R 12 It is possible to determine from common general knowledge which combinations of R that may result in unstable compounds are not stable, and more specifically, which linker chemistries are possible and do not interfere with the functional groups of other chemical entities. 1’ , R 8 , R 9 , R 9’ , L', Y, X, R 10 , R 11 , and R 12 is excluded from the scope of the claims.

[0052] For example, R 12b With respect to the polysaccharides and oligosaccharides, the respective groups (e.g., R 8 , Y, R 10 , or R 11 ) are combined.

[0053] For example, R 12cWith respect to the above, amino acids, oligopeptides, or polypeptides may be bonded through their amines, or through their carbonyl carbons, or optionally through their thiols (e.g., R 12b In the case of cysteine ​​having 8 , Y, R 10 , or R 11 ) are combined.

[0054] Fatty acids are R 12c For example, via a hydroxyl group (e.g., for castor oil), or via a carboxylic acid functional group, or optionally through a double bond group for unsaturated fatty acids, for example, by radical polymerization chemistry to the respective moieties (e.g., R 8 , Y, R 10 , or R 11 ) are combined.

[0055] Triglycerides or polyols derived from fatty acids by epoxidation and ring opening, e.g. with an alkali hydroxide base, can also be esterified through their hydroxyl functions, either directly by ether linkage or esterification, or optionally by secondary substitution, e.g. by bromination or oxidation to a ketone and, e.g., subsequent further substitution, or optionally by isocyanate-terminated R 5S The bond can be formed by reaction with a group.

[0056] In one embodiment, the polymeric liquid highly branched polysiloxane material of the present invention is one of the following, wherein: R 8 are -Cl, -Br, -I, -CN, -SCN, -N3, -NO2, -SO2OR 1’ and -OC(=O)R 1’ selected from the group consisting of; Y is [ka] selected from the group consisting of; R 10 teeth, [ka] selected from the group consisting of; R 11 is R 8 , and optionally R 12c is selected from; and R 12 is R 12a , R 12b , R 12c is selected from the group consisting of Where: R 12a is a linear or branched, substituted or unsubstituted C 1~18 Alkyl or C 2~18 alkenyl; R 12b is the following: - linear or branched, unsubstituted or terminally amino- or thiol-substituted alkyl or alkenyl ethers with a molecular weight of up to 3000 g / mol, optionally terminally amino- or thiol-substituted or unsubstituted poly(ethylene oxide), poly(propylene oxide) and polytetrahydrofuran; - polysaccharides or oligosaccharides with a molecular weight of up to 3000 g / mol, optionally poly-D-glucose, oligo-D-glucose, chitosan, deacetylated oligochitin, oligo-beta-D-galactopyranuronic acid, polyalginic acid, oligoalginic acid, polyamylose, oligoamylose, polygalactose, oligogalactose with a molecular weight of up to 3000 g / mol; and - optionally selected from the group consisting of unsubstituted polydimethylsiloxanes or polydivinylsiloxanes; and R 12c is the following: - amino acids and oligopeptides or polypeptides with a molecular weight of up to 3000 g / mol, optionally oligopeptides and polypeptides made of naturally occurring amino acids with a molecular weight of up to 3000 g / mol; and - C 12~24 Fatty acids, optionally naturally occurring C12~24 Fatty acids, optionally naturally occurring unsaturated fatty acids, optionally having 1 to 3 double bonds, naturally occurring C 12~24 Unsaturated fatty acids, optionally epoxidized fatty acids, such as epoxidized castor oil, soybean oil, sunflower oil, optionally ring-opened epoxidized fatty acid-based polyols, optionally natural oil based polyols (NOPs), such as castor oil, soybean oil or sunflower oil triglycerides. is selected from the group consisting of:

[0057] In another embodiment, the polymeric liquid highly branched polysiloxane material according to the present invention is one of the following, wherein R 8 are -Cl, -Br, -I, -CN, -SCN, -N3, -NO2, -SO2OR 1’ and -OC(=O)R 1’ selected from the group consisting of; Y is [ka] selected from the group consisting of; R 10 teeth, [ka] selected from the group consisting of; R 11 is R 8 , and optionally R 12c is selected from; and R 12 is R 12a , R 12b , R 12c is selected from the group consisting of Where: R 12a is a linear or branched, substituted or unsubstituted C 1~12 Alkyl and C 2~12 alkenyl; R 12b below: - linear unsubstituted or terminally amino-substituted alkyl ethers with a molecular weight of up to 2000 g / mol, optionally unsubstituted or terminally amino-substituted poly(ethylene oxide)s and poly(propylene oxide); and - polysaccharides or oligosaccharides with a molecular weight of up to 2000 g / mol, optionally poly-D-glucose, oligo-D-glucose, chitosan, deacetylated oligochitin and oligo-beta-D-galactopyranuronic acid and R 12c below: - oligopeptides or polypeptides made from amino acids and naturally occurring amino acids with a molecular weight of up to 2000 g / mol; - Castor oil, soybean oil, and sunflower oil triglycerides; and - Naturally occurring C 12~24 Fatty acids, optionally having 1 to 3 double bonds, 12~24 unsaturated fatty acids is selected from the group consisting of:

[0058] In a further embodiment, the polymeric liquid highly branched polysiloxane material of the present invention is one of the following, said material comprising: (v) at least two non-identical R 5 and / or monoorganofunctional T-type alkoxy terminated siloxane populations substituted with, each population comprising at least 3 mol % of all monoorganofunctional T-type groups in the material; (vi) a chiral monoorganofunctional T group in an amount of at least 3 mol % relative to all monoorganofunctional T groups in the material; 1 Type group.

[0059] As used herein, the term "population" refers to a collection of groups in a polymeric material or a given organofunctional T-type or D-type, or optionally M-type groups. As an example, the grafting or heterocondensation of two dissimilar T-type trialkoxysilanes, such as two randomly selected examples, vinyltrimethoxysilane and methyltriethoxysilane, onto a Q-type polysiloxane precursor results in two distinct populations (T 0 = unreacted monomer), T 1 , T 2 , and T 3 is organofunctional R 5 The substituents are -methyl and -vinyl, which are R to the central Si atom of each T-type. 5 Due to the effect of the substituents 29 They can be distinguished in the Si-NMR spectrum.

[0060] At least two non-identical R 5 The monoorganofunctional T-type alkoxy-terminated siloxane population substituted with R 5 For R 5U and R 5S Any combination of R in the polymeric liquid highly branched polysiloxane material is included. 5 At least 1 mol %, optionally at least 3 mol %, optionally at least 5 mol %, optionally at least 7 mol % of the groups are R 5S Insofar as it is a base.

[0061] The first condition (v) is that the material has an organofunctional substituent R 5 Monoorganofunctional (T-type) alkoxy-terminated siloxane groups (T 1 , T 2 , T 3 This should be understood to mean that the material contains at least two different populations of R 5 The functional group is characterized, and the minor species is present in detectable amounts (e.g. 29 Si-NMR).

[0062] The second condition (vi) is that the silicon atom must have four different substituents, i.e., one Si-O-Si bond, R 5 One Si-C bond linked to an organo functional group and two different alkoxy substituents R 1 For example, T having one ethoxy and one methoxy 1 This is filled by grafted groups of the type R 5 This occurs when only one population of T-type species functionalized with R is already present in the material. 1 Alkoxy groups can undergo ligand exchange in the Q and T groups. Figure 3 shows the ethoxy and methoxy R groups in the same material resulting in ethoxy / methoxy exchange in both the Q and T spectral signals. 1 R having both groups 5 of materials containing one type of T-shaped population functionalized with 29 The Si NMR spectrum is shown.

[0063] In another embodiment, the polymeric liquid highly branched polysiloxane material according to the present invention is one of the following, wherein (vii) Degree of polymerization DP of Q-type alkoxy end groups Q型 is in the range of 1.5 to 2.5; (viii) Degree of polymerization DP of D-type alkoxy-terminated siloxane groups D型 is in the range of 1.25 to 1.75; and / or (ix) Degree of polymerization DP of T-type alkoxy-terminated siloxane moiety T型 ranges from 1.3 to 2.2.

[0064] The degree of polymerization DP for any amorphous silicon oxide material (for the polysiloxane materials described herein, and for the corresponding methods and uses) is determined by dividing the number of metal atoms Si tot is defined herein as the ratio of bridging oxygen BO (the number of Si-O-Si bonds) to the total number of bridging oxygen bonds.

[0065] The term "alkoxy terminated" with respect to Q, T, and D type siloxane groups is understood to refer to the remaining substituents of said groups being essentially alkoxy groups, since the polymeric liquid materials are derived from alkoxy (ethoxy / methoxy) containing silane precursors in monomeric or oligomeric form. 0 Monomer and Q 1 , Q 2 , Q 3 , and Q 4 Regarding the group, the "alkoxy terminus" consists of 4, 3, 2, 1, and 0 alkoxy groups, respectively, and T 0 Monomer and T 1 , T 2 , and T 3 For the group, the above "alkoxy-terminated" means consisting of 3, 2, 1, and 0 alkoxy groups, respectively. 0 Monomer and D 1 and D. 2 For groups, the "alkoxy ends" mentioned above consist of 2, 1, and 0 alkoxy groups, respectively.

[0066] DP of materials Q型 , D.P. T型 , and D.P. D型 is the following formula:

number

number

number

[0067] DP Q型 In the above formula for A QnThe term Q is a Si atom coordinated by n siloxane bonds via bridging oxygen (BO) atoms. n Group-related quantitative 29 The Si-NMR peak areas (spectral signals) are represented by the Si-NMR peak areas (spectral signals) in which the bridging oxygen (BO) atom connects the silicon atom to its nearest neighboring Si atom and to the (4-n) non-bridging oxygen (NBO) atom, which is bonded to a terminal alkoxy group Si-OR as defined herein. Tn and A Dn corresponds to the T- and D-type groups, respectively 29 The Si-NMR peak areas (spectral signals) are shown.

[0068] In the above definition of DP, Q 2 and Q 3 All types of Q 2 and Q 3 "R" refers to species that include linear and single ring, as well as double ring species.

[0069] DP T型With respect to the formula, it is necessary to distinguish between bipodal T-type silanes and all other groups of "general" T-type silanes. The latter constitute the majority of commercially available T-type silanes and contain only a single Si atom bonded to three alkoxy groups and one organofunctional group. In contrast, bipodal silanes, which can be represented as (RO)3Si-(CH2)-X-(CH2)-Si(OR)3, contain further trialkoxysilyl units bonded to the first trialkoxysilyl unit via a suitable linker group "X", each spaced apart by at least one methylene (-CH2-) group. The introduction of a modified definition of the degree of polymerization of bipodal silanes takes into account that a single bond to the polysiloxane network is sufficient to covalently bond a functional group and to develop the desired interfacial functionality. For example, simultaneous grafting of a bipodal silane with both trimethoxysilyl groups is counterproductive in the sense that it rapidly induces branching and bonding from one polymer to another, and even low surface coverage of the bipodal T-type silanes leads to undesirable gelation. Thus, with regard to the form of a single trialkoxysilyl bond, DP T型、二脚シラン It makes sense to refer to, which leads to the definition given above.

[0070] For organofunctional T-type trialkoxysilanes and D-type dialkoxysilanes, 29 The fingerprint region of the Si spectrum gradually shifts further down the magnetic field, indicating that the organofunctional T m and D. l Non-organo functional group Q different from the group n FIG. 4 shows a schematic diagram of a material containing M, D, T, and Q type groups, each labeled. 29 The Si NMR spectrum is shown.

[0071] Optionally, the molar ratio of total silicon to free hydrolyzable alkoxy in the materials described herein ranges from 1:1.0 to 1:3.0, optionally from 1:1.2 to 1:2.5, optionally from 1:1.3 to 1:2.2, when the total content of diorganofunctional D-type siloxane groups (iii) in the polysiloxane material does not exceed 10 mol %.

[0072] Optionally, the number of moles of ethoxy terminated units (-OCH2CH3) in the materials described herein is at least twice the number of methoxy terminated units (-OCH3), and the material is essentially free of propoxy terminated units (-OCH2CH2CH3), e.g., less than 3% of all alkoxy terminated units are propoxy terminated units.

[0073] Optionally, the number of moles of methoxy terminal units (-OCH3) in the materials described herein is at least twice the number of ethoxy terminal units (-OCH2CH3), and the material is essentially free of propoxy terminal units (-OCH2CH2CH3), e.g., less than 3% of all alkoxy terminal units are propoxy terminal units.

[0074] For any of the polymeric liquid materials described herein, there are different modes of interconnection, namely i) siloxane bonds with two Q-type partners (QQ homocondensation), ii) siloxane bonds with two T-type partners (TT homocondensation), iii) siloxane bonds with two D-type partners (DD homocondensation), and iv) siloxane bonds with non-identical partners (QT, QD, TD, QM, TM, DM heterocondensation).

[0075] The concept of heterocondensation applies to both bonding states of statistical mixtures in the core only as well as in the core-shell materials, and is illustrated in the formula below for a QT type siloxane bond: [ka]

[0076] In the above example of QT heterocondensation, the organofunctional trialkoxysilane is 0 From T 1 while the Q-alkoxysilanes on the left side of the reaction (symbolically represented by three wavy siloxane bonds) are converted to Q 3 From Q 4 At the same time, each siloxane bond formed is converted to DP Q型 and D.P. T型 There are obviously many other combinations of grafting reactions possible, e.g., T 2 Seed Q 2 Grafting to T 3 and Q 3 or T 1 Seed Q 2 Grafting to T 2 and Q 3 as well as similar combinations involving D-type dialkoxysiloxane groups.

[0077] DP Q型 , D.P. T型 , and D.P. D型 are the primary parameters that define the polymeric liquid materials described herein, along with the atomic ratio of T to Q species in the material, and optionally the total molar content of D species in the material. All of these parameters are quantitatively 29 The DP value for the dipodal silane can be determined from the Si-NMR spectroscopic data. T型 Special provisions for the calculation of are given above.

[0078] Non-identical R 5 For materials containing more than one T-type subgroup with organofunctional substituents, two non-identical R 5 If the T-groups belonging to the subgroups can be sufficiently separated, the quantification of the two T-species in the material can be 29 This can be done directly from the quantitative analysis of the Si-NMR spectrum. 5 The spectral separation of the substituted T population is R 1Aminopropyl (AP) and vinyl (V) R = Me 5U Examples are shown for materials with -functional T-types (Figure 5). Alternatively, for example, methoxy / ethoxy R 1 When both R groups are present in the material, non-identical R 5 The T-type subgroup having 29 Fewer resolution limitations compared to Si-NMR data 1 H- or 13 It can be independently analyzed using C-NMR data.

[0079] Other parameters defining the polymeric liquid materials described herein can be measured using standard analytical tools, the content of hydroxy groups in the material can be measured, for example, by: 29 Si- and / or 1 The molar ratio of ethoxy and methoxy terminated alkoxy units in a material can be determined using H-NMR spectroscopy and Karl Fischer titration. 13 From C-NMR and independently 29 The Si-NMR data are directly accessible. Characterization of the reaction products in terms of viscosity is easily analyzed by standardized viscosity measurements, for example, a cylindrical rotational viscometer following ASTM E2975-15 "Standard Test method for Calibration of Concentric Cylinder Rotational Viscometers". Other viscosity testing methods are possible, for example, Staudinger capillary viscometer or modern dynamic viscosimetry.

[0080] In a further embodiment, the polymeric liquid highly branched polysiloxane material according to the present invention is one in which the total content of diorganofunctional D-type siloxane and / or the total content of triorganofunctional M-type siloxane groups is zero.

[0081] Optionally, the polymeric liquid highly branched polysiloxane material according to the present invention is one in which the monoorganofunctional T-type siloxane moiety comprises: (x)R 5 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro), propyl, (1H,1H,2H,2H-perfluoro)octyl, (1H,1H,2H,2H-perfluoro)dodecyl, and (1H,1H,2H,2H-perfluoro)hexadecyl; and (xi)R 5 a second population of monoorganofunctional T-shaped alkoxy terminated siloxane groups, wherein R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H,2H,2H-perfluoro)octyl, (1H,1H,2H,2H-perfluoro)dodecyl and (1H,1H,2H,2H-perfluoro)hexadecyl; 5 a second population of non-identical groups; (xii)R 5 But LZ, vinyl, [ka] or a monoorganofunctional T-type alkoxy-terminated siloxane group, (xiii)R 5 But R 5S A monoorganofunctional T-type alkoxy-terminated siloxane group,

[0082] The above options are aimed at tunable hydrophobic materials for the combination of (x) and (xi) and mixed hydrophobic / functional materials for the combination of (x) and (xii).

