Q-t-d-siloxane-based polymeric compositions with aminophenyl, isocyanate or epoxide functionality, and method for preparing same

Abstract

Functionalized polymeric liquid polysiloxane material compositions comprising non-organofunctional Q-type siloxane moieties and mono-organofunctional T-type and / or D-type siloxane moieties, wherein the composition comprises aminophenyl, secondary amine, isocyanate and / or epoxide functionalities, methods for producing the polymeric liquid polysiloxane material and associated uses, formulations and preparations of the material.

Description

[0001] Q-T-D-Siloxane-Based Polymeric Compositions with Aminophenyl , Isocyanate or Epoxide Functionality , and Method for Preparing Same

[0002] The present invention pertains to functionalized polymeric liquid polysiloxane material compositions comprising non- organofunctional Q-type siloxane moieties and mono- organofunctional T-type and / or D-type siloxane moieties , wherein the composition comprises aminophenyl and / or other secondary amine T / D-type siloxane moieties , isocyanate functionalities and / or epoxide functionalities . The present invention further pertains to methods for producing the polymeric liquid polysiloxane material as well as associated uses , formulations and preparations of the material .

[0003] WO 2019 / 234062 Al discloses a process for manufacturing a coreshell PEOS-core with an organofunctional silane shell material . WO 2019 / 234062 Al describes the preparation of a hyperbranched ethylsilicate "core" by means of non-hydrolytic acetic anhydride condensation chemistry and then the grafting of a shell , made preferentially from a selection of organofunctional T-type trialkoxysilanes in a second temporally separated step to create a hybrid organofunctional core-shell molecular building block . Both steps are preferably carried out in the presence of a tetraalkoxytitanate rearrangement catalyst .

[0004] WO 2022 / 058059 describes hyperbranched polyalkoxysiloxane materials comprising Q- and M- , D- and / or T-type functionality within the same macromolecule .

[0005] It is the obj ective of the present invention to provide improved, optionally more stable , and functionalized organofunctional hyperbranched polyalkoxysiloxane material compositions comprising Q- and T / D-siloxane moieties , methods for producing the same and various applications thereof . The above problem is solved by the polymeric liquid polysiloxane material according to claim 1 .

[0006] In a first aspect, the present invention is directed to a composition comprising a polymeric liquid polysiloxane material comprising or consisting of :

[0007] ( i ) non-organofunctional Q-type siloxane moieties selected from the group consisting of : and at least one of :

[0008] ( ii ) mono-organofunctional T-type siloxane moieties selected from the group consisting of : and / or

[0009] ( iii ) di-organofunctional D-type siloxane moieties selected from the group consisting of :

[0010] D1D2wherein at Si-0 <ww indicates a covalent siloxane bond to a silicon atom of another Q-, T- and / or D-type moiety as defined in (i) , (ii) and (iii) ;

[0011] R1is selected from the group consisting of methyl, ethyl and optionally propyl;

[0012] R5is L-Z, wherein

[0013] L is an aliphatic linker with the formula - (CH2)a_;

[0014] Z is selected from the group consisting of -SR6, -NHR6, N(R6)2 and -NR6R7, optionally -SR6, -NHR6, and -NR6R7, moiety moiety wherein R4is H if b is 0; moiety wherein moiety (III) comprises least one R6residue;

[0015] wherein a is an integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7 and 8, b is an integer selected from the group consisting of 0, 1 and 2,

[0016] R1' is selected from the group consisting of linear or branched methyl, ethyl, propyl, butyl, pentyl and hexyl; R4is a residue selected from the group consisting of -H, methyl, ethyl, -CH=CH2, -F, -Cl, -Br, -I, -CN, -SCN, -N3, -NO2, -SO2OH, - SO2OR1' and -C(=O)Rlf, and

[0017] R6is selected from the group consisting of:

[0018] O

[0019] A / r8eL ^NH ureas or thio-ureas, optionally 4 , p-hydroxy amines or p-hydroxy thioethers, optionally , and p-hydroxy ethers, optionally

[0020] R7is selected from the group consisting of Me and linear or branched - (CH2)a-CH3;

[0021] R8is

[0022] - an aliphatic, aromatic or unsaturated, substituted or nonsubstituted C4-20 hydrocarbon, optionally a methylene diphenyl, optionally an isocyanate-terminated and / or a glycidoxy-terminated aliphatic, aromatic or unsaturated, substituted or non-substituted C4-20 hydrocarbon, and / or

[0023] - an aliphatic, aromatic or unsaturated, substituted, optionally isocyanate-terminated and / or a glycidoxy- terminated, or non-substituted residue selected from the group consisting of p-hydroxy ethers, p-hydroxy thioethers, p-hydroxy amines, oxazolidones , ureas, cyanurates, thioureas, urethanes and combinations thereof in polymeric or oligomeric form having a mass-average molecular weight of 100 to 20'000 g / mol, 150 to 15'000 g / mol, or 170 to 10'000 g / mol, wherein R8comprises at least one moiety selected from the group consisting of an isocyanate and an epoxide, R9is selected from the group consisting of -OR7, -CeHs,

[0024] R10is selected from the group consisting of -R7, -OR7and -OH,

[0025] X is selected from the group consisting of 0, NH and -NR7,

[0026] R11is selected from the group consisting of -R7, -R9, -OR7and - OH, wherein the degree of polymerization of the T-type alkoxy-terminated siloxane moieties of the material DPT-type is in the range of 1.1 to 2.7; the degree of polymerization of the D-type alkoxy-terminated siloxane moieties in the material DPo-type is in the range of 1.0 to 1.9; the degree of polymerization of the Q-type alkoxy-terminated moieties of the material DPQ-typeis in the range of 1.4 to 2.8; the material optionally has a viscosity in the range of 5 mPas, 10 mPas or 12 mPas to 1'000 mPas, 5'000 mPas or 10'000 mPas; the composition optionally has a viscosity in the range of 100 mPas, 300 mPas or 500 mPas to 30'000 mPas, 50'000 mPas or 100'000 mPas; and the material optionally comprises less than 5 mol-%, 2 mol-% or 0.5 mol-% silanol groups (Si-OH) ; if the composition, or optionally the material, comprises isocyanate groups, the molar ratio of all R5residues to all isocyanate groups in the composition, or optionally in the material, is 1 to at least 5, optionally 1 to at least 6; if the composition, or optionally the material , comprises epoxide groups , the molar ratio of all R5residues to all epoxide groups in the composition, or optionally in the material , is 1 to at least 10 , optionally 1 to at least 17 , optionally 1 to at least 25 ; optionally the composition comprises less than 30 weight-%, less than 25 weight-% or less than 20 weight-% polyols that are not covalently bound to the polymeric liquid polysiloxane material relative to the total weight of the composition .

[0027] Optionally, the composition comprises a polymeric liquid polysiloxane material that comprises mono-organofunctional T- type siloxane moieties and no di-organofunctional D-type siloxane moieties with R5(e . g . comprises only D-type siloxane moieties with R2and R3attached to the Si-atom) and / or no di- organofunctional D-type siloxane moieties at all .

[0028] Optionally, the polymeric liquid polysiloxane material of the composition described herein further comprises :

[0029] ( iv) tri-organofunctional M-type siloxane moieties selected from the group consisting of :

[0030] > and / or

[0031] (v) di-organofunctional D-type siloxane moieties selected from the group consisting of : r)1 r\2

[0032] Mwherein * at si-O*wwindicates a covalent siloxane bond to a silicon atom of another Q-, T- , M- and / or D-type moiety as defined in ( i ) to (v) ;

[0033] R2is selected from methyl , vinyl and phenyl ; and

[0034] R3is selected from methyl , vinyl and phenyl ; wherein the degree of polymerization of the D-type alkoxy-terminated siloxane moieties in the material DPu-type is in the range of 1 . 0 to 1 . 9 ; the total content of tri-organofunctional M-type siloxane moieties in the polysiloxane material does not exceed 20 mol-% , optionally does not exceed 10 mol-% optionally does not exceed 5 mol-% ; and the total content of di-organofunctional D-type siloxane moieties in the polysiloxane material does not exceed 5 mol-% , 10 mol-% , or 15 mol-% .

[0035] As used herein and if not specifically stated otherwise , the term "material" refers to the polymeric liquid polysiloxane material , and the term " composition" refers to a composition that comprises the polymeric liquid polysiloxane material and optionally further components such as for example epoxy or isocyanate resins . The term "preparation" refers to a blend, mixture or reaction product obtained or obtainable as defined herein, in particular by reacting the composition as defined herein comprising the polymeric liquid polysiloxane material which comprises isocyanate groups and optionally further isocyanate containing compounds , resins or prepolymers , with hydroxyl- or mercapto-functional acrylates and / or methacrylates .

[0036] For example , the polymeric liquid polysiloxane material described herein for all aspects can be of a core-shell structure , wherein the core is composed of a maj ority of Q-type moieties and has a different composition than the shell , which is composed primarily of T- and / or D-type moieties , and optionally further comprises M- and non-R5-substituted D-type moieties . Herein, the core is also referred to as the "precursor (material ) " . Alternatively, the polymeric liquid material can also comprise a "core-only" material , meaning that there is no shell and that Q- and T / D-type moieties are essentially randomly distributed within said core . The term "core-shell" , as used herein, is commonly understood in the art ( see , e . g . , Nanoscale , 2010 , 2 , 829-843 or Nanoscale , 2011 , 3 , 5120-5125 ) . Concerning core-shell products , the interface between core and shell must be understood as a diffuse shell rather than a sharp boundary at which composition changes abruptly . This diffuse shell layer architecture , where the concentration of the functional shell species varies over a few bond lengths or Angstroms , is a direct result of the condensation chemistry, that is , the grafting of a functional silane shell onto a preformed 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 extent of grafting of the shell is highest on the periphery but there is no sharp cutoff . Nevertheless , the term core-shell still applies as grafting in the center of the core is highly hindered for both, steric reasons and reduced availability of reactive alkoxy groups , because the average connectivity (number of bridging oxygen linkages ( Si-O-Si bonds ) per silicon center) in the center of the core is higher than at the core perimeter . Consequently, the term core-shell will be used in the context of polymeric liquid materials in the sense of a polysiloxane core with a diffuse shell as described herein . Reference is also made to WO 2022 / 058059 , incorporated by references in its entirety, for figures illustrating the core- shell structure of the polysiloxane material (see in particular Fig. 1) .

[0037] For example, a typical material or composition according to the present invention may also comprise Q- , T-, D- and / or M-type silane monomers (Q°, T°, D°, M°) , e.g. in smaller molar quantities compared to the Qn, Tn, Dnand Mn, with n>l, moieties, 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 amounts, also as a monomer, e.g. also as a solvent or co-solvent. Similarly, the material or composition may optionally contain substantial fractions of smaller oligomers, for example a mixture of oligomers that spans a range from, e.g. dimer to pentamer polysiloxanes, optionally also featuring mixed Q-T and optionally Q-D bonding modes.

[0038] The material of the present invention optionally comprises less than 5 mol-%, 2 mol-% or 0.5 mol-% silanol groups (Si-OH) , this means that the OR1moieties of Q-, T- or D-type silanes are -OH groups to this extent.

[0039] It was found that the material described herein can be prepared, e.g. by using a rearrangement catalyst as described herein, without the need for any active condensation reagents such as acetic anhydride and that M-, D- and / or T-type silanes react with the Q-type precursor or core material in a nucleophilic substitution / condensation ("rearrangement") reaction. It was also found that the aminophenyl or other secondary amine substituents as used herein considerably reduce the kinetics of the alcohol siloxane condensation reaction of the Q(T / D) polysiloxane polymeric liquid materials compared to other aminofunctional Q(T / D) polysiloxanes. This means that such aminophenyl substituted Q(T / D) polysiloxanes have improved stability and reduced sensitivity to moisture during storage / handling either neat or in a product formulation or preparation. It was further surprisingly found that aminophenyl and / or other secondary amine substituents as used herein containing Q (T / D) polysiloxanes can be converted into neat / solvent-free reactive blends and compositions containing isocyanates , which in turn simplifies handling and commercial viability of such compositions because they can be handled, transported and stored with significantly less effort and allow for the preparation of solvent-free product formulations or preparations such adhesives , coatings etc .

[0040] It was further surprisingly found that for a composition according to the present invention comprising isocyanate and / or epoxide functionalities , the ratio between amine- or sulfur- bearing residues ( i . e . R5) and the isocyanate and / or epoxide groups of the composition correlates with the stability, e . g . the shelf-life , of the composition . In other words , by controlling the ratio between the R5residues and the total number of isocyanate and / or epoxide groups in the composition, the shelf-life can be extended . Therefore, this ratio is defined in the present compositions as follows : if the composition comprises isocyanate groups , the molar ratio of all R5residues to all isocyanate groups in the composition is 1 to at least 5 , optionally 1 to at least 6 ; if the composition comprises epoxide groups , the molar ratio of all R5residues to all epoxide groups in the composition is 1 to at least 10 , optionally 1 to at least 17 , optionally 1 to at least 25 ;

[0041] The features that "the composition comprises isocyanate / epoxide groups" and "all isocyanate / epoxide groups" and the corresponding molar ratios refer to any isocyanate and epoxide groups present in the composition, including isocyanate / epoxide groups on residues bound to a siloxane moiety and isocyanate / epoxide groups on molecules not bound to siloxane moieties but present in the composition . In other words , the ratio is defined as the ratio of the number of all R5residues to the number of all isocyanate / epoxide groups (bound and not bound to a residue bound to a siloxane moiety) present in the composition .

[0042] In an example , the composition of the present invention is one , wherein if the composition comprises both epoxide and isocyanate groups , in particular if the polymeric liquid polysiloxane material of the composition comprises R5residues with both epoxide and isocyanate groups (either in the same R5residue or in different R5residues ) , then the above-defined molar ratios of all R5residues to all isocyanate groups and epoxide groups do not apply, i . e . any ratio of R5residues to all isocyanate groups and epoxide groups is encompassed for the composition and / or the polymeric liquid polysiloxane material in this exemplary case .

[0043] It is noted that as used herein, the term epoxide (group / moiety) encompasses gylcidoxy groups , unless specifically stated otherwise .

[0044] For example , the composition according to the present invention can be essentially solvent-free , in particular free from organic solvents , and / or free of plasticizers . Essentially free means that less than 5 , 3 or 1 weight% of the composition is a solvent and / or plasticizer ( if both are present , the sum of is relevant ) .

