Functionalized QT-siloxane polymer materials with low siloxane ring content and specific degree of polymerization and their preparation method

Abstract

This invention relates to functionalized polymeric liquid polysiloxane materials comprising a non-organic functionalized Q-type siloxane moiety and a mono-organic functionalized T-type siloxane moiety, wherein the material contains a limited amount of quaternary Q-type siloxanes relative to the total Q-type siloxane species. 2 - and / or Q 3 The invention relates to a type-1 siloxane cyclic species, possessing a functionalized degree of polymerization and a T-to-Q-ratio. It also relates to a method for producing polymeric liquid polysiloxane materials and related uses of such materials.

Description

Technical Field

[0001] This invention relates to a functionalized polymeric liquid polysiloxane material comprising an organically functionalized Q-type siloxane moiety and a mono-organically functionalized T-type siloxane moiety, wherein the material contains a limited amount of quaternary Q-type siloxanes relative to the total Q-type siloxane species. 2 -type and / or Q 3 The invention relates to a type-1 siloxane cyclic species, possessing a functionalized degree of polymerization and a T-to-Q-ratio. It also relates to a method for producing polymeric liquid polysiloxane materials and related uses of such materials. Background Technology

[0002] In nanotechnology, organic / inorganic hybrid materials can be obtained through a variety of preparation techniques. For example, sol-gel based techniques operate in liquid solutions, starting from colloidal suspensions of molecular or oligomer precursors, leading to the spontaneous formation of nanoparticle components. Sols are prepared either in situ from the hydroxylation and condensation reactions of oligomeric polyhydroxyl hydrocarbons or by the hydrolysis of alkoxysilanes in a water-alcohol mixture. When a low degree of condensation is required, only a small amount of water reactant is used, which yields branched siloxane compounds with low molecular weights. An example of such a preparation technique employing acid-catalyzed hydrolysis in a pure system (solvent-free) is described in EP 1510520 A1. Typically, such a small amount of water is used to hydrolyze monomeric alkoxysilanes to produce oligomers. Many single-component compounds are commercially available. For example, for Q-tetraethoxysilane (TEOS), there are commercial oligomer mixtures of ethyl silicate with a silicate content of 40% or even up to 50%, commonly known as ethyl silicate 40, ethyl silicate 50, or by brand names such as Dynasylan 40 or DynasylanSilbond 50 (Evonik Industries).

[0003] Hyperbranched polyethoxysiloxanes (PEOS) are small molecular weight units, typically ranging from 500 to 50,000 Daltons, with sizes ranging from a few angstroms to single-digit nanometers. The term "hyperbranched" also implies that these compounds possess a large fraction of linear species, although they also contain siloxane rings to varying degrees. Preferred synthetic routes are under anhydrous or "non-hydrolyzed" reaction conditions. This is why, in general, the preparation of hyperbranched siloxane polymers is more versatile than the aforementioned hydrolytic routes and offers better control over the final reaction products, as the condensation reaction can be controlled by the stoichiometric addition of reactants. Furthermore, the synthesis can be carried out "purely," meaning that no additional co-solvents such as alcohols are required. Due to their highly dendritic structure, with a high degree of polymerization at the center and a lower degree of linear chain arms around its periphery, PEOSs exhibit lower melt viscosity and greater solubility in themselves and in other organic solvents than their linear-chain siloxane analogues.

[0004] Hyperbranched PEOS can be an interesting class of molecular precursors, applicable to various hybrid molecular structural units, and can be easily obtained through "non-hydrolysis" methods, for example:

[0005] 1) Condensation of metal hydroxides obtained by reacting metal alkoxides with alkali metal hydroxides (silanol route);

[0006] 2) Condensation of metal chlorides and metal alkoxides (chloride route);

[0007] 3) Elimination of a single metal alkoxide with itself via ether condensation;

[0008] 4) The mixed acetoxy-alkoxy-metal salts condense with themselves by eliminating the corresponding acetate (acetoxy route); or

[0009] 5) Elimination via acetate via condensation of metal alkoxides reacting with acetic anhydride in the presence of a suitable catalyst (anhydride route).

[0010] Method 2) is described in EP0728793A1, in which the preparation of hyperbranched polysiloxanes is carried out by heterocondensation of chlorosilanes and alkoxysilanes eliminated by haloalkane. The reaction is catalyzed by organometallic compounds containing titanium, vanadium, and zirconium.

[0011] Method 3) has not been well studied, but it is assumed that various transition metal oxides can be condensed following the pioneering work of Bradley et al. on the alkoxy rearrangement mechanism (J. Chem. Soc., 1958, 99–101).

[0012] Method 4) typically uses rather expensive acetoxysilanes. WO 00 / 40640A1 describes the preparation of mildly branched organosilicon compounds from dimethylsiloxane prepolymers crosslinked with trifunctional silanes via acetoxy derivatization. WO 00 / 40640A1 describes the usefulness of the classic acetoxy route when only a few condensation bonds need to be formed, i.e., when linking monomers with oligomeric / polymeric structural units to produce larger macromolecules. This can be accomplished, for example, by refluxing the silanol-terminated prepolymer with the alkoxy-terminated crosslinker at elevated temperatures in the presence of acetic acid, or directly with an acetoxy-terminated crosslinker (e.g., triacetoxysilane).

[0013] Method 5) was published by Moeller et al. (e.g., Macromolecules 2006, 39, 1701-1708). Compared to methods 1) through 4), it is a more advanced technique for the preparation of polyalkyl metal acids (PAMs) in terms of scalability, process safety, and ease of implementation. WO 2004 / 058859 A1 describes the preparation of single-component PAMs using an anhydride route.

[0014] WO 2019 / 234062 A1 discloses a method for fabricating a core-shell PEOS core using an organofunctionalized silane shell material. WO 2019 / 234062A1 describes the preparation of a hyperbranched tetraethyl orthosilicate “core” via a non-hydrolyzed acetic anhydride condensation chemistry, followed by the grafting of the shell, preferably from a selected organofunctionalized T-type trialkoxysilane, in a second time-separation step to create a hybrid organofunctionalized core-shell molecular structural unit. Both steps are preferably carried out in the presence of a tetraalkoxytitanate rearrangement catalyst.

[0015] PCT / EP2020 / 075890 describes hyperbranched polyalkoxysiloxane materials containing Q- and M-, D- and / or T-type functional groups in the same macromolecule. Summary of the Invention

[0016] The object of this invention is to provide improved and functionalized organofunctionalized hyperbranched polyalkoxysiloxane materials containing Q- and T- and optionally M- and D-type functional groups in the same macromolecule, their preparation methods, and various applications.

[0017] In a first aspect, the present invention relates to a polymeric liquid polysiloxane material comprising or consisting of the following:

[0018] (i) Non-organic functionalized Q-type siloxane moieties, selected from the group consisting of the following:

[0019]

[0020] (ii) Any triorganofunctionalized M-type siloxane moiety, selected from the group consisting of the following:

[0021]

[0022] (iii) An optional diorganofunctionalized D-siloxane moiety, selected from the group consisting of the following:

[0023] and (iv) a single organic functionalized T-type siloxane moiety, selected from the group consisting of:

[0024]

[0025] in

[0026] This refers to a covalent siloxane bond that connects silicon atoms to another Q-, M-, D-, and / or T-type portion as defined in (i), (ii), (iii), and / or (iv);

[0027] R 1 Choose from methyl, ethyl, propyl, -P (=O) (OR) 1’ (OH), -P(OR) 1’ )2. The group consisting of -P(=O)(OH)2, can be either methyl or ethyl;

[0028] R 1’ Selected from methyl, ethyl, propyl, and butyl, and optionally phenyl or in the following parts Replace R 1’ Substituted phenyl;

[0029] R 2 Selected from methyl, vinyl, and phenyl;

[0030] R 3 Selected from methyl, vinyl, and phenyl, and optionally -LZ 1 ;

[0031] R 5 Choose freely R 5N R 5U and R 5S The group formed

[0032] in

[0033] R 5N Choose from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, straight-chain, branched, or cyclic C. 5-16The group consisting of alkyl residues, optionally straight-chain or branched: hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H,2H,2H-perfluoro)octyl, cyclohexyl, cyclopentadienyl, cyclopentyl, (1H,1H,2H,2H-perfluoro)dodecyl and (1H,1H,2H,2H-perfluoro)hexadecyl.

[0034] R 5U Selected from -LZ 1 -LZ 2 and Z 3 ,in

[0035] L is an aliphatic linker selected from the group consisting of -CH2-, -CH2CH2-, -CH2CH2CH2-, -C6H4-, -C6H4-CH2- and -CH2-CH2-C6H4-CH2-;

[0036] Z 1 Is it a choice between -SH and -NH2? The parts that make up the group;

[0037] Z 2 Is it freedom to choose?

[0038] The part of the group; in which

[0039] R 7 The group consisting of methyl, ethyl, and n-butyl groups is chosen independently, and o is an integer from 1 to 3.

[0040] as well as

[0041] Z 3 Selected from vinyl, phenyl,

[0042] in,

[0043] n is an integer chosen from the set of 1, 2, 3, 4, and 5; and

[0044] R 6 Choose from methyl, ethyl, n-butyl, straight-chain or branched C 5-14 The group consisting of alkyl residues, optionally -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 11 CH3 and -(CH2) 13 CH3; R 5S Choose freely - L'-Y 1 -L'-Y 2 and Y3 The group formed

[0045] in

[0046] m is an integer selected from the group consisting of 1, 2, 3, and 4;

[0047] R 8 Choose freely from -Cl, -Br, -I, -F, -CN, -SCN, -N3, -NO2, -OH, -SO2OR 1 ', and -OC(=O)R 12 The group formed;

[0048] R 9 Choose freely from -Cl, -Br, -I, -F, -CN, -COOH, -COOR 1 The group consisting of ', phenyl, ortho-, meta- and para-vinylphenyl;

[0049] R 9’ Choose freely between -COOH and -COOR 1 'A group composed of;

[0050] L' is an aliphatic linker selected from the group consisting of -CH2-, -CH2CH2-, and -CH2CH2CH2-; and

[0051] Y 1 Is it freedom to choose?

[0052]

[0053] The part that makes up the group, where o is an integer from 1 to 3;

[0054] Y 2 Is it freedom to choose?

[0055] The part of the group, where SU indicates that it has been substituted or not substituted;

[0056] Y 3 Is it freedom to choose?

[0057]

[0058] The part of the group; in which

[0059] X is a vacancy, -(NH)-, or -O-;

[0060] R 10 Choose freely R 10a R 10b R 10c R10d R 12a and The group formed;

[0061] R 10a Choose a group composed of the following items:

[0062]

[0063]

[0064] R 10b Choose a group composed of the following items:

[0065] It exists in the form of monomers, biuret, and triisocyanurate;

[0066] R 10c Choose a group composed of the following items:

[0067]

[0068] Where q is an integer from 1 to 25.

[0069]

[0070] Each of q1 to q4 is an integer from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8; each of q5 to q7 is an integer from 0 to 24 and the sum of (q5+q6+q7) is from 3 to 24; and each of q8 and q9 is an integer from 0 to 6 and the sum of (q8+q9) is from 2 to 6.

[0071] R 10d Choose from the groups consisting of the following:

[0072]

[0073]

[0074] Where r is an integer from 1 to 100, s is an integer from 1 to 15, and t is an integer from 1 to 10;

[0075] R 11 Choose freely R 8 -XR 1’ and R 12c The group formed; and

[0076] R 12 Choose freely R 12a R12b and R 12c The group consisting of,

[0077] R 12a Choose free linear or branched, substituted or unsubstituted C 1-18 Alkyl, C 2-18 alkenyl and C 2-18 Alkyne groups and cyclic, substituted or unsubstituted C 3-18 Alkyl, C 5-18 alkenyl and C 8-18 Groups composed of alkynyl groups;

[0078] R 12b Choose a group composed of the following items:

[0079] - Straight-chain or branched, substituted or unsubstituted alkyl ethers, alkenyl ethers, alkynyl ethers with a molecular weight not exceeding 5000 g / mol, and cyclic, substituted or unsubstituted alkyl ethers and alkenyl ethers with a molecular weight not exceeding 5000 g / mol, optionally substituted or unsubstituted poly(ethylene oxide), poly(propylene oxide) and polytetrahydrofuran.

[0080] - Unsubstituted polydimethylsiloxane and polydivinylsiloxane; and

[0081] - Polysaccharides and oligosaccharides with a molecular weight not exceeding 5000 g / mol, optionally including poly-D-glucose, oligo-D-glucose, chitosan, deacetylated oligo-chitosan, oligo-β-D-galactopyranocyanate, polyalginic acid, oligoalginic acid, polyamyl starch, oligoamyl starch, polygalactose, and galacto-oligosaccharides with a molecular weight not exceeding 5000 g / mol; and

[0082] R 12c Choose a group composed of the following items:

[0083] - Amino acids, oligopeptides and polypeptides with a molecular weight not exceeding 5000 g / mol; optionally, oligopeptides and polypeptides with a molecular weight not exceeding 5000 g / mol made from naturally occurring amino acids; and

[0084] -C 12-24 Fatty acids, choose naturally occurring C. 12-24 Fatty acids, choose any naturally occurring unsaturated fatty acids, C is optional. 12-24 Naturally occurring unsaturated fatty acids with 1 to 3 double bonds, epoxidized fatty acids, epoxidized castor oil, soybean oil, sunflower oil, optional open-ring epoxidized fatty acid-based polyols, optional natural oil-based polyols (NOPs), optional castor oil, soybean oil, or sunflower oil triglycerides.

[0085] The condition is R 5S no

[0086]

[0087] in

[0088] D-alkoxy-terminated siloxane moiety DP D-型 The degree of polymerization is in the range of 1.0 to 1.9;

[0089] T-alkoxy-terminated siloxane moiety DP T-型 The degree of polymerization ranges from 1.1 to 2.7;

[0090] The total content of the tri-organofunctionalized M-type siloxane moiety (ii) in the polysiloxane material shall not exceed 20 mol-%, optionally not exceed 10 mol-%, optionally not exceed 5 mol-%.

[0091] The total content of the dual-organofunctionalized D-type siloxane moiety (iii) in the polysiloxane material does not exceed 5, 10 or 15 mol-%; the material has a viscosity of 2 to 100,000 cP, optionally about 5 to 50,000 cP, optionally 5 to 1,000 cP;

[0092] The material contains less than 5, 2.5, 2, 1.5, 1, or 0.5 mol% of silanol groups (Si-OH); and

[0093] Furthermore, among them

[0094] - The polysiloxane material contains less than 45, optionally less than 37, optionally less than 30, or less than 25 mol% of a quaternary combination of Q-type siloxane species relative to the total Q-type siloxane species. 2r -Type and Q 3s,d -Type siloxane cyclic species; and / or

[0095] - Polysiloxane materials contain relative to all Q 3 - Quaternary combinations of less than 70, optionally less than 63, optionally less than 56, or less than 50 mol-% of type siloxane species Q 3s,3d -Type siloxane cyclic species; and / or

[0096] - The polysiloxane material contains less than 4.5, optionally less than 4.0, optionally less than 3.5, or less than 3.0 mol-% of biquadrial Q-type siloxane species relative to the total Q-type siloxane species. 3d -Type siloxane cyclic species; and / or

[0097] - Polysiloxane materials contain relative to all Q 3 Biquaternary Q-type siloxane species less than 25, optionally less than 20, optionally less than 17, or less than 14 mol-% 3d -Type siloxane cyclic species.

[0098] Its features

[0099] -When all R of the T-type siloxane portion in the polysiloxane material 5 Residues, optional all R 5 At least 65 mol-%, 75 mol-%, or 85 mol-% of the residues are R 5N At that time, the degree of polymerization (DP) of the Q-type alkoxy-terminated moiety Q-型 The atomic ratio of T- to Q- species in the material is in the range of 1.65 to 2.35, optionally in the range of 1.8 to 2.25, and the atomic ratio of T- to Q- species in the material is in the range of 0.05:1 to 0.45:1, optionally in the range of 0.10:1 to 0.30:1;

[0100] -When all-LZ 1 and -L'-Y 1 The residues and all R of the T-type siloxane moiety in polysiloxane materials 5 The degree of polymerization (DP) of the Q-type alkoxy-terminated moiety is determined when the residues are at least 80 mol-%, 90 mol-%, or 95 mol-%. Q-型 The ratio is in the range of 1.75 to 2.25, optionally in the range of 1.85 to 2.2:1, and the atomic ratio of T- to Q- species in the material is in the range of 0.02:1 to 0.3:1, optionally in the range of 0.04:1 to 0.25:1;

[0101] -When all Z 3 and Y 3 and / or all - LZ 2 and -L'-Y 2 The total amount accounts for all R of the T-type siloxane portion in polysiloxane materials 5 At least 50 mol-%, 60 mol-%, or 70 mol-%, of the residues, and the material optionally further comprises R. 5 The residue is -LZ 1 Optional R 5 The residue is -L'-Y 1 and -LZ 1 When the total is less than 20 mol-%, the degree of polymerization (DP) of the Q-type alkoxy-terminated moiety is... Q-型 The ratio is in the range of 1.85 to 2.2, optionally in the range of 1.9 to 2.2:1, and the atomic ratio of T- to Q- species in the material is in the range of 0.02:1 to 0.3:1, optionally in the range of 0.04:1 to 0.25:1 or 0.04:1 to 0.20:1;

[0102] -When all-LZ 1 -L'-Y 1 and R 5NAll R in the T-type siloxane portion of polysiloxane materials 5 At least 90 mol-%, 95 mol-%, or 99 mol-%, of the residues, and at least 30 mol-% of the optional material R 5 The residue is -LZ 1 and / or -L'-Y 1 And the material contains at least 10 mol-% R 5 The residue is R 5N The degree of polymerization (DP) of the Q-type alkoxy-terminated moiety Q-型 Within the range of 1.8 to 2.4, optionally within the range of 1.85 to 2.3:1, and the atomic ratio of T- to Q- species in the material within the range of 0.05:1 to 0.4:1, optionally within the range of 0.07:1 to 0.35:1; and

[0103] -When all R 5N Z 3 Y 3 -L'-Y 2 and -LZ 2 All R in the T-type siloxane portion of polysiloxane materials 5 When the residues are at least 90 mol-%, 95 mol-%, or 99 mol-%, all Z are optional. 3 Y 3 -L'-Y 2 and -LZ 2 The and the proportion of materials R 5 At least 20 mol-% of residues, and at least 20 mol-% of optional materials R 5 The residue is R 5N The degree of polymerization (DP) of the Q-type alkoxy-terminated moiety Q-型 The ratio is in the range of 1.7 to 2.25, optionally in the range of 1.85 to 2.2:1, and the atomic ratio of T- to Q- species in the material is in the range of 0.05:1 to 0.25:1, optionally in the range of 0.06:1 to 0.22:1. Detailed Implementation

[0104] Bi-quaternary siloxane cyclic species and Q 2r Q 3s And Q 3d The terminology will be explained further below.