[0083] For example, by combining (x) and (xi), the polymeric liquid material can have multiple hydrophobic R 5-organofunctional T-type groups can be created that allow control over the steric accessibility and hydrophobic character of the material and thus its solubility and compatibility with polymers, solvents, inorganic and hybrid phases, etc. This allows, for example, tailoring of polymeric liquid materials with a degree of freedom in the formulation of virtually any specific application that is not achievable with today's commercially available silane monomer and pre-hydrolyzate systems.

[0084] For example, a combination of (x) with (xii) or (xiii), R having both hydrophobicity and specific functional groups (see feature (xii)) 5 The combination of groups then allows the overall compatibility with the matrix for a particular application to be tailored while also allowing for the introduction of additional chemical connectivity. For example, hydrophobic R selected from feature (x) 5 A material exhibiting a hydrophobic R while at the same time having a radical polymerizable group, e.g., a methacrylate group (selected from feature (xii)), can then control its interreaction / compatibility through the hydrophobic component and its essentially independent radical crosslinking reactivity by incorporation of said methacrylate component. By selecting the first type and the hydrophobic R 5 Having a functional group and a second R 5 Selecting groups to separate application-related system compatibility by introducing specific chemical functionalities is expected to greatly improve the performance and cost-effectiveness of silane and siloxane technology. The advantage of this approach would be that, while still benefiting from the core-shell structure, various combinations are possible and can be individually selected depending on the application: - R 5 R is as defined by feature (xii) in the core with the hydrophobic T-type siloxane (feature x) forming the shell, thus combining system compatibility with the ability to incorporate specific functions in the core. 5 The expansion of such functional group options through substitution further increases the scope of functional groups considerably. - R for hydrophobicity (characteristic (x)) and functionality (characteristic (xii))5 Both groups are present within the shell creating an interplay between tailored tuning of hydrophobicity / matrix compatibility and functional group density and activity. - hydrophobic (characteristic (x)) groups distributed inside the core and functional (characteristic (xii)) groups in the shell. - R 5S (An additional combination including feature (xiii)).

[0085] In another embodiment, the polymeric liquid highly branched polysiloxane material according to the present invention is one in which the relative atomic ratio of T and Q species is in the range of 0.02:1 to 0.75:1, optionally in the range of 0.03:1 to 0.5:1.

[0086] For example, the advantage of the polymeric liquid material according to the present invention is that the material is essentially free of silanol species (Si-OH). Specifically, the molar content of silanol relative to the total number of Si atoms present in the material is less than about 5, 2.5, 2, 1.5, 1, or 0.5%, optionally less than about 0.2%. This results in greatly improved stability and shelf life, as well as substantially greater structural control, over, for example, conventional sol-gel (e.g., hydrolysis-prepared)-based hybrid materials. In practical applications, they can be used "as is" in non-polar organic solvents, in blends, etc., or directly incorporated into hydrophobic matrices, such as polymer melts.

[0087] In another aspect, the present invention is directed to a hydrolysis product obtained by reacting at least one polymeric liquid material as described herein with a predetermined amount of water or a predetermined amount of a water-solvent mixture, optionally in the presence of at least one surfactant.

[0088] The amount of water or water-solvent mixture for hydrolysis or emulsification is determined, for example, by the molar amount of water relative to the total molar amount of Si in the system, limited by upper and lower limits in a typical formulation. The lower limit defining the molar ratio of water to total Si can be 0.02:1, optionally 0.1:1 or 0.5:1. The upper limit defining the molar ratio of water to total Si can be 5000:1, optionally 500:1 or 50:1. The amount of co-solvent can be selected independently and without the limitations technically imposed by the molar ratio of water to Si.

[0089] For example, the solvent for hydrolysis can be selected from the group consisting of water-soluble organic solvents, such as low molecular weight alcohols, ethers, carboxylic acids, examples of which include: ·R x -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 , and -CH 13 Formula R x -OH alcohols; ·R x ,R y is independently selected from the group consisting of -CH3, -C2H5 and -C3H7; x ,R y -(C=O) ketones; ·R x -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 , and -CH 13 Formula R x -COOH carboxylic acids; low molecular weight organic esters, for example ethyl acetate, methyl acetate, or ethyl formate, methyl formate; and / or ·R x ,R y is independently selected from the group consisting of -CH3, -C2H5, and -C3H7, or a cyclic ether, such as tetrahydrofuran; x -OR y of ether.

[0090] An acid or base can also be used as a hydrolysis / condensation catalyst together with the solvent. Typical acids used are inorganic acids and low molecular weight organic carboxylic acids. Typical bases are alkali hydroxides, ammonia, or aliphatic / aromatic primary, secondary or tertiary amines.

[0091] For example, surfactants for hydrolysis and / or emulsification can be selected from the group consisting of: non-ionic surfactants, such as polyethylene oxide / polypropylene oxide block copolymers or similar polyether block copolymer surfactants; Carboxylic acid-based ionic surfactants, in particular fatty acids and related saturated or unsaturated linear and / or branched aliphatic hydrocarbon-carboxylates, such as lauric acid, stearic acid, oleic acid, etc., and their corresponding alkali salts; ionic surfactants based on sulfonic or phosphonic acids, in particular saturated or unsaturated linear and / or branched aliphatic hydrocarbon-sulfonates, such as dodecylsulfonic acid (SDS), and their corresponding alkali salts; and / or · Ionic surfactants based on trialkylammonium salts, such as cetyltrimethylammonium bromide (CTAB) or cetyltrimethylammonium chloride (CTAC).

[0092] In another aspect, the present invention is directed to an emulsion, obtainable by emulsifying the polymeric liquid material described herein with an amount of water, optionally in the presence of at least one surfactant.

[0093] In another aspect, the present invention is directed to a method for preparing the polymeric liquid material of the present invention, the method comprising the steps of: - All R in the material 5 At least 1 mol %, optionally at least 3 mol %, optionally at least 5 mol %, optionally at least 10 mol %, optionally at least 20 mol % of the groups are R5U providing a polymeric liquid material as described herein; - R of the polymer liquid material 5U Functionalize the R 5 At least 1 mol%, optionally at least 3 mol%, optionally at least 5 mol%, optionally at least 7 mol% of R 5S obtaining a base; - recovering, optionally optionally isolating, and optionally optionally purifying the polymeric liquid material.

[0094] R 5S As used herein, modifying or R 5S The term functionalization means R 5U Residues are R 5S This means that a chemical reaction is carried out that is appropriate to convert the desired R to a residue. Suitable chemical reactions are known to those of skill in the art and may be used to 5S These are routinely selected to obtain residues.

[0095] Suitable non-limiting chemical reactions are, for example, as listed below.

[0096] Michael addition, aza-Michael addition (e.g., with amines or thiols and acrylates, alkenes, alkynes, carbonyl isocyanates, or unsaturated carbonyls); reaction with anhydrides (e.g., with amines and maleic anhydride); reaction with acid chlorides (e.g., with amines and the appropriate -C(=O)Cl group); ring opening of epoxides (e.g., with amines, thiols, CN - or with halogens); formation of imines (primary amines and ketones); thiol substitution on halogenoalkanes; various nucleophilic substitutions on halogenoalkanes (e.g., S N2); elimination on halogenoalkanes to form double bonds; reaction of halogenoalkanes with sodium azide to form alkyl azides, optionally followed by reaction of the alkyl azides, for example in click chemistry reactions (azide-alkyne cycloaddition), or through conversion to isocyanates; various functionalization reactions with diisocyanates and triisocyanates; reaction of alkenes, for example the "thiol-ene" reaction with thiols, electrophilic addition of halogens to alkenes, for example vinyls, followed by elimination to alkynes; reaction of tetrasulfides or thiols or unsaturated compounds (e.g. vinyls, methacrylates) with unsaturated aromatic or unsaturated aliphatic compounds in the presence of aliphatic or aromatic linear or cyclic epoxides in the presence of radical sources (e.g. radical initiators), organic and inorganic peroxides; Friedel-Crafts alkylation or acylation on aromatic rings, for example phenyl rings; or formation of peptide bonds through amine or carboxylic acid groups.

[0097] The skilled artisan knows which types of reactions and / or reaction conditions are compatible with the presence of (small amounts of) water and / or silanol groups. The skilled artisan will select the appropriate procedures for carrying out the individual synthetic steps in order to minimize undesired side reactions with water and / or silanol groups. R 5S -functionalization reactions may optionally be excluded from the scope of the present invention. R 5S The preferred procedure for the -functionalization reaction is to first functionalize 0 carried out on the monomer, followed by T 0 The monomer is grafted to the siloxane core, thus R 5S - avoiding reactions in the presence of water and / or silanol groups by temporarily setting aside functionalization.

[0098] The polymeric liquid polysiloxane materials prepared by the methods described herein are 5S-functionalized, i.e. all R 5 At least 1 mol %, optionally at least 3 mol %, optionally at least 5 mol %, optionally at least 7 mol % of the groups are R 5S group, where R 5S is R 5S The starting material for this method is R 5S -Does not have to be functionalized (all R 5 Essentially 100 mol % of the groups are R 5U group), or partially R 5S - may be functionalized (all R 5 At least 3 mol% of the moiety is R 5U The R 5S -functionalization is performed by the R 5U or optionally in some cases by functionalizing R 5S R 5S This can be achieved by further grafting a R-functionalized T-type silane. 5U R in the group 5S -functionalization can be carried out by known chemical methods. The steps of recovering, optionally isolating and optionally purifying the polymeric liquid material can be carried out as outlined below in connection with step (g) of the method.

[0099] In another aspect, the present invention is directed to a method for preparing the polymeric liquid material described herein, the method comprising the steps of: (a) providing a Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy) polysiloxane precursor; The precursor is optionally (a1) diorganofunctional D-type siloxane groups, and / or (a2)R 5 But R 5U and R 5Smay contain monoorganofunctional T-type siloxane groups selected from: Optionally, it may contain less than 12 mol % of the combined (a1) and (a2), based on the total amount of all Q-type species; Optionally, it may further comprise a recombinant catalyst; wherein the precursor comprises at least 28 mol %, optionally at least 35 mol %, and optionally at least 42 mol %, based on the total Q-type siloxane species, of four-membered Q-type siloxanes. 2r Type and Q 3s,d and / or The precursor is all Q 3 At least 60%, optionally at least 67%, optionally at least 75% of the four-membered Q 3s,3d type siloxane ring species; and Q-type polysiloxane DP Q型 is in the range of 1.5 to 2.7, optionally 1.5 to 2.5, optionally 1.7 to 2.5; (b) Below: (b1) Triorganofunctional M-type silanes Si(OR 1 )(R 2 )(R 3 )(R 4 ); and / or (b2) Diorganofunctional D-type silanes Si(OR 1 )2(R 2 )(R 3 ); and / or (b3) Monoorganofunctional T-type silanes Si(OR 1 )3(R 5 ) (where R 5は , R 5U and R 5S (selected from in monomeric or oligomeric form to the polysiloxane of (a); (c) optionally adding a recombinant catalyst to the mixture of step (b); (d) heating the mixture of (c) in the absence of water; (e) optionally repeating steps (b) through (d) at least one time; (f) Optionally, in some cases, R of the polymeric liquid material. 5U Functionalize the residues to make all R 5 At least 1 mol%, optionally at least 3 mol%, optionally at least 5 mol%, optionally at least 7 mol% of R relative to the residue 5S obtaining a residue; (g) recovering, optionally isolating, and optionally purifying the polymeric liquid material. Including, provided that at least one of steps (a2) or (b3) is carried out; and Provided that a recombinant catalyst is present in at least one of steps (a) or (c).

[0100] The Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy) polysiloxane precursor of step (a) can be any, for example, commercially available Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy) polysiloxane, provided that it is a non-organofunctional Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy) polysiloxane as defined for polysiloxane materials herein. 1 From Q 4 and wherein at least 28 mol %, optionally at least 35 mol %, optionally at least 42 mol % of all Q type species are four-membered Q siloxane moieties. 2 Type and Q 3 type siloxane ring species (including single and double rings) and / or all Q 3 At least 60%, optionally at least 67%, optionally at least 75% of the species are Q4 members joined together. 3s,3d The degree of polymerization of Q-type polysiloxane is DP Q型is in the range of 1.5 to 2.5, optionally 1.5 to 2.7, optionally 1.7 to 2.4. In the context of this method, the four-membered Q 3 The Q type siloxane ring species are those Q rings that are part of one or two four-membered rings, respectively. 3 The term "all Q type species" in the context of this method means all Q type siloxane species. 1 From Q 4 Siloxane species, as well as Q 0 Contains a silane monomer.

[0101] The Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy) polysiloxane of step (a) constitutes the precursor material described herein. When a core-shell structure is intended, typically a pure Q-type precursor material is used as the core. Typical and exemplary Q-type precursor materials include 29 The Si NMR spectrum is shown in Figure 6 (top), which shows a significant amount of Q 2r and Q 3s,d The tetrasiloxane ring species is shown. Grafting of T-shaped monomeric silanes significantly reduces the ring species, as also shown in Figure 6 (bottom).

[0102] For example, the following Q-type polymethoxy, polyethoxy, or mixed poly(methoxy / ethoxy) polysiloxanes can be used in step (a): commercially available oligomers of TEOS or TMOS, such as ethyl silicate with a total SiO2 equivalent content of 40% by weight, such as Dynasylan 40 (Evonik Industries), Wacker Silicate TES 40 WN (Wacker), TEOS-40 (Momentive), or simply referred to as "Ethyl Silicate-40" by many unbranded Asian suppliers. Also, oligomers with higher silicate content, such as Dynasylan Silbond 50, or equivalent products with, for example, up to 50% equivalent SiO2 solids, can be used. The same is true for TMOS oligomers, such as "Oligomeric Hydrolysates of Tetramethoxysilane" (Gelest Inc.) or "MKC Silicates" (Mitsubishi Chemicals), which exist in variations with SiO2 equivalent contents up to 59%, and can be used as a source for methyl silicate. The analogous propoxy-silicates can also be used if commercially available.

[0103] Alternatively, the Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy) polysiloxanes of step (a) can be synthesized according to procedures known in the art, including hydrolytic and non-hydrolytic methods, for example as described in the following examples, WO2019 / 234062A1, EP1576035B1, Macromolecules 2006, 39,5,1701-1708, Macromol. Chem. Phys. 2003, 204(7), 1014-1026, or Doklady Chem., vol. 349, 1996, 190-19.

[0104] In the context of this method, triorganofunctional M-type silanes Si(OR 1 )(R 2 )(R 3)(R 4 ), diorganofunctional D-type siloxane group Si(OR 1 )2(R 2 )(R 3 ), and monoorganofunctional T-type siloxane groups Si(OR 1 )3(R 5 The definitions of the chemical substituents in correspond to those given in connection with the polysiloxane materials described herein.

[0105] The term "in monomeric or oligomeric form" as used herein means that the M, D and T type silanes, when used as precursors, are not highly polymerized, i.e., are either monomers or small oligomers, typically mixtures of, for example, less than 10 monomer units in a typical oligomer.

[0106] The recombinant catalyst for use in the present method can be any catalyst that accelerates the grafting of T, D, and M type monomers or oligomers by nucleophilic substitution resulting in the polymeric liquid materials described herein. The catalyst concentration is generally in the range of 0.01 mol% to 1.5 mol% based on the total molar content of silicon in the material prepared. The catalyst can be present in step (a) or (c), or both, provided that it is present in at least one of steps (a) or (c).

[0107] In further embodiments, main groups, or transition metal salts, or organometallic compounds, or organic bases (eg, aliphatic amine bases or aminosilane bases) or inorganic bases are used as recombinant catalysts.

[0108] Recombinant catalysts, as used herein, can be advantageously identified, for example, by following the procedure (protocol) of Example 27 below. 0 At least 75% of the grafts (less than 25% remaining T 0 Any catalyst that elicits the synthesis of a recombinant saccharide (monomer) is a recombinant catalyst for use in the present invention.

[0109] The catalyst for use in the present process may be selected from the group of compounds having the following general formula: M(II)L1L2 (metal ions with an oxidation state of +2, e.g. Zn +2 or Fe +2 in the case of) M(III)L1L2L3 or O=M(III)L1 (metal ions with oxidation state +3, e.g. Ce +3 or Fe +3 in the case of) M(IV)L1L2L3L4 or O=M(IV)L1L2 (metal ions with oxidation state +4, e.g. Ti +4 or Hf +4 in the case of) M(V)L1L2L3L4L5 or O=M(V)L1L2L3 (metal ions with an oxidation state of +5, e.g. V +5 or Nb +5 in the case of) where M (II, III, IV, IV) is a transition metal ion with a main group or oxidation state of +2 to +5, bound by covalent, ionic or coordinate bonds, or a combination thereof, to identical or non-identical coordinated counterions and / or ligands L1 to L5, where at least one of these ligands is a halide (e.g., F - , Cl - , Br - , I - ), pseudohalides (e.g., SCN - , N3 - , C.N. - ), chalcogenides, inorganic acid counterions, organic carboxylates, organic alcoholates, acetylacetonates, organic sulfonic or phosphonic acid counterions, where preferably the main group or transition metal ion is selected from the group of the elements Fe, Al, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Zn, Ce, Co, Fe, and Mn in their naturally occurring oxidation states.