[0045] The mole number and corresponding ratios of R5residues and isocyanate / epoxide groups can be , for example , determined by means of the following methodology :

[0046] The number of NCO groups in a composition according to the present invention can be determined by titration according to DIN EN ISO 14896 . The I socyanate reacts in toluene with an excess of di-n-butylamine to form a urea . Unreacted (excess ) amine is determined by back titration with hydrochloric acid . NCO amount per kg is the calculated as : n(NC0)

[0047] NCO / kg = m(compositiori) n (NCO) is the molar amount of NCO groups and m ( composition) is the mass of the composition under analysis . Similarly, the number of epoxy groups in a composition of the present invention can be determined by titration according to DIN EN ISO 3001 or ASTM D1652 . The material under investigation or the composition is dissolved in an organic solvent (e . g . chloroform or methylene chloride ) . Afterwards , tetraethylammonium bromide (TEABr) reaction solution and glacial acetic acid are added, followed by the titration of the sample with standardized perchloric acid until the equivalence point is reached . n (ep oxy)

[0048] Epoxy / kg = m(composition) n (epoxy) is the molar amount of epoxy groups and m ( composition) is the mass of the composition under analysis . The total molar R5content can be determined by using29Si NMR with an internal standard . A known amount of an internal standard ( IS ) for example TMS or HMDSO, which has a well-defined chemical shift, is added to an NMR tube together with a known amount of a polysiloxane specimen .

[0049] Additionally, a relaxation agent ( 0 . 1 M chromium ( III ) acetylacetonate in deuterochloroform) is added into the NMR tube . Afterwards , a29Si NMR spectrum is recorded .

[0050] The29Si NMR spectrum is processed using a background correction to get rid of the broad background signal originating from the NMR tube and the probe and possible solid silicate signals (e . g . filler) . Quantification of the29Si NMR peak areas is carried out by integration of the individual signals . Assuming that the Q (T / D) polysiloxane contains only R5substituents , the molar amount of R5groups per kilogram of pure Q (T / D) -polysiloxane is then calculated according to :

[0051] 1000 where n (R5) / kg represents the molar amount of R5groups per 1 kg of the polysiloxane sample, A (T) and A ( D) are the summed up peak areas of all T-type and D-type peak areas of the material or composition, A (IS) is the peak area of the used internal standard, m (IS) is the mass of the used internal standard, M (IS) is the molar mass of the internal standard and m (Q (T / D)_PS) is the mass of the polysiloxane sample used for this NMR experiment .

[0052] The internal standard is chosen from a group of materials that does not contain any Si NMR signals in the chemical shift region typical for the Q-type, T-type or D-type species of the polysiloxane (appearing in the spectral range between +20ppm and -120ppm) , ensuring the chemical shift of the selected internal standard does not overlap with the signals of interest . Since each T-type Si atom contains exactly one R5group, the molar amount of R5groups can be calculated based on the total number of T-type Si atoms in the polysiloxane sample . The same holds for D-type Si atoms .

[0053] Additional analytical techniques such as GC or HPLC could be used to differentiate and quantify R5or blends of R5from each other and from other non-R5(T-type and / or D-type silane substituents which do not fall under the R5definition) substituents , respectively, if needed . In this way, the percentage of individual R5substituents of the total T and D signal can be evaluated and the n (R5) number corrected on a percentage basis , accordingly .

[0054] The mol-% numbers for the total content of siloxane moieties described herein are defined by the sum of all D- , M- or T-type silicon atoms divided by the sum of all silicon atoms in the material , e . g . as measured by means of quantitative29Si-NMR .

[0055] The mol-% numbers for the silanol groups ( Si-OH) are defined by the ratio of silanol SiOH to total amount of silicon species , e . g . as measured by means of quantitative NMR spectroscopy . This can be done for example by measuring a29Si-NMR spectrum and quantifying the Q1silanol-peak area (Q1siOH) and dividing it by the total Q1peak area in the29Si-NMR spectrum . Model29Si-NMR spectra illustrating the Si-OH signatures ( side peaks ) of the QI , Q2 and Q3 speciation subsets are shown in Figure 1 .

[0056] If not specifically stated otherwise , all molecular weights or molecular masses disclosed herein for oligomeric or polymeric compounds refer to the mass-average molecular weight , e . g . in the context of R8, which can be determined by known standard means in the art, e . g . , by chromatographic (gel permeation chromatography GPC) and / or static light scattering, small angle neutron scattering, X-ray scattering or high-resolution mass spectrometry methods , in particular MALDI-TOF mass spectrometry and GPC coupled with MALDI-TOF mass spectrometry . In an example , molecular weights or molecular masses disclosed herein are massaverage molecular weights determined by MALDI-TOF mass spectrometry . In certain instances , it may also be advantageous to characterize e . g . the R8substituent (purely organic) molecular weight information independently from the Q (T / D) - polysiloxane hybrid polymer by first carrying out a ( chromatographic) pre-separation of free isocyanate / epoxy containing polymers from the R8-bound hybrid polymer and then analyzing the two fractions independently according to standard methodologies in analytical chemistry for analyzing mixtures of polymeric resins.

[0057] If a material exhibits M-type moieties, this generally leads to an increase in DPQtype. Therefore, the limit of DPQtype in all materials disclosed herein is to be raised by 0.05 or optionally 0.1 DP units if the amount of M-type modification exceeds 5 mol-% or optionally 10 mol-%.

[0058] The chemical composition of R5can be identified and quantified by known spectroscopic means, e.g. by nuclear magnetic resonance spectroscopy, e.g. byXH-,13C-, and optionally15N or33S or31P - NMR, optionally with isotope enrichment for analytical verification of these functionalization reactions.

[0059] The skilled person is aware that any combination of residues or moieties disclosed herein for forming R5must lead to a stable compound, i.e., a compound that can be isolated and characterized using conventional means. The skilled person can determine from his common general knowledge which compound, i.e. combination of the residues or moieties is not stable enough for characterization and isolation and specifically which linker chemistries are possible and do not interfere with other chemical functionalities in the polymeric liquid material. Any combination of moieties or residues that would result in a not stable compound, i.e. a compound that cannot be isolated and characterized, is excluded from the scope of the claims.

[0060] The degree of polymerization DP for any non-crystalline silicon oxide material (for the polysiloxane material and for the corresponding methods and uses described herein) is defined here as the ratio of bridging oxygens BO (# of Si-O-Si bonds) to the total number of metalloid atoms Sitot in the system.29Si NMR spectra functional polysiloxane materials comprising three different types of grafted T-type moieties are shown in Figures 2, 3 and 4, respectively. From the spectra, the different key benchmark figures (DP, Q:T molar ratio) can be determined for example according to the protocol given here. The same applies to R5-bearing D-type moieties, where in an analogous manner Q:D molar ratio and DP for the D-type species can be obtained from29Si NMR spectral analysis.

[0061] The term "alkoxy-terminated" for the Q- , T- and D-type siloxane moieties is understood to refer to the residual substituents of said moieties which are essentially alkoxy groups, because the polymeric liquid material is derived from alkoxy (ethoxy / methoxy) containing silane precursors in monomeric or oligomeric form. This implies that for a Q° monomer and Q1, Q2, Q3and Q4moiety, said "alkoxy termination" is comprised of 4, 3, 2, 1 and 0 alkoxy groups, respectively, and for a T° monomer and T1, T2and T3moiety, said "alkoxy termination" is comprised of 3, 2, 1 and 0 alkoxy groups, respectively. Analogously, for a D° monomer and D1and D2moiety, said " alkoxy termination" is comprised of 2, 1 and 0 alkoxy groups, respectively.

[0062] DPQ- type, DPT-tyPe and DPD-tyPe of the material can be directly obtained from quantitative29Si-NMR data according to:

[0063] DPQ-type = S (n AQH ) / S (AQII) = (AQI + 2 AQ2 + 3 AQ3 + 4 AQ4) / (AQQ + AQI + AQ2 + AQ3 + AQ4 ) ,"

[0064] DPT-type = S (n Ain) / S (ATII) = (ATI + 2 AT2 + 3 AT3) / (ATO + An + AT2 + AT3) for general T-type silanes;

[0065] DPT-type, bipedal silanes=2*S (n ATn) / S (An)=2 (ATI + 2 AT2 + 3 AT3) / (ATO + ATI + AT2 + ATS) for bipodal T-type silanes; and

[0066] DPo-type = S (n Aon) / S (Ann) = (ADI + 2 AD2) / (ADO + ADI + AD2) •

[0067] In the above equation for DPQ-tyPe, the terms AQndenote the quantitative29Si-NMR peak area related to that Qnmoiety (spectral signature) , which is a Si atom coordinated by n siloxane bonds through bridging oxygen (BO) atoms, that connect it to its next-nearest-neighbor Si atoms and (4-n) non-bridging oxygen (NBO) atoms which are linked to terminal alkoxy groups Si-OR as defined herein. Analogously, ATn and Ann denote the29Si- NMR peak areas corresponding to the respective T-type and D-type moieties (spectral signatures) .

[0068] For the above definition of DP, Q2and Q3refer to all types of Q2and Q3species, including linear and single ring as well as double ring species.

[0069] Regarding the equation for DPT-type it is necessary to differentiate between the class of bipodal T-type silanes and all the other, "general" T-type silanes. The latter constitute the majority of commercially available T-type silanes and comprise only a single Si atom connected to three alkoxy and one organofunctional group. In contrast, bipodal silanes, which can be represented as (RO) 3Si- (CH2) -X- (CH2) -Si (OR) 3 contain a further trialkoxysilyl unit attached to the first one through a suitable linker group "X" and each spaced by at least one methylene (-CH2- ) group. The introduction of a modified definition for the degree of polymerization of bipodal silanes takes into account that a single connectivity to the polysiloxane network is sufficient to covalently attach the functional group and develop its targeted interface functionality.

[0070] For organofunctional T type tri- and D-type di-alkoxysilanes , the29Si spectral fingerprint regions are shifted progressively further downfield allowing a clear separation of the different non-organofunctional Qnfrom organofunctional Tmand D1moieties.

[0071] Optionally, the total silicon to free hydrolysable alkoxy molar ratio 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 if the total content of di-organofunctional D-type siloxane moieties in the polysiloxane material does not exceed 10 mol-%.

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

[0073] Optionally, the molar number of methoxy terminating units (-OCH3) in the material described herein is at least twice the number of ethoxy terminating units (-OCH2CH3) and the material is essentially free of propoxy terminating units (-OCH2CH2CH3 or - OCH(CH3)2) ) , e.g. less than 3 % of all alkoxy terminating units are propoxy terminating units .

[0074] Generally, parameters that define the polymeric liquid material described herein can be measured using standard analytical tools: The content of hydroxy groups in the material can be determined, e.g., using29Si- and / or1H-NMR spectroscopy and Karl Fischer titration. The molar ratio of ethoxy and methoxy terminal alkoxy units in the material are directly accessible from13C-NMR and independently from29Si-NMR data.

[0075] Viscosity is readily analyzed, e.g. at 20 °C, e.g. by means of standardized viscosity measurements such as a cylindrical rotation viscometer, e.g. at 20 °C, e.g. according to, e.g., ASTM E2975-15: "Standard Test Method for Calibration of Concentric Cylinder Rotational Viscometers". Other viscosity test methods are also possible such as, e.g., Staudinger-type capillary viscometers or modern, dynamic viscometry methods at 20 °C. The material and / or the composition of the present invention optionally has a viscosity in the range of 100 mPas to 100'000 mPas, optionally about 300 mPas to 50'000 cP, optionally 500 mPas to 30'000 mPas, for example as measured in a cylindrical rotation viscometer at 20 °C, e.g. according to ASTM E2975-15: "Standard Test Method for Calibration of Concentric Cylinder Rotational Viscometers". A viscosity measurement of the material is preferably done on a material essentially consisting of a polymeric polysiloxane material, which has previously been purified. Purification can be done, e.g., by means of a thin film evaporator setup at, e.g. 150°C, with a vacuum, e.g. < 10-1bar, which separates monomers and low molecular oligomers from the polymeric liquid material itself (see Macromolecules 2006, 39, 5, 1701-1708) .

[0076] Regarding the residue Z, if b is 0 (zero) , moiety (I) is as used herein and unless specifically stated otherwise, means that the phenyl ring can comprise 1, 2, 3, or 5 R4residues. If multiple R4residues are attached to the phenyl ring, these can be the same or different residues selected from the group consisting of -H, methyl, ethyl, -CH=CH2, -Cl, -Br, -I, -CN, -SCN, -N3, -NO2, -SO2OH, - SO2OR1' and -C(=O)R1'. If, for example, 1, 2, 3 or 4 R4(s) is / are not H, the other positions at the phenyl ring can be hydrogen.

[0077] R1' is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl and hexyl, which includes linear and branched propyl, butyl, pentyl and hexyl, e.g. a n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, n-hexyl etc .

[0078] R8is an aliphatic, aromatic or unsaturated, substituted or nonsubstituted C4-20 hydrocarbon, and / or an aliphatic, aromatic or unsaturated, substituted or non-substituted residue selected from the group consisting of [3-hydroxy ethers, (3-hydroxy thioethers, [3-hydroxy amines, oxazolidones , ureas, cyanurates thio-ureas, urethanes and combinations thereof in polymeric or oligomeric form having a mass-average molecular weight of 100 to 20'000 g / mol, 150 to 15'000 g / mol, or 170 to 10'000 g / mol .

[0079] Aliphatic, aromatic or unsaturated C4-20 hydrocarbons include C4-20 alkyl, alkenyl, alkynyl, and aromatic hydrocarbons, such as five and six membered aromatic rings, including, e.g. methylene diphenyl, optionally comprising at least one heteroatom. The C4-20 hydrocarbon and / or the residue can be linear or branched. Exemplary aliphatic, aromatic or unsaturated C4-20 hydrocarbons include C4-20 alkyl, alkenyl, alkynyl, and aromatic hydrocarbons that are substituted or in particular terminated with at least one glycidoxy and / or isocyanate group. When the C4-20 hydrocarbons include at least one isocyanate, gylcidoxy or epoxide moiety, this moiety can be installed in particular terminally or, alternatively, at any carbon atom(s) in the hydrocarbon. Exemplary C4-20 hydrocarbons include: (a) exemplary hydrocarbons such as fatty acids, amino-, mercapto-, sulfonate-, and / or halogen-substituted C4-20 hydrocarbons, e.g. including substituted phenyl and naphthyl hydrocarbons; and (b) exemplary hydrocarbons (including bis phenyl-comprising hydrocarbons) with epoxide, glycidoxy or isocyanate moieties, such as glycidyl- or isocyanate-substituted C4-20 hydrocarbons, optionally glycidyl- or isocyanate-substituted biphenyl compounds, for example based on Bisphenol A or F, glycidyl- or isocyanate-substituted linear or cyclic hydrocarbons, optionally C2-12 hydrocarbons or C4-6 hydrocarbons, methyl (trimethylcyclohexyl) , phenyl or methylphenyl. For example, R8can be an isocyanate-terminated (e.g. HDI Monomer (Desmodur H) ) and / or a glycidoxy-terminated aliphatic, aromatic or unsaturated, substituted or nonsubstituted C4-20 hydrocarbon and / or residue.