[0105] For example, the polymeric liquid polysiloxane material described herein for all aspects can be a core-shell structure, wherein the core consists primarily of Q-type portions and has a different composition from the shell, which is primarily composed of T-type portions, and optionally further includes M- and D-type portions. Here, the core is also referred to as the “precursor (material).” Alternatively, the polymeric liquid material may also comprise a “core-only” material, meaning there is no shell and the Q- and T-type portions are substantially randomly distributed within the core. As used herein, the term “core-shell” is as commonly understood in the art (see, for example, Nanoscale, 2010, 2, 829-843 or Nanoscale, 2011, 3, 5120-5125). Regarding core-shell products, the interface between the core and shell must be understood as a diffuse shell, rather than a sharp boundary with an abrupt change in composition. This diffuse shell structure, where the concentration of functionalized shell species varies within a few bond lengths or angstroms, is a direct result of condensation chemistry, i.e., grafting a functionalized silane shell onto a pre-formed polysiloxane core. Because the outer arms of the dendritic polysiloxane core are highly permeable to smaller silane monomers and oligomers, it is clear that the grafting degree of the shell is highest at the periphery, but there is no obvious cutoff. However, the term core-shell still applies because grafting at the core center is highly hindered due to steric circumstance and reduced availability of active alkoxy groups, as the average connectivity (the number of bridging oxygen bonds (Si-O-Si bonds) per silicon center) is higher at the core center than at the periphery. Therefore, the term core-shell will be used in the context of polymeric liquid materials, meaning a polysiloxane core having a diffused shell as described herein.

[0106] If R 5 If the silane portion is included, the resulting portion is called "bipod silane".

[0107] Due to the quaternary Q 2r -type and / or Q 3s,d The number of -type siloxane cyclic species is small, and the polysiloxane materials described in this paper are highly dendritic linear and liquid species.

[0108] For example, typical materials according to the present invention may also contain Q-, T-, D- and / or M-type silane monomers (Q 0 ,T 0 D 0 M 0 ), for example, with Q n T n D n and M nWhere n≥l is smaller than the molar amount, in other words, the total molar siloxane content must be higher than the total molar silane monomer content, excluding HMDSO which may be present in any amount, also as a monomer, for example, as a solvent or co-solvent. Similarly, the material may optionally contain a substantial portion of smaller oligomers, such as a mixture of oligomers spanning from dimers to pentamers of polysiloxanes, optionally also having mixed QT and optional QD bonding modes.

[0109] The materials of this invention contain less than 5, 2.5, 2, 1.5, 1, or 0.5 mol% silanol groups (Si-OH), which means that the OR of Q-, T-, or D-type silanes... 1 Some of them are -OH groups to this extent.

[0110] Surprisingly, it was found that, for example, by using rearrangement catalysts as described herein, without the need for any active condensing agents such as acetic anhydride, the materials described herein can be prepared, and M-, D-, and / or T-type silanes can react with Q-type precursors or nuclear materials in nucleophilic substitution / condensation (“rearrangement”) reactions. It was also found that improved technical properties were discovered within the scope of the published DP. Q-型 And its specific implementation, DP Q-型 It transforms into a fairly large "core" material, essentially constituting most of the dendritic polysiloxane backbone structure. The functionalized T-type portion grafted onto the Q-type rich core imparts functionality; however, even more surprisingly, DP... T-型 The stoichiometric ratio of Q-type non-organic functionalized species to T-type mono-organic functionalized species is secondary in determining product characteristics. It is the stoichiometric ratio of these functionalized polymer liquid materials that primarily determines the dendritic "macro" crosslinking reactivity.

[0111] Not wanting to be bound by theory, it is believed that one of the driving forces behind this substitution reaction (also known as "grafting") comes from the quaternary Q-type precursor material used to prepare the polysiloxane material described herein. 2r -type and / or Q 3s,d Ring strain of type-1 siloxane cyclic species. The release of ring strain in the Q-type core material is sufficient to efficiently add (i.e., graft) M-, D-, and / or T-type silanes onto the Q-type core material without requiring further chemical reagents such as acetic anhydride, and substantially no rearrangement catalyst as defined herein is needed if the reaction time can be significantly extended. An exemplary structural formula (2D representation) of such a core material is shown in Figure 1, where a selected general R... 1 Alkyl ligands, and can be determined from the surface-to-volume ratio and T 0 - Grafting can obtain R 1 The smaller (circle) is seen in terms of the relative amount of groups. Figure 1b ) and larger ( Figure 1aThe influence of polysiloxane molecules.

[0112] In addition, Figure 2a The diagram shows an exemplary representation of a similar structure to the material described herein, also as having a partial R 5S A general overview of various organic functionalized T, D, and M functional groups in T-type functionalization. More specific details are as follows... Figure 2b and Figure 2c As shown.

[0113]

[0114] As used herein, the terms "quaternary" ring, "polysiloxane" ring, or "Q-type" ring species always refer to all Q-type rings contained in a material. 2r and Q 3s,d A collection of type-1 components, which are part of a four-membered polysiloxane ring structure. Two representative examples of this typical structural component in single and double four-membered ring structures are shown in the equation above. Q 2r The ring portion appears in both "single" and "double" ring structures, and in each Q... 2r It contains two siloxane bonds, both of which are part of a ring structure, and two alkoxy groups (-OR). 1 Substituents. In the example on the left side of a single quaternary siloxane ring, only Q is present. 2r Ring (circular) and "single ring" Q 3s (Square) species are possible. In the second example shown on the right, with two connected tetra-membered siloxane rings (bicyclic structure), besides Q... 2r Ring species (circular) and "single-ring" Q 3s In addition to the (square) species, there is also the "double-ring" Q. 3d The (rectangular, dashed) sections are possible and they are located at the bridging points connecting the two rings. It is worth noting that in these Q... 3d In this species, all siloxane bonds are part of a bicyclic network. Furthermore, it is noteworthy that, with Q... 3s The wobble line on the partially connected oxygen atom represents the connection to any other possible Q atom with n ≥ 1. n T n D n Or M n Partial siloxane bonds. It must also be understood that in the examples of the typical configurations described above, the portion is Q-type, but these are merely examples to aid understanding and there is no actual limitation on the Q-type portion. In fact, within the scope of this disclosure, it is highly expected that T-type and / or D-type portions will also be present in such quaternary polysiloxane ring structures.

[0115] In this paper, Q in any quaternary siloxane ring structure 2 The species are referred to as "Q" in the single-ring structure.2r ” and “ Q. 3 "Species, in the double-ring structure, are called "Q" 3s ” and “ Q. 3d ".

[0116] For quantitative purposes, different metrics can be used to define or limit the aforementioned quaternary polysiloxane cyclic species. The first metric is defined as the Q species exceeding the total Q species in the material. 2r and Q 3s,d Total number of ring species:

[0117] % (Q) 2r &Q 3s,d ) Circulating species = 100·Σ(A Q2rings +A Q3rings ) / Σ(A Qn )

[0118] =100·(A) Q2r +A Q3s +A Q3r ) / (A Q0 +A Q1 +A Q2 +A Q3 +A Q4 );

[0119] The second metric is defined as exceeding all Q values ​​in the material. 3 Species Q 3s,d Total number of ring species:

[0120] %Q 3 (Q) 3s,d ) Circulating species = 100·Σ(A Q3rings ) / A Q3

[0121] =100·(A) Q3s +A Q3d ) / A Q3 =100(1-(A) Q3l / A Q3 ));

[0122] The third metric is defined as the Q species that exceed the total Q species in the material. 3d Total number of ring species:

[0123] % (Q) 3d ) Circulating species = 100·A Q3d / Σ(A Qn )

[0124] =100·A Q3d / (A Q0 +A Q1 +A Q2 +AQ3 +A Q4 );

[0125] The fourth indicator is defined as exceeding all Q values ​​in the material. 3 Species Q 3d Total number of ring species:

[0126] %Q 3 (Q) 3d ) Circulating species = 100·A Q3d / A Q3 ;

[0127] All mol-% numbers mentioned herein—unless otherwise explicitly stated—are defined as the sum of all D-, M-, or T-type silicon atoms divided by the sum of all silicon atoms in the material, e.g., by quantitative analysis. 29 Si-NMR measurements. Variable A is the spectral peak area, as further defined below.

[0128] Four Yuan Q 2 -type and / or Q 3 The mol% of type-Q siloxane cyclic species relative to the total Q-type siloxane species can be determined by... 29 Si-NMR analysis confirmed, as shown in the example below, that the polysiloxane material described herein contains less than a specified mol-% quaternary (Q-type) siloxane species relative to the total Q-type siloxane species. 2r &Q 3s,d ) and / or (Q 2r ) and / or (Q 3s (single) and / or (Q) 3d Bicyclic species. This means that the material cumulatively contains less than the specified mol-% quaternary Q. 2r -Type siloxane cyclic species, less than the specified mol-% quaternary Q 3s,d -Type siloxane cyclic species and / or less than the specified mol-% quaternary Q 2r -Type and Q 3s,d -Type siloxane cyclic species. For all embodiments described herein, quaternary Q 3s,d -Type siloxane cyclic species include Q 3s,d -Type siloxane species, one of which is Q 3s,d -Type siloxanes are part of one or two four-membered rings.

[0129] Even more surprisingly, DP Q-型 The degree of polymerization and the ratio of T-type to Q-type atoms in the material are the main factors determining the observed reactivity and properties. If DP is chosen... Q-型Smaller values ​​(e.g., below those disclosed herein) result in a rather limited average “core” size and require a large amount of T-type silane to achieve surface coverage with sufficiently large T-type portions, thereby truly imparting a significant R-value to the material emanating from the grafted T-type units. 5 Sensitivity. With DP Q-型 As the value increases (e.g., above the values ​​disclosed herein), the surface-to-volume ratio decreases rapidly, meaning that a lower amount of T-type fraction (a lower T-type:Q-type molar ratio) is required to impart significant Rw to the material. 5 Functionality. This argument is found in DP. Q-型 Above a certain minimum, this applies to virtually all materials across the entire range, and the macromolecular or dendritic characteristics of the material (or in other words, the efficiency of the use of the T-functionalized portion) increase with increasing core size. However, with DP... Q-型 As the viscosity increases, the material viscosity increases in a steep, strongly nonlinear manner, potentially leading to gelation or a significant increase in viscosity, which can make practical applications difficult in some cases. It has been proven that DP... Q-型 The minimum and maximum values ​​also depend on the type of T-type silane moiety grafted onto its periphery, and their properties also affect the ideal range of application-related properties. Furthermore, contrary to expectations, the atomic or molar ratio of T- to Q- species in the material primarily determines its surface functional properties and only to a lesser extent determines DP. T-型 This is because the latter is completely unrelated to the number of T-type parts associated with Q, but rather represents grafting "efficiency".

[0130] If the material exhibits an M-shaped portion, this typically leads to DP (Dual Productivity). Q-型 The increase in DP. Therefore, if the amount of M-type modification exceeds 5 mol-% or optionally 10 mol-%, the DP content in all materials disclosed herein will increase. Q-型 The limit will be increased by 0.05 or optionally 0.1 DP units.

[0131] Optionally, the polymer liquid hyperbranched polysiloxane material described herein is one in which...

[0132] -All R in the T-type siloxane portion of polysiloxane materials 5 At least 65 mol-% of the residues are R 5N The degree of polymerization (DP) of the Q-type alkoxy-terminated moiety Q-型 The atomic ratio of T- to Q- species in the material is in the range of 1.65 to 2.35, optionally in the range of 1.8 to 2.25, and the atomic ratio of T- to Q- species in the material is in the range of 0.05:1 to 0.45:1, optionally in the range of 0.10:1 to 0.30:1;

[0133] -All-LZ 1and -L'-Y 1 The residues and all R of the T-type siloxane moiety in polysiloxane materials 5 At least 80 mol-% of the residues, and the degree of polymerization (DP) of the Q-type alkoxy-terminated moiety. Q-型 The ratio is in the range of 1.75 to 2.25, optionally in the range of 1.85 to 2.2:1, and the atomic ratio of T- to Q- species in the material is in the range of 0.02:1 to 0.3:1, optionally in the range of 0.04:1 to 0.25:1;

[0134] -All Z 3 and Y 3 and / or all - LZ 2 and -L'-Y 2 All R in the T-type siloxane portion of polysiloxane materials 5 At least 50 mol-%, of the residues, and the material optionally further contains R. 5 The residue is -LZ 1 Optional R 5 The sum of the residues is -L'-Y 1 and -LZ 1 The degree of polymerization (DP) of the Q-type alkoxy-terminated moiety is less than 20 mol-%. Q-型 The ratio is in the range of 1.85 to 2.2, optionally in the range of 1.9 to 2.2:1, and the atomic ratio of T- to Q- species in the material is in the range of 0.02:1 to 0.3:1, optionally in the range of 0.04:1 to 0.25:1 or 0.04:1 to 0.20:1;

[0135] -All-LZ 1 -L'-Y 1 and R 5N All R in the T-type siloxane portion of polysiloxane materials 5 At least 90 mol-% of residues, and at least 30 mol-% of optional materials R 5 The residue is -LZ 1 and / or -L'-Y 1 And at least 10 mol-% R of the material 5 The residue is R 5N The degree of polymerization (DP) of the Q-type alkoxy-terminated moiety Q-型 Within the range of 1.8 to 2.4, optionally within the range of 1.85 to 2.3:1, and the atomic ratio of T- to Q- species in the material within the range of 0.05:1 to 0.4:1, optionally within the range of 0.07:1 to 0.35:1; and / or

[0136] -All R 5N Z 3Y 3 -L'-Y 2 and -LZ 2 All R in the T-type siloxane portion of polysiloxane materials 5 At least 90 mol-%, of the residues, optionally all Z 3 Y 3 -L'-Y 2 and -LZ 2 The and the proportion of materials R 5 At least 20 mol-% of residues, optional material R 5 At least 20 mol-% of the residues are R 5N The degree of polymerization (DP) of the Q-type alkoxy-terminated moiety Q-型 The ratio is in the range of 1.7 to 2.25, optionally in the range of 1.85 to 2.2:1, and the atomic ratio of T- to Q- species in the material is in the range of 0.05:1 to 0.25:1, optionally in the range of 0.06:1 to 0.22:1.

[0137] The atomic ratio of T- to Q- species in the material is equal to that of all T-type species (T... 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 The ratio of silicon atoms to silicon atoms.

[0138] The polymer liquid polysiloxane material described in this article is optionally R. 5S - Functionalized, for example, all R in the material 5U and R 5S The portion of at least 1 mol-%, optionally at least 3 mol-%, optionally at least 5 mol-%, optionally at least 7 mol-%, is R. 5S Part, of which R 5S It is considered a functionalized part. R 5S Functionalization can be achieved by selecting T-type silanes or already R-type silanes for the manufacture of polysiloxane materials. 5S - Functionalized siloxane moiety (i.e., pre-R used for rearrangement grafting) 5S -Functionalized T 0 Or T-type oligomer precursors) are introduced into polysiloxane materials, i.e., containing R 5S A portion of the T-type monomer or oligomer compound, for example to the extent defined herein, or optionally to a lesser extent, i.e., less than 1 mol-%. If the T-type siloxane or silane portion in the material does not contain or contains less than 1 mol-%. 5S(relative to all R) 5U and R 5S If the total molar number of T-type substituents is not the same as the material disclosed herein, then the T-type siloxane moiety can be functionalized by R on the already grafted T-type siloxane moiety. 5U Or through further grafting pre-R 5S - Functionalized T-type silanes or containing R 5S Some oligomers and R 5S - Functionalization. R 5U Partial functionalization can be performed using known chemical methods and is described in the context of this method. It should be noted that R, as described herein... 5S - Functionalization is a specific form of functionalization, while the general term "organofunctionalized silane or siloxane" refers to silanes / siloxanes that typically contain organic residues that are directly bonded to silicon atoms.

[0139] Optionally, for all aspects and implementation schemes described herein, all R in the material 5 Part of 0 mol-% is R 5S part.

[0140] In R 5U Selected from -LZ 1 In this case, it should be understood that if the following residues need to be functionalized, they must be deprotected by standard chemical reactions:

[0141] If the grafted T-type siloxane R 5U If partially functionalized, then within the scope of this invention, R can be expected. 5U and R 2 R 3 R 4 In cases where there is some difference in reactivity or comparable reactivity between substituents, or even no difference in chemoselectivity, if R 2 R 3 and / or R 4 Selected from phenyl and vinyl, relative to R 5U Some, for example, 5-95 mol-% or, for example, 25-90% R 2 R 3 and / or R 4 Partially functionalized. R 2 R 3 and / or R 4 Partial functionalization may result in the following exemplary chemical entities:

[0142]

[0143] R 2 R3 R 4 and R 5 Functionalization can be identified and quantified using known spectroscopic methods, such as nuclear magnetic resonance spectroscopy, and so on. 1 H-、 13 C- and optional 15 N or 33 S or 31 P-NMR, using isotope enrichment, can be used to analyze and verify these functionalization reactions. Specifically, in these types of organic reactions, such as addition or substitution or radical reactions, proton and carbon features undergo changes in their NMR responses due to changes in electronic structure and structural environment and their effects on magnetic coupling. Typically, when such organic reactions occur, features from protons or proton groups or carbon disappear, and new peaks appear in the upper or lower field of the spectrum, depending on how the functionalization reaction affects the magnetic coupling of the species in question. Therefore, the disappearance of old chemical features and the appearance of new features can both be quantitatively tracked using NMR spectroscopy. Quantitative reaction monitoring of organic reactions is common knowledge and requires no further explanation.