[0110] The "in the absence of water" referred to in step d) does not apply, optionally in some cases, to the reaction with triorganofunctional M-type silanes as defined in the present method, such as the grafting reaction and / or the recombination reaction. In the present method, the reaction step with triorganofunctional M-type silanes can be carried out in the presence of water, for example in the presence of an aqueous acid / cosolvent mixture (e.g., EtOH, water, ketones), as is commonly used in the art. Optionally in some cases, the grafting of M-type silanes is separated in time from the D-type and / or T-type grafting, which is carried out either before or after it.

[0111] To allow sufficiently fast reaction kinetics to obtain reasonable reaction times, the use of elevated temperatures along with a catalyst is typically required at least in step (d) and optionally in steps (b) through (e) described herein.

[0112] Each reaction step may take, for example, 30 minutes to several hours or days depending on the type and concentration of recombinant catalyst used, or, if radio frequency heating methods are used, reaction times may be significantly reduced.

[0113] All of steps (b) through (f) are optionally carried out under stirring. Optionally, stirring is continued for at least 30 minutes in steps d) and / or (f) after adding the M, D or T type silane.

[0114] For example, during steps (d) and / or (f), the overall degree of polymerization remains essentially constant when the reaction is carried out in the absence of water. As referred to herein, the degree of polymerization always refers to that of the siloxane material.

[0115] Optionally, in steps (d) and / or (f), low molecular weight reaction products and / or residual starting materials in the reaction mixture may be removed by vacuum distillation, for example by gradually reducing the pressure inside the reaction vessel and holding the final pressure, for example in the range of about 5-250 mbar, for a period of time, for example 2-60 min. Optionally, residual volatile organic compounds, solvent residues and / or low molecular weight starting products (VOCs) may be further removed at any stage in a work-up procedure by bubbling a purge gas into the reaction mixture, preferably while it is still warm or hot.

[0116] For example, each of steps (a) through (e) of the method is carried out essentially without chemical reactants other than the chemical reactants and / or recombinant catalysts to promote the polymerization and / or grafting reaction. For example, all of steps (a) through (e) are carried out essentially in the absence of acetic anhydride, acetic acid, or other anhydrides, or aliphatic or aromatic carboxylic acids, or water, and optionally in the absence of chlorosilanes, chlorosiloxanes, acetoxysilanes, or acetoxysiloxanes. "Essentially free" means that trace or catalytic amounts of the aforementioned substances may be present, but "essentially free" means that the amount is not sufficient to promote a detectable or significant polymerization reaction by these substances.

[0117] Without wishing to be bound by theory, it is believed that the driving force behind this substitution reaction (also called "grafting") in step (d) is the formation of a Q-type material in step (a) with four members bonded thereto, 2 Type and / or Q 3It is believed that the release of ring tension in the Q-type precursor or core material is sufficient to efficiently add, i.e., graft, M, D, and / or T-type silanes onto the Q-type core material without the need for additional chemical reactants, such as acetic anhydride. Optionally, in some cases, recombinant catalysts as defined herein are not required if the reaction temperature and duration are appropriately adjusted. As can be seen in the examples below, the mol% of ring species in the material of step (a) is significantly reduced in the product of the preparation method herein. As an example of a typical grafting reaction, FIG. 6 (bottom) shows the reaction product after recombinant of a typical example using polyethoxysiloxane Q-type precursor (FIG. 6 (top)) and MTES as the monomeric T-type precursor. A direct comparison between them shows that the grafted product is Q-type. 2r , and also Q 3s , Q 3d A significant decrease in both tetrasiloxane ring species, as well as Q, most likely due to partial Q-type depolymerization. 0 It can be seen that the increase in monomers is a feature of the reaction. At the same time, the linear Q-type group (Q 2l and Q 3l ) increased significantly. Figure 7 shows the Q 2r and Q 3s,d Transient decay of tetrasiloxane species ((Q 2r +Q 3s,d ) / Q tot The values ​​are shown in percentages as

[0118] The proviso that at least one of steps (a2) or (b3) is performed is that in the product of the method of the present invention, the polymeric liquid polysiloxane material described herein contains a monoorganofunctional T-type siloxane group as described herein and therefore has the formula Si(OR 1 )3(R 5 ) must be added in monomeric or oligomeric form in at least one step of the process, which is equivalent to saying that the product must contain a T group.

[0119] When step (e) is optional, the repetition of step (b) includes that the ingredients added during the repetition or further repetitions are not necessarily the same ingredients as in the previous repetition. For example, for the first repetition of step (b3), R 5 About R 5U If you select R 5U , R 5S or any combination thereof when step (b3) is repeated 5 The same applies to all other iterative steps, e.g., whether M, D, or T type silanes are added and / or R 1 , R 2 , R 3 and R 4 which type of catalyst is selected and what type and amount of catalyst is added during the repetition.

[0120] For the monoorganofunctional T-type siloxane groups and silanes of steps (a2) and (b3), R 5 is R 5U and R 5S This means that the T-type siloxane group / silane is selected from R 5S -Does not have to be functionalized (all T-type siloxane groups in the material / all R 5 Essentially 100 mol % of the groups are R 5U group), completely R 5S - may be functionalized (all T-type siloxane groups in the material / all R 5 Essentially 100 mol % of the moiety is R 5S group), or partially R 5S - may be functionalized (T-type siloxane groups / silanes may be R 5U and R 5S The R moiety of the monoorganofunctional T-type siloxane group in step (a2) of the method may optionally include 5 is R 5U It is.

[0121] Without step (f), all R 5 At least 1 mol %, optionally at least 3 mol %, optionally at least 5 mol %, optionally at least 7 mol % of the groups are R 5S When the T-type siloxane groups and silanes of steps (a2) and / or (b3) are selected such that R 5U Step (f) is an optional step insofar as functionalization of the residue is not required. The T-type siloxane groups and silanes of steps (a2) and / or (b3) are added to all R groups in the material. 5 At least 1 mol% of the moiety is R 5S Of course, step (f) can be carried out even if the product already has a functionalized R 5 The mole percentage of the residue can be increased.

[0122] Optionally, step (f) may be performed between steps (d) and (e), and the order of steps (e) and (f) is optionally interchangeable.

[0123] In a further embodiment, the methods described herein comprise: In step (a), R of the T-type siloxane group 5 But R 5U and; In step (b), R of T-type silane 5 But R 5U and - This method is for the R of polymer liquid materials. 5U Functionalize the residues to make all R 5 At least 1 mol%, optionally at least 3 mol%, optionally at least 5 mol%, optionally at least 7 mol% of R relative to the residue 5S The method includes a step (f) of obtaining a residue.

[0124] In another embodiment, the methods described herein comprise: In step (a), R of the T-type siloxane group5 But R 5U and; In step (b), R of at least one T-type silane 5 But R 5S in which case, in optional step (e), R of the T-type silane 5 But R 5U and R 5S and - the method optionally does not include step (f).

[0125] In steps (a2) and (b3), R 5S -functionalized or R 5S - The selection of non-functionalized T-type siloxane groups and silanes, together with optional steps (e) and (f), is carried out by adding all R 5 At least 1 mol %, optionally at least 3 mol %, optionally at least 5 mol %, optionally at least 7 mol % of the groups are R 5S Any permutation in the selection of starting materials, and R 5 It is within the skill of the art to carry out further functionalization reactions involving the groups using routine procedures.

[0126] R 5S The concept of variability of the functionalization procedures (protocols) can be illustrated by the NMR spectroscopy studies shown for three exemplary non-limiting model functionalizations, namely: i) Glycidyl R 5U On-polysiloxane functionalization of “Jeffamine” type PPG-diamines to polysiloxanes with the -T moiety (Figure 8 shows 1 H NMR spectrum is shown in Figure 9. 13 Figure 10 shows the C NMR spectrum. 29 Si NMR spectrum shown), ii) Aza-Micheal addition products of diacrylates and aminopropyl-triethoxysilane to pure Q-type polysiloxane precursors, “T 0Grafting functionalization (Figure 11) 1 H NMR spectrum, Figure 12 13 C NMR spectrum shown), iii) Aminopropyl R 5U On-polysiloxane functionalization of maleic anhydride to -T-type polysiloxane (Figure 13) 1 H NMR spectrum, Figure 14 13 (C NMR spectrum shown) where the bonds to the polysiloxane core in the diagram are symbolically represented by a single siloxane bond connecting the corresponding T-shaped unit to the poly"siloxane".

[0127] The products of the process are recovered in step (g) by collecting the materials from the reaction vessel. The products may optionally be isolated and purified by standard methods known in the art, such as by distillation, optionally using a thin film evaporator, stripping with a purge gas to remove VOCs, etc.

[0128] In an embodiment, the method described herein further comprises the step of reacting a triorganofunctional M-type silane, Si(OR 1 )(R 2 )(R 3 )(R 4 ), or M-type siloxane (R 2 )(R 3 )(R 4 )Si-O-Si(R 2 )(R 3 )(R 4 ), and optionally a diorganofunctional D-type silane, optionally in monomeric or oligomeric form, as described in step (b2), in the presence of water and a suitable co-solvent, and an acid catalyst, and then heating the mixture, optionally to reflux in some cases. If the addition is carried out before step (b), the water is removed before step (b) is started.

[0129] For example, triorganofunctional M-type silanes Si(OR 1)(R 2 )(R 3 )(R 4 ), and / or optionally the solvent for adding the diorganofunctional D-type siloxane can be selected from the group consisting of ethanol, methanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, dimethyl ether, methyl ethyl ether, diethyl ether.

[0130] For example, the acid catalyst may be selected from strong acids having a negative pKa value, preferably selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, hydrobromic acid, or hydroiodic acid.

[0131] In another embodiment, the reaction temperature for steps (c) to (e) of the process described herein is in the range of 30 to 170° C., optionally 50 to 150° C., or 70° C. to 120° C., and the pressure during steps (c) to (e) is in the range of 0.1 bar to 2 bar, optionally 0.5 bar to 1.4 bar, or 0.6 bar to 1.2 bar.

[0132] The optional functionalization step (f) does not necessarily have to be carried out at elevated temperatures, even if this step is carried out before step (e). Which reaction temperature is suitable for which type of R in step (f)? 5S - what is necessary for functionalization reactions is common general knowledge.

[0133] In a further embodiment, the recombinant catalyst for use in the method is selected from the group consisting of: - Ti(IV)(OR 13 )4 and Zr(IV)(OR 13 )4; - Ti(IV)X4 and Zr(IV)X4; - O=Ti(IV)X2 and O=Zr(IV)X2; - Ti(IV)X2(OR 13 )2 and Zr(IV)X2(OR 13 )2; - Ti(IV)X2(OAcAc)2 and Zr(IV)X2(OAcAc)2; - Ti(IV)(OSi(CH3)3)4 and Zr(IV)(OSi(CH3)3)4; - (R 13 O)2Ti(IV)(OAcAc)2 and (R 13 O)2Zr(IV)(OAcAc)2; - O=Ti(IV)(OAcAc)2 and O=Zr(IV)(OAcAc)2; - Ti(IV)(OAc)4 and Zr(IV)(OAc)4; - Ti(IV)(OAc)2(OR 13 )2 and Zr(IV)(OAc)2(OR 13 )2; and - O=Ti(IV)(OAc)2 and O=Zr(IV)(OAc)2; Where: R 13 is selected from the group consisting of -CH3, -CH2CH3, -CH(CH3)2, -CH2CH2CH3, -C(CH3)3, -CH2CH2CH2CH3, and CH2CH2CH(CH3)2; X is a halide, pseudohalide, nitrate, chlorate, or perchlorate anion; and The amount of catalyst in each of steps (a) or (c) is optionally between 0.01 and 5 mol %, optionally between 0.05 or 0.1 and 3 mol %, based on the total molar content of silicon present in said steps.

[0134] In another aspect, the present invention is directed to a product obtained or obtainable by any of the processes described herein.

[0135] In a further aspect, the present invention relates to the use of the polymeric liquid material described herein, wherein the polymeric liquid material comprises in the formulation as a crosslinker a vinyl, methacrylate, butaacrylate, acrylate, [ka] R is a radical polymerizable organic functional group selected from the group consisting of 5 and the content of the polymeric liquid material is in the range of 0.2% to 25% by weight of the formulation.

[0136] The term "formulation" as used herein refers to any product that includes the polymeric liquid material described herein, for example as a crosslinker or any other functional material. The formulation can be a liquid, paste or emulsion or slurry. Such formulations typically contain, for example, other compatible radically polymerizable monomers, oligomers or prepolymers or silane-terminated polymeric building block moieties, fillers and performance-enhancing or life-extending additives and stabilizers, such as: UV and light stabilizers, antioxidants, rheology modifiers, tack modifiers, film-forming additives, gloss additives, antistatic agents, nucleating agents, etc. If heat-activatable, such formulations also typically contain radical initiator molecules, selected, for example, to meet a designed cure initiation temperature.

[0137] In a further aspect, the present invention relates to the use of a polymeric liquid material, hydrolysis product or emulsion as described herein, wherein the polymeric liquid material is in a hydrophobic formulation, R 5 The present invention is directed to the use of a polymeric liquid material or the like that comprises at least one population of T-type alkoxy-terminated siloxane groups having an organic functional group selected from methyl, ethyl, vinyl, methacrylate, n-propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H,2H,2H-perfluoro)octyl, (1H,1H,2H,2H-perfluoro)dodecyl, and (1H,1H,2H,2H-perfluoro)hexadecyl, and the amount of polymeric liquid, hydrolysis product, or emulsion in the formulation is 0.5% to 25% by weight.

[0138] The following figures and examples serve to illustrate the invention and are not intended to limit the scope of the invention as set forth in the appended claims. [Brief description of the drawings]