[0080] Aliphatic, aromatic or unsaturated, substituted or nonsubstituted p-hydroxy ethers, p-hydroxy thioethers, p-hydroxy amines, oxazolidones , ureas, cyanurates, thio-ureas, urethanes and combinations thereof in polymeric or oligomeric form refer to aliphatic, aromatic or unsaturated (including mixed aliphatic - aromatic hydrocarbons) comprising p-hydroxy ethers, p-hydroxy thioethers, p-hydroxy amines, oxazolidones, ureas, cyanurates, thio-ureas and / or urethanes to from oligomers or polymers of the hydrocarbon moieties or repeat units. In other words, hydrocarbon-based monomers are connected by p-hydroxy ethers, p- hydroxy thioether, p-hydroxy amine, oxazolidone, urea, cyanurate, thio-urea and / or urethane linkages to make up oligomer or polymer chains / polycondensation products or so- called isocyanate- and / or epoxy-functional prepolymers. If R8does not comprise any aliphatic, aromatic or unsaturated C4-20 hydrocarbons with at least one moiety selected from the group consisting of an isocyanate and an epoxide, then the p-hydroxy ethers, p-hydroxy thioethers, p-hydroxy amines, oxazolidones, ureas, cyanurates, thio-ureas and / or urethanes comprise at least one isocyanate or epoxide functionality (i.e. an unreacted functionality with intact isocyanate or epoxide unit) which can, for example be a terminal isocyanate or epoxide group. For example, the p-hydroxy ethers, p-hydroxy thioethers, p-hydroxy amines, oxazolidones, ureas, cyanurates, thio-ureas and / or urethanes can be connected to R6by means of their functionalities, if chemically reasonable. For example, a p- hydroxyamine can form the following R6: wherein RB is a resin backbone structure (e.g. a diphenyl, e.g. substituted with gylcidoxy / epoxy-groups ) and HB is a hardener backbone structure (e.g. a linear branched or cyclic hydrocarbon structure, e.g. ethylene diamine, -CH2-CH (CH2NH2) -CH2-) , respectively and w is an integer including zero (e.g. 0 or 1 to 20, 1 to 10, or 1 to 6) suitable for achieving the mass-average molecular weight of 100 to 20'000 g / mol. In this example, R6can be the result of a siloxane-bound epoxide prepolymer comprising w repeating units (given by the structure in parentheses in the example of beta-hydroxyamine) with an attached terminal epoxy group. It is noted that for the determination of the massaverage molecular weight, only R8is considered, and not the atoms shown for R6. The R6residue may also include branched polymer structures as rendered possible by the use of multifunctional RB and / or HB subunits .

[0081] The hydrocarbons between the p-hydroxy ether, p-hydroxy thioether, p-hydroxy amine, oxazolidone, urea, cyanurate, thiourea and / or urethane moiety can be those hydrocarbons defined above. Exemplary p-hydroxy ethers, p-hydroxy thioethers, p- hydroxy amines, oxazolidones , ureas, cyanurates, thio-ureas and / or urethanes include typical isocyanate or epoxy functional prepolymer moieties i.e. the residue from typical reaction products involving either i) isocyanate precursors such as di- or triisocyanates, isocyanurates and other commonly used isocyanate functional precursors with diols, polyols, dithiols or polythiols, diamines or polyamines or ii) epoxide precursors such as bisphenol-based epoxy resins, novolac epoxy resins, etc., with diamines, triamines, polyamines, dithiols, polythiols, cyclic anhydrides, organic dicarboxylates and so on. Note that these exemplary residues have at least one residual terminal functional isocyanate or epoxy group attached to the terminal moiety where the other terminal reactive group through which it is attached through the R6of the polysiloxane was reacted off during this attachment / reactive blending step.

[0082] The skilled person, especially in the art of isocyanate / polyurethane chemistry or epoxy resin thermoset chemistry, will know well which combinations of raw materials and reaction conditions can be used to prepare such prepolymers or prepolymer blends. These blends can then be tethered to the Q(T / D) - polysiloxane backbone as described also in the method disclosed herein .

[0083] For example, and for all embodiments and aspects disclosed herein, the composition optionally further comprises molecules corresponding to R8which are not covalently bound to a siloxane moiety of the present material. Such "free" R8molecules are those chemical entities defined for R8but are not attached to a siloxane moiety, and e.g. comprise group that could react with the siloxane moiety did not. These "free" R8molecules can comprise isocyanate and / or epoxide moieties.

[0084] The mass-average molecular weight of R8(i.e. of the p-hydroxy ethers, p-hydroxy thioethers, p-hydroxy amines, oxazolidones , ureas, cyanurates, thio-ureas, urethanes and combinations thereof in polymeric or oligomeric form) refers to the massaverage molecular weight of the residue R8(i.e. the p-hydroxy ethers, p-hydroxy thioethers, p-hydroxy amines, oxazolidones, ureas, cyanurates, thio-ureas, urethanes and combinations thereof in polymeric or oligomeric form) before it is attached to R6. The term "non-substituted" as used herein shall mean substituted only with hydrogen. The term "substituted" as used herein, means that any one or more hydrogens on the designated atom or group is replaced, independently, with an atom different from hydrogen, optionally by a halogen, optionally by fluorine, chlorine, bromine, iodine, a thiol, a carboxyl, an acrylato, a cyano, a nitro, an alkyl (optionally Ci-Cio) , aryl (optionally phenyl, benzyl or benzoyl) , an alkoxy group, a sulfonyl group, by a tertiary or quaternary amine or by a selection from the indicated substituents, provided that the designated atom's normal valence is not exceeded, and that the substitution results in a stable compound, i.e., a compound that can be isolated and characterized using conventional means.

[0085] In the context of the present invention, it is understood that antecedent terms such as "linear or branched", "substituted or non-substituted" indicate that each one of the subsequent terms is to be interpreted as being modified by said antecedent term. For example, the scope of the term "linear or branched, substituted or non-substituted alkyl, alkenyl and alkynyl" encompasses linear, branched or cyclic, substituted or nonsubstituted alkyl; linear, branched or cyclic, substituted or non-substituted alkenyl; and linear, branched or cyclic, substituted or non-substituted alkynyl. For example, the term "C4-20 alkyl, C4-20 alkenyl and C4-20 alkynyl" indicates the group of compounds having 4 to 20 carbons and alkyl, alkenyl or alkynyl functionality.

[0086] The expression "alkyl" refers to a saturated, straight-chain or branched hydrocarbon group that contains the number of carbon items indicated, e.g. linear, branched or cyclic " (C4-20) alkyl" denotes a hydrocarbon residue containing from 4 to 20 carbon atoms, e.g. a n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, n-hexyl, 2 , 2 -dimethylbutyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cylcodecane, etc.

[0087] If an alkyl chain is characterized by a name that allows for linear or branched isomers, all linear or branched isomers are encompassed by that name. For example, "butyl" encompasses n- butyl, iso-butyl, sec-butyl and tert-butyl.

[0088] The expression "alkenyl" refers to an at least partially unsaturated, substituted or non-substituted straight-chain or branched hydrocarbon group that contains the number of carbon atoms indicated, e.g. " (Ch-20) alkenyl" denotes a hydrocarbon residue containing from 4 to 20 carbon atoms, for example an butenyl, iso-prenyl or hex-2-enyl group, or, for example, a hydrocarbon group comprising a methylene chain interrupted by one double bond as, for example, found in monounsaturated fatty acids or a hydrocarbon group comprising methylene-interrupted polyenes, e.g. hydrocarbon groups comprising two or more of the following structural unit - [CH=CH-CH2] -, as, for example, found in polyunsaturated fatty acids .

[0089] The expression "alkynyl" refers to at least partially unsaturated, substituted or non-substituted straight-chain or branched hydrocarbon groups that may contain, e.g. from 4 to 20 carbon atoms and at least one triple bond, for example a butinyl, acetylenyl, or propargyl group.

[0090] Optionally, the composition comprises less than 30 weight-%, less than 25 weight-% or less than 20 weight-% polyols that are not covalently bound to the polymeric liquid polysiloxane material relative to the total weight of the composition.

[0091] The term "polyols" as referred to herein, refers to organic polyols, e.g. diols, triols and tetrols, e.g. polyether, polyester, acrylic polyols, and polycarbonate polyols. For example, the polyols have a low-molecular weight, e.g. less than about 250 g / mol, e.g. mass-average molecular weight. Examples include ethylene glycol, propylene glycol, butylene glycol, glycerol, trimethyloylpropane, pentaerythritol, sugar alcohols such as xylitol, mannitol, etc. Further examples of polyols include alkyl ether polyols such as polyethylene glycol (PEG) , poly (propylene oxide) , poly-propylene glycol (PPG) and polytetrahydrofuran chains as homopolymer, heteropolymer or block copolymer polyols. Furthermore, also polycondensation polyols such as polyester polyols, polycarbonate polyols and polyamide polyols are encompassed by the term "polyols" as used herein. In the context of the present invention, polyols may be present as free polyols in a composition containing free epoxy reactive groups and / or resins as an ingredient. Alternatively, the polyols can be present in a composition comprising blocked isocyanates .

[0092] The weight-% of polyols is defined herein relative to the total weight of the composition. To determine the weight-%, the weight of the total composition is determined, e.g. on a balance, and the total weight of the polyols is determined for example by a prior separation step of the composition (extraction, chromatography etc.) and subsequent analysis for example by means of liquid chromatography (HPLC-MS, GPC) or other suitable analytical techniques known to the expert.

[0093] As used herein, a wording defining the limits of a range of length such as, e. g., "from 1 to 5" or " (C1-5) " means any integer from 1 to 5, i.e. 1, 2, 3, 4 and 5. In other words, any range defined by two integers explicitly mentioned is meant to comprise and disclose any integer defining said limits and any integer comprised in said range.

[0094] For example, the scope of the present invention includes those analogs of the compounds as described above and in the claims that feature the exchange of one or more carbon-bonded hydrogens, optionally one or more aromatic carbon-bonded hydrogens, with halogen atoms such as F, Cl, or Br, optionally F.

[0095] If a residue or group described herein is characterized in having two further residues of the same name, e.g. in Z being each of these further residues (in this example H or R1') can be independently selected from the definitions of this residue (in this example H or R1’) given herein .

[0096] For example, and for all embodiments and aspects disclosed herein, R4can be a residue selected from the group consisting of -H, methyl, ethyl, -CH=CH2, -Cl, -Br, -I, -SO2OH, -SO2OR1' and - C(=O)R1'. For example, and for all embodiments and aspects disclosed herein, one R4can be a residue selected from the group consisting of methyl, ethyl, -CH=CH2, -Cl, -Br, -I, -CN, - SCN, -N3, -NO2, -SO2OH, -SO2OR1' and -C(=O)R1', and the other four R4on the phenyl ring are hydrogen.

[0097] Optionally, polysiloxane material disclosed herein may be one, wherein

[0098] - the polysiloxane material comprises less than 45, optionally less than 37, optionally less than 30 or less than 25 mol-% four-membered combined Q2r-type and Q3s'd-type siloxane ring species relative to the total Q-type siloxane species; and / or

[0099] - the polysiloxane material comprises less than 70, optionally less than 63, optionally less than 56 or less than 50 mol-% four-membered combined Q3s'3d-type siloxane ring species relative to all Q3-type siloxane species; and / or - the polysiloxane material comprises less than 4 . 5 , optionally less than 4 . 0 , optionally less than 3 . 5 or less than 3 . 0 mol-% double four-membered Q3d-type siloxane ring species relative to the total Q-type siloxane species ; and / or

[0100] - the polysiloxane material comprises less than 25 , optionally less than 20 , optionally less than 17 or less than 14 mol-% double four-membered Q3d-type siloxane ring species relative to all Q3-type siloxane species .

[0101] The term " four-membered" ring or polysiloxane ring or Q-type ring species as referred to herein always refers to an ensemble of all Q2rand Q3s'd-type moieties comprised in the material which are part of a four membered polysiloxane ring structure . Two representative examples of such typical configurations of moieties in single and double four-membered ring structures are shown in the following formulas .

[0102] Q2rring moieties occur in both, " single" and "double" ring structures and comprise two siloxane bonds on each Q2rwhich are both part of the ring structure and two alkoxy group ( -OR1) substituents . In the example on the left of a single fourmembered siloxane ring, only Q2rring ( circle ) and " single ring" Q3s( square ) species are possible . In the second example of two connected four-membered siloxane rings (a bi-cyclic structure) shown on the right, in addition to Q2rring species ( circle) and " single ring" Q3s( square ) species , also "double ring" Q3d( rectangle , dashed line ) moieties are possible , which are located at the bridge sites connecting the two rings . It is noted that in these Q3dspecies , all siloxane bonds are part of the double ring network . Also, it is noted that the wiggly lines on the oxygen atoms connected to Q3smoieties represent a siloxane bond to any other possible Qn, Tn, Dnor Mnmoiety with n >= 1 . It must further be understood, that in the above examples for typical configurations , moieties are of Q-type but that these are only examples for assisting the skilled person' s understanding but in reality there is no restriction to Q-type moieties . In fact, it is within the scope of this disclosure and very much expected that in such four-membered polysiloxane ring structures also T-type and / or D-type moieties will be present .

[0103] Herein, Q2species in any four membered siloxane ring structures are termed "Q2r" and "Q3" species in single ring structures and in double ring structures are termed "Q3s" and "Q3d" , respectively .