[0144] The term "in monomer, biuret or triisocyanurate form" refers to selecting R from among them. 10b The described chemical entity may be in its monomer form, i.e., corresponding to the described entity, in its biuret form, i.e., corresponding to three or optionally up to five described monomers coupled with a diamide formed by an isocyanate functional group, or in its triisocyanurate form, i.e., corresponding to three of the described monomers coupled with a cyclic isocyanurate group formed by an isocyanate functional group.

[0145] Typically, biuret takes the form shown below:

[0146]

[0147] For example, monomers The biuret form is and the corresponding triisocyanurate form is Entities containing isocyanates are associated with -NC(=O)N- (e.g., for...) X = N and R 10 =R 10b ), -NC(=O)O- (for example, for X = O and R 10 =R 10b ) or -NC(=O)C- (for example, for X is missing and R is missing. 10 =R 10b The bond connects to the siloxane moiety via a NC-bond or directly (e.g., via an NC-bond, e.g., for...) And R 10=R 10b The connection to the siloxane portion is irrelevant and applies equally.

[0148] As used herein, the term "unsubstituted" means substituted only with hydrogen. As used herein, the term "substituted" means that any one or more hydrogen atoms on a specified atom or group are independently replaced with atoms other than hydrogen, optionally by halogen, optionally by fluorine, chlorine, bromine, iodine, thiol, carboxyl, acryloyl, cyano, nitro, alkyl (optionally C1-C) 10 The substitution may be made by substitution of aryl (optionally phenyl, benzyl, or benzoyl), alkoxy, or sulfonyl groups, by means of a tertiary or quaternary amine or by selection from specified substituents, provided that the substitution does not exceed the normal valence of the specified atom, and that the substitution yields a stable compound, i.e., a compound that can be isolated and characterized using conventional methods. Optionally, the substitution occurs at the β-position or ω-position (opposite to the terminal hydrocarbon, if R...) of the hydrocarbon chain. 5S Substituent linkage occurs at the α-position or optionally at the β or γ-position of the hydrocarbon chain (from the next or the next adjacent carbon to which the substituent linkage is located). In the case of unsaturated hydrocarbons, substitution optionally occurs at the β or ω-position of the hydrocarbon chain or optionally on a carbon that is part of a double or triple bond or on a carbon directly adjacent to it.

[0149] In the context of this invention, it should be understood that preceding terms such as "straight-chain, branched, or cyclic," "substituted or unsubstituted," indicate that each of the following terms will be interpreted as modified by said preceding term. For example, the scope of the term "straight-chain, branched, or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, carbocyclic" includes straight-chain, branched, or cyclic, substituted or unsubstituted alkyl groups; straight-chain, branched, or cyclic, substituted or unsubstituted alkenyl groups; straight-chain, branched, or cyclic, substituted or unsubstituted alkynyl groups; straight-chain, branched, or cyclic, substituted or unsubstituted alkylene groups; and straight-chain, branched, or cyclic, substituted or unsubstituted carbocyclic groups. For example, the term "C 1-18 Alkyl, C 2-18 alkenyl and C 2-18 "Alkyne" refers to a group of compounds having 1 or 2 to 18 carbons and alkyl, alkenyl or alkynyl functional groups.

[0150] The term "alkyl" refers to a saturated straight-chain or branched hydrocarbon group containing the number of carbon items indicated, such as straight-chain, branched, or cyclic. 1-18 "alkyl" refers to hydrocarbon residues containing 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, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, etc.

[0151] If an alkyl chain is characterized by a name that allows for straight-chain or branched isomers, then that name covers all straight-chain or branched isomers. For example, "butyl" includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0152] The term "alkenyl" refers to a straight-chain or branched hydrocarbon group that is at least partially unsaturated, substituted, or unsubstituted, and contains the indicated number of carbon atoms, for example, "(C 2-18 "Alkenyl" refers to a hydrocarbon residue containing 2 to 18 carbon atoms, such as vinyl (ethyl), propenyl (allyl), isopropenyl, butenyl, isopreneyl, or hex-2-alkenyl, or a hydrocarbon group containing a methylene chain interrupted by a double bond, such as those found in monounsaturated fatty acids, or a hydrocarbon group containing a polyene interrupted by a methylene group, such as a hydrocarbon group containing two or more of the following structural units -[CH=CH-CH2]-, such as those found in polyunsaturated fatty acids.

[0153] The term "alkynyl" refers to a straight-chain or branched hydrocarbon group that is at least partially unsaturated, substituted, or unsubstituted, and may contain, for example, 2 to 18 carbon atoms, such as ethynyl, propynyl, butynyl, acetylynyl, or propynyl.

[0154] The term "alkyl ether" refers to a saturated or unsaturated straight-chain or branched hydrocarbon group containing a number of atoms resulting in a molecular weight not exceeding 5000 g / mol. As used herein, an alkyl ether group should be understood to mean any straight-chain or branched, substituted or unsubstituted alkyl chain containing an oxygen atom as an ether motif, i.e., an oxygen atom 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 linked to the chemical formula provided in this invention via the oxygen atom of the ether residue. Optionally, if the ether residue is substituted at a carbon atom with a nucleophilic substituent, such as an amine or thiol, the ether residue can be linked to the chemical formula provided in this invention via the nucleophilic substituent.

[0155] As used in this article, the wording that defines the limitation of the length range, for example, "from 1 to 5" or "(C 1-5 ")" refers to any integer from 1 to 5, namely 1, 2, 3, 4, and 5. In other words, any range defined by the two explicitly mentioned integers is intended to include and publicly define any integers that define the limitation, as well as any integers contained within the range.

[0156] As used herein, when referring to polyol residues, those skilled in the art will recognize that attaching, for example, a straight-chain diol to a polysiloxane material will effectively result in the diol becoming a "monoalcohol" residue because one of the alcohol functional groups forms a coupling bond. In other words, the term polyol as used herein also includes diol reactants that form "monoalcohol" residues once attached to a polysiloxane material. Grafting multiple such groups onto a polymeric liquid polysiloxane material still results in a polyfunctionalized macromolecular polyol.

[0157] The scope of the invention includes those analogs of the compounds described above and in the claims, characterized by the exchange of one or more carbon-bonded hydrogens, optionally one or more aromatic carbon-bonded hydrogens, with a halogen atom, such as F, Cl, or Br, preferably F.

[0158] If a residue or group described herein is characterized as having two additional residues of the same name, e.g., in R 10a is each of these additional residues (in this example R 12 in) can independently be selected from the definition of this residue (in this example R 12 in) given herein.

[0159] Those skilled in the art will recognize that any combination of residues or moieties used to form R 5S e.g., R 1’ , R 8 , R 9 , R 9 ', L', Y, X, R 10 , R 11 and R 12 ) must result in a stable compound, i.e., a compound that can be isolated and characterized using conventional methods. Those skilled in the art can determine, based on their common general knowledge, which compounds, i.e., which residues or moieties (e.g., R 1’ , R 8 , R 9 , R 9 ', L', Y, X, R 10 , R 11 and R 12 ) are unstable, specifically, which linker chemistries are possible and do not interfere with other chemical functional groups in the polymeric liquid material. Any combination of moieties or residues (e.g., R 1’ , R 8 , R 9 , R 9 ', L', Y, X, R 10 , R 11 and R 12 ) that results in an unstable compound is excluded from the scope of the claims.

[0160] For example, R 12b In this context, polysaccharides and oligosaccharides are connected by an oxygen atom or optionally by a nitrogen atom (e.g., chitosan) to their respective moieties (e.g., with R). 8 Y, R 10 or R 11 )connect.

[0161] For example, R 12c Amino acids, oligopeptides, or polypeptides in the context are expressed through their amines, carbonyl carbons, or thiols (e.g., in compounds containing R). 12b In the case of cysteine) and their respective portions (e.g. with R) 8 Y 1-3 R 10 or R 11 )connect.

[0162] R 12c In the context, fatty acids, for example, are attached to their respective moieties (e.g., to R through hydroxyl groups (e.g., for castor oil) or through carboxylic acid functional groups, or optionally for unsaturated fatty acids through double bonds, for example through free radical polymerization chemistry. 8 Y 1-3 R 10 or R 11 Furthermore, in the case of, for example, epoxidized fatty acids or epoxidized fatty acid-based polyols, fatty acids can be linked by opening the epoxide / reacting with the epoxide.

[0163] Triglycerides or polyols derived from fatty acids through epoxidation and ring-opening with, for example, an alkali metal hydroxide matrix can also be linked via hydroxyl functional groups, directly via ether linkage or esterification, or optionally via secondary substitution, such as by bromination or oxidation to a ketone and, for example, subsequent further substitution, or optionally via R-termination with an isocyanate-terminated group. 5S The groups react to form a bond.

[0164] In one embodiment, the polymeric liquid hyperbranched polysiloxane material of the present invention is one in which R 5N Choose from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, straight-chain, branched, or cyclic C. 5-16 The group consisting of alkyl residues, optionally straight-chain or branched hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, cyclohexyl, cyclopentadienyl, and cyclopentyl;

[0165] Z 1 Is it a choice between Freedom-SH? The parts that make up the group;

[0166] R 8Choose from the group consisting of -Cl, -Br, -I, -CN, -SCN, and -N3;

[0167] Y 1 Choose a group composed of the following items:

[0168] Where o is an integer from 1 to 3;

[0169] Y 2 Is it freedom to choose?

[0170]

[0171] Part of the group; Y 3 Is it freedom to choose?

[0172]

[0173] The parts that make up the group;

[0174] in

[0175] X is a vacancy, -(NH)-, or -O-;

[0176] R 10 Choose freely R 10a R 10b R 10c R 10d and R 12a The group formed;

[0177] R 10a Choose a group composed of the following items:

[0178]

[0179] R 10b Choose a group composed of the following items:

[0180]

[0181] And X is N; R 10c Choose a group composed of the following items:

[0182]

[0183] Where q is an integer from 1 to 10.

[0184]

[0185] Each of q1 to q4 is an integer from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8; each of q5 to q7 is an integer from 0 to 24 and the sum of (q5+q6+q7) is from 3 to 24; and each of q8 and q9 is an integer from 0 to 6 and the sum of (q8+q9) is from 2 to 6.

[0186] R 10d Choose a group composed of the following items:

[0187]

[0188]

[0189] Where r is an integer from 1 to 25, s is an integer from 1 to 10, and t is an integer from 1 to 10;

[0190] R 11 Selected from R 8 and optional R 12c ;as well as

[0191] R 12 Choose freely R 12a R 12b and R 12c The group consisting of, among which

[0192] R 12a Choose free linear or branched, substituted or unsubstituted C 1-18 Alkyl and C 2-18 Groups composed of alkenyl groups;

[0193] R 12c Choose a group composed of the following items:

[0194] - Amino acids and oligopeptides or polypeptides with a molecular weight not exceeding 2000 g / mol; optionally, oligopeptides and polypeptides with a molecular weight not exceeding 2000 g / mol made from naturally occurring amino acids; and

[0195] -C 12-24 Fatty acids, choose naturally occurring C. 12-24 Fatty acids, any naturally occurring unsaturated fatty acids, any C with 1 to 3 double bonds. 12-24 Naturally occurring unsaturated fatty acids, epoxidized fatty acids, epoxidized castor oil, soybean oil, sunflower oil, open-ring epoxidized fatty acid polyols, natural oil-based polyols (NOPs), and castor oil, soybean oil, or sunflower oil triglycerides.

[0196] In another embodiment, the polymeric liquid hyperbranched polysiloxane material according to the present invention is one in which R 1Choose from the group consisting of methyl, ethyl, and propyl, with methyl and ethyl being optional;

[0197] R 5N Choose from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, straight-chain, branched, or cyclic C. 5-16 The group consisting of alkyl residues, optionally straight-chain or branched hexyl, octyl, dodecyl and hexadecyl;

[0198] L is an aliphatic linker selected from the group consisting of -CH2-, -CH2CH2-, -CH2CH2CH2- and -C6H4-;

[0199] Z 1 Is it a choice between Freedom-SH? The parts that make up the group;

[0200] Z 2 Is it freedom to choose?

[0201]

[0202] The parts that make up the group;

[0203] Z 3 Selected from vinyl and phenyl;

[0204] R 8 Choose the group consisting of -Cl, -Br, -I, -CN, and -N3;

[0205] R 9 Choose freely from -Cl, -CN, -COOH, -COOR 1 The group consisting of 'and phenyl';

[0206] Y 1 Choose a group composed of the following items:

[0207]

[0208] Where o is an integer from 2 to 3;

[0209] Y 2 Is it freedom to choose?

[0210]

[0211] The parts that make up the group;

[0212] Y 3 Is it freedom to choose?

[0213]

[0214] The part of the group; in which

[0215] X is a vacancy, -(NH)-, or -O-;

[0216] R 10 Choose freely R 10a R 10b R 10c and R 10d The group formed;

[0217] R 10a Choose a group composed of the following items:

[0218]

[0219] R 10b Choose a group composed of the following items:

[0220]

[0221] And X is N;

[0222] R 10c Choose a group composed of the following items:

[0223]

[0224] Where q is an integer from 1 to 6.

[0225]

[0226] Each of q1 to q4 is an integer from 0 to 8, and the sum of (q1+q2+q3+q4) is from 4 to 8; each of q5 to q7 is an integer from 0 to 8, and the sum of (q5+q6+q7) is from 3 to 12; each of q8 and q9 is an integer from 0 to 4, and the sum of (q8+q9) is from 2 to 4; R 10d Choose a group composed of the following items:

[0227]

[0228] Where r is an integer from 1 to 20, s is an integer from 1 to 8, and t is an integer from 1 to 10;

[0229] R 11 Selected from R 8 and optional R 12c ;as well as

[0230] R 12c Choose a group composed of the following items:

[0231] - Amino acids and oligopeptides or polypeptides with a molecular weight not exceeding 1000 g / mol; optionally, oligopeptides and polypeptides with a molecular weight not exceeding 1000 g / mol made from naturally occurring amino acids; and

[0232] -C 12-24 Fatty acids, choose naturally occurring C. 12-24 Fatty acids, choose naturally occurring C. 12-24 Unsaturated fatty acids, selected from naturally occurring C-type fatty acids with 1 to 3 double bonds. 12-24 Unsaturated fatty acids, optional epoxidized fatty acids, optional epoxidized castor oil, soybean oil, sunflower oil, optional open-ring epoxidized fatty acid polyols, optional natural oil-based polyols (NOPs), optional castor oil, soybean oil, or sunflower oil triglycerides;

[0233] In a further embodiment, the polymer liquid hyperbranched polysiloxane material of the present invention is one wherein the material comprises

[0234] (v) at least two different R 5 - A group of substituted mono-organic functionalized T-type alkoxy-terminated siloxanes, each group comprising at least 3 mol% of all mono-organic functionalized T-type moieties in the material; and / or

[0235] (vi) Chiral single-organic functionalized T-type moieties with an amount of at least 3 mol-% relative to all single-organic functionalized T-type moieties in the material. 1 - Type part.

[0236] As used herein, the term "group" refers to a collection of portions or a given organically functionalized T-type, D-type, or optionally M-type portions in a polymeric material. As an example, grafting or heterocondensing two different T-type trialkoxysilanes (e.g., vinyltrimethoxysilane and methyltriethoxysilane) as two randomly selected examples onto a Q-type polysiloxane precursor results in two distinct groups (T... 0 = Unreacted monomers), T 1 T 2 and T 3 Loaded with -methyl and -vinyl as organofunctionalized R 5 Substituents, due to R 5 The effects of substituents on their respective T-type central Si atoms can be observed separately. 29 It can be resolved in Si-NMR spectra.

[0237] The at least two different Rs mentioned in this article 5 - A group of substituted mono-organofunctionalized T-alkoxy-terminated siloxanes encompassing R 5 R 5N R 5U and R5S Any combination, optionally, of all R in the polymer liquid hyperbranched polysiloxane material. 5U and R 5S The portion of at least 1 mol-%, optionally at least 3 mol-%, optionally at least 5 mol-%, optionally at least 7 mol-%, is R. 5S Partially, and optionally further, the condition is that DP is satisfied. Q-型 one of the conditions stated in.

[0238] The first condition (v) should be understood as the material containing at least two groups of mono-organofunctionalized (T-type) alkoxy-terminated siloxane moieties (T... 1 T 2 T 3 Their organic functionalized substituents R 5 Different. This means that the material has at least two different R values. 5 Functional groups, and in a few species in detectable quantities (e.g., through...) 29 It exists (Si-NMR).

[0239] The second condition (vi) is determined by T having four different substituents on its silicon atoms. 1 -Type grafted siloxane partially satisfies the following conditions: one Si-O-Si bond and one bond connected to R. 5 The Si-C bond of the organic functionalized group and the two different alkoxy substituents R 1 For example, one ethoxy group and one methoxy group. When only one set of R groups exists in the material... 5 This has already occurred when T-type species are functionalized. Typically, different R... 1 Alkoxy groups can exchange ligands between Q- and T-type moieties.

[0240] In another embodiment, the polymeric liquid hyperbranched polysiloxane material according to the invention is one in which (vii) in all other cases besides those defined above, the degree of polymerization DP of the Q-type alkoxy-terminated moiety is... Q-型 Within the range of 1.6 to 2.4, and the atomic ratio of T- to Q- species in the material is within the range of 0.02:1 to 0.4:1; (viii) if the material comprises approximately or more than 5 mol-% of the M-type portion, the degree of polymerization (DP) of the Q-type alkoxy-terminated portion is... Q-型 The ratio is in the range of 1.7 to 2.5, and the atomic ratio of T- to Q- species in the material is in the range of 0.02:1 to 0.4:1;

[0241] (ix) Degree of polymerization (DP) of D-alkoxy-terminated siloxane moieties D-型 Within the range of 1.25 to 1.75; and / or

[0242] (x) Degree of polymerization (DP) of T-alkoxy-terminated siloxane moieties T-型 Within the range of 1.3 to 2.2.