[0139] [Figure 1] FIG. 1 shows exemplary 2D molecular structure representations of a typical pure Q-type precursor material or core in the general case (FIG. 1a) (all combinations of methoxy, ethoxy, propoxy are possible for R1) and three more specific cases: more ethoxy and less methoxy for R1 (FIG. 1b), roughly equal ethoxy and methoxy (FIG. 1c), and only ethoxy R1 groups but also a small amount of silanol groups (FIG. 1d). [Diagram 2] FIG. 2 shows an exemplary 2D molecular structural representation of a typical material described herein, based only on pure Q-type precursor materials. In the general case (FIG. 2a), all combinations of M, D and T functionalization are possible, as indicated by the presence of selected T1, T2, D1, D2 and M1 groups. In the general description, T3 groups are also possible, but they are not included in this simplified 2D structural representation. Furthermore, these three specific cases are limited to idealized compounds featuring (FIG. 2b) aminopropyl functionality with partial -R10 functionalization of amine groups, featuring both R5U and R5S, (FIG. 2c) R11-glycidoxypropyl-adduct functionality with complete functionalization, featuring only R5S, and (FIG. 2d) phenyl functionality with partial -R11 functionalization of phenyl (Ph) groups, featuring both R5U and R5ST-type siloxane moieties, in order to illustrate the aspects of diversity with respect to the Q-type precursor / single T-type grafted siloxane combination. These representations are for illustrative purposes only and do not imply any limitations on the combination of further T (R5S and R5U), D, M type grafts. [Diagram 3]Figure 3 shows the 29Si NMR spectra of materials prepared from ethoxy-based Q-type and methoxy-based T-type precursors, illustrating the ethoxy / methoxy ligand exchange in both the Q-type and T-type spectral domains in the final material. With the examples of the T0 and Q0 monomers, the ethoxy / methoxy exchange is shown in the form of partial signals split into various subpeaks. For T0, three subsets of peaks, T0a, T0b, are observed, which originate from the T0 group containing three ethoxy, as well as two ethoxy and one methoxy substituents. As this particular material is highly ethoxy-rich, the further peaks T0c (one ethoxy and two methoxy) and T0d (three methoxy) cannot be resolved (signals too small). Similarly, for the Q0 spectral range, a subset of five peaks Q0a, Q0b, Q0c are seen, which originate from Q0 groups containing 4 ethoxy, 3 ethoxy and 1 methoxy, 2 ethoxy and 2 methoxy, while Q0d (1 ethoxy and 3 methoxy substituents) and Q0e (4 methoxy) signals are again not visible. [Figure 4] FIG. 4 shows the 29Si NMR spectrum of a material prepared from an ethoxy-based Q-type precursor featuring both grafted M-type (from trimethylethoxysilane, TMES), D-type (from dimethyldiethoxysilane, DMDES), and unfunctionalized R5U and functionalized R5ST-type groups (from partially -R11-functionalized mercaptopropyltriethoxysilane, MPTES) in one material, with the signals of the spectral peaks of the individual moieties labeled. [Diagram 5]Figure 5 shows the 29Si NMR spectra of materials made from TEOS oligomeric Q-type precursors and two different triethoxysilane monomeric T-type precursors, namely vinyltriethoxysilane (VTES) and aminopropyltriethoxysilane (APTES), where the aminopropyl-functional T-types are partially R5S-functionalized with organic R10 groups, meaning that the vinyl T-type groups have only unfunctionalized R5U and the aminopropyl T-type groups have both unfunctionalized R5U and functionalized R5S. Individual groups belonging to the vinyl (V) and aminopropyl (AP, both R5U and R5S) R5-functional T-type subpopulations can be clearly separated in the spectrum and are labeled for clarity. [Figure 6] FIG. 6 shows the effect of recombinant grafting on the content of tetrasiloxane ring species. The top 29Si NMR spectrum of the polyethylsilicate Q-type precursor material shows the abundance of Q2r and Q3s,d tetrasiloxane ring species. The bottom 29Si NMR spectrum shows the material made from the polyethylsilicate Q-type precursor itself by Ti(IV)-catalyzed recombinant grafting with a single triethoxysilane monomer T-type precursor, along with the corresponding Q-type and T-type group peak assignments. It can be clearly seen that the product has much fewer Q2r and Q3s,d tetrasiloxane ring species than the original Q-type precursor material. Specifically, most of the Q2r species have been converted to Q2l, and most of the Q3d and some of the Q3s tetrasiloxane ring species have also disappeared and been replaced by linear Q3l species, likely as a result of the recombinant grafting reaction. [Figure 7] Figure 7 shows the disappearance of ring species, exemplified by the (Q2r&Q3s,d) ring species % index, during the model grafting reaction of MTES onto a Q-type model precursor compound with increasing reaction time. The disappearance of ring species during thermal treatment in the presence of recombinant catalyst is simultaneous with the grafting of monomeric T-type model silane compounds onto the Q-type precursor. [Figure 8]Figure 8 shows the R5S-functionalization reaction monitoring by 1H NMR spectra of various intermediates used for the preparation of R5S-functionalized QT polysiloxane materials by functionalization "on polysiloxane". The various spectra show the reference spectra of the organic substrates used for R5S-functionalization, α,ω amino terminated polypropylene glycol (Jeffamine D400, Figure 8a), R5U non-functionalized (R5U = glycidoxypropyl (Gly)) polysiloxane with T-type groups (Figure 8b), and the R5S-functionalized polysiloxane polymeric liquid material obtained by epoxide ring-opening functionalization with the organic substrate (Figure 8c). [Figure 9] Figure 9 shows the R5S-functionalization reaction monitoring by 13C NMR spectra of various intermediates used in the preparation of R5S-functionalized QT polysiloxane materials by "on-polysiloxane" functionalization. The various spectra show the reference spectra of the organic substrates used for R5S-functionalization, α,ω amino terminated polypropylene glycol (Jeffamine D400, Figure 9a), R5U non-functionalized (R5U = glycidoxypropyl (Gly)) polysiloxane with T-type groups (Figure 9b), and R5S-functionalized polysiloxane polymeric liquid material obtained by epoxide ring-opening functionalization with organic substrates (Figure 9c). [Figure 10] FIG. 10 shows the 29Si NMR spectra of a polysiloxane with R5U=glycidoxypropyl (Gly) T-type groups (top) and the same material after R5S-functionalization by epoxide ring-opening with α,ω amino-terminated polypropylene glycol (Jeffamine D400) (bottom). [Figure 11]Figure 11 shows the R5S-functionalization reaction monitoring by 1H NMR spectra of the materials used to prepare the QT polysiloxane material without R5S-functionalization using the "T0 grafting" approach. The various spectra show the monomeric T-type silane APTES without R5S-functionalization (R5U = -CH2CH2CH2-NH2) (Figure 11a), the reference spectrum of the organic substrate diethylene glycol-diacrylate (DEGDA) used for R5S-functionalization (Figure 11b), the DEGDA-R5S-functionalization product with APTES (Figure 11c), which constitutes the T0 monomer with functionalized R5S- used later for condensation grafting, and finally the polysiloxane material characterized by the T-type group with grafted R5S (Figure 11d). [Figure 12] Figure 12 shows the R5S-functionalization reaction monitoring by 13C NMR spectra of the materials used for the preparation of the R5S-functionalized QT polysiloxane material. The various spectra show the monomeric T-type silane APTES that is not R5S-functionalized (R5U = -CH2CH2CH2-NH2) (Figure 12a), the reference spectrum of the organic substrate diethylene glycol-diacrylate (DEGDA) used for the R5S-functionalization (Figure 12b), the DEGDA-R5S-functionalized product with APTES that constitutes the T0 monomer with functionalized R5S that is later used for the condensation grafting (Figure 12c), and finally the polysiloxane material characterized by the T-type group with said grafted R5S (Figure 12d). [Figure 13] Figure 13 shows the R5S-functionalization reaction monitoring by 1H NMR spectra of the materials used to prepare the R5S-functionalized QT polysiloxane material by R5S-functionalization "on polysiloxane". The different spectra show the reference spectrum of the organic substrate used for R5S-functionalization, phthalic anhydride (PhA, Figure 13a), a polysiloxane with T-type groups where R5S is not functionalized (R5U = aminopropyl (AP)) (Figure 13b) and the R5S-functionalized polysiloxane polymeric liquid material obtained by amide coupling with the organic substrate (Figure 13c). [Figure 14] Figure 14 shows the R5S-functionalization reaction monitoring by 13C NMR spectra of the various materials used for the preparation of the R5S-functionalized QT polysiloxane material by R5S-functionalization "on polysiloxane". The various spectra show the reference spectrum of the organic substrate phthalic anhydride (PhA) used for R5S-functionalization (Figure 14a), the polysiloxane with T-type groups that is not R5S-functionalized (R5U = aminopropyl (AP)) (Figure 14b) and the R5S-functionalized polysiloxane polymeric liquid material obtained by amide coupling with the organic substrate (Figure 14c). EXAMPLES

[0140] In all examples, the mole percentages of (tetrasiloxane) ring species are the percentages of all Q species relative to the total number of Q species, unless otherwise specifically stated. 2 and Q 3 This refers to the total number of ring species, and in this specification, (Q 2r &Q 3s,d ) also known as ring species%.

[0141] In all examples, the mole percentages of (tetrasiloxane) ring species are the percentages of all Q species relative to the total number of Q species, unless otherwise specifically stated. 2 and Q 3 This refers to the total number of ring species, and in this specification, (Q 2r &Q 3s,d ) Also called ring species %. The examples are configured as follows.

[0142] Example 1 is R 5S -non-functionalized (i.e. R 5U Various procedures for preparing the liquid material (having

[0143] Example 2 shows the results of the R 5U -T-type monomer R 5S Examples of functionalization include R 5U R 5SGeneral procedures are described with examples resulting in complete or partial conversion to substituents.

[0144] Example 3 describes various functionalization procedures using different functionalization procedures (specifically, "on polysiloxane" organic functionalization, in which the organic functionalization reaction is carried out on R on QT(D,M) polysiloxane). 5U The term "T" refers to a group having a T shape. 0 In this case, the previously prepared R 5S -non-functionalized (i.e. R 5U A T-shaped monomer (or oligomer) having the following structure is grafted by a recombinant grafting mechanism.

[0145] Next, Example 4 shows that in one material, R 5S - combining at least one of each type of functionalization to form "on polysiloxane" functionalization and "T 0 "Grafting" and "Organic R 5S -functionalization combinations are described.

[0146] <Example 1: R 5S -Non-functionalized D-50 / (APTMS:TMCS) polycondensate material (n Q型 :(n T型 :n M型 )=1:(0.20:0.05:0.05)) combination> 483 g / 3.78 mol Si equivalents of commercially available ethylsilicate Q-type precursor "Dynasylan Silbond 50" (Evonik Industries) or equivalent was placed in a 1 L round bottom flask equipped with a reflux column in an oil bath along with 134.2 g / 0.75 mol of monomeric T-type precursor methyltriethoxysilane (MTES) and 28.0 g / 0.19 mol of monomeric D-type precursor dimethyldiethoxysilane (DMDES). The mixture was heated to a temperature of 100° C. at which point recombinant catalyst tetrakis(trimethylsiloxy)titanium(IV) was added to the hot mixture. The mixture was continued to stir for 40 hours at which point 20.5 g / 0.19 mol of monomeric M-type precursor trimethylchlorosilane (TMCS) was added and continued to stir for 30 minutes. A solution containing 120 g of absolute ethanol and 5.5 g / 0.31 mol of water was then added to the hot reaction mixture, which was then left to reflux for 2 hours. Finally, the reflux condenser was replaced with a distillation bridge and the residual solvent was removed by distillation. Approximately 125 g of condensate and 669.8 g of crude reaction product were isolated. 29 Si NMR analysis showed that the product contained less than 8% T 0 -monomer, and less than 19% of Q-type tetrasiloxane ring species.

[0147] <Example 1b: D-50 / (APTMS:DVDMS:TMCS) polycondensate material (n Q型 :(n T型 :n D型 :n M型 )=1:(0.20:0.05:0.05)) alternative synthesis> The procedure given in Example 1 above was modified with respect to the manner of addition of the TMCS M-type precursor, which was added with 50 ml of ethanol, but no additional water was added initially with the Q-type precursor. 5UDuring the -T grafting, the D type monomer (diphenyldimethoxysilane, DPhDMS, 46.2 g / 0.19 mol) precursor was also added. The M and Q type precursors were first refluxed at 100° C. for 7 h, after which the T and D type precursors and the recombinant catalyst were added (same amounts). After 37 h reaction time, the excess volatiles were removed by distillation, first at ambient pressure and then at 200 mbar vacuum.

[0148] <Example 1c: TEOS polycondensate / (PTES+N3-PTES) polycondensate material (n Q型 :(n T型 )=1:(0.05+0.08)) compound, > DPQ prepared by non-hydrolytic condensation of tetraethoxysilane (TEOS) with acetic anhydride in the presence of titanium(IV) isopropoxide recombinant catalyst 型 334 g of the Q-type precursor having 2.17 and 44.7% ring species was placed in a 1 L round bottom flask followed by 27.4 g / 0.13 mol of the monomeric T-type precursor propyltriethoxysilane (PTES) and 52.2 g / 0.21 mol of the second T-type precursor 3-azidopropyltrimethoxysilane (N3-PTES) together with no further recombinant catalyst addition. The mixture was heated to a temperature of 118° C. and allowed to stir for 9 hours, at which point any remaining volatiles were removed by pulling a vacuum of 250 mbar for 5 minutes. 29 The total T, as measured by the total amount of T-type moieties, was less than 6.5% each by Si NMR analysis. 0 The product was determined to contain % monomer, as well as less than 27% Q-type tetrasiloxane ring species.

[0149] <Example 1d:R 5S -Non-functionalized ethyl silicate polycondensate / (PTES+APTMS) polycondensate material (n Q型 :(n T型 )=1:(0.05+0.15))> Again, the material was prepared using exactly the same synthetic procedure as in Example 1c above, with the only difference being that O=Zr(IV)(OAcAc)2 was added as a catalyst instead of titanium(IV) isopropoxide for the recombination grafting of the T-type precursor, and the amount and type of the second T-type precursor (APTMS instead of N3-PTES) were changed.

[0150] <(Example 1e):R 5S -Non-functionalized TEOS polycondensate / (PTES+N3-PTES) polycondensate material (n Q型 :(n T型 )=1:(0.05+0.08)) alternative synthesis, > The material was prepared using exactly the same synthetic procedure as in Example 1c above, with the main difference being that the first T-type precursor, PTES, was already added together with TEOS during the preparation step of the Q-type precursor; Q型 :n T型 A mixed QT precursor with a molar ratio of 1:0.05 was generated. During the second condensation step, an additional portion of the second recombinant catalyst Hf(NO3)4 was added, while the remaining parameters and preparation steps remained unchanged. 29 Si NMR analysis showed that the product contained less than 4.5% total T 0 -monomers, and less than 25% Q-type tetrasiloxane ring species and less than 49% (Q 3s,d ) / Q 3 It was confirmed that it contains % ring species.

[0151] <Example 1f:R 5S -Non-functionalized TEOS polycondensate / (alkynyl-functional T-type) polycondensate materials (n Q型 :(n T型 )=1:(0.03)) synthesis> 0.46 mol equivalent of DP_Q, previously prepared by controlled hydrolysis of commercially available ethyl silicate-40, 型A Q-type precursor having an average molecular weight of 1.84 and 41.2% cyclic species was placed in a 100 ml round bottom flask. Then, 4.2 g / 13.8 mmol of an alkenyl-terminated T-type precursor (O-(propargyl)-N-triethoxysilylpropylcarbamate, Gelest Inc.) and 250 ppm of titanium(IV) t-butoxide recombinant catalyst were added. With stirring, the mixture was heated to a temperature of 109° C. The reaction solution was held at that temperature for 14 hours under a nitrogen gas atmosphere, at which point the mixture was cooled to room temperature. 29 Si NMR analysis showed that the product contained less than 8% total T 0 It was determined to contain monomer as well as less than 31% Q-type tetrasiloxane ring species.

[0152] <Example 1g:R 5S -Non-functionalized ethyl silicate polycondensate / (PTES+APTMS) polycondensate material (n Q型 :(n T型 )=1:(0.05+0.15))> Again, the materials were prepared using exactly the same synthetic procedure as in Example 1c above, except that O=Zr(IV)(OAcAc)2 was added as a catalyst instead of titanium(IV) isopropoxide to recombine and graft the T-type precursor, and the amount and type of the second T-type precursor (APTMS instead of N3-PTES) was changed. 29 Si NMR analysis showed that the product contained less than 5% total T 0 -monomer, and less than 24% of Q-type tetrasiloxane ring species.

[0153] <Example 1h:R 5S -Non-functionalized methyl silicate polycondensate / (oligo-PTES+APTMS) polycondensate material (n Q型 :(n T型 )=1:(0.05+0.15))> The material was prepared using exactly the same synthetic procedure as in Example 1g above, except that the Q-type precursor was DP Q型The first T-type precursor, PTES, was added in oligomeric form (oligo-PTES). 29 Si NMR analysis showed that the product contained less than 13% total T 0 -monomer, and less than 21% of Q-type tetrasiloxane ring species.

[0154] <Example 1i:R 5S -Non-functionalized TMOS / TEOS / TPOS polycondensate / (Cl-PTES:DMDES) polycondensate materials (n Q型 :(n T型 :n D型 )=1:(0.20:0.05) combination> 1.33 mol equivalents of Q-type precursor were prepared by controlled hydrolysis of a mixture of TMOS, TEOS, and TPOS in a molar ratio of 0.3:0.4:0.3. The first recombinant grafting step was carried out by mixing the precursor with 48.0 g / 0.20 mol of 3-chloropropyltriethoxysilane (Cl-PTES) for 19 min in a microwave autoclave reactor. Bis-acetylacetonato-titanium(IV)-diisopropoxide was used as the recombinant catalyst. For the second grafting, an additional 16.0 g / 0.067 mol Cl-PTES T-type precursor and 9.9 g / 0.067 mol DMDES D-type precursor were added and the reaction was carried out again in the same microwave autoclave reactor for another 67 min. The resulting reaction product was isolated and residual volatiles were removed on a laboratory rotary evaporator. 29 Si NMR analysis showed that the product contained less than 9% T and D groups, as measured by the combined amount of T and D groups, respectively. 0 -monomers and D less than 11% 0 -monomer combination, and was confirmed to contain less than 22% Q-type tetrasiloxane ring species.

[0155] <Example 1j:R 5S-Non-functionalized ethyl silicate 40 / GPTMS polycondensate material (n Q型 :(n T型 )=1:(0.10)) combination> 380 g / 2.6 mol ethyl silicate with 40% SiO2 solids from Wacker (Wacker Silicate TES 40 WN) was poured into a covered airtight autoclave and 62.4 g / 0.26 mol of the T-type precursor (3-glycidyloxypropyl)trimethoxysilane, together with O=Zr(IV)(NO3)2 as catalyst, were added. The autoclave was then sealed and heated to a temperature of 108°C, resulting in a pressure rise. The mixture was allowed to react for 14 hours, after which the autoclave was cooled to room temperature and the crude reaction product was isolated. 29 Si NMR analysis showed that the product contained less than 9.5% total T groups, as measured by the total amount of T groups. 0 -monomer, and less than 22% of Q-type tetrasiloxane ring species.