[0104] For quantification purposes , there are different indicators that can be used to define or constrict the above mentioned four membered polysiloxane ring species . A first indicator is to be defined as the total number of Q2rand Q3s'dring species over the total Q species in the material ( for disambiguation, the "1" in AQ3i stands for linear) :

[0105] % (Q2r&Q3s'd) ring Species = 100 • 3 (AQ2rings + AQ3rings ) / S (AQn)

[0106] = 100 • (AQ2r + AQ3S + AQ3r ) / (AQQ + AQI + AQ2 + AQ3 + AQ4 ) ;

[0107] A second indicator is to be defined as the total number of Q3s'dring species over all Q3species in the material : % (Q3s, d) ring species within Q3= 100 • S (AQ3rings) / AQ3 = 100 • (AQ3S + AQ3d) / AQ3 = 100 ( 1 - (AQ31 / AQ3 ) )

[0108] A third indicator is to be defined as the total number of Q3dring species over the total Q species in the material : % (Q3d) ring species = 100 • AQ3d / S (Aqn)

[0109] = 100 • AQ3d / (AQ0+ AQI + AQ2 + AQ3 + AQ4 ) A fourth indicator is to be defined as the total number of Q3dring species over all Q3species in the material : % (Q3d) ring species within Q3= 100 • AQ3d / AQ3 .

[0110] The mol-% of four-membered Q2-type and / or Q3-type siloxane ring species relative to the total Q-type siloxane species can be determined by29Si-NMR analysis , as known in the art . The polysiloxane material described herein comprises less than the stated mol-% four-membered (Q2r& Q3s'd) and / or (Q2r) and / or (Q3ssingle ) and / or (Q3ddouble) ring species relative to the total Q- type siloxane species . This means that the material comprises either less than the stated mol-% four-membered Q2r-type siloxane ring species , less than the stated mol-% four-membered Q3s'd-type siloxane ring species and / or less than the stated mol-% fourmembered Q2r-type and Q3s'd-type siloxane ring species , cumulatively . For all embodiments described herein, the fourmembered Q3s'd-type siloxane ring species includes Q3s'd-type siloxane species , wherein one Q3s'd-type siloxane is part of one or two four-membered rings .

[0111] In an embodiment of the composition according to the present invention, which may be combined with any of the embodiments of the composition preaddressed or still to be addressed unless in contradiction, the composition, optionally the polymeric liquid polysiloxane material , comprises at least 0 . 05 mmol / g, 0 . 1 mmol / g, 0 . 2 mmol / g, 0 . 5 mmol / g, or 1 . 0 mmol / g of isocyanate and / or epoxide groups on a total resins basis . In other words , the total number (mmol ) of all isocyanates and epoxides in the composition, optionally in the polymeric liquid polysiloxane material , are counted together relative to the weight of all resin materials present in the composition . All isocyanates and epoxides in the polymeric liquid polysiloxane material refer to all isocyanate and epoxide groups on residues bound to a siloxane moiety of the polysiloxane material . The "total resins basis" is the weight of all resin materials in the composition, which includes all polymeric components but excludes , for example , solvents , fillers , plasticizers or monomeric components . Alternatively, the relationship between the total number of isocyanate and / or epoxide groups in the composition, optionally on the polymeric liquid polysiloxane material , can be characteri zed by parts NCO or parts epoxy per hundred rubber (phr) on a mass basis as follows : the composition, optionally the polymeric liquid polysiloxane material , comprises at least 0 . 5 phr, 1 . 0 phr, 2 . 0 phr, 3 . 5 phr, or 5 . 0 phr of isocyanate and / or epoxide groups .

[0112] In an embodiment of the composition according to the present invention, which may be combined with any of the embodiments of the composition preaddressed or still to be addressed unless in contradiction, Z is selected from the group consisting of -SR6, -NHR6, -NR6R7, moiety ( I ) : moiety wherein R4is H or CH=CH2 , and wherein R4is H if b is 0 ; and and optionally -N (R6) 2 , optionally wherein the composition or the polymeric liquid polysiloxane material comprises at least at least 0 . 1 mmol / g, optionally at least 0 . 2 mmol / g, optionally at least 0 . 35 mmol / g, optionally at least 0 . 5 mmol / g of isocyanate and / or epoxide groups on a total resins basis .

[0113] In an embodiment of the composition according to the present invention, which may be combined with any of the embodiments of the composition preaddressed or still to be addressed unless in contradiction, R8is

[0114] - an aliphatic or aromatic, substituted or non-substituted C4-20 hydrocarbon, and / or

[0115] - an aliphatic or aromatic, substituted or non-substituted residue selected from the group consisting of p-hydroxy ethers , p-hydroxy thioethers , p-hydroxy amines , ureas , cyanurates , thio-ureas , urethanes and combinations thereof in polymeric or oligomeric form having a mass-average molecular weight of 170 g / mol to 10 ' 000 g / mol .

[0116] In an embodiment of the composition according to the present invention, which may be combined with any of the embodiments of the composition preaddressed or still to be addressed unless in contradiction, R4is H or CH=CH2 .

[0117] Optionally, the composition, in particular the composition not making up or comprised in the formulation or preparation described herein, as described herein is one , wherein R8is not a residue selected from the group consisting of :

[0118] In an embodiment of the composition according to the present invention, which may be combined with any of the embodiments of the composition preaddressed or still to be addressed unless in contradiction, the composition is one , wherein, in particular if the composition does not make up or is not comprised in the formulation or preparation described herein, for Z being -SR6or -NHR6, R8is not a residue selected from the group consisting of : wherein REis Ci-is alkyl , C2-18 alkenyl or C2-18 alkynyl ,

[0119] In an embodiment of the composition according to the present invention, which may be combined with any of the embodiments of the composition preaddressed or still to be addressed unless in contradiction, a is 1 , 2 , 3 or 4 , and / or b is 0 or 1 , and / or

[0120] R1' is selected from the group consisting of methyl , ethyl , propyl and butyl ;

[0121] R4is selected from the group consisting of H or CH=CH2, and / or

[0122] Z is selected from the group consisting of -SR6, -NHR6, -NR6R7, moiety wherein R4is H if b is 0 , and moiety wherein moiety ( HI ) comprises least one R5residue ; and optionally -N (R6) 2.

[0123] In an embodiment of the composition according to the present invention, which may be combined with any of the embodiments of the composition preaddressed or still to be addressed unless in contradiction, R6comprises R8that is selected from the group consisting of biuret , uretdione and triisocyanurate form;

[0124] wherein r is an integer from 1 to 100, s is an integer from 1 to

[0125] 15 and t is an integer from 1 to 10.

[0126] The term "in monomeric, biuret, uretdione or tri-isocyanurate form" means that the depicted chemical entities may be in their monomeric form, i.e. correspond to the entity depicted, in their biuret form, i.e. correspond to three or optionally up to five, of the depicted monomers coupled by the diamide formed from isocyanate functionalities, in their uretdione form, i.e. as a dimer, or in their tri-isocyanurate from, i . e . correspond to three of the depicted monomers coupled by a cyclic isocyanurate group formed from isocyanate functionalities .

[0127] For example , the uretdione form of an R5attached monomer is

[0128] Generally, the biuret form is as shown below :

[0129] For example , the biuret form of the R5attached monomer

[0130] and the corresponding tri-isocyanurate form is

[0131] In an embodiment of the composition according to the present invention, which may be combined with any of the embodiments of the composition preaddressed or still to be addressed unless in contradiction, the atomic ratio of T- to Q-species in the polymeric liquid polysiloxane material is in the range of 0.01:1 to 0.5:1, optionally in the range of 0.03:1 to 0.35:1.

[0132] The atomic ratio of T- to Q-species in the material is the ratio between the silicon atoms of all T-type species (T°, T1, T2and T3) and the silicon atoms of all Q-type species (Q°, Q1, Q2, Q3and Q4) .

[0133] In an embodiment of the composition according to the present invention, which may be combined with any of the embodiments of the composition preaddressed or still to be addressed unless in contradiction, the degree of polymerization of the Q-type alkoxy-terminated moieties of the material DPQ-type is in the range of 1.6 to 2.4 and the atomic ratio of T- to Q-species in the material is in the range of 0.02:1 to 0.4:1; if the material comprises about or more than 5 mol-% M-type moieties, the degree of polymerization of the Q-type alkoxyterminated moieties of the material DPQ-type 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 ; the degree of polymerization of the D-type alkoxy-terminated siloxane moieties of the material DPo-type is in the range of 1 . 25 to 1 . 75 ; and / or the degree of polymerization of the T-type alkoxy-terminated siloxane moieties of the material DPT-type is in the range of 1 . 3 to 2 . 2 .

[0134] Optionally, the composition as described herein is one, wherein the total content of di-organofunctional D-type siloxane and / or the total content tri-organofunctional M-type siloxane moieties in the polymeric liguid polysiloxane material is zero .

[0135] Further obj ectives are achieved by the products , methods compositions , formulations and preparations according to claims 11 to 15 .

[0136] In another aspect which may be combined with any of the embodiments or aspects preaddressed or still to be addressed unless in contradiction, the present invention is directed to a hydrolysis or emulsion product, optionally a water-based composition, obtainable by reacting a composition as described herein with a predetermined amount of water or with a predetermined amount of a water-solvent mixture , optionally in the presence of at least one surfactant for the hydrolysis product, or a predetermined amount of water, optionally in the presence of at least one surfactant for the emulsion product .

[0137] The predetermined amount of water or water-solvent mixture for hydrolysis or for emulsifying is determined, e . g . by the molar amount of water to total molar amount of Si in the system confined in typical formulations by upper and lower bound limits . A lower bound value defining the water to total Si molar ratio can be 0.02:1, optionally 0.1 :1 or 0.5:1. An upper bound value defining the water to total Si molar ratio can be 5'000:1, optionally 500:1 or 50:1. The amount of cosolvent can be chosen independently and technically without limitation imposed by the water to Si molar ratios .

[0138] For example, solvents for hydrolysis can be selected from the group consisting of water-soluble organic solvents such as low- molecular weight alcohols, ethers, carboxylic acids, e.g. :

[0139] • alcohols of formula RX-OH with Rxbeing selected from the group consisting of -CH3, -C2H5, -C3H7, -C4H9, -C5H11, and -CsHia;

[0140] • ketones of formula Rx,Ry- (C=O) with Rx,Ryindependently selected from the group consisting of -CH3, -C2H5, and -C3H7;

[0141] • carboxylic acids of formula RX-COOH with Rxbeing selected from the group consisting of -CH3, -C2H5, -C3H7, -C4H9, -C5H11, and -C6H13;

[0142] • low-molecular weight organic esters such as ethyl acetate, methyl acetate or ethyl formate, methyl formate; and / or

[0143] • ethers of formula Rx-O-Rywith Rx,Rybeing independently selected from the group consisting of -CH3, -C2H5, and -C3H7 or cyclic ethers such as tetrahydrofuran.

[0144] Together with the solvent, also an acid or a base can be used as a hydrolysis / condensation catalyst. Typical acids to be used are mineral inorganic acids and low-molecular organic carboxylic acids. Typical bases are alkali hydroxides, ammonia or aliphatic / aromatic primary, secondary or tertiary amines.

[0145] For example, surfactants for hydrolysis and / or emulsification can be selected from the group consisting of

[0146] • non-ionic surfactants such as polyethylene-oxide / polypropylene oxide block copolymers or similar polyether block copolymer surfactants; • carboxylic acid based ionic surfactants , particularly fatty acids and related saturated or unsaturated linear and or branched aliphatic hydrocarbon-carboxylates such as lauric acid, stearic acid, oleic acid etc . and their corresponding alkali salts ;

[0147] • sulfonic acid or phosphonic acid based ionic surfactants , particularly saturated or unsaturated linear and or branched aliphatic alkyl-sulfonates such as dodecylsulfonic acid ( SDS ) or methylsulfonic acid (MSA) or aromatic sulfonates such as toluene sulfonic acid and their corresponding alkali salts ; and / or

[0148] • trialkylammonium salt based ionic surfactants such as cetyltrimethylammonium bromide (CTAB) or cetyltrimethylammonium chloride (CTAC) .

[0149] In another aspect which may be combined with any of the embodiments or aspects preaddressed or still to be addressed unless in contradiction, the present invention is directed to a method for preparing a composition comprising the polymeric liquid material disclosed herein, comprising the following steps :

[0150] (a) providing a Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly (methoxy / ethoxy / propoxy) polysiloxane precursor, optionally comprising

[0151] (al ) di-organofunctional D-type siloxane moieties ; and / or (a2 ) mono-organofunctional T-type siloxane moieties , optionally comprising less than 12 mol-% of (al ) and (a2 ) combined relative to the total amount of all Q-type species ; optionally further comprising a rearrangement catalyst and / or tri-organofunctional M-type siloxane moieties ; and wherein degree of polymerization of the Q-type polysiloxane moieties of the material DPQ-typeis in the range of 1.5 to 2.5, optionally 1.6 to 2.4, optionally 1.65 to 2.35;

[0152] (b) adding:

[0153] (bl) optionally tri-organofunctional M-type silane

[0154] Si (OR1) (Me)3; and adding at least one of

[0155] (b2) di-organofunctional D-type silane Si (OR1) 2 (R2) (R5) , and / or

[0156] (b3) mono-organofunctional T-type silane Si (OR1) 3 (R5) ; in mono- or oligomeric form to the polysiloxane of (a) ;

[0157] (c) optionally adding a rearrangement catalyst to the mixture of step (b) ;

[0158] (d) heating the mixture of (c) , optionally in the absence of water;

[0159] (e) optionally repeating steps (b) to (d) at least once;

[0160] (f) retrieving, optionally isolating and optionally purifying the polymeric liquid material;

[0161] (g) mixing the material of step (e) or (f) with a compound or mixture of compounds in oligomeric or polymeric form, each compound comprising at least one isocyanate or epoxide functional group; in particular wherein if the compound comprises at least one isocyanate group, the compound is mixed in an amount such that the molar ratio of all R5residues to all isocyanate groups in the composition is 1 to at least 5, optionally 1 to at least 6; if the compound comprises at least one epoxide group, the compound is mixed in an amount such that the molar ratio of all R5residues to all epoxide groups in the composition is 1 to at least 10, optionally 1 to at least 17, optionally 1 to at least 25; optionally with the proviso that at least one of steps (a2) or (b3) is carried out, and with the proviso that a rearrangement catalyst is present in at least one of steps (a) or (c) .