[0243] Here, the degree of polymerization (DP) of any amorphous silica material (for polysiloxane materials and for the corresponding methods and uses described herein) is defined as the ratio of the number of bridging oxygen (BO) (the number of Si-O-Si bonds) to the total number of metal atoms (Si) in the system. tot The ratio.

[0244] The term "alkoxy-terminated" for Q-, T-, and D-type siloxane moieties is understood to refer to residual substituents that are essentially alkoxy groups in the moieties, since the polymeric liquid materials are derived from alkoxy (ethoxy / methoxy) groups containing silane precursors in monomeric or oligomeric form. This means that for Q... 0 Monomer and Q 1 Q 2 Q 3 and Q 4 In some cases, the "alkoxy terminus" is composed of 4, 3, 2, 1, and 0 alkoxy groups, respectively, and for T... 0 Monomer and T 1 T 2 and T 3 In some cases, the "alkoxy terminus" is composed of 3, 2, 1, and 0 alkoxy groups, respectively. Similarly, for D... 0 monomers and D 1 and D 2 In some cases, the "alkoxy terminus" is composed of 2, 1, and 0 alkoxy groups, respectively.

[0245] DP of materials Q-型 DP T-型 and DP D-型 From quantitative 29 Si-NMR data were obtained directly, based on:

[0246] DP Q-型 =Σ(n A) Qn ) / Σ(A Qn )=(A Q1 +2A Q2 +3A Q3 +4A Q4 ) / (A Q0 +A Q1 +A Q2 +A Q3 +A Q4 );

[0247] DP T-型 =Σ(n A) Tn) / Σ(A Tn )=(A T1 +2A T2 +3A T3 ) / (A T0 +A T1 +A T2 +A T3 For typical T-type silanes;

[0248] DP T-型,双足硅烷 =2·Σ(n A) Tn ) / Σ(A Tn ) = 2(A T1 +2A T2 +3A T3 ) / (A T0 +A T1 +A T2 +A T3 For bipedal T-type silanes; and

[0249] DP D-型 =Σ(n A) Dn ) / Σ(A Dn )=(A D1 +2A D2 ) / (A D0 +A D1 +A D2 ).

[0250] In the above DP Q-型 In the equation, term A Qn Indicates with Q n Quantitative analysis related to some (spectral characteristics) 29 The Si-NMR peak area is determined by the Si atom coordinated by an n-siloxane bond through a bridging oxygen (BO) atom, which connects it to its next nearest-neighbor Si atom and a (4-n) non-bridging oxygen (NBO) atom connected to a terminal alkoxy group Si-OR as defined herein. Similarly, A Tn and A Dn This indicates the corresponding T-type and D-type portions (spectral characteristics). 29 Si-NMR peak area.

[0251] Regarding the definition of DP above, Q 2 and Q 3 This refers to all types of Q. 2 and Q 3 Species, including linear, single-ring, and double-ring species.

[0252] Regarding DP T-型The equation necessitates a distinction between bipodial T-silanes and all other "general" T-silanes. The latter constitute the majority of commercially available T-silanes and contain only one Si atom linked to three alkoxy groups and one organic functional group. In contrast, a bipodial silane, which can be represented as (RO)3Si-(CH2)-X-(CH2)-Si(OR)3, contains a further trialkoxysilyl unit linked to the first via a suitable linking group "X," and each is separated by at least one methylene (-CH2-) group. A modified definition of the degree of polymerization of bipodial silanes is introduced considering that a single link with the polysiloxane network is sufficient to covalently link functional groups and develop their target interface functionalization. For example, simultaneous grafting of two trimethoxysilyl residues via a bipodial silane would be counterproductive, as it would rapidly lead to branching and attachment from one macromolecule to another, resulting in undesirable gelation even in the low surface coverage range of bipodial T-silanes. Therefore, regarding the single trialkoxysilyl linkage, refer to DP... T-型,双足硅烷 This makes more sense, leading to the above definition.

[0253] For organofunctionalized T-type tri- and D-type bis-alkoxysilanes 29 The Si spectral fingerprint region gradually shifts to lower fields, thus clearly distinguishing different non-organic functionalized Q. n With organic functionalization T m and D l Partially separated.

[0254] Optionally, if the total amount of the dual-organofunctionalized D-type siloxane moiety (iii) in the polysiloxane material does not exceed 10 mol-%, the molar ratio of total silicon to free hydrolyzable alkoxy groups in the material described herein is in the range of 1:1.0 to 1:3.0, optionally 1:1.2 to 1:2.5, optionally 1:1.3 to 1:2.2.

[0255] Optionally, the molar number of ethoxy-terminated units (-OCH2CH3) in the material described herein is at least twice the number of methoxy-terminated units (-OCH3), and the material is substantially free of propoxy-terminated units (-OCH2CH2CH3), for example, less than 3% of all alkoxy-terminated units are propoxy-terminated units.

[0256] Optionally, the molar number of methoxy-terminated units (-OCH3) in the material described herein is at least twice the number of ethoxy-terminated units (-OCH2CH3), and the material is substantially free of propoxy-terminated units (-OCH2CH2CH3), for example, less than 3% of all alkoxy-terminated units are propoxy-terminated units.

[0257] For any polymeric liquid material described herein, there are different interconnection modes, namely i) siloxane bond with two Q-type partners (QQ homogeneous condensation), ii) siloxane bond with two T-type partners (TT homogeneous condensation), iii) siloxane bond with two D-type partners (DD homogeneous condensation), and iii) siloxane bond with different partners (QT, QD, TD, QM, TM, DM heterogeneous condensation).

[0258] The concept of heterocondensation applies to the bonding states of statistical mixtures in pure core materials and core-shell materials, respectively, and is illustrated in the following QT-type siloxane bonding equation:

[0259]

[0260] In the QT heterocondensation example above, the organically functionalized trialkoxysilane condenses from T... 0 Transform into T 1 The Q-type alkoxysilane (represented by three wavy siloxane bonds) on the left side of the reaction reacts from Q... 3 To Q 4 This indicates that each siloxane bond formed simultaneously increases DP. Q-型 and DP T-型 Clearly, there are other possible combinations of grafting reactions, for example, T... 2 Species grafting to produce T 3 and Q 3 Q 2 Up, or T 1 Species grafting to produce T 2 and Q 3 Q 2 The above and similar combinations involving D-type dicoxysiloxane moieties.

[0261] DP Q-型 DP T-型 and DP D-型 These are the key parameters defining the polymeric liquid materials described herein, along with the atomic ratio of T-type to Q-type and, optionally, the total molar content of D-type species in the material. These parameters can all be derived from the DP values ​​given above for calculating bipod silanes. T-型 Specially specified quantitative 29 The Si-NMR spectral data were determined.

[0262] For containing more than one different R 5 Materials with T-type subgroups of organically functionalized substituents, if belonging to two different R groups within the T-spectral window 5 The T-type portion of the subgroup can be fully resolved, and the quantification of the two T-type chemical species within the material can be directly derived from... 29Quantitative analysis using Si-NMR spectra is complete. Alternatively, for example, when methoxy / ethoxy R coexist in the material. 1 When a group is present, it can be obtained through 1 H- or 13 C-NMR data, such as with 29 Si-NMR data has fewer resolution limitations compared to other methods, allowing for independent analysis of different R-type subgroups. 5 .

[0263] Typically, other parameters defining the polymeric liquid materials described herein can be measured using standard analytical tools: the hydroxyl content in the material can be measured, for example, using... 29 Si- and / or 1 The molar ratio of ethoxy and methoxy-terminated alkoxy units in the material can be determined by H-NMR spectroscopy and Karl Fischer titration. 13 Obtained directly from C-NMR, and independently of 29 Si-NMR data. According to, for example, ASTM E2975-15: "Standard Test Method for Calibration of Concentric Cylindrical Rotational Viscometers," the viscosity characterization of reaction products can be easily analyzed using standardized viscosity measurements, such as cylindrical rotational viscometers. Other viscosity testing methods are also possible, such as Staudinger-type capillary viscometers or modern dynamic viscosity determination methods. Sample preparation is often related to determining the true viscosity of the polymer liquid material, as the percentage of monomer and / or solvent residues is already very low and will significantly affect the measured values. Therefore, viscosity measurements are typically performed on polymer sample materials (i.e., materials that are essentially composed of polymer materials) that have been previously purified. For example, this can be done using a thin-film evaporator device at, for example, 150°C, under vacuum (e.g., <10 °C). -1 Purification is carried out at mbar, which separates monomers and low molecular weight oligomers from the polymer liquid material itself (see Macromolecules 2006, 39, 5, 1701–1708).

[0264] To determine whether the material itself is or includes the polymeric liquid material described herein, the following exemplary analytical methods can be used. First, at 150°C and 10... -1 The sample was purified using a thin-film evaporator at a vacuum level of mbar until the change in the amount of low-molecular-weight volatiles no longer exceeded 1%. Then, it was purified by... 29 The purified material was obtained through Si NMR spectroscopy analysis. Then, the corresponding DP was calculated based on the measured spectra and the Q:T atomic ratio. Q-型 and DP T-型The value is used to determine whether they fall within the range specified herein. If so, the material comprises at least this polymeric liquid material. The natural sample can then be analyzed side-by-side prior to the thin-film evaporator purification step. If the DP between the original sample and the purified sample... Q-型 The difference in measured values ​​should be less than 5%. For rapid testing, the original sample itself should meet the requirements for polymer liquid materials as described in this article.

[0265] In a further embodiment, the polymeric liquid hyperbranched polysiloxane material according to the present invention is one in which the total content of the dual-organofunctionalized D-type siloxane and / or the total content of the tri-organofunctionalized M-type siloxane moiety is zero.

[0266] Optionally, the polymeric liquid hyperbranched polysiloxane material according to the present invention is one in which the single organic functionalized T-type siloxane moiety comprises (xi) and (xii)(xiii) or (xiv):

[0267] (xi) The first group of monoorganofunctionalized T-type alkoxy-terminated siloxane moieties, wherein R 5 It is R 5N ,

[0268] (xii) Group II of T-alkoxy-terminated siloxane moieties with mono-organofunctionalized T-type alkoxy groups, wherein R 5 It is R 5N R of the first and second groups 5 Different functional groups

[0269] (xiii) A single organic-functionalized T-alkoxy-terminated siloxane moiety, wherein R 5 It is R 5U ,

[0270] (xiv) Mono-organofunctionalized T-alkoxy-terminated siloxane moiety, wherein R 5 It is R 5S .

[0271] The above options are for customizable hydrophobic materials for combinations of (x) and (xi) and hybrid hydrophobic / functionalized materials for combinations of (x) and (xii).

[0272] For example, by combining (x) and (xi), multiple hydrophobic R can be used. 5 - Organic functionalization of T-type moieties to produce polymeric liquid materials allows for control over the material's steric accessibility and hydrophobicity, thereby controlling its solubility and compatibility with polymers, solvents, inorganic phases, and hybrid phases. For example, this allows polymeric liquid materials to be formulated for virtually any specific application, with a degree of freedom unattainable by currently commercially available silane monomers and pre-hydrolyzed systems.

[0273] For example, combinations of (x) and (xii) or (xiii) result in R with hydrophobicity and specific functionality (see feature (xii)). 5 The combination of these components then allows for customization of overall compatibility with specific application matrices, while also introducing more chemical bonding options. For example, the material exhibits two hydrophobic R... 5 Selected from feature (x), which simultaneously carries radical polymerizable groups, such as methacrylate groups (selected from feature (xii)), their interactions / compatibility can then be controlled by the hydrophobic component, and their radical crosslinking reactivity can be controlled substantially independently by the loading of said methacrylate component. By selecting the first type and loading hydrophobic R... 5 Functional groups and the selection of the second R 5 By classifying system compatibility with applications by introducing specific chemical functions, the grouping of functional groups is expected to significantly improve the performance and cost-effectiveness of silane and siloxane technologies. The advantages of this approach appear to further benefit from the core-shell architecture, with different combinations possible and individual selections depending on the application.

[0274] -R 5 As defined in feature (xii), a shell is formed within the core with a hydrophobic T-type siloxane (feature x), thus combining system compatibility with the ability to incorporate specific functions into the core. This is achieved through R... 5 - The option to replace extended functionality further greatly expands the scope of features.

[0275] - Hydrophobicity (characteristic (x)) and functionality (characteristic (xii)) R 5 Some of them are present in the shell, and they interact with each other in terms of hydrophobic / matrix compatibility adjustment and functional group density and activity.

[0276] - The hydrophobic (characteristic (x)) portion is distributed within the nucleus, while the functional (characteristic (xii)) portion is distributed within the shell.

[0277] - Involves R 5S Other combinations of (characteristic (xiii)).

[0278] For example, the advantages of the polymeric liquid materials according to the invention are that they are substantially free of silanol species (Si-OH). Specifically, their molar content 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%. Compared to conventional sol-gel based hybrid materials (e.g., prepared by hydrolysis), this provides, for example, greatly improved stability and shelf life, and significantly improved structural control. In practical applications, they can be used "as is" in nonpolar organic solvents, blends, etc., or directly incorporated into hydrophobic matrices such as polymer melts.

[0279] In another embodiment, the polymeric liquid hyperbranched polysiloxane material according to the present invention is one in which...

[0280] -If the material has at least 5 mol-% R 5 The residue is -LZ 1 and / or LY 1 Excluding -SH The polysiloxane material contains less than 750, 500, or 300 mol-ppm of rearrangement catalyst;

[0281] - The polysiloxane material contains a rearrangement catalyst ranging from 0 to 1500 mol-ppm based on the total molar silicon content present in the material; and / or

[0282] -All R in the material 5U and R 5S R is at least 1 mol-%, optionally at least 3 mol-%, optionally at least 5 mol-%, preferably at least 7 mol-%. 5S part.

[0283] The term “mol-ppm” as used in this article refers to one part per million of the total molar amount of silicon (Si) in the material (given by the sum of all Q, T, D, M type moieties and monomers).

[0284] In another aspect, the present invention relates to a hydrolysis product which can be obtained by reacting at least one polymeric liquid material described herein with a predetermined amount of water or with a predetermined amount of a water-solvent mixture, the reaction optionally being carried out in the presence of at least one surfactant.

[0285] For example, the predetermined amount of water or water-solvent mixture used for hydrolysis or emulsification is determined by upper and lower limits on the ratio of the molar amount of water to the total molar amount of Si in a typical formulation. The lower limit for the water-to-total Si molar ratio can be 0.02:1, optionally 0.1:1 or 0.5:1. The upper limit for the water-to-total Si molar ratio can be 5,000:1, optionally 500:1 or 50:1. The amount of co-solvent can be independently selected technically, without being limited by the water-to-Si molar ratio.

[0286] For example, the solvent used for hydrolysis can be selected from the group consisting of water-soluble organic solvents, such as low molecular weight alcohols, ethers, and carboxylic acids, for example:

[0287] ·Form R x Alcohols with -OH groups, where R x Choose freely from -CH3, -C2H5, -C3H7, -C4H9, -C5H 11and -C6H 13 The group formed;

[0288] ·Form R x ,R y -(C=O) ketones, where R x R y Independently select the group consisting of -CH3, -C2H5, and -C3H7;

[0289] ·Form R x Carboxylic acids of -COOH, where R x Choose freely from -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 and -C6H 13 The group formed;

[0290] • Low molecular weight organic esters, such as ethyl acetate, methyl acetate, or ethyl formate, methyl formate; and / or

[0291] ·Form R x -OR y ethers, wherein R x R y It is independently selected from the group consisting of -CH3, -C2H5 and -C3H7, or cyclic ethers such as tetrahydrofuran.

[0292] Along with solvents, acids or bases can also be used as hydrolysis / condensation catalysts. Typical acids used are mineral inorganic acids and low-molecular-weight organic carboxylic acids. Typical bases are alkali metal hydroxides, ammonia, or aliphatic / aromatic primary, secondary, or tertiary amines.

[0293] For example, surfactants used for hydrolysis and / or emulsification can be selected from the group consisting of:

[0294] • Nonionic surfactants, such as polyethylene oxide / polypropylene oxide block copolymers or similar polyether block copolymer surfactants;

[0295] • Ionic surfactants based on carboxylic acids, especially fatty acids and related saturated or unsaturated straight-chain and / or branched-chain aliphatic hydrocarbons-carboxylate salts, such as lauric acid, stearic acid, oleic acid and their corresponding alkali metal salts;

[0296] • Sulfonic or phosphonic ionic surfactants, particularly saturated or unsaturated straight-chain and / or branched aliphatic hydrocarbon sulfonates, such as dodecyl sulfonic acid (SDS) and its corresponding alkali metal salts; and / or

[0297] • Ionic surfactants based on trialkylammonium salts, such as hexadecyltrimethylammonium bromide (CTAB) or hexadecyltrimethylammonium chloride (CTAC).

[0298] On the other hand, the present invention relates to emulsions that can be obtained by emulsifying a polymeric liquid material as described herein with a predetermined amount of water, optionally in the presence of at least one surfactant.

[0299] On the other hand, the present invention relates to a method for preparing the polymer liquid material of the present invention, comprising the following steps:

[0300] - Provide polymeric liquid materials as described herein, wherein 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-% is R 5U part;

[0301] - R of polymer liquid material 5U Residue functionalization to obtain relative to all R 5U and R 5S At least 1 mol% of the residues, optionally at least 3 mol%, optionally at least 5 mol%, optionally at least 7 mol% of R 5S residues;

[0302] - To recover, optionally separate, and optionally purify polymeric liquid materials.

[0303] As this article is used to obtain R 5S Residue term modification or R 5S - Functionalization refers to the process of appropriately converting R... 5U Residues converted to R 5S Chemical reactions of residues. Suitable chemical reactions are known to those skilled in the art and are usually chosen to obtain the desired R. 5S Residues.

[0304] Suitable non-restrictive chemical reactions are listed below.