[0156] <Example 1k:R 5S -Non-functionalized TMOS+TPOS: DMDES polycondensate precursor / (MTES) polycondensate material (n Q型 :(n T型 :n D型 )=1:(0.05:0.05)) combination> n Q型 :n D型 DPQ was prepared by non-hydrolytic condensation of a 50:50 molar mixture of TMOS and TPOS, including the D-type silane co-precursor DMDES in a molar ratio of 1:0.05. 型 Q-type precursor with 2.03 and 44.7% ring species, 2.2 mol Si equivalents, was placed in a 1 L round bottom flask. Grafting of the T-type precursor MTES was then carried out using additional Ti(IV) ethoxide as a recombinant catalyst. 29 Si NMR analysis showed that the product contained less than 7.0% total T 0 -monomer, and less than 25% of Q-type tetrasiloxane ring species.

[0157] <Example 1l:R 5S -Non-functionalized TEOS&TMOS / SH-PTMS polycondensate material (n Q型 :(n T型 )=1:(0.15)) combination> Tetramethoxysilane (TMOS), 511 g / 2.66 mol Si, and tetramethoxysilane (TEOS), 277 g / 1.33 mol Si, and zirconium(IV)-isobutoxide catalyst were placed in a 1 L round bottom flask with a distillation bridge to provide a 2:1 relative molar ratio of TMOS to TEOS monomers for the preparation of the Q-type precursor. The flask was purged with nitrogen, sealed, placed under nitrogen pressure (balloon), and immersed in a hot oil bath, which was held at 130°C. The Q-type monomer / catalyst mixture was brought to temperature with stirring at 500 rpm. Once at temperature, a selected amount (465.3 g / 4.56 mol) of acetic anhydride was added in small portions. Shortly thereafter, reflux of the reaction by-product, ethyl acetate, occurred. After approximately 8 minutes, a continuous stream of methyl acetate and ethyl acetate was distilled up through the distillation bridge and collected in a collection vessel. The reaction was continued for a total period of about an additional 75 minutes, at which point the reaction was stopped upon cessation of methyl / ethyl acetate distillation. After a total reaction time of 1 hour 40 minutes, the collection vessel was removed and emptied, giving a total mass of 725 g of collected condensate and 465 g of Q-type precursor. 29 Si NMR analysis revealed that the precursor was DP_Q 型 It was determined to have 2.22 and 51.0% Q-type tetrasiloxane ring species. This precursor was then mixed with 117.8 g / 0.6 mol mercaptopropyltrimethoxysilane (SH-PTMS) as the T-type precursor. The mixture was then heated again in the same reaction vessel with stirring to a temperature of 115° C. and held for 5 hours, at which point the heat source was removed and the product was allowed to cool to room temperature. 29 Si NMR analysis showed that the product had less than 8.3% total T 0 Monomer, and less than 22% Q-type tetrasiloxane ring species, and less than 43.2% (Q 3s,d ) / Q3 It was confirmed that it contains % ring species.

[0158] <Example 1m:R 5S -Non-functionalized TEOS / (PhTES+PTMS:DPhDES) polycondensate material (n Q型 :(n T型 :n D型 )=1:(0.10+0.05:0.05))> An amount of Q-type precursor containing 4.5 mol Si equivalents prepared by controlled hydrolysis of TEOS was injected into a sealed stirred glass reactor (Buechi versoclave, 1 l) set at a temperature of 105° C. Then, 108.2 g / 0.45 mol and 37.0 g / 0.23 mol of the first and second T-type monomer precursors phenyltriethoxysilane (PhTES) and propyltrimethoxysilane (PTMS) were injected into the hot autoclave together with 56.2 g / 0.23 mol of the D-type precursor diphenyldimethoxysilane (DPhDMS) and titanium(IV)-methoxide as catalyst. The mixture was kept at the given temperature with stirring for 13 hours, then removed from the heat source and allowed to cool to room temperature. 29 Si NMR analysis showed that the product contained less than 16% T and D groups, as measured by the combined amount of T and D groups, respectively. 0 -monomers and D less than 11% 0 -monomer, and less than 26.9% of Q-type tetrasiloxane ring species.

[0159] <Example 1n:R 5S -Non-functionalized TEOS / (PhTES+PTMS) polycondensate materials (n Q型 :(n T型 )=1:(0.10+0.05))> The material was prepared using exactly the same synthetic procedure as in Example 1m above, with the only difference being that the D-type precursor was omitted during synthesis. 29 Si NMR analysis showed that the product contained less than 13% T, as measured by the combined amount of T and D moieties. 0 -monomer, and less than 26.9% of Q-type tetrasiloxane ring species.

[0160] <Example 1o:R 5S -Non-functionalized TEOS (oligomer) / (TESPT+VTES) polycondensate material (n Q型 :(n T型 )=1:(0.17+0.06))> 2.66 mol Si equivalents of Q-type precursor made by the above "Silanol Route" (preparation of triethoxysilanol from TEOS with sodium hydroxide, followed by work-up and condensation of the triethoxysilanol) was placed in a capped 500 ml glass cylinder. Then, 185.8 g / 0.44 mol of the first T-type precursor, bis(triethoxysilylpropyl) tetrasulfide (TESPT), and 23.1 g / 0.16 mol of the second T-type precursor, vinyltriethoxysilane (VTES), were added along with bis-acetylacetonate-titanium(IV)-diisopropoxide recombinant catalyst. The mixture was heated to 80° C. and kept stirring for 6 days. Residual solvent was removed by pulling a 100 mbar vacuum for 30 min. 29 Si NMR analysis showed that the product contained less than 42% T as measured by the total amount of T-type groups. 0 species, as well as less than 29.2% of Q-type tetrasiloxane ring species.

[0161] <Example 1p:R 5S -Non-functionalized TEOS (oligomer) / MaPTMS polycondensate material (n Q型 :n T型 =1:0.10) combination> This material was prepared using the same procedure as described in Example 1j, with the major differences being that the T-type precursor was 3-methacryloxypropyltrimethoxysilane (MaPTMS) dissolved in a co-solvent (methyl ethyl ketone), the autoclave was heated by a microwave source, and a shortened reaction time of 3.5 hours was used. 29 Si NMR analysis showed that the product contained less than 11% total T 0-monomer, and less than 24% of Q-type tetrasiloxane ring species.

[0162] <Example 2a-l: R used for recombinant grafting 5S -Functionalized graftable T 0 General synthetic procedures (protocols) for preparing monomers (or oligomers) In a typical test, R 5S -Unfunctionalized "R 5U The "R monomer" (or oligomer) is functionalized using the following procedure: 5U The "monomer" is used neat or dissolved in a solvent (SO). It is then reacted with a suitable organic substrate (SU), exemplified by specific examples a to l in Table 1 below, by slowly dosing the latter. The stoichiometry of the reaction is selected according to the multifunctional capabilities of the individual SU compounds. The addition mode may be reversed, meaning that the organic substrate may be placed in the vessel first (with the solvent SO) and then "R 5U "Monomer" means that the T-type silane may be added slowly. Roughly speaking, the material that is the stoichiometric limiting component is the one that is added to the component that is present in excess. The reaction is then held at the desired reaction temperature with stirring for the desired reaction time (TR), if necessary in the presence of a suitable catalyst. Depending on the type of reaction, work-up and purification steps may be required. The resulting R 5S - Functionalized T 0 The monomers can then be used for recombinant grafting onto suitable Q(T,D) precursor materials as exemplified in Example 3 below.

[0163] [Table 1]

[0164] [Table 2]

[0165] [Table 3]

[0166] [Table 4]

[0167] <Examples 3a-t: R according to the present invention can be prepared using one of two separate preparation approaches. 5S -General synthetic procedures (protocols) for the preparation of functionalized polymeric liquid materials In a typical test, a polymeric liquid material having at least one T-type silane is subjected to R 5S -R 5S -Functionalized graftable T 0 ii) by recombinant grafting of monomers or oligomers, or ii) by using specific organic functionalization reactions to attach suitable R groups already grafted onto the material. 5U Either one of these procedures can be used interchangeably and multiple times where chemically meaningful and applicable, but for clarity, in this example, a single R 5S Only R -functionalization was selected. A list of typical examples a to t is shown above in Table 2. 5S Note that for the -functionalization, a specific "organofunctionalization" procedure (protocol) is assigned to suit. The choice of procedure depends on the given siloxane (R 5 ) / organic (SU) substrate combination.

[0168] "T 0 Graft" R 5S -Functionalization methodology: R having an organofunctional group that can be selected from the list of examples in Table 1 5S - Functionalized T 0 The monomer or oligomer may be, for example, any of those described in Example 1.5S -non-functionalized (i.e. R 5U The recombination reaction grafting is carried out by grafting the polymeric liquid material having the above-mentioned R 5S The method is carried out by reacting a -functionalized T-type monomer or oligomer with a polymeric liquid material in the presence of a recombinant catalyst. The temperature, catalyst and duration of the reaction are selected to achieve a satisfactory grafting effect. Optionally, different grafting conditions are tested to find the ideal grafting state. 29 The effectiveness of the grafting can be analyzed by Si NMR spectroscopy.

[0169] R on "polysiloxane" 5S -Functionalization methodology: In this case, organic R 5S -Functionalization is performed by using suitable R 5U As in Example 2, the functionalization is carried out directly on the T-shaped group having the R 5U The T-type grafted polysiloxane featuring - groups (all explanations in Example 1 are generally applicable, except for Example 1k, but there are many other possible combinations) is used undiluted or dissolved in a solvent (SO). It is then reacted with a suitable organic substrate (SU), as exemplified by the specific examples in Table 2 above, by slowly dosing the latter. Here again, the stoichiometry of the reaction is selected according to the polyfunctional capacity of the individual SU compounds. The addition may be reversed, meaning that the organic substrate may be placed in the vessel first (with the solvent SO) and then the organic substrate (SU) may be slowly added. Roughly speaking, the material that is the stoichiometric limiting component is the one that is added to the component that is present in excess. The reaction is then held at the desired reaction temperature, with stirring, for the desired reaction time (TR), if necessary, in the presence of a suitable catalyst. Depending on the type of reaction, post-treatment and purification steps may be necessary.

[0170] <Example 4a> Example 1k by R 5S- A non-functionalized TMOS+TPOS:MTES:DMDES polycondensate material was prepared. 5S - Functionalized T 0 Monomers were prepared and grafted using standard recombinant grafting procedures (90° C., 32 h, Ti(IV) isopropoxide recombinant catalyst). 29 Si NMR analysis showed that the product contained less than 10.5% total T 0 -monomers, and less than 22% Q-type tetrasiloxane ring species and less than 41.1% (Q 3s,d ) / Q 3 It was confirmed that it contains % ring species.

[0171] <Example 4b> R according to the simplified procedure shown in Example 3q 5S A non-functionalized QT polycondensate was prepared from the starting material according to Example 1l. A second R polycondensate according to Example 2i was then prepared. 5S - Functionalized T 0 The monomers were grafted using the standard recombinant grafting procedure (100° C., 24 h, Ti(IV) isopropoxide recombinant catalyst). 29 Si NMR analysis showed that the product had less than 7.2% total T 0 -monomer, and less than 25% of Q-type tetrasiloxane ring species.

[0172] <Example 4c> The same material as described in Example 4b was prepared, but with the addition of the T 0 The difference was that an additional M-type precursor, ethoxytrimethyl-silane (ETMS), was added during grafting of the monomer. 29 Si NMR analysis showed that the product had less than 8.5% total T 0 -monomer, and less than 24% of Q-type tetrasiloxane ring species.

[0173] <Example 4d> Propyl and azidopropyl R5U R is characterized by a substituent 5S A non-functionalized QT polymeric liquid material was prepared according to Example 1c. Then, R 5S - Functionalized T 0 The monomer was prepared separately and grafted using standard recombinant grafting procedures (100 °C, 24 h, Ti(IV) isopropoxide recombinant catalyst). The azidopropyl substituent was then grafted to the desired R of 40% by Cu(s)-catalyzed click chemistry. 5S It was partially functionalized with 4-chlorohexyne at a functionalization level. 29 Si NMR analysis showed that the product contained less than 6.1% total T 0 -monomer, and less than 26% of Q-type tetrasiloxane ring species.

[0174] <Example 4e> At the end of the synthesis, a second T according to example 2e 0 The monomer was grafted onto the polysiloxane liquid material using the standard recombinant grafting procedure (100° C., 24 hours, no additional recombinant catalyst added), the same material as prepared in Example 4d. 29 Si NMR analysis showed that the product contained less than 7.1% total T 0 -monomer, and less than 30% of Q-type tetrasiloxane ring species.

[0175] <Example 4f> Propyl and aminopropyl R 5U R is characterized by a substituent 5S A non-functionalized QT polymeric liquid material was prepared according to Example 1h. Then, R 5S - Functionalized T 0 The monomer was prepared separately and grafted using a standard recombinant grafting procedure (100 °C, 24 h, Ti(IV) isopropoxide recombinant catalyst). The remaining R 5UThe -aminopropyl substituents were fully functionalized by reaction with excess hexamethylene diisocyanate (HDI) in toluene according to Example 3e. 29 Si NMR analysis showed that the product contained less than 9.7% total T 0 -monomer, and less than 22% of Q-type tetrasiloxane ring species.

[0176] <Example 4g> The same material as in Example 4f was prepared, but with a second T 0 The only difference was that during the grafting of the monomers, the D-type silane dimethyldiethoxysilane and an additional recombinant catalyst were also added to the grafting solution. 29 Si NMR analysis showed that the product contained less than 5.9% total T 0 -monomer, and less than 26% of Q-type tetrasiloxane ring species.

[0177] <Example 4h> Propyl and phenyl R 5U R is characterized by a substituent 5S A non-functionalized QT polymeric liquid material was prepared according to Example 1n. Then, R 5S - Functionalized T 0 The monomer (only partial conversion with excess aminosilane monomer) was prepared separately and grafted using the standard recombinant grafting procedure (100 °C, 24 h, Ti(IV) isopropoxide recombinant catalyst). The remaining R 5U The -aminopropyl substituents were fully functionalized by reaction with an excess of diglycidyl ether of bisphenol A (DGEBA). 29 Si NMR analysis showed that the product contained less than 11% total T 0 -monomer, and less than 22% of Q-type tetrasiloxane ring species.

[0178] <Example 4i> The same material as in Example 4h was prepared, but after the reaction was completed, R 5U The only difference was that the -phenyl group was partially functionalized by Friedel-Crafts acylation. 29 Si NMR analysis showed that the product contained less than 9.7% total T 0 -monomer, and less than 29% of Q-type tetrasiloxane ring species.

[0179] <Example 4j> The same material as in Example 4i was prepared, but with the R 5S - Functionalized T 0 The difference was that during the grafting of the monomers, the D-type monomer diphenyl-dimethoxysilane (DPhDMS) and an additional recombinant catalyst were also added to the grafting solution. Furthermore, during the Friedel-Crafts acylation, some of the reactions were carried out with the phenyl group of the D-type group (in this case R 2 , R 3 This occurred in the presence of 1,2-dichlorophenyl ether (which is also reactive). 29 Si NMR analysis showed that the product had less than 7.4% total T 0 -monomer, and less than 23% of Q-type tetrasiloxane ring species.

[0180] <Example 4k> A Q-type precursor prepared by controlled hydrolysis of TEOS was used as the precursor, on which two R 5S - Functionalized T 0 The monomers were grafted using the standard recombinant grafting procedure (100° C., 24 h, Ti(IV) isopropoxide recombinant catalyst). 29 Si NMR analysis showed that the product contained less than 4.2% total T 0 -monomer, and less than 27% of Q-type tetrasiloxane ring species.

[0181] <Example 4l> The material prepared according to Example 4k was first mixed with the M-type precursor HMDSO in 98% ethanol and reacted at 85° C. for 1 hour in the presence of a catalytic amount of hydrochloric acid. An aliquot of hexamethyldisilazane was then added to the mixture and stirring was continued for an additional 45 minutes. Residual volatiles were then removed by vacuum distillation. A third R-type precursor, independently prepared according to Example 2j, was then added to the mixture and reacted at 85° C. for 1 hour. 5S - Functionalized T 0 Monomer was added and grafted using standard recombinant grafting procedures (100° C., 24 h, Ti(IV) isopropoxide recombinant catalyst). 29 Si NMR analysis showed that the product contained less than 6.7% total T 0 -monomer, and less than 28% of Q-type tetrasiloxane ring species.

[0182] <Example 4m> Example 1o by R 5S - A non-functionalized TEOS:TESPT+VTES polycondensate material was prepared. Next, R 5S - Functionalized T 0 The monomer was prepared and grafted using a standard recombinant grafting procedure (90 °C, 32 h, Ti(IV) isopropoxide recombinant catalyst). 5U Functionalization of the -group was achieved by reacting the mixture with acrylonitrile in a controlled radical polymerization procedure. 29 Si NMR analysis showed that the product contained less than 7.7% total T 0 -monomers and less than 44.2% (Q 3s,d ) / Q 3 It was confirmed that it contains % ring species.