[0162] An exemplary method for preparing a composition comprising the polymeric liquid material disclosed herein, comprises the following steps :

[0163] (h) providing a Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly (methoxy / ethoxy / propoxy) polysiloxane precursor, optionally comprising

[0164] (al) di-organofunctional D-type siloxane moieties; and / or (a2) mono-organofunctional T-type siloxane moieties, optionally comprising less than 12 mol-% of (al) and (a2) combined relative to the total amount of all Q-type species ; optionally further comprising a rearrangement catalyst and / or tri-organofunctional M-type siloxane moieties; and wherein degree of polymerization of the Q-type polysiloxane moieties of the material DPQ-typeis in the range of 1.5 to 2.5, optionally 1.6 to 2.4, optionally 1.65 to 2.35;

[0165] (i) adding at least one of a

[0166] (bl) tri-organofunctional M-type silane Si (OR1) (Me) 3; and / or (b2) di-organofunctional D-type silane Si (OR1) 2 (R2) (R3) , wherein

[0167] R2is selected from methyl, vinyl and phenyl; and

[0168] R3is selected from methyl, vinyl and phenyl; and / or

[0169] (b3) mono-organofunctional T-type silane Si (OR1) 3 (R5) ; in mono- or oligomeric form to the polysiloxane of (a) ;

[0170] (j) optionally adding a rearrangement catalyst to the mixture of step (b) ; ( k) heating the mixture of ( c) , optionally in the absence of water;

[0171] ( l ) optionally repeating steps (b) to (d) at least once ;

[0172] (m) retrieving, optionally isolating and optionally purifying the polymeric liquid material ;

[0173] (n) mixing the material of step (e ) or ( f ) with a compound or mixture of compounds in oligomeric or polymeric form, each compound comprising at least one isocyanate or epoxide functional group; in particular wherein if the compound comprises at least one isocyanate group, the compound is mixed in an amount such that the molar ratio of all R5residues to all isocyanate groups in the composition is 1 to at least 5 , optionally 1 to at least 6 ; if the compound comprises at least one epoxide group, the compound is mixed in an amount such that the molar ratio of all R5residues to all epoxide groups in the composition is 1 to at least 10 , optionally 1 to at least 17 , optionally 1 to at least 25 ; with the proviso that at least one of steps (a2 ) or (b3 ) is carried out, and with the proviso that a rearrangement catalyst is present in at least one of steps (a) or ( c) .

[0174] The definitions of chemical substituents in the tri- organofunctional M-type silane Si (OR1) (Me) 3, the di- organofunctional D-type siloxane moieties Si (OR1) 2 (R2) (R3) and Si (OR1) 2 (R2) (R5) , and the mono-organofunctional T-type siloxane moieties Si (OR1) 3 (R5) in the context of the present method correspond to the definitions given in the context of the polysiloxane material described herein . Regarding the Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly (methoxy / ethoxy / propoxy) polysiloxane for use in the present method, in particular the synthesis and characterization thereof, reference is made to WO 2022 / 058059, incorporated by reference in its entirety, specifically pages 42-43. Reference is also made to WO 2022 / 058059 regarding the definition and examples of the rearrangement catalyst for use in the present method, specifically to pages 43-44. Further definitions and examples provided in WO 2022 / 058059 on pages 44-46 apply to the method of the present invention and the definitions and examples are included by reference.

[0175] The compound in step (g) is a compound which reacts with the polymeric liquid material of step (f) to form the R5as defined herein for the polymeric liquid polysiloxane material. The skilled person can determine suitable reactants to obtain the material defined herein.

[0176] For example, an acid catalyst can be selected from of strong acids with a negative pKa value, preferably selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, hydrobromic or hydroiodic acid or organosulf onic acids (methane-, amido- or benzene-sulfonic acid) .

[0177] For example, the reaction temperature for steps (c) through (e) of the method described herein can be in the range from 30 to 170, optionally 50 to 150 or 70°C to 120°C, and the pressure during steps (c) through (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.

[0178] For example, the method can be one, wherein the rearrangement catalyst is selected from the group consisting of

[0179] Ti(IV) (OR13) 4 and Zr(IV) (OR13)4;

[0180] Ti(IV)X4and Zr(IV)X4; - O=Ti(IV)X2and O=Zr(IV)X2);

[0181] - Ti (IV) X2(OR13)2and Zr (IV) X2(OR13)2;

[0182] - Ti (IV) X2(OAcAc)2and Zr ( IV) X2(OAcAc)2;

[0183] - Ti (IV) (OSi (CH3) 3) 4 and Zr (IV) (OSi (CH3) 3) 4;

[0184] - (R13O)2Ti (IV) (OAcAc)2and (R13O)2Zr ( IV) (OAcAc)2;

[0185] - alkali or earth alkali metal ions, optionally selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, optionally Li, Na, K, Rb, optionally Li, Na, K;

[0186] - O=Ti(IV) (OAcAc)2and O=Zr(IV) (OAcAc)2;

[0187] - Ti(IV) (OAc) 4 and Zr(IV) (OAc)4;

[0188] - Ti (IV) (OAc)2(OR13)2and Zr ( IV) (OAc)2(OR13)2; and

[0189] - O=Ti(IV) (OAC)2and O=Zr(IV) (OAc)2; wherein R13is selected from the group consisting of -CH3, - CH2CH3, -CH(CH3)2, -CH2CH2CH3, -C(CH3)3, -CH2CH2CH2CH3and

[0190] CH2CH2CH (CH3)2and wherein X is a halide, a pseudohalide, nitrate, chlorate or perchlorate anion, and wherein the catalyst amount in each of steps (a) or (c) is optionally between 0.01 and 5 mol-%, optionally between 0.05 or 0.1 to 3 mol-%, based on the total molar silicon content present in said step.

[0191] The composition obtained from the method disclosed herein has a specific ratio of R5residues to isocyanate and epoxide groups in the composition. In the context of the present method, the skilled person can either adjust the number of R5residues added during method steps (al) , (a2) , (b2) and / or (b3) relative to the isocyanate and epoxide groups present in the compound or mixture of step (g) , or the skilled person can adjust the amount of compounds and / or the number of epoxide and isocyanate groups in these compounds during step (g) to arrive at the inventive composition, wherein if the composition comprises isocyanate groups, the molar ratio of all R5residues to all isocyanate groups in the composition is 1 to at least 5 , optionally 1 to at least 6 ; if the composition comprises epoxide groups , the molar ratio of all R5residues to all epoxide groups in the composition is 1 to at least 10 , optionally 1 to at least 17 , optionally 1 to at least 25 .

[0192] In another aspect which may be combined with any of the embodiments or aspects preaddressed or still to be addressed unless in contradiction, the present invention is directed to a product obtained or obtainable by the method described herein . In another aspect which may be combined with any of the embodiments or aspects preaddressed or still to be addressed unless in contradiction, the present invention is directed to a blocked isocyanate formulation comprising a composition comprising a polymeric liquid polysiloxane material as described herein, comprising free isocyanate groups , wherein the formulation further comprises a blocking agent for isocyanates , optionally selected from the group consisting of diethyl malonate , dibutyl malonate, sodium bisulfite , 3 , 5- dimethylpyrazole , methylethyl-ketone oxime (MEKO) , phenol and caprolactam, wherein a part or all of the isocyanate groups in the composition are reversibly blocked by chemical reaction with the blocking agent .

[0193] The blocking agent as described herein can be any protecting group for isocyanates known in the art , in particular a protecting group that can be removed by heating the composition beyond a specific blocking temperature which will remove the protecting group . In other words , the scope of the present claims also encompasses formulations , wherein the isocyanate groups are protected or blocked . Formulations comprising blocked isocyanates according to the well-known state of the art in the polyurethane chemistry and products industry (e . g . adhesives and coatings ) and isocyanate containing formulations within the scope of this invention shall account blocked isocyanate groups in much the same way as unreacted or "free" isocyanate groups when it comes to assessing the R5to isocyanate ( -NCO) molar ratio . This is because according to the common logic, blocked isocyanates are labile at room temperature but do not form the final , thermodynamically stable product in the blocked state but only after deblocking and reaction with a suitable reaction partner such as a polyol , amine , or thiol compound a thermodynamically stable final state will be reached . Thus , blocked isocyanate groups retain their reactivity and chemical characteristics of an unblocked NCO group and thus shall be accounted as such herein .

[0194] In another aspect which may be combined with any of the embodiments or aspects preaddressed or still to be addressed unless in contradiction, the present invention is directed to a urethane or thiourea acrylate or methacrylate preparation obtained or obtainable by reacting a composition as defined herein with a hydroxyl- or mercapto-functional acrylate or methacrylate in monomeric or oligomeric form, wherein the composition as described herein comprises isocyanate groups and the molar ratio of all R5residues in the composition to all isocyanate groups in the composition is any molar ratio, or optionally the molar ratio of all R5residues in the composition to all isocyanate groups in the composition is larger than 10 : 1 , optionally larger than 20 : 1 optionally larger than 100 : 1 and / or further optionally, the preparation is essentially free of isocyanate groups (which groups reacted with the acrylate or methacrylate ) .

[0195] The preparation, as used herein (optionally a product ) , comprises the urethane or thiourea acrylates or methacrylates obtained as indicated above . In an embodiment of the preparation according to the present invention, which may be combined with any of the embodiments of the preparation and composition preaddressed or still to be addressed unless in contradiction, the hydroxyl- or mercaptofunctional acrylate or methacrylate is selected from the group consisting of 2-hydroxyethylacrylate (HEA) , 2- hydroxyethylmethacrylate (HEMA) , diethyleneglycol monomethacrylate, diethyleneglycol mono-acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, hydroxypentyl methacrylate, hydroxypentyl acrylate hydroxyhexyl methacrylate, hydroxyhexyl acrylate, 2- mercaptoethyl methacrylate, mercaptopropyl methacrylate, mercaptobutyl methacrylate, mercaptopentyl methacrylate, and mercaptohexyl methacrylate, in particular 2-hydroxyethylacrylate (HEA) , 2-hydroxyethylmethacrylate (HEMA) , diethyleneglycol monomethacrylate, diethyleneglycol mono-acrylate, hydroxyhexyl methacrylate, hydroxyhexyl acrylate, 2-mercaptoethyl methacrylate, and mercaptohexyl methacrylate.

[0196] In an embodiment of the preparation according to the present invention, which may be combined with any of the embodiments of the preparation and composition preaddressed or still to be addressed unless in contradiction, the mass ratio between the composition according to any of claims 1 to 10 and the sum of all the hydroxyl- or mercapto-functional acrylates and methacrylates is from 1:0.03 to 1:5, optionally from 1:0.05 to 1:2, optionally from 1:0.05 to 1:0.85, in particular wherein the molar ratio of all R5residues in the composition to all isocyanate groups in the composition is any molar ratio, optionally is larger than 10:1, optionally larger than 20:1 optionally larger than 100:1, further optionally, the preparation is essentially free of isocyanate groups (which groups reacted with the acrylate or methacrylate) . In an example, the composition used for obtaining the preparation disclosed herein is a composition, wherein R1is methyl or ethyl;

[0197] L has the formula -(CH2)a_, wherein a = 1 to 3, in particular 1 or 3;

[0198] Z is moiety (II) , wherein b is 0, moiety (III) , wherein b is 0, moiety (V) , wherein b is 0, or moiety (IV) or moiety (VI) , wherein b is 0, a in moiety (IV) or (VI) is 1, R9is -COOEt or -COOMe, X is 0, and R10is -OEt or -OMe; and optionally R8is an aliphatic isocyanate residue, aliphatic isocyanurate residue, aromatic isocyanate residue and / or isocyanurate residue.

[0199] An exemplary protocol for obtaining the preparation disclosed herein includes the following steps: (Ala) providing or preparing a polymeric liquid polysiloxane material, optionally comprising moiety (III) , (IV) , (V) or (VI) as Z, according to standard protocols, for example prepared as described in Example 1 below, and (Alb) reacting said polymeric liquid polysiloxane material or the composition with an amount of an isocyanate compound in monomeric or oligomeric form or an isocyanate functional prepolymer, e.g. in neat form and / or at a temperature between 40°C and 80°C, preferably at around 60°C, e.g. for a period of half an hour, e.g. with stirring, in particular until the initially turbid mixture clears up, or

[0200] (A2) providing a composition as disclosed herein, followed by (B) reacting the mixture of (Alb) or (A2) with an amount of a hydroxy-functional acrylate, methacrylate or mercaptofunctional methacrylate, optionally in the presence of a polyurethane catalyst such as, e.g., DABCO or DBTDL, e.g. at a temperature between 20°C and 65°C, optionally in the presence of a solvent or monomer / dimer / trimer acrylate or methacrylate as a reactive diluent, optionally with stirring .

[0201] In another aspect which may be combined with any of the embodiments or aspects preaddressed or still to be addressed unless in contradiction, the present invention is directed to a IK or 2K curable composition, optionally a water-based IK or 2K curable composition, comprising the composition and / or the preparation as described herein.

[0202] The IK or 2K water-based composition can be, e.g., a surface coating composition, a water-based epoxy binder composition, a film former ingredient for example for water based sizings or finishings in glass fiber technology applications. Other application examples may include applications in water-based coatings and adhesives such as 2K water-based epoxy coatings or IK polymer dispersion adhesives and coatings such as acrylate, SBR, latex, PVA and PU dispersions.

[0203] In the following, the invention will be illustrated by reference to Figures which are not intended to limit the scope of the invention as described in the appended claims.

[0204] FIGURES

[0205] Fig. 1 shows a29Si NMR spectrum of a pure Q-Type polysiloxane (containing no grafted T-type moieties) with DPQ=1.99 and silanol moieties (shown as QI, Q2 and Q3 Si-OH) amounting to approximately 6.5 mol%.

[0206] Fig. 2 shows a29Si NMR spectrum of a R5-unfunctionalized (i.e. R6=H) ethyl silicate / APTMS polycondensate material with nQ-tyPe : nT-type = 1 : 0 . 15 as described in Example la and combined Q2r-type and Q3s'd-type siloxane ring species content of approximately 23% .

[0207] Fig . 3 shows a29Si NMR spectrum of a R5-unfunctionalized ( i . e . R6=H) D-50 / APTES polycondensate material with nQ-tyPe : nT-tyPe = 1 : 0 . 20 as described in Example lb with a combined Q2r-type and Q3s'd-type siloxane ring species content of approximately 15% .

[0208] Fig . 4 shows a29Si NMR spectrum of a R5-unfunctionalized ( i . e .

[0209] R6=H) ethyl silicate / PAPTMS polycondensate material with nQ-type: nT-type= 1 : 0 . 15 as described in Example Id and a combined Q2r- type and Q3s'd-type siloxane ring species content of approximately 25% .

[0210] EXAMPLES

[0211] As used herein, R5-unsubstituted and R5-unfunctionalized means that R6is H .

[0212] Example 1 describes the preparation of various R5-unsubstituted ( i . e . R6=H) polymeric liquid Q (T / D) -polysiloxane materials which are then used to prepare isocyanate and epoxy derivatized materials and compositions .

[0213] Example 2 describes the preparation of epoxy and / or isocyanate derivatized materials and compositions .