[0305] Michael addition, aza-Michael addition (e.g., amines or thiols with acrylates, alkenes, alkynes, carbonyl isocyanates, or unsaturated carbonyl compounds); reactions with acid anhydrides (e.g., amines with maleic anhydrides); reactions with acyl chlorides (e.g., amines with suitable -C(=O)Cl moieties); ring opening of epoxides (e.g., with amines, thiols, CN-, or halogens); imine formation (primary amines with ketones); substitution of thiols with haloalkanes; various nucleophilic substitutions on haloalkanes (e.g., S-...). N2) Elimination of double bonds on haloalkanes; reaction of haloalkanes with sodium azide to form alkyl azides, optionally followed by an alkyl azide reaction, for example in a click chemistry reaction (azide-alkyne cycloaddition) or by conversion to isocyanates; various functionalization reactions with diisocyanates and triisocyanates; reactions of alkenes, for example, the "thiol-alkene" reaction with thiols, electrophilic addition of halogens to alkenes, such as 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 a radical source (e.g., a radical initiator), organic and inorganic peroxides, or in the presence of aliphatic or aromatic, linear or cyclic epoxides; Friedel-Crafts alkylation or acylation of aromatic rings, such as benzene rings; or formation of peptide bonds via amines or carboxyl groups.

[0306] Those skilled in the art know which types of reactions and / or reaction conditions are compatible with the presence of (small amounts) water and / or silanol groups. They will select appropriate schemes for each synthetic step to minimize undesirable side reactions with water and / or silanol groups. Rs that are incompatible with the presence of water and / or silanol groups and must be carried out in their presence... 5S Functionalization reactions are optionally excluded from the scope of this invention. R, which is sensitive to water and / or silanol groups. 5S - Preferred options for functionalization reactions include first at T 0 Functionalization is performed on the monomer, and then T 0 Monomers are grafted onto the siloxane core, thereby via R 5S - Functionalized temporary separation avoids reactions in the presence of water and / or silanol groups.

[0307] The polymeric liquid polysiloxane material prepared by the method described herein is optional. 5S - Functionalized, for example, all R in the material 5U and R 5S The portion of at least 1 mol-%, optionally at least 3 mol-%, optionally at least 5 mol-%, optionally at least 7 mol-%, is R. 5S Part, of which R 5S Considered R 5S - Functionalization. The starting material for this method can be non-R... 5S - Functionalized (basically all R in the material) 5U and R 5S The 100 mol-% of the sum of the parts is R 5U (partial) or partial R 5S - Functionalized (all R in the material) 5U and R 5SAt least 3 mol-% of the total is R. 5U (Partial). R of the starting material 5S - Functionalization can be achieved by enabling the grafted T-type siloxane moiety to undergo R-functionalization. 5U Functionalization or optionally by further grafting to include R in the form of monomers or oligomers 5S Partial pre-R 5S - This is accomplished by functionalizing T-type silanes. R 5U Part of R 5S Functionalization can be carried out by known chemical methods. Recovery, optional separation, and optional purification of the polymeric liquid material can be performed in the context of step (g) of the following method.

[0308] On the other hand, the present invention relates to a method for preparing a polymeric liquid material as described herein, comprising the steps of: (a) providing a Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy)polysiloxane precursor,

[0309] Optional to include

[0310] (a1) Biorganofunctionalized D-siloxane moiety; and / or

[0311] (a2) Mono-organofunctionalized T-type siloxane moiety, wherein R 5 Selected from R 5N R 5U and R 5S ;

[0312] Optionally include combinations of (a1) and (a2) that are less than 12 mol-% of the total amount of all Q-type species;

[0313] Optionally further comprising a rearrangement catalyst and / or a triorganofunctionalized M-type siloxane moiety;

[0314] The precursor comprises at least 28, optionally at least 35, optionally at least 42 mol% of a quaternary combination of Q relative to the total Q-type siloxane species. 2r -Type and Q 3s,d -Type siloxane cyclic species; and / or

[0315] The precursor contains relative to all Q. 3 A quaternary combination of at least 60%, optionally at least 67%, and optionally at least 75% of a type-1 siloxane species. 3s,3d -Type siloxane cyclic species; and

[0316] The degree of polymerization (DP) of Q-type polysiloxanes Q-型 Within the range of 1.5 to 2.5, optionally 1.6 to 2.4, or optionally 1.65 to 2.35;

[0317] (b) Add at least one

[0318] (b1) Triorganofunctionalized M-type silane Si(OR) 1 (Me)3; and / or

[0319] (b2) Bi-organofunctionalized D-type silane Si(OR) 1 )2(R 2 (R) 3 ); and / or

[0320] (b3) Single-organic functionalized T-type silane Si(OR) 1 )3(R 5 ), where R 5 Selected from R 5N R 5U and R 5S ;

[0321] In the form of monomers or oligomers of (a) polysiloxane;

[0322] (c) Optionally, a rearrangement catalyst may be added to the mixture from step (b);

[0323] (d) Heating the mixture from (c), optionally without water:

[0324] (e) Optionally repeat steps (b) through (d) at least once;

[0325] (f) Optionally, make the R of the polymer liquid material 5U Residue functionalization to obtain relative to all R 5U and R 5S At least 1 mol% of the residues, optionally at least 3 mol%, optionally at least 5 mol%, optionally at least 7 mol% of R 5S residues;

[0326] (g) Recovery, optional separation, and optional purification of polymeric liquid materials;

[0327] The condition is that at least one of steps (a2) or (b3) is performed, and

[0328] The condition is that the rearrangement catalyst is present in at least one of steps (a) or (c).

[0329] The Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy)polysiloxane precursor in step (a) can be any, for example, commercially available Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy)polysiloxane, as long as it contains the non-organic functionalized Q as defined herein for polysiloxane materials. 1-To Q 4 The Q-type siloxane moiety, wherein at least 28, optionally at least 35, optionally at least 42 mol-% of all Q-type species are quaternary Q-type species. 2 -Type and Q 3 Part of a type siloxane cyclic species (including monocyclic and bicyclic), and / or all of which Q 3 At least 60%, optionally at least 67%, optionally at least 75% of the type-1 species are quaternary Q. 3s,3d Part of the Q-type siloxane ring, and only if the degree of polymerization DP of the Q-type polysiloxane is... Q-型 Within the range of 1.5 to 2.5, optionally 1.5 to 2.7, and optionally 1.7 to 2.4. In the context of this method, the quaternary Q... 3 -Type siloxane cyclic species are those Q 3 Q-type siloxane species, which are part of one or two four-membered rings, respectively. In the context of this method, the term "all Q-type species" includes all Q... 1 To Q 4 Siloxane species and Q 0 Silane monomers.

[0330] The Q-type polymethoxy, polyethoxy, polypropoxy, or mixed (methoxy / ethoxy / propoxy)polysiloxane of step (a) constitutes the precursor material as described herein. If a core-shell structure is targeted, a pure Q-type precursor material is typically used as the core. Typical and exemplary Q-type precursor materials are provided. 29 Si NMR spectrum as follows Figure 3 As shown in the upper part, a large number of Q values ​​are displayed. 2r and Q 3s,d Tetrasiloxane cyclic species. After grafting with T-type monomeric silanes, the number of cyclic species is significantly reduced, such as... Figure 3 As shown in the lower part.

[0331] For example, the following Q-type polymethoxy, polyethoxy, or mixed poly(methoxy / ethoxy)polysiloxanes can be used in step (a): commercial oligomers of TEOS or TMOS, such as tetraethyl orthosilicates with a total SiO2 equivalent content of 40%, such as Dynasylan40 (Evonik Industries), Wacker Silicate TES 40WN (Wacker), TEOS-40 (Momentive), or simply "ethylsilicate-40" as many non-branded Asian suppliers. Additionally, oligomers with higher silicate content, such as Dynasylan Silbond 50, or equivalent products with up to 50% equivalent SiO2 solids content, can be used. The same applies to TMOS oligomers, such as "tetramethoxysilane, oligomer hydrolysate" (Gelest Inc.) or "MKC silicate" (Mitsubishi Chemicals), which vary with a SiO2 equivalent content of up to 59% and can be used as a source of methylsilicates. If commercially available, similar propoxysilicates may also be used.

[0332] Alternatively, the Q-type polymethoxy, polyethoxy, polypropoxy, or mixed poly(methoxy / ethoxy / propoxy)polysiloxane of step (a) can be synthesized according to schemes known in the art, including hydrolytic and non-hydrolytic methods, for example as described in the following examples in WO 2019 / 234062 A1, EP1576035 B1, Macromolecules 2006, 39, 5, 1701-1708, Macromol.Chem.Phys.2003, 204(7), 1014-1026, or Doklady Chem., Vol.349, 1996, 190-19.

[0333] The triorganofunctionalized M-type silane Si(OR) in the context of this method 1 (Me)3, Bi-organofunctionalized D-type siloxane moiety Si(OR) 1 )2(R 2 (R) 3 ) and single-organofunctionalized T-type siloxane moiety Si(OR) 1 )3(R 5 The definition of chemical substitutes corresponds to the definition given in the context of polysiloxane materials described herein.

[0334] As used herein, the term "monomer or oligomer form" refers to M-, D-, and T-type silanes that are not highly polymerized when used as precursors, i.e., monomers or small oligomers, for example, common mixtures having fewer than ten monomer units in typical oligomers.

[0335] The rearrangement catalyst used in this method can be any catalyst that accelerates the grafting of T-, D-, and M-type monomers or oligomers via nucleophilic substitution to produce the polymeric liquid material described herein. Based on the total molar silicon content in the prepared material, the catalyst concentration is typically in the range of 0.01 mol-% to 1.5 mol-%. The catalyst may be present in step (a) or (c), or both, provided that it is present in at least one of step (a) or (c).

[0336] In a further embodiment, a group or transition metal salt or organometallic compound or an organic (e.g., aliphatic amine or aminosilane) or inorganic base is used as a rearrangement catalyst.

[0337] The rearrangement catalysts used herein can be definitively identified, for example, by following the scheme of Example 4. For the MTES model compound defined in the scheme of Example 4, any catalyst capable of initiating at least 75% of the T... 0 Grafting (less than 25% residual T) 0 The catalysts (monomers) are all rearrangement catalysts used in this invention.

[0338] The catalyst used in this method can be selected from a group of compounds having the summative formula.

[0339] M(II)L1L2 is used for metal ions in the +2 oxidation state, such as Zn. +2 or Fe +2

[0340] M(III)L1L2L3 or O=M(III)L1 is used for metal ions in the +3 oxidation state, such as Ce. +3 or Fe +3

[0341] M(IV)L1L2L3L4 or O=M(IV)L1L2 is used for metal ions in the +4 oxidation state, such as Ti. +4 or Hf +4

[0342] M(V)L1L2L3L4L5 or O=M(V)L1L2L3 is used for metal ions in the +5 oxidation state, such as V +5 or Nb +5

[0343] Where M(ll,III,IV,IV) are main group or transition metal ions in oxidation states +2 to +5 and are bonded to the same or different coordination counter ions and / or ligands L1 to L5 via covalent, ionic, or coordinate bonds or combinations thereof, wherein at least one of these ligands is selected from the halide group (e.g., F). - Cl - ,Br - I- ), pseudohalogenates (e.g., SCN) - N3 - CN - ), sulfides, inorganic acid counterions, organic carboxylates, organic alcohols, acetylacetonates, organic sulfonic acids or phosphonic acid counterions, wherein preferably main group or transition metal ions are selected from elements in naturally occurring oxidation states such as Fe, Al, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Zn, Ce, Co, Fe and Mn.

[0344] The phrase "in the absence of water" as described in step d) optionally does not apply to reactions, such as grafting and / or rearrangement reactions with triorganofunctionalized M-type silanes as defined in this method. In this method, the reaction steps with triorganofunctionalized M-type silanes can be carried out in the presence of water, for example, in the presence of aqueous acid / cosolvent mixtures commonly used in the art (e.g., EtOH, water, ketones, etc.). Optionally, M-type silane grafting is time-separated from D-type and / or T-type grafting, occurring before or after the grafting.

[0345] In order to allow for sufficiently fast kinetics to produce a reasonable reaction time, at least in step (d), and optionally in steps (b) through (e) as described herein, it is generally necessary to use elevated temperatures in conjunction with a catalyst.

[0346] Each reaction step can take, for example, from half an hour to several hours or days, depending on the type and concentration of the rearrangement catalyst used. Alternatively, if a radio frequency assisted heating method is used, the reaction time can be significantly shortened.

[0347] All steps (b) through (f) are optionally carried out under stirring. After the addition of M-, D-, or T-type silane, stirring may optionally continue for at least 30 minutes in steps d) and / or (f).

[0348] For example, during steps (d) and / or (f), if the reaction is carried out in the absence of water, the overall degree of polymerization remains substantially constant. As described herein, the degree of polymerization always refers to the degree of polymerization of the siloxane material.

[0349] Optionally, in steps (d) and / or (f), low-molecular-weight reaction products and / or residual starting materials in the reaction mixture can be removed by vacuum distillation, for example by gradually reducing the pressure within the reaction vessel and maintaining the final pressure for a period of time, for example, between about 5 and 250 mbar, such as between 2 and 60 minutes. Optionally, residual volatile organic compounds, solvent residues, and / or low-molecular-weight starting products (VOCs) can be further removed at any stage of the post-treatment process by bubbling purge gas through the reaction mixture, preferably still warm or hot.

[0350] For example, each step (a) to (e) of this method is carried out substantially in the absence of any chemical reagents and / or any chemical reagents other than the rearrangement catalyst used to promote polymerization and / or grafting reactions. For example, all steps (a) to (e) are carried out substantially in the absence of acetic anhydride, acetic acid or other acid anhydrides or aliphatic or aromatic carboxylic acids or water, optionally in the absence of chlorosilanes, chlorosiloxanes, acetoxysilanes or acetoxysiloxanes. “Substantially absent” means that trace or catalytic amounts of the aforementioned substances may be present; however, “substantially absent” means that the amount is insufficient to promote a detectable or significant polymerization reaction by these substances.

[0351] Not wanting to be bound by theory, it is believed that the driving force for this substitution reaction (also known as "grafting") in step (d) comes at least largely from the quaternary Q-type material in step (a). 2 -type and / or Q 3 Ring strain of type-1 siloxane cyclic species. The release of ring strain in the Q-type precursor or core material is sufficient to effectively add (i.e., graft) M-, D-, and / or T-type silanes onto the Q-type core material without the need for further chemical reagents such as acetic anhydride. Optionally, a rearrangement catalyst as defined herein is also not required if the reaction temperature and duration are adjusted accordingly. As can be seen in the following examples, the mol-% of cyclic species in the material of step (a) is significantly reduced in the product according to this preparation method. As an example of a typical grafting reaction, Figure 3 (Below) shows the use of polyethoxysiloxane Q-type precursor ( Figure 3 (above) and the reaction products following a typical example of MTES rearrangement as a monomeric T-type precursor. By direct comparison, it is noted that the grafted products are characterized by Q... 2r and Q 3s Q 3d The significant reduction in tetrasiloxane cyclic species and Q 0 The increase in monomers is likely due to partial Q-type depolymerization. Simultaneously, the linear Q-type portion (Q...) 2l and Q 3l The proportion of ) has increased significantly. Figure 4 This demonstrates Q during a typical rearrangement grafting reaction. 2r and Q 3s,d The time decay of tetrasiloxane species (denoted as (Q)) 2r +Q 3s,d ) / Q tot (in%).

[0352] The condition for performing at least one of steps (a2) or (b3) is that the product of this method is a polymeric liquid polysiloxane material as described herein, which contains a mono-organofunctionalized T-type siloxane moiety as described herein. Therefore, in at least one step of the method of the present invention, Si(OR) must be added in the form of a monomer or oligomer. 1 )3(R 5 The T-type silane. This is synonymous with saying that the product must contain a T-type component.

[0353] When step (e) is optionally performed, the repetition of step (b) includes the addition of material during that step or further repetitions that is not necessarily the same material as in previously performed steps. For example, if for the first execution of step (b3), R 5 Select R 5U Then, when repeating step (b3), R can be used. 5 Select R 5U R 5S R 5N Or any combination thereof. This also applies to all other recurring steps, such as whether to add M-, D-, or T-type silanes and / or which type of R... 1 R 2 and R 3 And the type and amount of catalyst added during the repetition process.

[0354] For the monoorganofunctionalized T-type siloxane moiety and silane in steps (a2) and (b3), R 5 Selected from R 5N R 5U and R 5S This means that T-type siloxane moiety / silane can be non-R 5S - Functionalized (basically all T-type siloxane portions / all R-type silanes in the material) 5U Part of 100 mol-% is R 5N or R 5U Partial), complete R 5S - Functionalized (basically all T-type siloxane portions / all R-type silanes in the material) 5U and R 5S The 100 mol-% of the sum of the parts is R 5S (partial) or partial R 5S - Functionalized (T-type siloxane moiety / silane containing R in any possible proportion) 5S and R 5U and / or R 5N (Partial). Optionally, the R of the monoorganofunctionalized T-type siloxane moiety in step (a2) of this method. 5 For R 5N or R5U .

[0355] For example, if the T-type siloxane moiety of steps (a2) and / or (b3) is selected and the silane is optionally selected such that all R in the product of the method are present without step (f). 5U and R 5S The portion of at least 1 mol-%, optionally at least 3 mol-%, optionally at least 5 mol-%, optionally at least 7 mol-%, is R. 5S Partially, then regarding R 5U Functionalization of residues is non-mandatory, and step (f) is optional. Of course, for example, even if the T-type siloxane moiety and silane of steps (a2) and / or (b3) have already been generated, all R residues in the material may be optional. 5U and R 5S At least 1 mol-% of the sum of the parts is R 5S The product, step (f) can be performed, for example, by functionalizing R. 5 Mole percentage of residues.

[0356] Optionally, step (f) can also be performed between steps (d) and (e), and the order of steps (e) and (f) can optionally be interchanged.

[0357] In a further implementation, the method described herein is one in which...