[0183] <Example 4n> An identical material was prepared as in Example 4m, except that after the last step (controlled radical polymerization), the remaining vinyl groups were functionalized in a separate reaction step by a thiol-ene reaction with an excess of 1-hexene according to Example 3r. 29Si NMR analysis showed that the product had less than 7.4% total T 0 -monomers, and less than 26% Q-type tetrasiloxane and less than 42.5% (Q 3s,d ) / Q 3 It was confirmed that it contains % ring species.

[0184] <Example 5: TEOS / (iBTES:TMES) polycondensate material (n Q型 :(n T型 :n D型 )=1:(0.20:0.05)) combination> 311 g of the crude precursor from Example 4 was placed in a 1 L round bottom flask along with 146.0 g / 0.53 mol of monomeric T-type precursor octyltriethoxysilane (OTES) and 27.2 g / 0.13 mol of monomeric D-type precursor dimethyldiethoxysilane (DMDES). The mixture was heated to a temperature of 100° C., at which point recombinant catalyst bis-acetylacetonate-titanium(IV)-diacetate was added to the hot mixture. The mixture was allowed to stir for 48 hours, at which point any residual solvent was removed by applying a 250 mbar vacuum for 5 minutes. 29 Si NMR analysis showed that the product contained less than 11% T and D groups, as measured by the combined amount of T and D groups. 0 -Monomer and less than 5% D 0 -monomer, and less than 23% of Q-type tetrasiloxane ring species.

[0185] <Example 5b: TEOS / (OTES:DVDMS) polycondensate material (n Q型 :(n T型 :n D型 )=1:(0.25:0.05)) alternative synthesis> Instead of adding both T-type and D-type monomers together with the pre-made Q-type precursor from Example 4, here we used a pre-made precursor that already contains the D-type group introduced during the precursor condensation step according to Example 4d. Thus, the pre-made raw precursor batch from Example 4d was further premixed with 182.4g / 0.66mol of the monomeric T-type precursor, octyltriethoxysilane (OTES), and the same type and amount of recombinant catalyst. The remaining procedure was the same as that described in Example 5. 29 Si NMR analysis showed that the product contained less than 15% T, as measured by the combined amount of T and D groups. 0 -Monomer and less than 5% D 0 -monomers, and less than 29.5% Q-type tetrasiloxane ring species, and 45.8% Q 3s,d / Q 3 It was confirmed that it contains ring species.

[0186] <Example 6: TEOS / (APTMS+PTES) polycondensate material (n Q型 :n T型 1: (0.20+0.05)) 334 g of the crude precursor from Example 4b was combined and placed in a 1 L round bottom flask, followed by the addition of 27.4 g / 0.13 mol of the monomeric T-type precursor propyltriethoxysilane (PTES) and 95.0 g / 0.53 mol of the second T-type precursor 3-aminopropyltrimethoxysilane (APTMS) along with recombinant catalyst zirconium(IV) chloride. The mixture was heated to a temperature of 125° C. and allowed to stir for 5.5 hours, at which point any residual solvent was removed by pulling a 250 mbar vacuum for 5 minutes. 29 Si NMR analysis showed that the product contained less than 7% total T 0 -monomer, and less than 27% of Q-type tetrasiloxane ring species.

[0187] <Example 6b: TEOS / (APTMS+PTES) polycondensate material (n Q型 :n T型 1: Alternative synthesis of (0.20+0.05)) Similar to Example 5b, the entire pre-made unpurified precursor batch from Example 4e, which now already contains PTES T-type functional silane in QT oligomer form, was also mixed with 95.0 g / 0.53 mol of a second T-type precursor, 3-aminopropyltrimethoxysilane (APTMS), and the same type and amount of recombinant catalyst. The remaining procedure was the same as that described in Example 6. 29 Si NMR analysis showed that the product contained less than 6% total T 0 -monomer, and less than 24% of Q-type tetrasiloxane ring species.

[0188] Example 7: Ethyl silicate-40 / (iBTES:TMES) polycondensate material (n Q型 :(n T型 +n M型 )=1:0.15:0.05) combination> The batch of precursor material prepared in Example 4f was poured into a sealable 1 L glass bottle and additional catalyst Ti(IV) bromide was added along with 87.8 g / 0.40 mol of T-type precursor isobutyl-triethoxysilane (iBTES) and 31.1 g / 0.26 mol of M-type precursor trimethylethoxysilane (TMES). The bottle was lightly sealed and placed in a heating cabinet, which was set at a constant temperature of 100° C. The mixture was reacted at this temperature for 100 hours, after which the crude reaction product was isolated. 29 Si NMR analysis showed that the product contained less than 10% total T 0 -monomer, and less than 21% of Q-type tetrasiloxane ring species.

[0189] Example 8: TMOS / GPTMS polycondensate material (n Q型 :n T型 =1:0.10) combination> The batch of precursor material prepared in Example 4c was poured into a covered airtight autoclave and additional catalyst was added along with 62.4 g / 0.26 mol of the T-type precursor, (3-glycidyloxypropyl)trimethoxysilane. The autoclave was then sealed and heated to a temperature of 110° C. resulting in a pressure increase. The mixture was allowed to react for 14 hours after which the autoclave was cooled to room temperature and the crude reaction product was isolated. 29 Si NMR analysis showed that the product contained less than 8% total T 0 -monomer, and less than 23% of Q-type tetrasiloxane ring species.

[0190] <Example 9: Preparation of a Q-type polycondensate precursor material having a target DP_Q type = 2.44 from tetraethoxysilane or its oligomer> Tetraethoxysilane (TEOS) in monomeric or oligomeric form was reacted with DP_Q in the presence of a cosolvent. 型 The precursor material was hydrolyzed according to state of the art using a standard hydrolysis / condensation catalyst with the stoichiometric amount of water required to achieve the desired degree of polymerization of PO = 2.44. Upon completion of hydrolysis, excess co-solvent and alcohol released during hydrolysis were removed by vacuum distillation. 29 Si NMR analysis revealed 54.9% Q-type tetrasiloxane ring species in the precursor material.

[0191] Example 9b: Preparation of a Q-type polycondensate precursor material having a target DP_Q type of 2.0 from tetrapropoxysilane or its oligomers. By using tetrapropoxysilane (TPOS) as the starting Q-type monomer or oligomer and adjusting the stoichiometric amount of water added, the degree of polymerization DP_Q 型 The same material as in Example 9 was prepared, except that the precursor material 29 Si NMR analysis revealed 44.5% Q-type tetrasiloxane ring species.

[0192] Example 9c: Preparation of a Q-type polycondensate precursor material having a target DP_Q type of 1.72 from tetraethoxysilane or its oligomers. By adjusting the stoichiometric amount of water added, the degree of polymerization DP_Q 型 The same material as in Example 9 was prepared, except that the .DELTA..times ... 29 Si NMR analysis revealed 33.7% Q-type tetrasiloxane ring species.

[0193] Example 9d: Preparation of a precursor material of a Q-type polycondensate having a target DP_Q type of 2.2 from tetraethoxysilane or its oligomer. By adjusting the stoichiometric amount of water added, the degree of polymerization DP_Q 型 The same material as in Example 9 was prepared, except that the precursor material had a pH of 2.2. 29 Si NMR analysis revealed 47.0% Q-type tetrasiloxane ring species.

[0194] Example 9e: Preparation of a Q-type polycondensate precursor material having a target DP_Q type of 2.56 from tetraethoxysilane or its oligomers. By adjusting the stoichiometric amount of water added, the degree of polymerization DP_Q 型 The same material as in Example 9 was prepared, except that the .DELTA..times ... 29 Si NMR analysis revealed 57.0% Q-type tetrasiloxane ring species.

[0195] Example 9f: Preparation of a Q-type polycondensate precursor material having a target DP_Q type of 2.0 from tetraethoxysilane or its oligomers by adding a recombinant catalyst. The same material as in Example 9b was prepared, except that in addition to the standard hydrolysis / condensation catalyst, a certain amount of Hf(IV) ethoxide was added as a recombinant catalyst toward the end of the hydrolysis process. 29 Si NMR analysis revealed 46.8% Q-type tetrasiloxane ring species.

[0196] Example 9g: Targeted DP_Q from Ethyl Silicate-40 and DMDMS 型 =2.2 and DP_D 型 Mixed Q-type / D-type polycondensate precursor material (n Q型 :n D型 =1:0.05) The same material as in Example 9d was prepared, except that in addition to oligomeric ethylsilicate-40 (Q-type source), DMDMS, a D-type source, was used in the preparation in an amount of 5% measured by the respective Si molar amounts. Furthermore, the stoichiometry of the added water was adjusted to obtain the targeted DP_D 型 = 1.5 value of the precursor material. 29 Si NMR analysis revealed 45.2% Q-type tetrasiloxane ring species.

[0197] Example 9h: Targeted DP_Q from Ethyl Silicate-40 and DMDCS 型 =2.2 and DP_D 型 Mixed Q-type / D-type polycondensate precursor material (n Q型 :n D型 =1:0.05) alternative preparation> The same material as in Example 9g was prepared, except that dimethyldichlorosilane (DMDCS) was used as the D-type source instead of DMDMS. At the end of the reaction, residual hydrochloric acid was removed by blowing nitrogen as a purge gas. 29 Si NMR analysis revealed 43.6% Q-type tetrasiloxane ring species.

[0198] Example 10: TPOS (oligomer) / (Cl-PTMS:HMDSO) polycondensate material (n Q型 :(n T型 +n M型 )=1:0.15:0.09) combination> 5.87 mol Si equivalents of Q-type precursor prepared according to Example 9b were placed in a 2 L round bottom flask equipped with a reflux column and a resistive heating mantle together with 146.1 g / 0.90 mol of dimeric M-type precursor hexamethyldisiloxane (HMDSO). To this mixture was added a solution consisting of 25 ml ethanol and 0.3 ml trifluoroacetic acid (TFA). The apparatus was then heated to a mantle temperature of 110° C. with stirring and reacted for 2 hours in the first reaction step a), at which point the reflux column was replaced with a distillation bridge and residual volatiles were distilled off first at ambient pressure and then using a vacuum reaching 180 mbar towards the end, at which point distillate collection stopped completely.

[0199] The vacuum pump was turned off and the reaction vessel was then brought to ambient pressure with nitrogen and 140.0 g / 0.70 mol of monomeric T-type precursor (3-chloropropyl)trimethoxysilane (Cl-PTMS) and Ti(IV)-methoxide as catalyst were added. The mixture was kept at 120° C. for an additional 6 hours with stirring for the second reaction step b), then removed from the heat source and cooled to room temperature. 975.4 g of crude reaction product was isolated. 29 Si NMR analysis showed that the product contained less than 5% T 0 -monomer, and less than 26% of Q-type tetrasiloxane ring species.

[0200] Example 11: TEOS (oligomer) / (GPTMS+VTMS) polycondensate material (n Q型 :n T型 1: (0.10+0.05)) 18.4 g / 137 mmol of the Q-type precursor prepared in Example 9f was placed in a 50 ml Teflon vessel together with the first ((3-glycidyloxypropyl)trimethoxysilane (GPTMS), 3.3 g / 14 mmol) and the second (vinyltrimethoxysilane (VTMS), 1.0 g / 7 mmol) T-type precursor and placed inside a compatible organic synthesis microwave reactor (flexiWAVE, Milestone Inc.). A pre-set synthesis sequence with a synthesis temperature up to 190° C. was performed and lasted for 6 min. After cooling, 22.6 g of crude reaction product was isolated. NMR analysis showed that the product contained less than 4% T, as measured by the total amount of T-type groups, respectively. 0 -monomer, and less than 21% of Q-type tetrasiloxane ring species.

[0201] Example 12: TEOS (oligomer) / MaPTMS polycondensate material (n Q型 :n T型 =1:0.10) combination> This material was prepared using the same procedure as described in Example 8, with the major differences being that the Q-type precursor material prepared according to Example 9c and 3-methacryloxypropyltrimethoxysilane (MaPTMS) were used as starting materials, along with a co-solvent (ethyl acetate), and the autoclave was heated by a microwave source and a shortened reaction time of 3 hours was used. 29 Si NMR analysis showed that the product contained less than 13% total T, as measured by the total amount of T-type groups. 0 -monomer, and less than 24% of Q-type tetrasiloxane ring species.

[0202] Example 13: Ethyl silicate-40 / (HS-PTMS:DMDMS) polycondensate material (n Q型 :(n T型 :n D型 )=1:(0.15:0.05)) combination> This material was prepared using the same procedure as described in Example 8, with the major difference being that the Q-type precursor material prepared according to Example 9g and 3-mercaptopropyltrimethoxysilane (HS-PTMS) were used as starting materials. 29 Si NMR analysis showed that the product contained less than 4% total T, as measured by the combined amount of T and D groups. 0 - Monomer and total D less than 4% 0 -monomer, and less than 24% of Q-type tetrasiloxane ring species.

[0203] Example 13b: Ethyl silicate-40 / (HS-PTMS:DMDCS) polycondensate material (n Q型 :(n T型 :n D型 )=1:(0.15:0.05)) combination> This material was prepared using the same procedure as described in Example 13, with the major difference being that the precursor material prepared according to Example 9h was used as the starting material. 29 Si NMR analysis showed that the product contained less than 6% total T, as measured by the combined amount of T and D groups, respectively. 0 - Monomer and total D less than 3% 0 -monomer, and less than 26% of Q-type tetrasiloxane ring species.

[0204] Example 14: TEOS (oligomer) / (VTES:HMDSO) polycondensate material (n Q型 :(n T型 :n M型 )=1:(0.25:0.26)) combination> This material was prepared using the same procedure as described in Example 10, with the major difference that the Q precursor material prepared according to Example 9d and 3-mercaptopropyltrimethoxysilane (HS-PTMS) were used as starting materials and in higher molar amounts during the second reaction step b) (target Q to T Si molar ratio of 1:0.25). During the first reaction step a), a 5-fold molar excess of HMDSO was used relative to the desired Q to M Si molar ratio, and the first reaction step was carried out at 105° C. for 4 hours. 29 Si NMR analysis showed that the product contained less than 19% total T, as measured by the total amount of T-type groups. 0 -monomer, and less than 17% Q-type tetrasiloxane ring species.

[0205] Example 15: TEOS (oligomer) / (VTES:MTMS) polycondensate material (n Q型 :(n T型 :n D型 )=1:(0.30:0.12)) combination> This material was prepared using the same procedure as described in Example 6, with the major difference being that the precursor material prepared according to Example 9e, and vinyltriethoxysilane (VTES) and methyltrimethoxysilane (MTMS) were used as the Q- and T-type starting materials, respectively. Oxo-titanium(IV) diacetylacetonate was used as the recombinant catalyst. 29 Si NMR analysis showed that the product contained less than 9% combined T groups as measured by the total amount of T groups. 0 -monomer, and less than 22% of Q-type tetrasiloxane ring species.

[0206] <Example 16: TEOS / (APTES+MTMS+PTES) polycondensate material (n Q型 :n T型 1: (0.20+0.05+0.05)) This material was prepared using the same procedure as described in Example 6, with the major difference being that the precursor material prepared according to Example 9d made from TEOS, and 3-aminopropyltriethoxysilane (APTES), methyltrimethoxysilane (MTMS), and propyltriethoxysilane (PTES) were used as the Q-type, and the first, second, and third T-type starting materials, respectively. A mixture of Zr(IV) ethoxide and Ti(IV) n-propoxide was used as the recombinant catalyst. 29 Si NMR analysis showed that the product contained less than 7% combined T groups as measured by the total amount of T groups. 0 -monomer, and less than 16% Q-type tetrasiloxane ring species.

[0207] <Example 16b: TEOS / (APTES+MTMS+PTES) polycondensate material (n Q型 :n T型 1: Alternative synthesis of (0.20+0.05+0.05)) This material was prepared using the same procedure as described in Example 16, with the major difference that a portion of at least one of the three T-type precursors was already included during the preparation of the precursor material according to Example 9d, similar to the co-condensation route of the non-hydrolyzed precursor, acetic anhydride, described in Example 6c. A mixture of O=Ti(IV)(SCN)2 and O=Zr(IV)(OAc)2 was used as the recombinant catalyst. 29 Si NMR analysis showed that the product contained less than 5% combined T groups, as measured by the total amount of T groups. 0 -monomer, and less than 20% of Q-type tetrasiloxane ring species.