[0214] Example 3 describes a comparative test highlighting the advantage of phenyl-amino R5bearing isocyanate compositions over their non-phenyl amine and mercapto counterparts in terms of stability .

[0215] In all examples , the mol-percentage of (tetrasiloxane ) ring species refers to the sum of all Q2and Q3ring species relative to the total number of Q species also referred herein as

[0216] % (Q2r&Q3s, d) ring species unless specifically mentioned otherwise .

[0217] Example la : synthesis of an R5- unfunctionalized ethylsilicate I APTMS polycondensate material with nQ-type : nx-type = 1 : 0 . 15 625.0 g / 4.66 mol Si equivalent of a Q-type precursor with a DP_QtyPe of 1.99 and 39.8% ring species prepared by nonhydrolytic condensation of tetraethoxysilane (TEOS) with acetic anhydride in the presence of a Titanium (IV) isopropoxide rearrangement catalyst were placed inside a 1 L Pyrex glass bottle with cap and then 125.4 g / 0.70 mol of a monomeric T-type precursor 3- aminopropylrimethoxysilane (APTMS) was mixed in without further rearrangement catalyst addition. The flask was then capped and placed inside a heating cabinet set at 105°C and kept there for a period of 36 hours. Residual volatiles were removed by bubbling dry nitrogen through the product for a period of 24 hours at an elevated temperature of 60 °C.29Si NMR analysis confirmed that the product contained less than 6.5% of T°-monomer measured by the total amount of T-type moieties (A(T°) / A(Ttota1) ) , as well as less than 24% of Q-type tetrasiloxane ring species .

[0218] Example lb: Synthesis of an R5- unfunctionalized D-50 I APTES polycondensate material with nQ-type : nT-type = 1 : 0.20

[0219] 855.0 g / 6.38 mol Si equivalent of a commercial ethylsilicate Q-type precursor "Dynasylan Silbond 50 (D-50) " (Evonik Industries) or equivalent was placed inside a 2 L glass reactor with refluxing column in an oil bath together with 282.5 g / 1.28 mol of a monomeric T-type precursor 3-aminopropyltri- ethoxysilane (APTES) . The mixture was heated to a temperature of 120°C at which point a rearrangement catalyst tetrakis (tri- methylsiloxy) titanium ( IV) was added to the hot mixture. The mixture was kept stirring for a period of 18 hours. The reflux condenser was then replaced with a distillation bridge to remove the remaining volatiles through distillation.29Si NMR analysis confirmed that the product contained less than 11% T°-monomer measured by the total amount of T-type moieties, as well as less than 16% of Q-type tetrasiloxane ring species. Example 1c: Synthesis of an R5- unfunctionalized ethylsilicate / BAPTMS polycondensate material with ng-type : nT-type = 1 : 0.10

[0220] The same procedure shown in the Example la was used with the difference that n-butylaminopropyltrimethoxysilane (BAPTMS) in the amount of 109.8g / 0.46 mol was used as the T-type precursor. The reaction temperature and time were adjusted to 105°C and 26 hours and Zr ( IV) -acetoxyacetate was used as the rearrangement catalyst.29Si NMR analysis confirmed that the product contained less than 15% T°-monomer measured by the total amount of T-type moieties, as well as less than 23.5% of Q-type tetrasiloxane ring species.

[0221] Example Id: Synthesis of an R5- unfunctionalized ethylsilicate / PAPTMS polycondensate material with ng-type : nT-type = 1 : 0.15

[0222] The same procedure shown in the Example la was used with the difference that N-phenylaminopropyltrimethoxysilane (PAPTMS, commercially available as Silquest™ Y-9669, Momentive) in the amount of 178.7g / 0.70 mol was used as the T-type precursor. The reaction temperature and time were adjusted to 105°C and 24 hours.29Si NMR analysis confirmed that the product contained less than 10% T°-monomer measured by the total amount of T-type moieties, as well as less than 26% of Q-type tetrasiloxane ring species .

[0223] Example le : Synthesis of an R5- unfunctionalized ethylsilicate I VBPEADITMS polycondensate material with ng-type : nT-type = 1 : 0.08

[0224] The same procedure shown in the Example la was used with the difference that Nl- (Vinylbenzyl) -N2- (3- (trimethoxysilyl) propyl) - ethane-1 , 2-diamine hydrochloride (VBPEADITMS, commercially available as DOWSIL™ SZ 6032, Dow Inc.) was used as the T-type precursor. DOWSIL™ SZ 6032, which comprises 40% silane in methanol, was added in the amount of 349.83g (equivalent to 0.37 mol of the T-silane) to the Q-type precursor. The reaction temperature and time were adjusted to 105°C and 36 hours.29Si NMR analysis confirmed that the product contained less than 9.8% T°-monomer measured by the total amount of T-type moieties, as well as less than 21.6% of Q-type tetrasiloxane ring species.

[0225] Example If : Synthesis of an R5- unfunctionalized ethylsilicate / BPEDATMS polycondensate material with ng- type : nT-type = 1 : 0.18

[0226] The same procedure shown in the Example la was used with the difference that N-benzyl-N [3- (trimethoxysilyl) propyl] ethylenediamine monohydrochloride (BPEDATMS, commercially available as Silquest™ A-1128, Momentive) was used as the T-type precursor. Silquest™ A-1128, which comprises 50% silane in methanol, was added in the amount of 585.9g (equivalent to 0.84 mol of the T-silane) to the Q-type precursor. The reaction temperature and time were adjusted to 105°C and 34 hours.29Si NMR analysis confirmed that the product contained less than 14.5% T°-monomer measured by the total amount of T-type moieties, as well as less than 22.6% of Q-type tetrasiloxane ring species.

[0227] Example 1g: Synthesis of an R5- unfunctionalized TEOS I APTMS (+ moiety II, b = 2, R1' = Et, R4= Cl) polycondensate material with nQ-type : nT-type=1 : 0.10

[0228] Substituted phenylsilane I

[0229] The same procedure shown in the Example la was used with the difference that a T-silane with the following specifications: moiety II, b=2, R1,=Et, R4= Cl described here was used as the T-type precursor and added in the amount of 214.63g / 0.47 mol to the Q-type precursor. The reaction temperature and time were adjusted to 105°C and 34 hours.29Si NMR analysis confirmed that the product contained less than 9.4% T°-monomer measured by the total amount of T-type moieties, as well as less than 20.6% of

[0230] Q-type tetrasiloxane ring species. Example Ih: Synthesis of an R5- unfunctionalized ethylsilicate / APTMS (+ moiety II, b = 1, Rv= H, R4= NO2) polycondensate material with ng- type : nT-type = 1 : 0.20

[0231] Substituted Phenylsilane II

[0232] The same procedure shown in the Example la was used with the difference that a T-silane with the following specifications: moiety II, b = 1, Rv= H, R4= NO2 described here was used as the T-type precursor and added in the amount of 320.38g / 0.93 mol to the Q-type precursor. The reaction temperature and time were adjusted to 105°C and 30 hours.29Si NMR analysis confirmed that the product contained less than 15% T°-monomer measured by the total amount of T-type moieties, as well as less than 18.8% of Q-type tetrasiloxane ring species.

[0233] Example li : Synthesis of an R5- unfunctionalized ethylsilicate I MPTMS polycondensate material with nQ-type : nT-type = 1 : 0.12

[0234] The same procedure shown in the Example la was used with the difference that (3-Mercaptopropyl) trimethoxysilane (MPTMS, commercially available as Dynasylan® MTMO, Evonik Industries AG) in the amount of 109.81g / 0.56mol was used as the T-type precursor. The reaction temperature and time were adjusted to 100°C and 26 hours.29Si NMR analysis confirmed that the product contained less than 9% TO-monomer measured by the total amount of T-type moieties, as well as less than 16.5% of Q-type tetrasiloxane ring species.

[0235] Example 1 j : Synthesis of R5- unfunctionalized ethylsilicate / 1 , 4-diethyl N- [3- (trimethoxy silyl) propyl] aspartate polycondensate material with ng-type : nT-type = 1 : 0.15

[0236] 100 g of 3-aminopropylrimethoxysilane (APTMS) was mixed with 96.03 g of diethyl maleate in a reaction flask to prepare 1,4- Diethyl N- [3- (trimethoxysilyl) propyl] aspartate (the diethyl maleate-APTMS adduct which will serve as a monomeric T-type precursor) via aza-Michael addition. The mixture was kept at 50°C for 2 hours under continuous stirring.

[0237] 450.0 g / 3.36 mol Si equivalent of a Q-type precursor with a DP_QtyPe of 1.99 and 39.8% ring species prepared by nonhydrolytic condensation of tetraethoxysilane (TEOS) with acetic anhydride in the presence of a Titanium (IV) isopropoxide rearrangement catalyst were placed inside a 1 L Pyrex glass bottle with cap and then 176.91 g / 0.503 mol of the above monomeric T-type precursor 1,4-diethyl N- [3- (trimethoxysilyl) propyl] aspartate was mixed in without further rearrangement catalyst addition. The flask was then capped and placed inside a heating cabinet set at 100°C and kept there for a period of 36 hours. Residual volatiles were removed by bubbling dry nitrogen through the product for a period of 24 hours at an elevated temperature of 95 °C.29Si NMR analysis confirmed that the product contained less than 5.6% of T°-monomer measured by the total amount of T-type moieties (A(T°) / A(Ttota1) ) , as well as less than 24.2% of Q-type tetrasiloxane ring species.

[0238] Example Ik: Synthesis of R5- unfunctionalized ethylsilicate I dibutyl maleate-APTMS adduct polycondensate material with ng-type : Hr-type — 1 ■ 0.10

[0239] 100 g of 3-aminopropylrimethoxysilane (APTMS) was mixed with 127.39 g of dibutyl maleate in a reaction flask to prepare dibutyl maleate-APTMS adduct (monomeric T-type precursor) via aza-Michael addition. The mixture was kept at 50 °C for 2 hours under continuous stirring. 400.0 g / 2.99 mol Si equivalent of a Q-type precursor with a DP_QtyPe of 1.99 and 39.8% ring species prepared by nonhydrolytic condensation of tetraethoxysilane (TEOS) with acetic anhydride in the presence of a Titanium (IV) isopropoxide rearrangement catalyst were placed inside a 1 L Pyrex glass bottle with cap and then 125.76 g / 0.298 mol of the above monomeric T-type precursor (dibutyl maleate-APTMS adduct) was mixed in without further rearrangement catalyst addition. The flask was then capped and placed inside a heating cabinet set at 100°C and kept there for a period of 28 hours. Residual volatiles were removed by bubbling dry nitrogen through the product for a period of 24 hours at an elevated temperature of 60 °C.29Si NMR analysis confirmed that the product contained less than 5.0% of T°-monomer measured by the total amount of T-type moieties (A(T°) / A(Ttota1) ) , as well as less than 22.6% of Q-type tetrasiloxane ring species.

[0240] Example 11 : Synthesis of R5- unfunctionalized ethylsilicate / dimethyl itaconate-APTMS adduct polycondensate material with ng- type • Uj-type=1 I 0.20

[0241] 150 g of 3-aminopropylrimethoxysilane (APTMS) was mixed with 132.31 g of dimethyl itaconate in a reaction flask to prepare dimethyl itaconate-APTMS adduct (monomeric T-type precursor) via aza-Michael addition. The mixture was kept at 50 °C for 2 hours under continuous stirring. 380.0 g / 2.84 mol Si equivalent of a Q-type precursor with a DP_Qtypeof 1.99 and 39.8% ring species prepared by nonhydrolytic condensation of tetraethoxysilane (TEOS) with acetic anhydride in the presence of a Titanium (IV) isopropoxide rearrangement catalyst were placed inside a 1 L Pyrex glass bottle with cap and then 207.14 g / 0.567 mol of the above monomeric T-type precursor (dimethyl itaconate-APTMS adduct) was mixed in without further rearrangement catalyst addition. The flask was then capped and placed inside a heating cabinet set at 100°C and kept there for a period of 24 hours. Residual volatiles were removed by bubbling dry nitrogen through the product for a period of 24 hours at an elevated temperature of 60 °C.29Si NMR analysis confirmed that the product contained less than 5.3% of T°-monomer measured by the total amount of T- type moieties (A(T°) / A(Ttota1) ) , as well as less than 23.5% of Q- type tetrasiloxane ring species. Example Im: Synthesis of R5- unfunctionalized ethylsilicate / ethyl cinnamate-APTMS adduct polycondensate material with ng-type : nj-type=1 • 0 • 04

[0242] 200 g of 3-aminopropylrimethoxysilane (APTMS) was mixed with 196.65 g of ethyl cinnamate in a reaction flask to prepare ethyl cinnamate-APTMS adduct (monomeric T-type precursor) via azaMichael addition. The mixture was kept under nitrogen at 115 °C for 24 hours with continuous stirring. 600.0 g / 4.48 mol Si equivalent of a Q-type precursor with a DP_Qtype of 1.99 and 39.8% ring species prepared by nonhydrolytic condensation of tetraethoxysilane (TEOS) with acetic anhydride in the presence of a Titanium (IV) isopropoxide rearrangement catalyst were placed inside a 1 L Pyrex glass bottle with cap and then 63.62 g / 0.179 mol of a monomeric T-type precursor (ethyl cinnamate- APTMS adduct) was mixed in without further rearrangement catalyst addition. The flask was then capped and placed inside a heating cabinet set at 100°C and kept there for a period of 33 hours. Residual volatiles were removed by bubbling dry nitrogen through the product for a period of 24 hours at an elevated temperature of 60 °C.29Si NMR analysis confirmed that the product contained less than 5.0% of T°-monomer measured by the total amount of T-type moieties (A(T°) / A(Ttota1) ) , as well as less than 24.1% of Q-type tetrasiloxane ring species.

[0243] Example In synthesis of R5-ethylsilicate I cinnamon! tri le -APTMS adduct polycondensate material with nQ-type : nT-type = 1 : 0.07

[0244] 200 g of 3-aminopropylrimethoxysilane (APTMS) was mixed with 149.18 g of cinnamonitrile in a reaction flask to prepare cinnamonitrile-APTMS adduct (monomeric T-type precursor) via aza-Michael addition. The mixture was kept at 50 °C for 9 hours under continuous stirring. 600.0 g / 4.48 mol Si equivalent of a Q-type precursor with a DP_Qtype of 1.99 and 39.8% ring species prepared by nonhydrolytic condensation of tetraethoxysilane (TEOS) with acetic anhydride in the presence of a Titanium (IV) isopropoxide rearrangement catalyst were placed inside a 1 L Pyrex glass bottle with cap and then 96.61 g / 0.313 mol of a monomeric T-type precursor (cinnamonitrile-APTMS adduct) was mixed in without further rearrangement catalyst addition. The flask was then capped and placed inside a heating cabinet set at 105°C and kept there for a period of 36 hours. Residual volatiles were removed by bubbling dry nitrogen through the product for a period of 17 hours at an elevated temperature of 75°C.29Si NMR analysis confirmed that the product contained less than 5.0% of T°-monomer measured by the total amount of T-type moieties (A(T°) / A(Ttotai) ) , as well as less than 21.6% of Q-type tetrasiloxane ring species.