[0358] - In step (a), the R of the T-type siloxane moiety 5 For R 5N and / or R 5U ;

[0359] - In step (b), the R of the T-type silane 5 For R 5N and / or R 5U ;as well as

[0360] - The method includes step (f) causing the polymer liquid material R 5U Residue functionalization to obtain relative to all R 5U and R 5S At least 1 mol% of the residues, optionally at least 3 mol%, optionally at least 5 mol%, optionally at least 7 mol% of R 5S Residues.

[0361] In another implementation, the method described herein is one in which...

[0362] - In step (a), the R of the T-type siloxane moiety 5 For R 5U ;

[0363] - In step (b), at least one T-type silane's R 5 For R 5S In optional step (e), the R of the T-type silane 5 Selected from R 5U and R 5S ,as well as

[0364] - This method may optionally exclude step (f).

[0365] In R 5 In the context of this section, any arrangement of starting materials and further functionalization reactions is routinely implemented within the capabilities of those skilled in the art.

[0366] R 5S The concept of variability in functionalization schemes can be illustrated through NMR spectroscopy studies, in which reactants and products are first analyzed by... 1 H and 13 Identification by C NMR spectroscopy. R 5S The degree of functionalization can then be assessed through standard spectral interpretation / reaction monitoring, as this is a standard procedure in preparative organic chemistry.

[0367] The product of this method is recovered in step (g) by collecting material from the reaction vessel. The product can optionally be separated and purified by standard methods known in the art, such as by distillation, optionally using a thin-film evaporator, or by stripping with a purge gas to remove VOCs, etc.

[0368] In one embodiment, the method herein further includes, before step (b) or after step (d) or (e), the addition of a triorganofunctionalized M-type silane or M-type siloxane and optionally a diorganofunctionalized D-type silane in the form of a monomer or oligomer as described in step (b2) in the presence of water, a suitable co-solvent, and an acid catalyst, followed by heating the mixture, optionally under reflux. If the addition is performed before step (b), any residual water (if any) and optionally alcohols or other co-solvents are removed before the start of step (b).

[0369] For example, the solvent used to add a triorganofunctionalized M-type silane and / or optionally a diorganofunctionalized 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, and diethyl ether.

[0370] For example, the acid catalyst can be selected from strong acids with negative pKa values, preferably from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, hydrobromic acid or hydroiodic acid or organic sulfonic acids (methanesulfonic acid, amide sulfonic acid or benzenesulfonic acid).

[0371] In another embodiment, the reaction temperature of steps (c) to (e) of the method described herein is in the range of 30 to 170, optionally 50 to 150, or 70 to 120°C, and the pressure during steps (c) to (e) is in the range of 0.1 bar to 2 bar, optionally in the range of 0.5 bar to 1.4 bar, or in the range of 0.6 bar to 1.2 bar.

[0372] The optional functionalization step (f) does not necessarily have to be carried out at an elevated temperature, even if it occurs before step (e). Which type of R in step (f)... 5S The required reaction temperature for functionalization reactions is common knowledge.

[0373] In a further embodiment, the rearrangement catalyst used in this method is selected from the group consisting of:

[0374] -Ti(IV)(OR 13 )4 and Zr(IV)(OR 13 4;

[0375] -Ti(IV)X4 and Zr(IV)X4;

[0376] -O=Ti(IV)X2 and O=Zr(IV)X2;

[0377] -Ti(IV)X2(OR 13 )2 and Zr(IV)X2(OR 13 )2;

[0378] -Ti(IV)X2(OAcAc)2 and Zr(IV)X2(OAcAc)2;

[0379] -Ti(IV)(OSi(CH3)3)4 and Zr(IV)(OSi(CH3)3)4;

[0380] -(R 13 O)2Ti(IV)(OAcAc)2 and (R 13 O)2Zr(IV)(OAcAc)2;

[0381] -O=Ti(IV)(OAcAc)2 and O=Zr(IV)(OAcAc)2;

[0382] -Ti(IV)(OAc)4 and Zr(IV)(OAc)4;

[0383] -Ti(IV)(OAc)2(OR 13 )2 and Zr(IV)(OAc)2(OR 13 )2; and

[0384] -O=Ti(IV)(OAc)2 and O=Zr(IV)(OAc)2;

[0385] Where R 13 The catalyst is selected from the group consisting of -CH3, -CH2CH3, -CH(CH3)2, -CH2CH2CH3, -C(CH3)3, -CH2CH2CH2CH3 and CH2CH2CH(CH3)2, wherein X is a halide, pseudohalide, nitrate, chlorate or perchlorate anion, and wherein the amount of catalyst in each step (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 silicon content present in the step.

[0386] In another respect, the present invention relates to products that are obtained or available by any of the methods described herein.

[0387] On the other hand, the present invention relates to the use of the polymeric liquid material described herein as a crosslinking agent in a formulation, the polymeric liquid material comprising at least one group having R 5 The T-type siloxane moiety, R 5 The free radical polymerizable organic functional residues are selected from vinyl groups, methacrylates, butyl acrylates, and acrylates.

[0388] The composition group contains polymer liquid material in the range of 0.2% to 25% by weight of the formulation.

[0389] As used herein, the term "formulation" refers to any product containing the polymeric liquid material described herein, for example, as a crosslinking agent or any other functional entity. The formulation may be a liquid, paste, emulsion, or slurry. Such formulations typically contain, for example, other compatible radical-polymerizable monomers, oligomers or prepolymers or silane-terminated polymeric structural unit portions, fillers, and performance- or lifetime-enhancing additives and stabilizers, such as UV and light stabilizers, antioxidants, rheology modifiers, viscosity modifiers, film-forming additives, gloss additives, antistatic agents, nucleating agents, etc. If thermally activated, such formulations typically also contain, for example, radical initiator molecules selected to meet the designed curing initiation temperature.

[0390] In another aspect, the present invention relates to the use of the polymeric liquid materials, hydrolysates, or emulsions described herein in hydrophobic formulations, wherein the polymeric liquid materials, hydrolysates, or emulsions comprise at least one group having an organic functional group of type R. 5The T-alkoxy-terminated siloxane moiety, wherein the organic functional group is selected from methyl, ethyl, vinyl, methacrylate, n-propyl, isopropyl, n-butyl, tert-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 polymer liquid, hydrolysate or emulsion is loaded in the formulation at an amount of 0.5% to 25% by weight.

[0391] The following figures and examples are for illustrative purposes only and are not intended to limit the scope of the invention as set forth in the appended claims. Attached Figure Description

[0392] Figure 1 shows an exemplary two-dimensional molecular structure representation of a typical pure Q-type polyalkoxysilane material described herein, in which two different DPs Q-型 The value has a universal R 1 Substituents are used to illustrate that the surface-to-volume ratio depends on its size or more specifically on DP. Q-型 Value. In Figure 1a The image shows a typical Q-type precursor, characterized by a cyclic species with 20 silicon atoms, and DP... Q-型 With a value of 2.25 and 1.5 available alkoxy groups (circles) per Si atom, T-type silane moieties can be grafted onto them. Figure 1b The image shows a Q-type condensation polymer with 7 silicon atoms and DP. Q-型 With a value of 1.57 and 2.14 available alkoxy groups (circles) per Si atom, T-type silane moieties can be grafted onto them. This indicates... Figure 1b The surface-to-volume ratio of the medium structure is much higher, and full functionalization would require a significantly higher T:Q molar ratio, thus disqualifying it from being a direct precursor for the materials described herein. Furthermore, in Figure 1b In the case shown, the dendritic "macromonomer" aspect (the number of graftable sites per molecule) is significantly smaller.

[0393] Figure 2 shows an exemplary two-dimensional molecular structure representation of the typical material described herein, which is based solely on a pure Q-type precursor material. Figure 2a The image shows a grafted material containing M, D, and T portions with R... 5U R 5S But without R 5N Sensitivity. In Figure 2b The text shows only R. 11 Functionalization R 5S Glycidyl oxypropyl T-type grafted polymer liquid material, R 1The residues are composed of ethoxy and methoxy groups. Figure 2c The image shows a grafted polymer liquid material containing two T-types, namely R... 10 Functionalization R 5S aminopropyl and nonfunctionalized R 5N propyl moiety, R 1 The residues consist of ethoxy and methoxy groups. These representations are for illustrative purposes only and do not represent an indication of further T(R) 5N R 5S and R 5U Any restrictions on D, M-type grafting and functionalization combinations.

[0394] Figure 3 The effect of rearrangement grafting on the content of tetrasiloxane ring species is shown. Upper part of polyethyl silicate Q-type precursor material. 29 The Si NMR spectrum showed abundant Q 2r and Q3 s,d Tetrasiloxane cyclic species. Lower part 29 Si NMR spectroscopy revealed the peak assignments of the corresponding Q- and T-type moieties in the material prepared by grafting this precise polyethyl silicate Q-type precursor with a Ti(IV)-catalyzed rearrangement of a single triethoxysilane monomer T-type precursor. The Q-type moieties contained in the product are clearly visible. 2r and Q3 s,d The number of tetrasiloxane cyclic species is far less than that of the Q-type precursor materials used to produce this product. Specifically, most of the Q-type precursors are... 2r The species has been transformed into Q 2l And most Q 3d and some Q 3s Tetrasiloxane cyclic species have disappeared and have been linearized by Q. 3l Species replacement, which may be a result of rearrangement grafting reactions.

[0395] Figure 4 It shows time-dependent 29 Analysis of Si NMR data showed that during the model grafting reaction of MTES on Q-type model precursor compounds, the percentage (Q) was [missing information]. 2r &Q 3s,d The cyclic species indicator, as an example, disappears with increasing reaction time. During heat treatment in the presence of a rearrangement catalyst, the disappearance of the cyclic species occurs simultaneously with the grafting of the monomeric T-type model silane compound onto the Q-type precursor.

[0396] Example

[0397] In all examples, the molar percentage of (tetrasiloxane) cyclic species refers to all Q species relative to the total number of Q species. 2 and Q 3The sum of cyclic species, also referred to in this paper as % (Q 2r &Q 3s,d ) Ring species, unless otherwise specified.

[0398] In all examples, the molar percentage of (tetrasiloxane) cyclic species refers to all Q species relative to the total number of Q species. 2 and Q 3 The sum of cyclic species, also referred to in this paper as % (Q 2r &Q 3s,d ) Ring species, unless otherwise specified. Example structure is as follows:

[0399] Example 1 describes non-R 5S - Functionalization (i.e., containing R) 5N and R 5U The selected preparation scheme for the liquid material.

[0400] Example 2 describes the preparation of R 5S - Selected examples of functionalized materials. Through 1 H and 13 C10 NMR spectroscopy confirmed that R 5S Modification.

[0401] Example 3 illustrates DP through a simple test. Q-型 The effect of the atomic T:Q ratio on application-related properties.

[0402] Example 1a: Having n Q-型 :(n T-型 Synthesis of TEOS condensate / (PTES+N3-PTES) condensate material with a ratio of 1:(0.05+0.08)

[0403] 334 g of a product with DP was prepared by non-hydrolytic condensation of tetraethoxysilane (TEOS) and acetic anhydride in the presence of a titanium (IV) isopropoxy rearrangement catalyst (1250 ppm, present in the Q-type precursor). Q-型 The Q-type precursor, containing 2.17% and 44.7% cyclic species, along with 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), was placed in a 1 L round-bottom flask equipped with a reflux condenser. No further rearrangement catalyst was added after this. The mixture was heated to 124 °C and stirred for 9 hours, during which any residual volatiles were removed by applying a 250 mbar vacuum for 5 minutes. 29 Si NMR analysis confirmed that the product contained less than 8.2% total T. 0 Monomers (measured by total T-type fractions) and less than 29.2% of Q-type tetrasiloxane cyclic species.

[0404] Example 1b: Having n Q-型 :(n T-型 ) = 1:(0.08+0.11) non-R 5S Synthesis of functionalized ethyl silicate condensate / (PTES+OTES) condensate materials

[0405] The material was prepared using the same synthetic steps as in Example 1a above, except that i) the Q-type precursor was prepared by hydrolysis of a commercially available tetraethyl orthosilicate oligomer (Wacker silicate TES 40WN), ii) 1100 ppm O=Zr(IV)(OAcAc)2 was used as a catalyst instead of titanium(IV) isopropoxy for the rearrangement grafting of the T-type precursor, and iii) the two nonfunctionalized R-type precursors used in the rearrangement process were changed. 5N The quantity and type of T-type silanes (PTES-propyltriethoxysilane and OTES-n-octyltriethoxysilane) were determined, and the reaction time was 12 h. 29 Si NMR analysis confirmed that the product contained less than 13.5% total T. 0 - Monomers (measured by total T-type fractions) and less than 24.8% of Q-type tetrasiloxane cyclic species.

[0406] Example 1c: with n Q-型 :(n T-型 ) = 1:(0.03+0.15) non-R 5S Synthesis of functionalized ethyl silicate condensate / (PTES+APTMS) condensate materials

[0407] The material was prepared using the exact same synthetic steps as in Example 1b above, the only difference being the addition of 250 ppm Ti(OEt)4 as a catalyst for the rearrangement grafting of the T-type precursor, the change in quantity, and the replacement of OTES with a functionalized R-type precursor (APTMS-aminopropyltrimethoxysilane). 5U type. 29 Si NMR analysis confirmed that the product contained less than 6.1% total T. 0 - Monomers (measured by total T-type fractions) and less than 23.8% of Q-type tetrasiloxane cyclic species.

[0408] Example 1d: with n Q-型 :(n T-型 ) = 1:(0.05+0.15) non-R 5S Synthesis of functionalized methylsilicate condensate / (oligoVTES+APTMS) condensate materials

[0409] The material was prepared using the exact same synthetic steps as the 1g example described above, except that the Q-type precursor was prepared from DP. Q-型 A methylsilicate precursor was prepared from tetramethoxysilane (TMOS) with a value of 1.94, and the first T-type precursor VTES was added in oligomeric form (oligoVTES). 29 SiNM analysis confirmed that the product contained less than 13% total T. 0 - Monomers (measured by total T-type fractions) and less than 25.7% of Q-type tetrasiloxane cyclic species.

[0410] Example 1e: Having n Q-型 :(n T-型 )=1:(0.22) of non-R 5S Synthesis of functionalized methylsilicate condensate / (VTES) condensate materials

[0411] The material was prepared using the exact same synthesis steps as in Example 1c above, except that the VTES T-type precursor was added in monomer form and APTMS was not used. 29 Si NMR analysis confirmed that the product contained less than 13% total T. 0 - Monomers (measured by total amount of T-type moiety), and less than 25.3% of Q-type tetrasiloxane cyclic species.

[0412] Example 1f: with n Q-型 :(n T-型 )=1:(0.15) of non-R 5S Synthesis of Functionalized TEOS & TMOS / SH-PTMS Condensate Materials

[0413] 4 mol of DP-containing material was prepared by hydrolysis-condensation. Q-型 A mixture of 2.19 g (66% TMOS / 33% TEOS) of Q-type precursor and 51.0% of Q-type tetrasiloxane was mixed with 117.8 g / 0.6 mol mercaptopropyltrimethoxysilane (SH-PTMS) as a T-type precursor. Then, 670 ppm of titanium(IV) isopropoxy was added to a glass reactor, and the mixture was reheated to 115 °C and stirred for 17 hours. At this point, the heat source was removed, and the product was separated. 29 Si NMR analysis confirmed that the product contained less than 8.3% total T. 0 - Monomer (measured by total T-type moiety), and less than 22% of Q-type tetrasiloxane cyclic species and less than 44.8% of (Q) 3s,d ) / Q 3 Ring species.

[0414] Example 1g: has n Q-型 :(nT-型 :n D-型 The non-R of ) = 1:(0.03+0.15:0.05) 5S Synthesis of functionalized TEOS / (PhTES+APTMS:DPhDES) condensate materials

[0415] A Q-type precursor, prepared by controlled hydrolysis of TEOS containing 4.5 mol Si equivalents, was injected into a sealed stirred glass reactor (Büchi versoclave, 1l) set to 105 °C. Next, 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 aminopropyltrimethoxysilane (PTMS), along with 56.2 g / 0.23 mol of the D-type precursor diphenyldimethoxysilane (DPhDMS) and a titanium(IV)-methanol salt as a catalyst, were injected into a hot autoclave. The mixture was maintained at this temperature with stirring for 29 hours, then removed from the heat source and cooled to room temperature. 29 Si NMR analysis confirmed that the product contained less than 16% T. 0 - Monomers and less than 11% D 0 - Monomers (measured by total amount of T-type and D-type moieties), and less than 22.7% of Q-type tetrasiloxane cyclic species.

[0416] Example 2a: Preparation of R based on the material prepared according to Example 1a 5S Functionalized materials

[0417] The material prepared according to Example 1a undergoes R-reaction on its azide (L-N3) group by reacting directly "on polysiloxane" with a mixture of alkynylated polypropylene glycol (A-PPG) and cyclically substituted alkyne difluorinated cyclooctylene (DIFO). 5S Functionalization leads to partial -L'-Y 2 Functionalization. A-PPG materials were first prepared by reacting 450 g / mol PPG with alkynes in the presence of SO₂F₂ in a system with DMSO as the solvent / activator. Equimolar amounts of A-PPG and DIFO were used in the presence of a Cu catalyst at a total alkyne to azide ratio of 0.82:1, resulting in partial substitution, with NMR analysis confirming a yield of 58%.

[0418] Example 2b: Preparation of R based on the material prepared according to Example 1b 5S Functionalized materials

[0419] The R-containing material prepared according to Example 1b 5N And does not contain functionalizable R 5U The material of the group was previously prepared with functionalized T0 The "T" of the monomer 0 Functionalization was achieved through grafting. The functionalized monomer was prepared by refluxing 2-hydroxyacetophenone with aminopropyltriethoxysilane (APTES) in methanol for 3 hours and removing the MeOH solvent by distillation. Then, the functionalized T... 0 The monomers were rearranged and grafted onto the material prepared according to Example 1b at 100°C for 32 hours.