[0208] <Example 16c: TEOS / (APTES+MTMS+PTES) polycondensate material (n Q型 :n T型 1: Alternative synthesis of (0.20+0.05+0.05)) This material was prepared using the same procedure as described in Example 16b, with the significant difference that a portion of at least one of the three T-type trialkoxysilane precursors included in the preparation of the precursor material by the modified process described derived from Example 9d was replaced by a trichlorosilane counterpart. 29 Si NMR analysis showed that the product contained less than 9% combined T groups as measured by the total amount of T groups. 0 -monomer, and less than 23% of Q-type tetrasiloxane ring species.

[0209] <Example 16d: TEOS / (APTES+MTMS+PTES) polycondensate material (n Q型 :n T型 1: Alternative synthesis of (0.20+0.05+0.05)) This material was prepared using the same procedure as described in Example 16, with the major difference being that APTES was first grafted onto the Q-type precursor material prepared according to Example 9d in a first recombination procedure. For this, equal amounts of Q-type precursor and first T-type precursor were heated to 125°C and reacted for 4 hours in the presence of (EtO)2Zr(IV)(OAcAc)2 as a catalyst. The reaction mixture was then cooled to a temperature of 90°C, at which point methyltrimethoxysilane (MTMS) and propyltriethoxysilane (PTES) were then added as the second and third T-type precursors. The mixture was then reacted at that temperature for an additional 26 hours. 29 Si NMR analysis showed that the product contained less than 14% combined T groups as measured by the total amount of T groups. 0 -monomer, and less than 22% of Q-type tetrasiloxane ring species.

[0210] <Example 17: Preparation of a Q-type polycondensate precursor material having a target DP_Q type of 2.4 from tetramethoxysilane or its oligomer> As in Example 9, tetraethoxysilane (TMOS) in monomeric or oligomeric form was reacted with DP_Q 型The hydrolysis was carried out according to state of the art using standard hydrolysis / condensation catalysts with the stoichiometric amount of water required to achieve the desired degree of polymerization of the precursor material, which is = 2.4. Upon completion of the hydrolysis, excess co-solvent and alcohol released during hydrolysis were removed by vacuum distillation. 29 Si NMR analysis revealed 53.0% Q-type tetrasiloxane ring species in the precursor material.

[0211] <Example 18: TEOS (oligomer) / (TESPT:VTES) polycondensation material (n Q型 :(n T型 :n M型 )=1:(0.17:0.06)) combination> 242.6 g of the raw precursor from Example 17 was placed in a 500 ml glass cylinder with a cap. Then, 185.8 g / 0.44 mol of the first T-type precursor bis(triethoxysilylpropyl) tetrasulfide (TESPT) and 23.1 g / 0.16 mol of the second T-type precursor vinyltriethoxysilane (VTES) were added along with bis-acetylacetonate-titanium(IV)-diisopropoxide recombinant catalyst. The mixture was heated to 75° C. and kept stirring for 6 days. Residual solvent was removed by pulling a vacuum of 100 mbar for 30 minutes. 29 Si NMR analysis showed that the product contained less than 44% T as measured by the total amount of T-type groups. 0 -monomer, and less than 29.2% of Q-type tetrasiloxane ring species.

[0212] Example 19: Preparation of mixed Q-type polycondensate precursor material with target DP_Q type = 2.28 from tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) Tetramethoxysilane (TMOS) at 511 g / 2.66 mol Si and tetramethoxysilane (TEOS) at 277 g / 1.33 mol Si, and zirconium(IV)-isobutoxide catalyst were placed in a 1 L round bottom flask equipped with a distillation bridge. In other words, the relative molar ratio of TMOS monomer to TEOS monomer used was 2:1. The flask was purged with nitrogen, sealed, placed under nitrogen pressure (balloon) and immersed in a hot oil bath, which was held at 130°C. The Q-type monomer / catalyst mixture was brought to temperature with stirring at 500 rpm. Once at temperature, a selected amount (465.3 g / 4.56 mol) of acetic anhydride was added in small portions. Reflux of the reaction by-product, ethyl acetate, occurred fairly quickly. After approximately 8 minutes, a continuous stream of methyl acetate and ethyl acetate distilled through the distillation bridge and was collected in a collection vessel. The reaction was continued for an additional total time of about 70 min, at which point the reaction was stopped as the methyl / ethyl acetate distillation ceased. After 1 h and 25 min total reaction time the collection vessel was removed and emptied to give a total mass of 725 g of collected condensate and 465 g of Q-type precursor. 29 Si NMR analysis revealed that the precursor had a DP_Q of 2.22. 型 and 51.0% Q-type tetrasiloxane ring species.

[0213] <Example 20: TEOS / (APTMS:DMDMS) polycondensate material (n Q型 :n T型 1:n D型 1:(0.20:0.10)) combination> 310 g of the crude precursor from Example 19 was combined and placed in a 1 L round bottom flask, followed by the addition of 0.27 mol (Si based) of the oligomeric form of the T-type precursor 3-aminopropyltrimethoxysilane (oligo-APTMS) and 16.0 g / 0.13 mol of the D-type precursor dimethyldimethoxysilane (DMDMS) together with no additional recombinant catalyst beyond the amount already present in the Q-type precursor from Example 19. The mixture was heated to a temperature of 110° C. and allowed to stir for 29 hours, at which point any residual solvent was removed by pulling a vacuum of 250 mbar for 5 minutes and nitrogen was bubbled through the reaction mixture for 15 minutes to remove additional VOCs. 29 Si NMR analysis showed that the product contained less than 7% total T, as measured by the combined amount of T and D groups, respectively. 0 - Monomer and total D less than 22% 0 -monomer, and less than 25% of Q-type tetrasiloxane ring species.

[0214] Example 21: Preparation of a Q-type polycondensate precursor material having a target DP_Q type of 1.52 from a mixture of tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) A mixture of tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) in a molar ratio of 20% to 80% was subjected to DP_Q in the presence of a co-solvent. 型 The precursor material was hydrolyzed according to state of the art using a standard hydrolysis / condensation catalyst with the stoichiometric amount of water required to achieve the desired degree of polymerization of the precursor material, where K=1.52. Upon completion of the hydrolysis, excess co-solvent and alcohol released during hydrolysis were removed by vacuum distillation. 29 Si NMR analysis revealed 35.7% Q-type tetrasiloxane ring species in the precursor material.

[0215] <Example 22: TMOS+TEOS / (tFPTMS) polycondensate material (n Q型 :(n T型 )=1:0.07) synthesis> An amount of mixed methoxy / ethoxy terminated Q-type precursor containing 1.92 mol Si equivalents, prepared according to Example 21, was loaded into a 500 ml round bottom, which was then placed into a resistive heating mantle and set at a temperature of 95° C. Then, 29.3 g / 0.13 mol of monomeric T-type precursor (3,3,3-trifluoropropyl)trimethoxysilane (tFPTMS) and Ti(IV) tetraethoxide (TEOT) catalyst were added. The mixture was held at 95° C. with stirring for an additional 19 hours, then removed from the heat source and cooled to room temperature. 29 Si NMR analysis showed that the products contained less than 18% T 0 -monomer, and less than 24% of Q-type tetrasiloxane ring species.

[0216] <Example 23: Preparation of Q-type polycondensate precursor material with target DP_Q type = 2.0 from tetraethoxysilane (TEOS) by silanol method> Sodium triethoxysilanolate was prepared by first mixing 1 g (3.5 mol) powdered sodium hydroxide with a solution of 728 g (3.5 mol) tetraethoxysilane in 1.3 l toluene under stirring at 5° C. After 2 hours at that temperature, the solvent phase consisting of toluene and ethanol formed during the reaction was distilled under vacuum. The oily residue was dried overnight in a vacuum drying chamber at 50 mbar and 40° C. to obtain 628 g of crude product.

[0217] A solution of sodium triethoxysilanolate in toluene from the above step was prepared from 322 g of the crude product by filling it with toluene to a total volume of 1800 ml in a 3 l round bottom flask. This solution was added dropwise to a solution of a stoichiometric amount of acetic acid in 1 l of toluene at 0° C., again with vigorous stirring. The amount of acetic acid consumed stoichiometrically was calculated based on the theoretical formula for sodium triethoxysilanolate and assuming 100% purity of the crude product. After filtering off the precipitated sodium acetate and washing with toluene, the residual solvent (mainly toluene) was again removed by distillation from the combined reaction mixture and the sodium acetate washings at 45° C. and <15 mbar absolute pressure. The product yield was 133.9 g of a yellowish liquid, which was identified as triethoxysilanol. The final polyethoxysiloxane Q-type precursor was then synthesized by adding the resulting triethoxysilanol (133.9 g) to a water-free solution of 22.5 g ammonia (dehydrated over sodium hydroxide pellets) in 100 ml absolute ethanol over a period of 90 minutes at -30°C. After warming the mixture to room temperature, the reaction mixture was left to stand overnight, after which the residual ammonia and ethanol were again removed by vacuum distillation, followed by bubbling nitrogen purge gas for 10 minutes to yield 102.7 g of yellow polyethoxysiloxane Q-type precursor material. 29 Si NMR analysis revealed 45% Q-type tetrasiloxane ring species.

[0218] Example 24: TEOS / (VTES+MTMS:TMMS) polycondensate material (n Q型 :(n T型 :n M型) =1:(0.1+0.05:0.1)) combination> A quantity containing 1.92 mol Si equivalents of mixed methoxy / ethoxy terminated Q-type precursor prepared according to Example 21 was loaded into a 500 ml round bottom, which was then placed in a resistive heating mantle and set at a temperature of 90° C. Then, 36.5 g / 0.19 mol of the first monomeric T-type precursor, vinyltriethoxysilane (VTES), and 13.1 g / 0.1 mol of the second monomeric T-type precursor, methyltrimethoxysilane (MTMS), and Ti(IV)-bromide recombinant catalyst were added. The mixture was heated to 110° C. with stirring for 8 hours and held at 110° C., after which the temperature was reduced again to 90° C. and 20.0 g / 0.19 mol of the M-type precursor, trimethylmethoxysilane (TMMS), was charged to the reaction mixture over 30 minutes. The mixture was then continued to stir at 90° C. for an additional 12 hours and removed from the heat source. 29 Si NMR analysis showed that the products contained less than 14% T 0 -monomer, and less than 24% of Q-type tetrasiloxane ring species.

[0219] Example 25: Preparation of Q-type polycondensate precursor material with target DP_Q type = 2.1 from a mixture of tetraethoxysilane (TEOS) and silicon tetrachloride (SiCl4) via the "chloride route" A mixture containing tetraethoxysilane (TEOS) and silicon tetrachloride in a 2:1 molar ratio was heated to a temperature of 145°C inside a closed autoclave vessel, at which point 0.75% zirconium tetrachloride (ZrCl4) was added as a condensation catalyst. The mixture was kept stirring under an inert gas atmosphere. After 21 hours, the reaction was stopped and the mixture was allowed to reach room temperature, after which the ethyl chloride by-product and residual volatiles were removed by distillation. The Q-type polycondensate material was a slightly yellowish liquid, which was collected after workup and analyzed. 29 Si NMR analysis revealed 51.5% Q-type tetrasiloxane ring species in the precursor material.

[0220] Example 25b: Preparation of the target DPhDCS from a mixture of tetraethoxysilane (TEOS), silicon tetrachloride (SiCl4) and diphenyldichlorosilane (DPhDCS) via the "chloride route". _ Q 型 =2.0 and DP D型 A Q-type / D-type polycondensate precursor material having n Q型 :n _ D 型 =1:0.05) alternative preparation> Using the same procedure as in Example 25, mixed Q / D precursor material was prepared. Instead, 1.95:0.94:0.05 molar ratio of tetramethoxysilane (TMOS), silicon tetrachloride and diphenyldichlorosilane (DPhDCS) were used as starting materials. The reaction was carried out at 135°C for 25 hours using 0.9% zirconium (IV) tetraacetate as condensation catalyst. The mixed Q / D polycondensate material was a slightly yellowish liquid, which was collected and analyzed after cooling, depressurizing the autoclave, and working up. 29 Si NMR analysis revealed 48.6% Q-type tetrasiloxane ring species in the precursor material.

[0221] <Example 26: TEOS / (PhTES+PTMS:DPhDES) polycondensate material (n Q型 :(n T型 :n D型 )=1:(0.10+0.05:0.05))> A quantity containing 4.5 mol Si equivalents of the Q-type precursor prepared according to Example 25 was placed in a stirred glass reactor (Buechi versoclave, 1 liter) set at a temperature of 105° C. Then, 108.2 g / 0.45 mol and 37.0 g / 0.23 mol of the first and second T-type monomer precursors, phenyltriethoxysilane (PhTES) and propyltrimethoxysilane (PTMS), were charged into the reactor along with 56.2 g / 0.23 mol of the D-type precursor, diphenyldimethoxysilane (DPhDMS) and titanium(IV)-methoxide as catalyst. The mixture was held at temperature with stirring for 13 hours, then removed from the heat source and cooled to room temperature. 29Si NMR analysis showed that the product had less than 26% T and D groups, as measured by the combined amount of T and D groups, respectively. 0 -monomers and D less than 16% 0 -monomer, and less than 26.9% of Q-type tetrasiloxane ring species.

[0222] <Example 26b: TEOS / (PhTES+PTMS:DPhDCS) polycondensate material (n Q型 :(n T型 :n D型 )=1:(0.10+0.05:0.05)) alternative synthesis> The material was prepared using a similar procedure as in Example 26, except that a separately prepared mixed Q / D type precursor material was used. As a result, no additional D type monomers were required to be added during the preparation, but only PhTES and PTMS were added to the precursor material. All other steps and reactants remained unchanged. 29 Si NMR analysis showed that the product had less than 23% T and D groups, as measured by the combined amount of T and D groups, respectively. 0 -monomers and D less than 11% 0 -monomer, and less than 27.2% of Q-type tetrasiloxane ring species.

[0223] Example 27: Efficiency testing of potential recombinant catalysts A procedure was devised to test various model catalysts for their efficiency in catalyzing the grafting of a T-type monomer model silane, methyltriethoxysilane (MTES). Briefly, commercially available Dynasylan Silbond 50 was used as the Q-type precursor. The molar ratio of 1:0.15 was used. nQ型 :n T型Using a 30 ml aliquot of the premixed solution containing the Q-type and T-type silane precursors, was filled into a 50 ml glass bottle with a lid. 1% by weight of the model recombinant catalyst was added to each bottle, and a blank sample was also included in the study. All the glass bottles were simultaneously placed in a heating cabinet maintained at 100° C., and the samples were left there for a 24-hour incubation period. They were then removed from the heating cabinet and cooled to room temperature. 29 It was analyzed by Si NMR spectroscopy.

[0224] [Table 5]

[0225] Following NMR spectroscopy, the performance and suitability of the catalysts were evaluated using T 0 Its ability to graft monomers (DP T-T型 and T 0 % indicator), as well as the percentage of remaining tetrasiloxane ring species after the grafting step ((Q 2r &Q 3s,d ) / Q tot % and (Q 3s,d ) / Q 3 It can be evaluated in terms of a percentage (% index).

[0226] Example 28: Hydrolysis of polymeric liquid materials 40 g of ethanol and 29.3 g of the crude reaction product from Example 3j were mixed and heated to 40° C. in an Erlenmeyer flask with stirring. Once the temperature was equilibrated, 4 ml of 0.1 M methanesulfonic acid solution was added, followed by 3 ml of distilled water. After a gentle mixing step (magnetic stirrer), the solution was transferred into a glass bottle with a sealed cap and kept in an oven at 40° C. for 16 hours. The final hydrolysis product was then filtered and stored in a refrigerator.

[0227] Example 29: Preparation of water-in-oil emulsion A 228 g sample of the material sample of Example 3k was mixed with 600 ml of distilled water and 50 g of surfactant (Tween 20) was added. The two-phase system was then vigorously stirred for 1 hour at 35° C. using a mechanical impeller stirrer. The resulting emulsion was a low viscosity, stable emulsion with a shelf life of several weeks without any noticeable settling effect.

[0228] Example 30: Preparation of oil-in-water emulsion A 90 g sample of the material sample of Example 4k was mixed with 34.5 ml distilled water and 2.2 g sodium dodecyl sulfate (SDS). The two-phase system was then homogenized using a high rpm mechanical homogenizer. The resulting emulsion was a creamy paste that had a shelf life of several weeks when kept in a closed container.