[0245] Example lo: Synthesis of an R5- unfunctionalized ethylsilicate I APMDMS polycondensate material with ng-type : no-type = 1 : 0.16

[0246] The same procedure shown in the Example la was used with the difference that a D-type silane precursor aminopropylmethyldimethoxysilane (APMDS) in the amount required to reach the above indicated molar ratio was used instead of the T-type analogue APTMS .29Si NMR analysis confirmed that the product contained less than 8.1% D°-monomer measured by the total amount of D-type moieties, as well as less than 22.9% of Q-type tetrasiloxane ring species.

[0247] Example Ip: Synthesis of an R5- unfunctionalized ethylsilicate /

[0248] PAPMDMS polycondensate material with ng-type : no-type = 1 : 0.17

[0249] The same procedure shown in the Example Id was used with the difference that N-phenylaminopropyl-methyldimethoxysilane

[0250] (PAPMDS) in the amount required to reach the above indicated molar ratio was used as the R5-bearing D-type precursor.29Si NMR analysis confirmed that the product contained less than 7.4% D°- monomer measured by the total amount of D-type moieties , as well as less than 23 . 2% of Q-type tetrasiloxane ring species .

[0251] Example Iq: Synthesis of R5- unfunctionalized ethylsilicate I 1 , 4-diethyl N- [3- (trimethoxy silyl) propyl] aspartate polycondensate material with ng-type : nT-type : no-type = 1 : 0.09 : 0.06

[0252] The same procedure shown in the Example Ij was used with the difference that the aspartrate functional monomer silane was a blend of T-type and D-type R5precursors , prepared by i ) blending aminopropyltrimethoxysilane (APTMS ) and aminopropylmethyldimethoxysilane (APMDMS ) in as 3 : 2 molar ratio and ii ) reacting it with an equimolar amount of diethyl maleate in the same way as in example Ij to create the T- and D-type silane aspartate functional silane blend . Grafting of this blend was then carried out in the same way, yielding the product .29Si NMR analysis confirmed that the product contained less than 7 . 4 % D°- monomer measured by the total amount of D-type moieties , as well as less than 21 . 5% of Q-type tetrasiloxane ring species .

[0253] Example Ir : Synthesis of R5-ethylsilicate / cinnamon! tri le -APMDMS adduct polycondensate material with ng-type : no-type = 1 : 0.07

[0254] The same procedure shown in the Example In was used with the difference that the functional silane used for grafting was first prepared by reacting aminopropyl-methyldimethoxysilane (APMDMS ) in the amount required to reach the above indicated molar ratio was used as the R5D-type precursor .29Si NMR analysis confirmed that the product contained less than 6 . 2 % D°- monomer measured by the total amount of D-type moieties , as well as less than 22 . 0% of Q-type tetrasiloxane ring species .

[0255] Comparative Example 2a :

[0256] 50g of a material from example la was pre-heated to 60 ° C in a round bottom flask together with 130 . 05 g of pre-warmed ( 60 ° C) bisphenol A based epoxy resin (Araldite® LY556, Huntsman) . Next, 1, 8-Diazabicyclo [5.4.0] undec-7-ene (DBU) was added as a catalyst and the mixture was heated to 100°C with stirring. The initially opaque whitish mixture turned clear and homogeneous over the course of approximately 60 minutes at which point the heating was turned off and the mixture was allowed to cool to room temperature. The final product had an epoxy group to R5molar ratio of 6.5:1. When kept at room temperature / 50 °C in a heating cabinet, the composition gelled after approximately 11 weeks / 20 days, respectively, indicating an insufficient shelflife .

[0257] Example 2a:

[0258] A composition identical to the one given in comparative example 2a was prepared with the main difference that after following the above preparation step, to the final mixture an additional amount of 303.46 g of the same bisphenol A epoxy resin prewarmed to 60 °C was added to the mixture. The resulting product was then stirred at 60°C for 5 minutes to ensure proper homogenization. The resulting composition had an epoxy group to R5molar ratio of 24.0:1 and was a slightly yellow, viscous liquid with a shelf life at room temperature of over 18 months with no noticeable viscosity increase. Even when stored in the heating cabinet, the product remained liquid after up to 6 months at 50 °C, indicating good long-term stability of the product.

[0259] Comparative Example 2b:

[0260] 1550g of a material produced according to a protocol identical to the one described in example 1c was placed inside a stirred 201 glass reactor and pre-heated to 95°C, at which point, 850g of a bisphenol A based epoxy resin (Epilox M 1052G, Leuna Harze, Germany) pre-heated to 95 °C was added with stirring. The mixture was heated to 110°C with stirring and a tertiary amine base (dimethylphenylamine) was added as a catalyst. The reaction mixture was stirred for approximately 135 minutes at which point it had completely cleared up. The heating was turned off and the mixture allowed to cool to 70 °C. The procedure yielded a slightly yellowish transparent resin with an epoxy to R5ratio of around 4.09 : 1 and a viscosity of around 1700-1900 mPa-s. Over time, however the viscosity of the mixture increased all the way to the point of gelation, indicating unsatisfactory shelf like of less than 4 months.

[0261] Example 2b:

[0262] The same protocol as in Comparative example 2b was employed to prepare this material, however at the end of the procedure, an additional amount of 2756g of the same Epilox M1052 G epoxy resin was added at the end of the reaction with stirring. The hot reaction mixture was then allowed to cool to room temperature, producing slightly yellowish transparent resin with an epoxy to R5ratio of around 20.57 : 1 and a viscosity around 1200-1400 mPa's. Over time, however, the viscosity of the mixture did not longer increase considerably, and the composition when tested after 15 months displayed still the same viscosity and performance as when freshly prepared.

[0263] Comparative Example 2c:

[0264] A protocol identical to the one given in Comparative Example 2a was used with the difference, that as QT-polysiloxane, 50g of a material from Example Id and 53.59g of bisphenol F based epoxy resin (Araldite GY282) were used. The material was prepared in such a way as to yield an epoxide to R5molar ratio of 6.2 : 1. The product was not stable, gelling after 12 days of accelerated aging storage conditions in a heating cabinet at 55 °C.

[0265] Example 2c: The above material from Comparative Example 2c was further diluted with 208.25g of Araldite GY282 epoxy resin at 55°C to yield an epoxide to R5molar ratio of 34.2 : 1. The product did not show any signs of aging or viscosity increase after 3 months of accelerated aging in a heating cabinet at 55°C.

[0266] Comparative Example 2d:

[0267] A protocol identical to the one given in Comparative Example 2b was used with the difference, that as QT-polysiloxane, a material from Example lb and a novolac epoxy resin with a functionality of 2.5 (D.E.N. 425, Olin Corporation) were used. The material was prepared in such a way as to yield an epoxide to R5molar ratio of 6.6 : 1. The product showed poor storage stability, gelling after 8 days of accelerated aging storage conditions in a heating cabinet at 50 °C and after 22 days when kept at room temperature.

[0268] Example 2d:

[0269] The above material from Comparative Example 2d was further diluted with D.E.N. 425 epoxy resin. The resulting composition had an epoxide to R5molar ratio of 40.8 : 1. The product did not show any signs of aging or viscosity increase after 3 months of accelerated aging in a heating cabinet at 50°C.

[0270] Example 2e :

[0271] A protocol identical to the one given in Comparative Example 2b was used with the difference, that as QT-polysiloxane, a material from Example lh and an epoxidized vegetable oil epoxy resin (Lankroflex™ E2307 with EEW of 242 g / Eq, Valtris Specialty Chemicals) were used. The material was prepared in such a way as to yield an epoxide to R5molar ratio of 16.9 : 1. The composition was stable for more than 18 months and did not show any noticeable increase in viscosity after 7 weeks storage in a heating cabinet at 60 °C. Comparative Example 2f:

[0272] 125g of a polysiloxane material from Example Id pre-heated to 60 °C is added to a round bottom flask under nitrogen together with 87.3 g of pre-heated (60°C) aliphatic polyisocyanate resin based on hexamethylene diisocyanate (HDI) commercially available as Desmodur® ultra N 3900 (Covestro) . The mixture is heated to 60°C and stirred by means of an overhead stirrer for 30 min until the mixture turns clear. Next, 1.25g of a stabilizer was added to the mixture and the final product was collected. The composition is a viscous liquid with an isocyanate to R5ratio of approximately 3.48 : 1. When stored under ambient conditions, it has a shelf life of approximately 3-4 months, at which point the product gels. Gelation happens after about 3 weeks when kept at 50°C in a heating cabinet.

[0273] Example 2f:

[0274] A product just like the one in the comparative example 2f above was prepared with the main difference that a second portion of 145.2 g Desmodur® ultra N 3900 isocyanate (again pre-heated to 60 °C) was added and the mixture was stirred at elevated temperature for another 20 minutes. The stabilizer was added at the end of the procedure (only one addition with a total amount of 1.25g) . This composition is also a viscous liquid but with an isocyanate to R5ratio of approximately 10.94 : 1 but it had a shelf-life of over 12 months without gelation and did not show any signs of increased viscosity when stored in a heating cabinet for 4 months at 50°C.

[0275] Comparative Example 2g:

[0276] 500g of a polysiloxane material from Example 1c was placed in a stirred glass reactor under inert gas atmosphere. Then, 450ml of water-free butyl acetate was added and the mixture was preheated to 55°C. Next, 260g of an aliphatic HDI polyisocyanate resin (Desmodur® ultra N 3900, Covestro) was preheated to 65°C and added over the course of 10 minutes from a heated round bottom reservoir vessel by means of a transfer capillary. The mixture was kept stirring at 60 °C for roughly 45 min at which point it had turned clear. Next, 5.4g of a stabilizer was added to the mixture and the final product was collected. The composition is a viscous liquid with an R5to isocyanate ratio of approximately 3.58 : 1. When stored under ambient conditions, it has a shelf life of approximately 3-4 months, at which point the product gels. Gelation happens after about 3 weeks when kept at 50°C in a heating cabinet.

[0277] Example 2g:

[0278] A product just like the one in the comparative example 2g above was prepared with the main difference that a second portion of 423g Desmodur® ultra N 3900 isocyanate (again pre-heated to 60 °C) was added and the mixture was stirred at elevated temperature for another 20 minutes. The stabilizer was added at the end of the procedure (only one addition with a total amount of 1.25g) . The composition is a viscous liquid with an R5to isocyanate ratio of approximately 11.03 : 1 This composition had a shelf-life of over 12 months without gelation and did not show any signs of increased viscosity when stored in a heating cabinet for 4 months at 50°C.

[0279] Example 2h:

[0280] A product just like the one in the comparative example 2f above was prepared, with the main difference that a second portion of 58.1 g of a different isocyanate resin (Tolonate HDB-LV, Vencorex) was added. The composition is a slightly yellow viscous liquid with an isocyanate to R5ratio of approximately 6.3 : 1 and a shelf-life of around 15 months when kept at room temperature . Example 21

[0281] 50 g of a material from Example Id pre-heated to 60°C was placed inside a round bottom flask under Argon. 22.2 g of pre-heated (60 °C) aromatic polyisocyanate based on diphenylmethane diisocyanate (MDI) commercially available as Desmodur® VL was then added at a constant rate over the course of 5 minutes. The mixture was then heated to 60 °C under stirring for 30 min until the mixture turned clear. A second portion of Desmodur® VL preheated to 60°C (14.8 g) was added to the mixture. After 20 minutes of stirring at 60°C, 0.45 g of a stabilizer was added to the mixture. The final product is collected. The composition is a yellow viscous liguid with an isocyanate to R5ratio of approximately 5.4 : 1 and a shelf-life of around 8 months at which point the product gels. Gelation also happened within 2 months when kept at 50 °C in a heating cabinet.

[0282] Comparative example 2 j :

[0283] 125g of a polysiloxane material from Example Ih was placed in a stirred glass vessel under inert gas atmosphere and the mixture was pre-heated to 55°C. Then, 460g of an aliphatic IPDI polyisocyanate resin (Desmodur® Z 4470 BA, Covestro) was preheated to 65 °C and added over the course of 10 minutes from a heated round bottom reservoir vessel by means of a transfer capillary. The mixture was kept stirring at 60°C for roughly 40 min at which point it had turned clear. Next, 1.4g of a stabilizer was added to the mixture and the final product was collected. The composition is a light yellow viscous liquid with an isocyanate to R5ratio of approximately 4.18 : 1. When stored under ambient conditions, it has a shelf life of approximately 3-4 months, at which point the product gels. Gelation happens after about 3 weeks when kept at 50 °C in a heating cabinet.

[0284] Example 2j A product just like the one in the comparative example 2j was prepared with the main difference that a second portion of 600g Desmodur® Z 4470 BA isocyanate (again pre-heated to 60°C) was added and the mixture was stirred at elevated temperature for another 20 minutes. Then, the stabilizer was added at the end of the procedure (only one addition with a total amount of 1.4g) . This material is a yellow viscous liquid with an isocyanate to R5ratio of approximately 10.94 : 1 and had a shelf-life of over 12 months without gelation and did not show any signs of increased viscosity when stored in a heating cabinet for 5 months at 50 °C.

[0285] Example 2k

[0286] An isocyanate containing product was prepared using a polyethylyene oxide based hexymethylene diisocyanate (HDI) prepolymer. To this purpose, HDI was reacted in a 0.98:1 molar ratio with a polyethylene glycol diol with a molecular weight of roughly lOOOg / mol (PEG-OH 1000) in the presence of a tin-based catalyst. The prepolymer was then reacted with a material from Example le in such a way that a isocyanate to R5ratio of approximately 7.1 : 1 was reached. To the final product, 0.3% of a stabilizer was added. The viscous liquid was a stable composition with good shelf life (> 16 months at room temperature) and good film-forming properties.