[0420] Example 2c: Preparation of R based on the material prepared according to Example 1c 5S Functionalized materials

[0421] The material prepared according to Example 1c undergoes R on its amino group (L-NH2) by reacting directly "on the polysiloxane" with triacrylate (trimethylolpropane triacrylate-TMPTA). 5S Functionalization leads to complete -L'-Y 1 Functionalization. A 2:1 molar ratio (50% molar excess TMPTA) based on the effective ratio of amine protons to acrylate groups was used. The reaction was carried out at room temperature for 24 hours, and the product was confirmed by NMR.

[0422] Example 2d: Preparation of R based on the material prepared according to Example 1d 5S Functionalized materials

[0423] The material prepared according to Example 1d was subjected to R-polymerization on its vinyl (-CH=CH2) groups via direct "on polysiloxane" free radical polymerization in a gel emulsion containing a low concentration of the polymer precursor methyl methacrylate (MMA). 5S Functionalization leads to the use of oligomeric hybrid PMMA for -Y 3 Functionalization. A 6:1 molar ratio of vinyl groups to MMA precursors was used, and the reaction was initiated by a photoinitiator and a 365 nm UV light source. The reaction products were identified and confirmed by NMR analysis.

[0424] Example 2e: Preparation of R based on the material prepared according to Example 1f 5S Functionalized materials

[0425] The material prepared according to Example 1f was modified by direct "on polysiloxane" with isocyanate (methylene diphenyl diisocyanate-MDI) to R-modify its mercapto (-L-SH) groups. 5S Functionalization leads to the use of grafted MDI units for L'-Y 1 Isocyanate (R) 10b (X=N) functionalization. A thiol group was reacted with MDI reagent at a molar ratio of 1:2.38 at 0°C with stirring overnight. The reaction product was identified and confirmed by NMR analysis.

[0426] Example 2f: Preparation of R based on the material prepared according to Example 1g 5S Functionalized materials

[0427] The material prepared according to Example 1g was modified by direct "on polysiloxane" with an epoxide precursor (bisphenol F diglycidyl ether - BFDGE) to R-modify its amino group (-L-NH2). 5S Functionalization leads to the use of grafted BFDGE units for L'-Y 1 Epoxy (R) 10d Functionalization. The reaction was carried out overnight at 80°C using 1% dimethylbenzylamine catalyst at a molar ratio of 1:2 based on the effective amine proton to BFDGE molar ratio. The reaction products were identified and confirmed by NMR analysis.

[0428] Example 2g: R prepared using the preparation method described in Example 1g 5U Preparation of polysiloxane materials R 5S Functionalized materials

[0429] The material was first prepared using the same protocol as in Example 1g, but using 3-(2-aminoethylamino)propyltrimethoxysilane (AEAPTMS) (a mixed T-type amine containing secondary and primary amines). 0 The precursor was used instead of APTMS, and the T:Q molar ratio of the aminotrimethoxysilane was 0.11:1 instead of the previously used 0.15:1 during the grafting process. Then, the material was modified directly "on the polysiloxane" using the same epoxide precursor (bisphenol F diglycidyl ether - BFDGE) to R-modify its amino (-L-NH-(CH2)2-NH2) groups. 5S Functionalization led to the use of grafted BFDGE units for epoxy (R) production. 10d Functionalization. The reaction was carried out overnight at 80°C using 1% dimethylbenzylamine catalyst at a molar ratio of 1:1.5 based on the effective amine proton to BFDGE molar ratio. The reaction products were identified and confirmed by NMR analysis.

[0430] Example 2h: R based on the material prepared according to Example 1g 5S Replacement preparation of functionalized materials

[0431] The material prepared according to Example 1g was modified by direct "on polysiloxane" with chlorine (aromatic halogenation) in the presence of an AlCl3 catalyst, thereby modifying its phenyl (Y) 3 –R 8 R on the group 5S Functionalization to produce Y 3 (R 8 Functionalization on phenyl groups.

[0432] Example 2i: R based on the material prepared according to Example 1g 5S Improved preparation of functionalized materials

[0433] The same material as described above was prepared by the following steps: First, trichlorophenylsilane was chlorinated using Cl2 and AlCl3 catalysts to produce (p-chlorophenyl)trichlorosilane, which was then purified by distillation, but this time a more suitable "T" was used. 0 The "grafting" method was used. (p-chlorophenyl)trichlorosilane was then converted to (p-chlorophenyl)trimethoxysilane by quenching and separation in methanol. The resulting (p-chlorophenyl)trichlorosilane was then grafted together with phenyltrimethoxysilane (PhTMS) in the desired amount, using the same method as described in Example 1g, to produce the desired degree of Y. 3 (R 8 Functionalization on phenyl groups.

[0434] Example 2j: R based on the material prepared according to Example 1f 5S Replacement preparation of functionalized materials

[0435] The material prepared according to Example 1f was modified by direct "on polysiloxane" with an epoxy precursor (bisphenol A diglycidyl ether -BADGE) to R-modify its thiol (-L-SH) groups. 5S Functionalization leads to the use of grafted BADGE units for L'-Y 1 Epoxy (R) 10d Functionalization. A 1:4 molar ratio of mercapto(-SH) with BADGE was used, and the reaction was carried out overnight at 90°C with 0.5% dimethylbenzylamine catalyst. The reaction products were identified and confirmed by NMR analysis.

[0436] Example 2k: Preparation of R based on the material prepared according to Example 1e 5S Functionalized materials

[0437] The material prepared according to Example 1e is processed via the functionalization of T-monomers using the "T" method. 0 "Grafting" for R 5S Functionalization of the T-monomer was achieved by reacting aminopropyltriethoxysilane (APTES) with pyromellitic dianhydride (PDA) at a molar ratio of 1:0.62 (amine protons to PDA). In a second step (90°C, 35 hours), the reaction mixture was subjected to T-reaction on top of the pre-existing VTES T-type moiety at a T:Q ratio of 0.06:1 without the presence of an additional rearrangement catalyst. 0 Grafting. The reaction products were identified and confirmed by NMR analysis.

[0438] Example 2l: R based on the material prepared according to Example 1e 5S Replacement preparation of functionalized materials

[0439] In the material prepared according to Example 1e, a second T-type monomer was first grafted onto bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) at a T:Q molar ratio of 0.04:1 using an additional rearrangement catalyst (600 ppm Ti(IV)-isopropoxy). The reaction product was then modified with a small amount of styrene monomer in a diluted organic solution using an organic peroxide as a radical initiator. The viscous modified (vinyl and TESPT units) radical reaction product was identified and confirmed by NMR analysis.

[0440] Example 2m: Preparation of R based on the material prepared according to Example 1f 5S Functionalized materials

[0441] The material prepared according to Example 1f was modified by directly "on polysiloxane" with epoxidized fatty acid (epoxidized soybean oil) to R-modify its thiol (-L-SH) groups. 5S Functionalization leads to direct -SR 12c Functionalization. A 1:1.42 molar ratio of thiol groups to epoxidized soybean oil reagent was reacted in toluene at 65 °C. The reaction products were identified and confirmed by NMR analysis.

[0442] Example 3a: DP Q-型 Effect of T:Q molar ratio on the reactivity of vinyl-functionalized polymer liquid materials

[0443] A series of compounds according to Example 1e were prepared, but starting from an ethoxylated polysiloxane Q-type precursor. Ten ml aliquots of the resulting material were then placed in an oil bath at 140°C and stirred. Once the temperature was reached, 50 mg of dicumyl peroxide (DCP) was added as a free radical initiator. All materials were prepared using DP... Q-型 The values ​​were all above 1.8, and they exhibited self-polymerization, likely due to their "macromonomer" characteristics. The polymerization time recorded at 140°C demonstrates the effect of radical polymerization / crosslinking reactivity on DP. Q-型 Dependence on the T:Q molar ratio.

[0444] In the table below, we can see that at 140℃ (after adding DCP), the polymerization time is related to DP... Q-型 It is related to the T:Q ratio.

[0445] <![CDATA[DP Q-型 ]]> 1.82 1.97 2.15 T:Q ratio = 0.15:1 4 minutes 3 minutes 2 minutes T:Q ratio = 0.26:1 1 minute 1 minute <1 minute

[0446] Example 3b: Showing low DP Q-型 Comparative examples of the lack of reactivity in vinyl-functionalized polymer liquid materials

[0447] The same materials as described above were prepared and tested, but this time starting with a tetraethyl orthosilicate (DYNASYLAN 40, Evonik Industries) precursor to which VTMS was grafted, resulting in T:Q ratios of 0.16:1 and 0.26:1, similar to the example above. When self-polymerization was performed with DCP at 140°C in the same manner as described in Example 3a, no polymerization was observed even after 1 hour at the temperature, indicating insufficient reactivity. This can be attributed to a lack of "macromonomer" or resin properties, which is characteristic of DP. Q-型 Lower direct consequences.

[0448] Example 3c: DP Q-型 For BADGE-(epoxy)R 5S Effect of functionalized thiol-functionalized polymer liquid materials on reactivity

[0449] Three types of BADGE-modified thiol-containing polysiloxanes, DP, were prepared according to the preparation scheme described in Example 2f. Q-型 The values ​​were 1.77, 1.92, and 2.18, respectively, and the T:Q molar ratio was constant at 0.15:1. The corresponding BADGE modified compounds were reacted with 10% by weight of a standard epoxy resin amine curing agent in a heated chamber. The curing time of each epoxy resin system varied with DP... Q-型 The values ​​increased sequentially and decreased, recorded at 95, 78, and 55 minutes respectively, further demonstrating the dependence of reactivity on DP-values.

[0450] Example 3d: T:Q molar ratio of MDI-(isocyanate)R 5S Effect of functionalized thiol-functionalized polymer liquid materials on reactivity

[0451] Three MDI-modified mercapto-containing polysiloxanes were prepared according to the preparation scheme described in Example 2e, DP Q-型 The value remained constant at 2.19, but the T:Q ratio (the mercapto R group of the polysiloxane prepared before MDI functionalization) was different. 5U The T:Q ratios were chosen to be 0.07:1, 0.15:1, and 0.24:1, respectively, and the weight of the modified MDI was taken from Example 2e, and remained the same for all three T:Q ratio examples (the amount of isocyanate was constant in all cases). The corresponding MDI-modified compounds were reacted with 4000 MW of PPG polyol in the presence of 1% DABCO as a catalyst. The curing times of the respective epoxy resin systems decreased with increasing T:Q molar ratio. The corresponding measured curing times (from lowest to highest T:Q ratio) in the series were 71, 52, and 19 minutes, respectively, showing a significant effect on the reactivity of the system.

[0452] Example 3e: DP Q-型The T:Q molar ratio of DPGDA-(diacrylate)R 5S Effect of functionalized amino-functionalized polymer liquid materials on reactivity

[0453] A series of materials similar to those shown in Example 1c were prepared from Q-type precursors with different DP-values, and then different APTMS grafting degrees were selected. Compared to the materials described in Example 1c, the prepared R... 5U R is not present in the analogues. 5N The material contains a nonfunctionalizable T-type silane (propyltriethoxysilane, PTES), meaning it contains APTMS as the sole grafted T-type silane. Then these R... 5U The material was subjected to R-coating with "amino protons" in a given molar ratio of DPGDA (dipropylene glycol diacrylate). 5S Functionalization to produce the corresponding diacrylate Michael adduct.

[0454] Next, the stability of these compounds in the absence of any stabilizers was investigated, which is a measure of their self-polymerization tendency and therefore their reactivity. For this purpose, DPGDA (-L'-Y) was studied. 1 )R 5S The functionalized polymer liquid materials were stored at 45°C and room temperature, respectively. The table below shows the gelation / self-polymerization time versus DP. Q-型 Relationship with T:Q molar ratio: Samples at 40℃ have a constant T:Q molar ratio, therefore the DPGDA content in the material is also constant. This indicates that as DP... Q-型 The increase in precursor core size makes the material more reactive and polymerizes faster.

[0455] The following room temperature study shows that in moderate DP Q-型 However, samples prepared with varying T:Q molar ratios are more stable at lower T:Q ratios, which is significant because it also translates to a lower total functionality / R in the material. 5S The degree of functionalization. Interestingly, the lowest DP... Q-型 The T:Q ratio is 1.85, and the intermediate T:Q ratio (0.15:1) results in the material still being reactive, but it appears to be fairly stable at room temperature.

[0456]

[0457] Example 4: Efficiency testing of potential rearrangement catalysts

[0458] A scheme was designed to test the efficiency of various model catalysts in catalyzing the grafting of the T-type monomer model silane methyltriethoxysilane (MTES). Briefly, commercially available Dynasylan Silbond 50 was used as the Q-type precursor. A molar ratio n was used...Q-型 :n T-型 A 1:0.15 ratio was used to fill 30 ml aliquots of the premixed solution containing the Q-type and T-type silane precursors into 50 ml capped glass vials. 1% (by weight) of the model rearrangement catalyst was added to each vial, and blank samples were also included in the study. All vials were simultaneously placed in a heating cabinet maintained at 100°C, and the samples were incubated there for 24 hours. Afterward, they were removed from the cabinet and cooled to room temperature. 29 The analysis was performed using Si NMR spectroscopy.

[0459]

[0460]

[0461] Following spectral NMR analysis, the grafted T... 0 Single-unit capability (DP) T-型 and %T 0 The percentage of residual tetrasiloxane ring species after grafting (%) and Q 2r &Q 3s,d ) / Q tot and %(Q 3s,d ) / Q 3 Indicators are used to evaluate the performance and suitability of catalysts.

Claims

1. A polymeric liquid hyperbranched polysiloxane material comprising or consisting of: (i) non-organofunctional Q-type siloxane moieties selected from the group consisting of: and (ii) mono-organofunctional T-type siloxane moieties selected from the group consisting of: wherein represents a covalent siloxane bond to a silicon atom of another Q- and / or T- moiety as defined in (i) and / or (ii); R 1 is selected from the group consisting of methyl, ethyl, propyl, -P(=0)(OR 1’ )(OH), -P(OR 1’ )2, -P(=0)(OH)2; R 1’ is selected from methyl, ethyl, propyl and butyl; R 5 is selected from the group consisting of R 5N , R 5U , and R 5S , wherein R 5N is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, straight chain, branched or cyclic C 5-16 alkyl residues; R 5U selected from -L-Z 1 , -L-Z 2 and Z 3 wherein L is an aliphatic linker selected from the group consisting of -CH2-, -CH2CH2-, -CH2CH2CH2-, -C6H4-, -C6H4-CH2- and -CH2-CH2-C6H4-CH2-; Z 1 is a moiety selected from the group consisting of -SH, -NH2, consisting of -SH, -NH2, Z 2 is selected from the group consisting of part of the group consisting of; wherein R 7 is independently selected from the group consisting of methyl, ethyl and n-butyl, and o is an integer from 1 to 3, and Z 3 selected from the group consisting of vinyl, phenyl, wherein, n is an integer selected from the group consisting of 1, 2, 3, 4 and 5; and R 6 is selected from the group consisting of methyl, ethyl, n-butyl, straight-chain or branched C 5-14 alkyl residues; R 5S is selected from the group consisting of -L'-Y 1 , -L'-Y 2 , and Y 3 , wherein m is an integer selected from the group consisting of 1, 2, 3 and 4; R 8 selected from the group consisting of -CI, -Br, -I, -F, -CN, -SCN, -N3, -N02, -OH, -S02OR 1' , and -0-C(=0)R 12 ; R 9 consisting of -CI, -Br, -I, -F, -CN, -COOH, -COOR 1' , phenyl, o-, m- and p-vinylphenyl; R 9’ selected from the group consisting of -COOH and -COOR 1' consisting of -COOH and -COOR L’ is an aliphatic linker selected from the group consisting of -CH2-, -CH2CH2- and -CH2CH2CH2-; and Y 1 is selected from the group consisting of a moiety selected from the group consisting of -NR1R2, -OR1, -SR1, -NHR1, -N(R1)2, -N=C(R1) Y 2 is selected from the group consisting of a group consisting of -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2 Y 3 is selected from the group consisting of part of the group consisting of; wherein X is a void, -(NH)- or -O-; R 10 selected from the group consisting of R 10a , R 10b , R 10c , R 10d , R 12a , and ; R 10a selected from the group consisting of: R 10b is a monomer selected from the group consisting of: or a biuret form or isocyanurate form of said monomer; R 10c selected from the group consisting of: wherein q is an integer from 1 to 25, where each of q1 to q4 is an integer from 0 to 8 and the sum of (q1 + q2 + q3 + q4) is from 4 to 8, where each of q5 to q7 is an integer from 0 to 24 and the sum of (q5 + q6 + q7) is from 3 to 24, where each of q8 and q9 is an integer from 0 to 6 and the sum of (q8 + q9) is from 2 to 6; R 10d is selected from the group consisting of: wherein r is an integer from 1 to 100, s is an integer from 1 to 15, t is an integer from 1 to 10; R 11 is selected from the group consisting of R 8 , -X-R 1’ , and R 12c ; and R 12 is selected from the group consisting of R 12a , R 12b , and R 12c , wherein R 12a selected from the group consisting of straight-chained or branched, substituted or unsubstituted C 1-18 alkyl, C 2-18 alkenyl and C 2-18 alkynyl, and cyclic, substituted or unsubstituted C 3-18 alkyl, C 5-18 alkenyl and C 8-18 alkynyl; R 12b selected from the group consisting of: - linear or branched, substituted or unsubstituted alkyl ethers, alkenyl ethers, alkynyl ethers having a molecular weight of not more than 5000 g / mol, and cyclic, substituted or unsubstituted alkyl ethers and alkenyl ethers having a molecular weight of not more than 5000 g / mol; - unsubstituted polydimethylsiloxanes and polydivinylsiloxanes; and - polysaccharides and oligosaccharides having a molecular weight of not more than 5000 g / mol; and R 12c selected from the group consisting of: - amino acids, oligo- and polypeptides having a molecular weight of not more than 5000 g / mol; and -C 12-24 fatty acid; provided that R 5S is not wherein The degree of polymerization DP of the T-type alkoxyl terminated siloxane moiety T-型 in the range of 1.1 to 2.7; the material has a viscosity of 2 to 100’000 cP; the material comprises less than 5 mol-% of silanol groups (Si-OH); and further wherein - the polysiloxane material comprises less than 45 mol-% of tetrad Q 2r - type and Q 3s,d - type siloxane ring species; and / or - polysiloxane material with respect to all Q 3 - siloxane species of the type Q4SiO2 / 2comprises less than 70 mol-% of the tetrad Q 3s,3d - siloxane ring species of the type Q4SiO2 / 2; and / or - the polysiloxane material comprises less than 4.5 mol-% of di-tetra Q relative to the total Q-type siloxane species 3d - type siloxane ring species; and / or - polysiloxane material is all Q 3 - siloxane species of the type DQ4 contains less than 25 mol-% of bisquaternary Q 3d - siloxane ring species of the type DQ4 wherein "Q 2r ” refers to any tetra-siloxane ring structure in which Q 2 species, "Q 3s Q" refers to any monoringsiloxane structure in which Q 3 species, and "Q 3d ” refers to any bicyclic siloxane structure in which Q 3 species, characterized in that -When all R of the T-type siloxane portion in the polysiloxane material 5 At least 65 mol-% of the residues are R 5N At that time, the degree of polymerization (DP) of the Q-type alkoxy-terminated moiety Q-型 Within the range of 1.65 to 2.35, and the atomic ratio of T- to Q- species in the material is within the range of 0.05:1 to 0.45:1; - when all -L-Z 1 and -L'-Y 1 residues, at least 80 mol-% of all R 5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization DP Q-型 is in the range of 1.75 to 2.25, and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.3:1 ; - when the sum of all Z 3 and Y 3 and / or the sum of all -L-Z 2 and -L'-Y 2 comprises at least 50 mol-% of all R 5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization DP Q-型 of the Q-type alkoxy end-capping moieties is in the range of 1.85 to 2.2, and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.3:1 ; - when all -L-Z 1 , -L'-Y 1 and R 5N sum to at least 90 mol-% of all R 5 residues of T-type siloxane moieties in the polysiloxane material, the degree of polymerization DP Q-型 of the Q-type alkoxy endcapping moieties is in the range of 1.8 to 2.4, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.4:1 ; and - when the sum of all R 5N , Z 3 , Y 3 , -L'-Y 2 and -L-Z 2 groups accounts for at least 90 mol-% of all R 5 residues of the T-type siloxane moieties in the polysiloxane material, the degree of polymerization DP Q-型 of the Q-type alkoxy end-capping moieties is in the range of 1.7 to 2.25 and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.25:

1.

2. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein R 5N is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, straight chain, branched or cyclic C 5-16 alkyl residues; Z 1 is a moiety selected from the group consisting of -SH, consisting of -SH, R 8 selected from the group consisting of -CI, -Br, -I, -CN, -SCN, and -N3; Y 1 is selected from the group consisting of: wherein o is an integer from 1 to 3; Y 2 is selected from the group consisting of part of the group consisting of; Y 3 is selected from the group consisting of part of the group consisting of wherein X is a void, -(NH)- or -O-; R 10 selected from the group consisting of R 10a , R 10b , R 10c , R 10d , and R 12a ; R 10a is selected from the group consisting of: R 10b is selected from the group consisting of: and Y 1 X is -(NH)-; R 10c is selected from the group consisting of: wherein q is an integer from 1 to 10, where each of q1to q4is an integer from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8, where each of q5to q7is an integer from 0 to 24 and the sum of (q5+q6+q7) is from 3 to 24, where each of q8and q9is an integer from 0 to 6 and the sum of (q8+q9) is from 2 to 6; R 10d selected from the group consisting of: wherein r is an integer from 1 to 25, s is an integer from 1 to 10, and t is an integer from 1 to 10; R 11 selected from R 8 and / or R 12c ; and R 12 is selected from the group consisting of R 12a , R 12b , and R 12c , wherein R 12a selected from the group consisting of straight-chained or branched, substituted or unsubstituted C 1-18 alkyl and C 2-18 alkenyl groups; R 12c selected from the group consisting of: - amino acids and oligo- or polypeptides having a molecular weight of not more than 2000 g / mol; and -C 12-24 Fatty acids.

3. The polymeric liquid hyperbranched polysiloxane material according to claim 1 or 2, wherein R 1 is selected from the group consisting of methyl, ethyl, propyl; R 5N is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, straight chain, branched or cyclic C 5-16 alkyl residues; L is an aliphatic linker selected from the group consisting of -CH2-, -CH2CH2-, -CH2CH2CH2- and -C6H4-; Z 1 is a moiety selected from the group consisting of -SH, consisting of -SH, Z 2 is selected from the group consisting of part of the group consisting of wherein R 7 is independently selected from the group consisting of methyl, ethyl; Z 3 selected from ethenyl, phenyl; R 8 selected from the group consisting of -CI, -Br, -I, -CN, -N3; R 9 selected from the group consisting of -CI, -CN, -COOH, -COOR 1' and phenyl; Y 1 is selected from the group consisting of: wherein o is an integer from 2 to 3; Y 2 is selected from the group consisting of part of the group consisting of Y 3 is selected from the group consisting of part of the group consisting of; wherein X is a void, -(NH)- or -O-; R 10 selected from the group consisting of R 10a , R 10b , R 10c , and R 10d ; R 10a is selected from the group consisting of: R 10b is selected from the group consisting of: and Y 1 X is -(NH)-; R 10c is selected from the group consisting of: wherein q is an integer from 1 to 6, wherein each of q1to q4is an integer from 0 to 8 and the sum of (q1+q2+q3+q4) is from 4 to 8, wherein each of q5to q7is an integer from 0 to 8 and the sum of (q5+q6+q7) is from 3 to 12, wherein each of q8and q9is an integer from 0 to 4 and the sum of (q8+q9) is from 2 to 4; R 10d selected from the group consisting of: wherein r is an integer from 1 to 20, s is an integer from 1 to 8 and t is an integer from 1 to 10; R 11 selected from R 8 and / or R 12c ; and R 12c is selected from the group consisting of: - amino acids and oligo- or polypeptides having a molecular weight of not more than 1000 g / mol; and -C 12-24 fatty acid.

4. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein the material comprises - at least two different groups of R 5 - substituted monoorganofunctional T-type alkoxyl terminated siloxane, each group representing at least 3 mol-% of all monoorganofunctional T-type moieties in the material; and / or - chiral monoorganofunctional T- type moieties in an amount of at least 3 mol-% relative to all monoorganofunctional T- type moieties in the material 1 - type moieties.

5. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein The degree of polymerization DP of the T-type alkoxyl terminated siloxane moiety T-型 In the range of 1.3 to 2.

2.

6. The polymeric liquid hyperbranched polysiloxane material of claim 1, wherein, the total content of di-organofunctional D-type siloxanes and / or the total content of tri-organofunctional M-type siloxane moieties is zero.

7. The polymeric liquid hyperbranched polysiloxane material according to claim 1, wherein, - if at least 5 mol-% of the residues of the material are -L-Z 5 and / or -L'-Y 1 and / or -L'-Y 1 excluding -SH, then the polysiloxane material comprises less than 750 mol-ppm of rearrangement catalyst; - the polysiloxane material comprises 0 to 1500 mol-ppm of rearrangement catalyst based on the total molar silicon content present in the material; and / or - all R in the material 5U and at least 1 mol-% of R 5S in the sum of moieties and 5S moieties.

8. The polymeric liquid hyperbranched polysiloxane material according to claim 1, further comprising at least one of: - a polydimethylsiloxane having a molecular weight of not more than 5000 g / mol; and - a polydivinylsiloxane having a molecular weight of not more than 5000 g / mol. (iii) triorganofunctional M-type siloxane moieties selected from the group consisting of: (iv) diorganofunctional D-type siloxane moieties selected from the group consisting of: wherein R 2 is selected from the group consisting of methyl, ethenyl and phenyl; R 3 selected from methyl, ethenyl and phenyl, wherein The degree of polymerization DP of the D-type alkoxyl terminated siloxane moiety D-型 in the range of 1.0 to 1.9; the total content of triorganofunctional M-type siloxane moieties (iii) in the polysiloxane material is not more than 20 mol-%; the total content of diorganofunctional D-type siloxane moieties (iv) in the polysiloxane material is not more than 15 mol-%.

9. The polymeric liquid hyperbranched polysiloxane material according to claim 8, wherein - if the material comprises 5 mol-% or more of M-form moieties, the degree of polymerization DP of the Q-form alkoxy end-capping moieties Q-型 in the range of 1.7 to 2.5, and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.4:1 ; and / or the degree of polymerization DP of the D-type alkoxyl terminated siloxane moiety D-型 in the range of 1.25 to 1.

75.

10. The polymeric liquid hyperbranched polysiloxane material of claim 1, wherein R 5N is selected from the group consisting of linear or branched hexyl, octyl, dodecyl, hexadecyl, cyclohexyl, and cyclopentyl.

11. The polymeric liquid hyperbranched polysiloxane material of claim 1, wherein R 6 is selected from the group consisting of -(CH2)5CH3, -(CH2)6CH3, -(CH2)7CH3, -(CH2)8CH3, -(CH2)9CH3, -(CH2) 11 -(CH2)10CH3, -(CH2)11CH3, -(CH2)12CH3, -(CH2)13CH3, -(CH2)14CH3, -(CH2)15CH3, -(CH2)16CH3, -(CH2)17CH3, -(CH2)18CH3, -(CH2)19CH3, -(CH2)20CH3, -(CH2) 13 CH3, and -(CH2)20CH3.

12. The polymeric liquid hyperbranched polysiloxane material of claim 1, wherein R 12b is selected from the group consisting of: - substituted or unsubstituted poly(ethylene oxide), poly(propylene oxide) and polytetrahydrofuran; and - poly-D-glucose, oligo-D-glucose, chitosan, deacetylated oligo-chitins, oligo-β-D- galacturonic acid pyranose, polyalginic acid, oligo-alginic acid, polyamylose, oligo-amylose, polygalactose and oligogalactose having a molecular weight of not more than 5000 g / mol.

13. The polymeric liquid hyperbranched polysiloxane material of claim 1, wherein R 12c is selected from the group consisting of: - oligo- and polypeptides made from naturally occurring amino acids having a molecular weight of not more than 5000 g / mol; and - naturally occurring C 12-24 fatty acids.

14. The polymeric liquid hyperbranched polysiloxane material of claim 13, wherein R 12c is selected from naturally occurring C 12-24 unsaturated fatty acids.

15. The polymeric liquid hyperbranched polysiloxane material of claim 13, wherein R 12c selected from C 12-24 naturally occurring unsaturated fatty acids.

16. The polymeric liquid hyperbranched polysiloxane material of claim 1, wherein when the sum of all Z 3 and Y 3 and / or the sum of all -L-Z 2 and -L'-Y 2 comprises at least 50 mol-% of all R 5 residues of T-type siloxane moieties in the polysiloxane material, the material further comprises R 5 residues that are -L-Z 1 , R 5 residues that are -L'-Y 1 and -L-Z 1 , the degree of polymerization DP Q-型 of the Q-type alkoxy endcapping moieties is in the range of 1.85 to 2.2 and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.3:

1.

17. The polymeric liquid hyperbranched polysiloxane material of claim 1, wherein when the sum of -L-Z 1 , -L'-Y 1 , and R 5N comprises at least 90 mol-% of all R 5 residues of T-type siloxane moieties in the polysiloxane material, at least 30 mol-% of R 5 residues of the material are -L-Z 1 and / or -L'-Y 1 , and at least 10 mol-% of R 5 residues of the material are R 5N , the degree of polymerization DP Q-型 of the Q-type alkoxyl-terminated moieties is in the range of 1.8 to 2.4, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.4:

1.

18. The polymeric liquid hyperbranched polysiloxane material of claim 1, wherein when the sum of all R 5N , Z 3 , Y 3 , -L'-Y 2 , and -L-Z 2 comprises at least 90 mol-% of all R 5 residues of T-type siloxane moieties in the polysiloxane material, the sum of all Z 3 , Y 3 , -L'-Y 2 , and -L-Z 2 comprises at least 20 mol-% of R 5 residues of the material, at least 20 mol-% of R 5 residues of the material being R 5N , the degree of polymerization DP Q-型 of the Q-type alkoxy-terminated moieties is in the range of 1.7 to 2.25, and the atomic ratio of T- to Q-species in the material is in the range of 0.05:1 to 0.25:

1.

19. A hydrolyzate or emulsion product obtainable by reacting at least one polymeric liquid hyperbranched polysiloxane material according to any one of claims 1 to 18 with - a predetermined amount of water or a predetermined amount of a water-solvent mixture, - a predetermined amount of water or a predetermined amount of a water-solvent mixture in the presence of at least one surfactant of the hydrolyzate, or - a predetermined amount of water in the presence of at least one surfactant of the emulsion product.

20. A process for the preparation of a polymeric liquid hyperbranched polysiloxane material according to any one of claims 1 to 18, comprising the steps of: - providing a polymeric liquid hyperbranched polysiloxane material according to claims 1 to 18, wherein all R 5 moieties in the material are R 5U moieties; - functionalizing the R residues of said polymeric liquid hyperbranched polysiloxane material to obtain a polymeric liquid hyperbranched polysiloxane material having at least 1 mol-% of R residues and at least 1 mol-% of R residues relative to all R residues and R residues 5U 5U 5S 5S ;​​​ - recovering, isolating and / or purifying the polymeric liquid hyperbranched polysiloxane material.

21. A process for the preparation of a polymeric liquid hyperbranched polysiloxane material according to claim 1, comprising the steps of: (a) providing a Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly(methoxy / ethoxy / propoxy) polysiloxane precursor, wherein the precursor comprises at least 28 mol-% tetrafunctional Q with respect to total Q-type siloxane species 2r - type and Q 3s,d - type siloxane ring species; and / or wherein said precursor is at least 60% of the tetrameric combination Q 3 - the siloxane species of the -type comprises at least 60% of the tetrameric combination Q 3s,3d - the siloxane ring species of the -type; and wherein the degree of polymerization DP of the Q-type polysiloxane Q-型 in the range of 1.5 to 2.5; (b) adding at least one of the following: (b1 ) triorganofunctional M-type silane Si(OR 1 (Me)3; and / or (b2) bisorganofunctional D-type silane Si(OR 1 )2(R 2 )(R 3 ); and / or (b3) monoorganofunctional T-type silane Si(OR 1 )3(R 5 ); wherein R 5 is selected from R 5N , R 5U and R 5S ; in monomeric or oligomeric form of the polysiloxane of (a); (d) heating the mixture; (g) recovering, isolating and / or purifying the polymeric liquid hyperbranched polysiloxane material; with the proviso that (b3) is performed, and with the proviso that a rearrangement catalyst is present in step (a).

22. The process according to claim 21, wherein the Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly(methoxy / ethoxy / propoxy) polysiloxane precursor comprises: (a1) diorganofunctional D-type siloxane moieties; (a2) monoorganofunctional T-type siloxane moieties, wherein R 5 selected from R 5N , R 5U and R 5S ; and / or further comprising a rearrangement catalyst and / or triorganofunctional M-type siloxane moieties; with the proviso that at least one of steps (a2) or (b3) is performed.

23. The process according to claim 22, wherein the Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly(methoxy / ethoxy / propoxy) polysiloxane precursor comprises less than 12 mol-% of (a1) and (a2) combined relative to the total amount of all Q-type species.

24. The method according to claim 21, further comprising: (c) adding a rearrangement catalyst to the mixture of step (b).

25. The method according to claim 24, wherein the amount of catalyst in each of steps (a) or (c) is between 0.01 and 5 mol-%, based on the total molar silicon content present in the step.

26. The method according to any one of claims 21 to 25, wherein the rearrangement catalyst is selected from the group consisting of: -Ti(IV)(OR 13 )4and Zr(IV)(OR 13 )4; - Ti(IV)X4and Zr(IV)X4; - O = Ti(IV)X2and O = Zr(IV)X2 2) ; Ti(IV)X2(OR 13 )2and Zr(IV)X2(OR 13 )2; - Ti(IV)X2(OAcAc)2and Zr(IV)X2(OAcAc)2; - Ti(IV)(OSi(CH3)3)4and Zr(IV)(OSi(CH3)3)4; -(R 13 O)2Ti(IV)(OAcAc)2and (R 13 O)2Zr(IV)(OAcAc)2; - O=T1(IV)(OAcAc)2and O=Zr(IV)(OAcAc)2; - Ti(IV)(OAc)4and Zr(IV)(OAc)4; Ti(IV)(OAc)2(OR 13 )2and Zr(IV)(OAc)2(OR 13 )2; and - O=T1(IV)(OAc)2and O=Zr(IV)(OAc)2; wherein R 13 is selected from the group consisting of -CH3, -CH2CH3, -CH(CH3)2, -CH2CH2CH3, -C(CH3)3, -CH2CH2CH2CH3, and CH2CH2CH(CH3)2 and wherein X is a halide, pseudohalide, nitrate, chlorate, or perchlorate anion.

27. The method according to claim 21, further comprising: (d) heating the mixture of (c) in the absence of water.

28. The method according to claim 27, further comprising: (e) repeating steps (b) to (d) at least once.

29. The method of claim 28, wherein, After step (d) or (e), the method further comprises the step of adding a triorganofunctional M-type silane or M-type siloxane and / or a diorganofunctional D-type silane in the form of a monomer or oligomer as described in step (b2) in the presence of water, a suitable co-solvent and an acid catalyst, followed by heating the mixture or refluxing the mixture.

30. The method according to claim 28, further comprising: - in step (a), R of the T-shaped siloxane moiety is 5 R 5U ; - in step (b), R of the at least one T-type silane is 5 R 5S ; and wherein in step (e) R 5 selected from R 5U and R 5S .

31. The method according to claim 21, further comprising: (f) R of polymer liquid hyperbranched polysiloxane material 5U Residue functionalization to obtain relative to all R 5U and R 5S residues and at least 1 mol-% R 5S Residues.

32. The method according to claim 31, wherein - in step (a), R of the T-type siloxane moiety is 5 R 5N and / or R 5U ; and - in step (b), R of the T-shaped silane is 5 R 5N and / or R 5U .

33. A product obtainable by the method according to any one of claims 21 to 32.

Images