Claims

1. The following unit formula: (i) [Formula 1] Non-organofunctional Q-type siloxane groups selected from the group consisting of: (iv) [Case 2] A monoorganofunctional T-type siloxane group selected from the group consisting of: (ii) [C3] A triorganofunctional M selected from the group consisting of １ Siloxane group: (iii) [C4] A diorganofunctional D-type siloxane group selected from the group consisting of: a polymeric liquid polysiloxane material consisting of or comprising only (i) units and (iv) units, consisting of or comprising only (i), (iv) and (ii) units, consisting of or comprising only (i), (iv) and (iii) units, or consisting of or comprising only (i), (iv), (ii) and (iii) units, In the above formula, [C5] represents a covalent siloxane bond to a silicon atom of another Q, M, D and / or T type moiety as defined in (i), (ii), (iii) and / or (iv); R １ is methyl, ethyl, propyl, -P(=O)(OR １’ )(OH), -P(OR １’ ) ２ , -P(=O)(OH) ２ selected from the group consisting of: R １’ is selected from methyl, ethyl, propyl, and butyl; R ２ , R ３ , and R ４are each independently selected from the group consisting of methyl, ethyl, phenyl, cyclohexyl, vinyl, and cyclopentadienyl; R ５ is R ５Ｕ and R ５Ｓ is selected from the group consisting of R ５Ｕ is methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, linear, branched or cyclic C ５～１６ Alkyl residues, linear or branched hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H,2H,2H-perfluoro)octyl, (1H,1H,2H,2H-perfluoro)dodecyl, (1H,1H,2H,2H-perfluoro)hexadecyl, vinyl, phenyl, cyclohexyl, cyclopentadienyl, cyclopentyl, [C6] and -LZ; Where: R ６ is methyl, ethyl, n-butyl, linear or branched C ５～１４ alkyl residues; n is an integer selected from the group consisting of 1, 2, 3, 4, and 5; L is -CH ２ --, --CH ２ CH ２ --, --CH ２ CH ２ CH ２ -, -C ６ H ４ -, -C ６ H ４ -CH ２ - and -CH ２ -CH ２ -C ６ H ４ -CH ２ - an aliphatic linker selected from the group consisting of: and Z is Cl, Br, I, -OH, -SH, 【Chemistry 7】 is a moiety selected from the group consisting of where R ７ is independently selected from the group consisting of methyl, ethyl, and n-butyl; R ５Ｓ teeth, 【Chemistry 8】 and -L'-Y; Where: m is an integer selected from the group consisting of 1, 2, 3, and 4; R ８ is -Cl, -Br, -I, -F, -CN, -SCN, -N ３ , -NO ２ , -OH, -SO ２ OR １’ 、 and -O-C(=O)R １２ selected from the group consisting of: R ９ is -Cl, -Br, -I, -F, -CN, -COOH, -COOR １’ phenyl, o-, m- and p-vinylphenyl; R ９’ is -COOH and -COOR １’ selected from the group consisting of: L' is -CH ２ --, --CH ２ CH ２ - and -CH ２ CH ２ CH ２ - an aliphatic linker selected from the group consisting of: and Y is, 【Chemistry 9】 【Chemistry 10】 is a group selected from the group consisting of Where: X is absent, -(NH)- or -O-; R １０ teeth, 【Chemistry 11】 【Chemistry 12】 selected from the group consisting of: R １１ is R ８ , -X-R １’ , and R １２ｃ selected from the group consisting of: R １２ is R １２ａ , R １２ｂ , and R １２ｃ is selected from the group consisting of where R １２ａ is a linear or branched, substituted or unsubstituted C １～１８ Alkyl, C ２～１８ Alkenyl and C ２～１８ alkynyl; R １２ｂ teeth, linear or branched, substituted or unsubstituted alkyl ethers, alkenyl ethers, alkynyl ethers with a molecular weight of up to 5000 g / mol; - unsubstituted polydimethylsiloxanes and polydivinylsiloxanes; and - selected from the group consisting of polysaccharides and oligosaccharides with a molecular weight of up to 5000 g / mol; and R １２ｃ teeth, - amino acids, oligopeptides and polypeptides with a molecular weight of up to 5000 g / mol; and - C １２～２４ selected from the group consisting of fatty acids; However, R ５Ｓ but, 【Chemistry 13】 Provided that it is not Where: Degree of polymerization DP of Q-type alkoxy end groups Ｑ型 is in the range of 1.3 to 2.7; Degree of polymerization of D-type alkoxy-terminated siloxane groups DP Ｄ型 is in the range of 1.0 to 1.9; Degree of polymerization of T-type alkoxy-terminated siloxane groups DP Ｔ型 is in the range of 1.1 to 2.7; the total content of triorganofunctional M-type siloxane groups (iii) in the polysiloxane material does not exceed 10 mol%; the total content of diorganofunctional D-type siloxane groups (iii) in the polysiloxane material does not exceed 50 mol%; the material has a viscosity in the range of 10 to 100,000 cP; the material contains less than 5 mol % silanol groups (Si—OH); the atomic ratio of T species to Q species in said material is in the range of 0.01:1 to 1:1; All R in the material ５ At least 1 mol % of the moieties are R ５Ｓ is a group; The following points: - the polysiloxane material contains less than 45 mol % of four-membered Q-type siloxane species combined; ２ｒ Type and Q ３ｓ，ｄ and / or - Polysiloxane material is all Q ３ Less than 70 mol % of the four-membered Q ３ｓ，３ｄ and / or - the polysiloxane material contains less than 4.5 mol % of double four-membered Q siloxane species relative to the total Q siloxane species; ３ｄ and / or - Polysiloxane material is all Q ３ Less than 25 mol % of the double four-membered Q ３ｄ containing siloxane ring species of the type A polymeric liquid polysiloxane material comprising:

2. R ８ is -Cl, -Br, -I, -CN, -SCN, -N ３ , -NO ２ , -SO ２ OR １’ and -O-C(=O)R １’ selected from the group consisting of: Y, [C14] selected from the group consisting of: R １０ but, [C15] [C16] selected from the group consisting of: R １１ But, R ８ , and R １２ｃ Selected from: R １２ But, R １２ａ , R １２ｂ , R １２ｃ selected from the group consisting of: Where: R １２ａ is a linear or branched, substituted or unsubstituted C １～１８ Alkyl or C ２～１８ alkenyl; R １２ｂ but, - linear or branched, unsubstituted or terminally amino- or thiol-substituted alkyl or alkenyl ethers with a molecular weight of up to 3000 g / mol; - polysaccharides or oligosaccharides with a molecular weight of up to 3000 g / mol, and - selected from the group consisting of unsubstituted polydimethylsiloxanes or polydivinylsiloxanes; and R １２ｃ but, - amino acids and oligopeptides or polypeptides with a molecular weight of up to 3000 g / mol; and - C １２～２４ 2. The polymeric liquid polysiloxane material of claim 1, selected from the group consisting of fatty acids.

3. R ８ is -Cl, -Br, -I, -CN, -SCN, -N ３ , -NO ２ , -SO ２ OR １’ and -O-C(=O)R １’ selected from the group consisting of: Y, [C17] selected from the group consisting of: R １０ but, [C18] selected from the group consisting of: R １１ But, R ８ , and R １２ｃ and R １２ But, R １２ａ , R １２ｂ , R １２ｃ is selected from the group consisting of Where: R １２ａ is a linear or branched, substituted or unsubstituted C １～１２ Alkyl and C ２～１２ alkenyl; R １２ｂ but, - linear, unsubstituted or terminally amino-substituted alkyl ethers with a molecular weight of up to 2000 g / mol; and - polysaccharides or oligosaccharides with a molecular weight of up to 2000 g / mol and R １２ｃ but, - oligopeptides or polypeptides made up of amino acids with a molecular weight of up to 2000 g / mol and naturally occurring amino acids; - castor oil, soybean oil and sunflower oil triglycerides; and - Naturally occurring C １２～２４ fatty acid, 3. The polymeric liquid polysiloxane material according to claim 1 or 2, selected from the group consisting of:

4. The material is (v) at least two non-identical R ５ substituted monoorganofunctional T-type alkoxy-terminated siloxane populations, each population constituting at least 3 mol % of all monoorganofunctional T-type groups in the material; and / or (vi) a chiral monoorganofunctional T group in an amount of at least 3 mol % relative to all monoorganofunctional T groups in the material; １ type group 4. The polymeric liquid polysiloxane material according to claim 1 , comprising:

5. (vii) Degree of polymerization DP of Q-type alkoxy terminal group Ｑ型 is in the range of 1.5 to 2.5; (viii) Degree of polymerization of D-type alkoxy-terminated siloxane groups DP Ｄ型 is in the range of 1.25 to 1.75; and / or (ix) Degree of polymerization DP of T-type alkoxy-terminated siloxane groups Ｔ型 5. The polymeric liquid polysiloxane material according to claim 1, wherein the β-

6. 6. The polymeric liquid polysiloxane material according to any one of claims 1 to 5, wherein the total content of diorganofunctional D-type siloxane and / or the total content of triorganofunctional M-type siloxane groups is 0 (zero).

7. 7. The polymeric liquid polysiloxane material according to any one of claims 1 to 6, wherein the relative atomic ratio of T and Q species is in the range of 0.02:1 to 0.75:

1.

8. R １２ｂ but, - substituted or unsubstituted poly(ethylene oxide), poly(propylene oxide) and polytetrahydrofuran; and - selected from the group consisting of poly-D-glucose, oligo-D-glucose, chitosan, deacetylated oligochitin, oligo-beta-D-galactopyranuronic acid, polyalginic acid, oligoalginic acid, polyamylose, oligoamylose, polygalactose and oligogalactose with a maximum molecular weight of 5000 g / mol; and R １２ｃ but, - oligopeptides and polypeptides made up of naturally occurring amino acids with a molecular weight of up to 5000 g / mol; and - Naturally occurring C １２～２４ 8. The polymeric liquid polysiloxane material according to any one of claims 1 to 7, selected from the group consisting of unsaturated fatty acids, epoxidized fatty acids, epoxidized castor oil, soybean oil, sunflower oil, ring-opened epoxidized fatty acid based polyols, natural oil based polyols (NOP), castor oil, soybean oil or sunflower oil triglycerides.

9. 9. A hydrolysis product obtainable by reacting at least one polymeric liquid polysiloxane material according to any one of claims 1 to 8 with an amount of water or with an amount of a water-solvent mixture in the presence or absence of at least one surfactant.

10. 9. An emulsion obtainable by emulsifying the polymeric liquid polysiloxane material according to any one of claims 1 to 8 with an amount of water, in the presence or absence of at least one surfactant.

11. 9. A method for producing the polymeric liquid polysiloxane material according to any one of claims 1 to 8, comprising the following steps: - All R in the material ５ At least 1 mol % of the groups are R ５Ｕ providing a polymeric liquid polysiloxane material according to any one of claims 1 to 7, - R of said polymeric liquid polysiloxane material ５Ｕ The residues are functionalized to form all R ５ At least 1 mol % of R ５Ｓ Obtaining a residue; - recovering the polymeric liquid polysiloxane material; A method comprising:

12. 9. A method for producing the polymeric liquid polysiloxane material according to any one of claims 1 to 8, comprising the following steps: (a) providing a Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy) polysiloxane precursor; The precursor is (a1) diorganofunctional D-type siloxane groups; and / or (a2) R ５ But, R ５Ｕ and R ５Ｓ with or without monoorganofunctional T-type siloxane groups selected from Contains less than 12 mol % of combined (a1) and (a2), based on the total amount of all Q-type species; with or without further comprising a recombinant catalyst; Where: The precursor contains at least 28 mol % of the four-membered Q siloxane species combined. ２ｒType and Q ３ｓ，ｄ and / or The precursor is all Q ３ At least 60% of the four-membered Q ３ｓ，３ｄ type siloxane ring species; and Degree of polymerization DP of Q-type polysiloxane Ｑ型 is in the range of 1.5 to 2.7; (b) Below: (b1) Triorganofunctional M-type silanes Si(OR １ ) (R ２ ) (R ３ ) (R ４ ), and / or (b2) Diorganofunctional D-type silanes Si(OR １ ) ２ (R ２ ) (R ３ ), and / or (b3) Monoorganofunctional T-type silanes Si(OR １ ) ３ (R ５ ) (wherein, R ５ is R ５Ｕ and R ５Ｓ (selected from in monomeric or oligomeric form to the polysiloxane of (a); (c) adding or not adding a recombinant catalyst to the mixture of step (b); (d) heating the mixture of (c) in the absence of water; (e) repeating or not repeating steps (b) through (d) at least once; (f) R of the polymeric liquid polysiloxane material ５Ｕ The residues are functionalized to form all R ５ At least 1 mol % of R ５Ｓ obtaining or not functionalizing the residue; (g) recovering the polymeric liquid polysiloxane material. Including, provided that at least one of steps (a2) or (b3) is carried out, and The method, provided that a recombinant catalyst is present in at least one of steps (a) or (c).

13. In step (a), R of the T-type siloxane group ５ But, R ５Ｕ and In step (b), R of the T-type silane ５ But, R ５Ｕ and - the method comprises the step of: ５Ｕ The residues are functionalized to form all R ５ At least 1 mol % of R ５Ｓ The method of claim 12, further comprising a step (f) of obtaining a residue.

14. In step (a), R of the T-type siloxane group ５ But, R ５Ｕ and In step (b), R of at least one T-type silane ５ But, R ５Ｓ in which case, in optional step (e), R of the T-type silane ５ But, R ５Ｕ and R ５Ｓ and The method according to claim 12, wherein the method includes or does not include step (f).

15. After step (d) or (e), the method further comprises reacting a triorganofunctional M-type silane Si(OR １ ) (R ２ ) (R ３ ) (R ４ ), or M-type siloxane (R ２ ) (R ３ ) (R ４ )Si-O-Si(R ２ ) (R ３ ) (R ４15. The method according to any one of claims 12 to 14, further comprising the step of adding diorganofunctional D-type silane in monomeric or oligomeric form as described in step (b2) with or without addition in the presence of water and a suitable co-solvent and an acid catalyst, and then heating the mixture to reflux with or without reflux.

16. 16. The process according to any one of claims 12 to 15, wherein the reaction temperature for steps (c) to (e) is in the range of 30 to 170°C and the pressure during steps (c) to (e) is in the range of 0.1 bar to 2 bar.

17. The recombinant catalyst - Ti(IV)(OR １３ ) ４ and Zr(IV)(OR １３ ) ４ ; - Ti(IV)X ４ and Zr(IV)X ４ ; - O=Ti(IV)X ２ and O=Zr(IV)X ２ ; - Ti(IV)X ２ (OR １３ ) ２ and Zr(IV)X ２ (OR １３ ) ２ ; - Ti(IV)X ２ (OAcAc) ２ and Zr(IV)X ２ (OAcAc) ２ ; - Ti(IV)(OSi(CH ３ ) ３ ) ４ and Zr(IV)(OSi(CH ３ ) ３ ) ４ , - (R １３ O) ２ Ti(IV)(OAcAc) ２ And (R １３ O) ２ Zr(IV)(OAcAc) ２; - O=Ti(IV)(OAcAc) ２ and O=Zr(IV)(OAcAc) ２ ; -Ti(IV)(OAc) ４ and Zr(IV)(OAc) ４ ; -Ti(IV)(OAc) ２ (OR １３ ) ２ and Zr(IV)(OAc) ２ (OR １３ ) ２ and - O=Ti(IV)(OAc) ２ and O=Zr(IV)(OAc) ２ is selected from the group consisting of Here, R １３ But -CH ３ , -CH ２ CH ３ , -CH(CH ３ ) ２ , -CH ２ CH ２ CH ３ , -C(CH ３ ) ３ , -CH ２ CH ２ CH ２ CH ３ , and C.H. ２ CH ２ CH (CH ３ ) ２ and X is a halide, pseudohalide, nitrate, chlorate, or perchlorate anion; and 17. The process of any one of claims 12 to 16, wherein the amount of catalyst in each of steps (a) or (c) is between 0.01 and 5 mol%, based on the total molar content of silicon present in said steps.

18. Use of the polymeric liquid polysiloxane material according to any one of claims 1 to 8, wherein the polymeric liquid polysiloxane material is used in combination with vinyl, methacrylate, butacrylate, acrylate, meth ... [C19] R as the radically polymerizable organofunctional residue selected from the group consisting of ５ and the content of the polymeric liquid polysiloxane material is in the range of 0.2% to 25% by weight of the formulation.

19. Use of the polymeric liquid polysiloxane material according to any one of claims 1 to 8, the hydrolysis product according to claim 9 or the emulsion according to claim 10 in a hydrophobic formulation, wherein the polymeric liquid polysiloxane material is ５ 5. Use comprising at least one population of T-type alkoxy terminated siloxane groups having an organofunctional group selected from methyl, ethyl, vinyl, methacrylate, n-propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H,2H,2H-perfluoro)octyl, (1H,1H,2H,2H-perfluoro)dodecyl, and (1H,1H,2H,2H-perfluoro)hexadecyl, wherein the loading of the polymeric liquid polysiloxane material, hydrolysis product, or emulsion in the formulation is from 0.5% to 25% by weight.

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