[0287] Example 21

[0288] A material similar to the one described in Example 2k above was prepared with the key differences being the type of prepolymer and the blending ratio. As polyol, a commercial acrylic polyol with a molecular weight Mw = 2200 was used and the prepolymer was prepared using a mixture of 60 parts IPDI and 40 parts MDI by mass. The composition had a isocyanate to R5ratio of 8.2 : 1 and was a stable at room temperature / 50 °C for more than 18 months / 4 months, respectively. Example 2m

[0289] A material similar to the one described in Example 2k was prepared with the difference that the isocyanate prepolymer was based on a blended low-molecular weight polyol - prepolymer mixture . Said mixture was prepared by reacting a 36% by mass and 64% by mass mixture of glycerine and propylene glycol with a stoichiometric amount of toluene diisocyanate (TDI ) . Said prepolymer was then reacted with a material from Example 1g to reach a isocyanate to R5of 7 . 8 : 1 . The product showed excellent shelf-life and stability as well as high crosslink reactivity when used in 2K PU adhesive products .

[0290] Example 2n

[0291] A material similar to the one described in Example 2k was prepared with the difference that a commercial polyester polyol was used to prepare the isocyanate prepolymer . The prepolymer was prepared from a Baycoll® AD 2055 commercial polyester polyol (Covestro ) using a mixture of 60 parts IPDI and 40 parts MDI by mass . The composition had a isocyanate to R5ratio of 5 . 9 : 1 and was a stable at room temperature / 50 °C for more than 18 months / 4 months , respectively .

[0292] Example 2o

[0293] A material similar to the one described in Example 2k was prepared with the difference that a custom-made polyester polyol was used to prepare the isocyanate prepolymer . The prepolymer was prepared from a polyester synthesized from ethylene glycol and a mixture of adipic anhydride and maleic anhydride which was then reacted with an MDI / TDI blend . The composition had a isocyanate to R5ratio of 9 . 2 : 1 and was a stable at room temperature without any noticeable change in viscosity over the course of more than 18 months .

[0294] Example 2p A material identical to the one in Example 2 f was prepared but with the difference that after the second addition of the Desmodur N3900 isocyanate addition step, an amount of a bisphenol A epoxy resin (BE188EL, Chang Chun Plastic) was added with continuing stirring the blend at temperature for an additional 20 minutes such that the resulting product had a isocyanate to R5ratio of approximately 10 . 94 : 1 and an epoxy to R5ratio of 4 . 4 : 1 . The product was stable for over 14 months at room temperature without any noticeable change in viscosity .

[0295] Example 2q

[0296] A material identical to the one in Example 2e was prepared but with the difference that after complete epoxy resin addition, a portion of Desmodur N3200 isocyanate resin was also added with continuing stirring the blend at temperature for an additional 20 minutes . The resulting product had an epoxy to R5ratio of 16 . 9 : 1 and a isocyanate to R5ratio of approximately 2 . 2 : 1 . The product was stable for over 14 months at room temperature without any noticeable change in viscosity .

[0297] Example 2r :

[0298] 87g of a polysiloxane material from Example li was placed in a stirred glass reactor under inert gas atmosphere . Then, 74ml of water-free butyl acetate was added and the mixture was preheated to 55 ° C . Next , 68g of an aliphatic HDI polyisocyanate resin (Desmodur® ultra N 3900 , Covestro ) was preheated to 65 ° C and added over the course of 5 minutes from a heated round bottom reservoir vessel by means of a transfer capillary . The mixture was kept stirring at 60 ° C for roughly 25 min . A second portion of 53g Desmodur® ultra N 3900 isocyanate (again preheated to 60 ° C) was added into the mixture in the same way as the first portion of the isocyanate and the whole mixture was stirred at elevated temperature for another 25 minutes . Then, 0 . 8g of a stabilizer was added into the mixture and the final product was collected . The composition is a viscous liquid with an R5to isocyanate ratio of approximately 9 . 21 : 1 . When stored under ambient conditions , it has a shelf life of approximately 12 months without gelation and did not show any signs of increased viscosity when stored in a heating cabinet for 3 months at 50 ° C .

[0299] Example 2s

[0300] A material similar to the one described in Example 2t was prepared starting with a polysiloxane material from Example comprising cinnamonitrile groups according to Example In . The molar ratio between Desmodur® ultra N 3900 isocyanate and the R5functional groups in the polysiloxane material was kept roughly the same . The resulting composition had a isocyanate to R5ratio of 9 . 1 : 1 and was a stable at room temperature without any noticeable change in viscosity over the course of more than 15 months under ambient conditions .

[0301] Example 2t :

[0302] 188 . 2g of a polysiloxane material from Example Ij was placed in a stirred glass vessel under inert gas atmosphere and the mixture was pre-heated to 55 ° C . Then, 118 . 1g of an aliphatic polyisocyanate resin based on hexamethylene diisocyanate (HDI ) commercially available as Desmodur® ultra N 3900 (Covestro) was preheated to 65 ° C and added over the course of 10 minutes from a heated round bottom reservoir vessel by means of a transfer capillary . The mixture was kept stirring at 60 ° C for roughly 35 min at which point it had turned clear . A second portion of 196 . 9g Desmodur® ultra N 3900 isocyanate (again pre-heated to 60 ° C) was added and the mixture was stirred at elevated temperature for another 20 minutes . This material is a yellow viscous liquid with an isocyanate to R5ratio of approximately 10 . 65 : 1 . The product had a shelf-life of over 12 months without gelation and showed no signs of increased viscosity after being stored in a heating cabinet at 50 ° C for 5 months .

[0303] Example 2u

[0304] A material similar to the one described in Example 2t was prepared starting with a polysiloxane material from Example Im . The molar ratio between Desmodur® ultra N 3900 isocyanate and the R5functional groups in the polysiloxane material was kept roughly the same . The resulting composition had a isocyanate to R5ratio of 8 . 7 : 1 and was a stable at room temperature without any noticeable change in viscosity over the course of more than 15 months under ambient conditions .

[0305] Example 2v

[0306] A material identical to the one in Example 2 i was prepared but with the difference that a polysiloxane material from Example 11 was used as a starting material . Using a higher molar excess of isocyanate during its preparation, the composition had a isocyanate to R5ratio of approximately 10 . 6 : 1 and showed no increase in viscosity after 6 months of storage at 50 ° C in a heating cabinet .

[0307] Example 2w

[0308] A material similar to the one in Example 2q was prepared but it differed in the R5precursor and the type and mode of addition and molar ratios of epoxy and isocyanate resins . The composition was based on a polysiloxane material similar from Example lo to which first an amount of bisphenol A diglycidyl ether (BADGE ) epoxy resin was added and the mixture kept stirring at 80 ° C for 7h . next , a second amount of epoxy resin was added together with an isocyanate resin Desmodur® ultra N 3900 . The resulting product had an epoxy to R5ratio of 11 . 6 : 1 and a isocyanate to R5ratio of approximately 5 . 6 : 1 . The product was stable for over 11 months at room temperature only a slight change in viscosity .

[0309] Example 2x A material identical to the one in Example 2c was prepared but with the difference that it was based on a polysiloxane material from Example Ip with an epoxide to R5molar ratio after the second epoxy resin addition of 19 . 4 : 1 . The product did not show any signs of aging or viscosity increase after 3 months of accelerated aging in a heating cabinet at 55 ° C .

[0310] Example 2y

[0311] A material identical to the one in Example 2 f was prepared but with the difference that it was based on a polysiloxane material according to Example Iq . The amount of isocyanate resin during preparation of the composition was kept equimolar in terms of R5to the Example 2 f . The resulting product had an isocyanate to R5ratio of approximately 10 . 2 : 1 . The product was stable for over 12 months at room temperature with only a small change in viscosity .

[0312] Example 2z

[0313] A material identical to the one in Example 2j was prepared but with the difference that it was based on a polysiloxane material according to Example lr . The amounts of the isocyanate resin Desmodur® Z 4470 BA during preparation of the composition were kept equimolar in terms of R5to the Example 2j . The resulting product had an isocyanate to R5ratio of approximately 9 . 7 : 1 . The product was stable for over 6 months in a heating cabinet at 55 ° C .

[0314] Example 3 This example describes several solvent-free isocyanate containing compositions obtained by blending various amino-and mercapto R5functional QT polysiloxanes with isocyanates in neat form and their reactivity / stability . As a quick screening test, an amount of a QT-polysiloxane was placed inside a round bottom flask which had previously been flame annealed to remove traces of water and purged with nitrogen . For each test, a QT- polysiloxane according to Examples la through Ih plus one additional QT-polysiloxane with mercaptopropyltrimethoxysilane (example li ) as a grafted T-type silane (Test #9 ) was added to an amount of Desmodur N3300 isocyanate which had previously been warmed to 55 ° C under stirring . The amount of the isocyanate precursor was chosen individually for each test to result in an isocyanate to R5ratio of 7 . 2 : 1 . Table 1 In the summary Table 1 it can be seen that there is a clear trend in terms of product stability . All Phenyl-substituted amino-bearing R5compositions (tests # 4 , 5 , 6 , 7 and 8 ) were stable whereas primary (tests # 1 , 2 ) and secondary aliphatic amine-bearing R5compositions (test #3 ) as well as the mercaptopropyl-trimethoxysilane-bearing R5compositions (test # 9 ) were not stable . This indicates that solvent-free long-term stable compositions comprising Q (T / D) -polysiloxanes and isocyanates can be produced using phenylamino-functional Q (T / D) - polysiloxanes , due to the improved stability . It was also confirmed that uniform and stable reaction products in an analog manner to materials according to Examples 1c through Ih could be obtained with secondary amine materials prepared from Micheal addition prepared secondary amines according to examples Ij through Im (data not shown) . Furthermore, materials prepared from R5-bearing QD-polysiloxanes showed the same stability trend ( see examples 2w - 2 z ) .

[0315] Example 4 Demonstration of reduced silicate curing kinetics

[0316] To demonstrate , that polymeric liquid materials with R5- unsubstituted amine-type R5residues ( containing only H or R1' substituents on R5aminic nitrogens ) containing Moieties ( II ) through (VI ) react much more slowly with moisture , pure liquid amine-polysiloxanes of four selected types were prepared according to Example 1 . Next, films of selected polymeric liquid amine-functional materials were cast using a 300pm coating bar at 22 ° C and 50% relative humidity and the self-condensation of the films with ambient moisture observed .

[0317] Both, tack-free times and full cure times were recorded for each material . From the table it can be seen that phenylamino and Michael adduct-modified secondary amino functional polymeric liquid materials self-condensate / cure much more slowly (timescale of hours , tests 12 and 13 ) than their standard primary and secondary butylamino silane counterparts (Tests 10 and 11 , timescale of several minutes ) . The slower moisture curing reactivity also seems to go hand in hand with the reactivity with isocyanate and / or epoxy groups and positively correlates also with the stability of R5-substituted isocyanate and / or epoxy compositions .

[0318] Example 5 : Examples of blocked isocyanate formulations

[0319] Example 5a

[0320] A material identical to the one described in Comparative Example 2g was prepared . The sample has a free NCO content of 6 . 3% . 62g of that material was placed inside a reaction flask . Next, an equimolar amount ( 16 . 1g, 93 mmol ) of 2-chloro-4-nitrophenol dissolved in 55ml of butyl acetate was added at 40 ° C over the course of 30minutes . After a reaction time of 25 minutes , the vessel temperature was increased to 50 ° C and the butyl acetate solvent was removed under vacuum distillation . The blocked composition had a free NCO content below 0 . 5% .

[0321] Example 5b

[0322] A material identical to the one described in the above Example 5a was prepared with the key difference that 62g of a material according to Example 2g (not Comparative Example 2g ! ! ) with a free NCO content of 12 . 4% was used . Consequently, the equimolar stoichiometric amount of 2-chloro-4-nitrophenol was 31.9g / 184mmolwhich was dissolved in 100ml butyl acetate. The otherwise analogously prepared, blocked composition had a free NCO content below 0.5%. Both samples from Example 5a and 5b were stable for over 12 months without significant increase in viscosity at room temperature, illustrating that for blocked isocyanate compositions, the R5to total isocyanate molar ratio no longer affects a products stability in the same way as for the unblocked compositions.

[0323] Example 5c

[0324] A material identical to the one described in Example 2i was prepared. The sample had a free NCO content of 11.3%. 90g of that material was placed inside a reaction flask. Next, an equimolar amount (21.2g, 243 mmol) of methylethyl ketone oxyme (MEKO) was added at 40 °C and the mixture stirred for a period of 2 hours. The resulting blocked isocyanate composition had a free NCO content below 0.5% and was stable over 3 months when kept in a heating cabinet at 50 °C with only minimal increase in viscosity .

[0325] Example 5d

[0326] A material identical to the one described in Example 2v was prepared. The sample had a free NCO content of 10.6%. 50g of that material was placed inside a reaction flask. Next, an equimolar amount (10.3g, 126 mmol) of 2-methylimidazole dissolved in acetone and this solution was added to the material slowly at 50°C and the mixture stirred for a period of 2 hours. After that, the blocked isocyanate was isolated by removing any residual solvent by vacuum distillation at 50°C. The blocked isocyanate composition had a free NCO content below 0.5% and was stable over 3 months when kept in a heating cabinet at 50 °C with no detectable increase in viscosity. Example 6 : Urethane / thiourea acrylate or methacrylate preparations

[0327] Example 6a

[0328] A material identical to Comparative Example 2g was prepared but with the difference that the amount of aliphatic HDI polyisocyanate resin (Desmodur® ultra N 3900, Covestro) used was only 145g instead of 260g and no stabilizer was added after the reaction was complete. To the resulting isocyanate composition, which had a very low R5to isocyanate ratio of approximately 1.55 : 1, an amount of hydroxyethylacrylate (HEA) of 161.3g (a 200% molar excess with respect to the total isocyanate in the composition) was added to the mixture together with 3.7g of a catalyst 1 , 4-diazabicyclo [2.2. 2]octane (DABCO) . The reparation was kept stirring for 24h at 40°C and become increasingly more viscous over time. To the urethane acrylate preparation, 500ppm of Genorad 22 (Rahn AG, Switzerland) was added.

[0329] Example 6b

[0330] A material identical to Example 2t was prepared but with the difference that only one small portion of 60g of the aliphatic HDI polyisocyanate resin (Desmodur® ultra N 3900, Covestro) was added (instead of two additions of 118.1g and 196.9g used in the original protocol) and no stabilizer was added after the reaction was complete. The resulting isocyanate composition had a very low R5to isocyanate ratio of approximately 1.22 : 1. To the composition, 100ml butyl acvetate was added as a solvent. Subsequently, an amount of hydroxyethylacrylate (HEA) of 24.0g (a 15% molar excess with respect to the total isocyanate in the composition) was added to the mixture together with 1.2g of a catalyst 1 , 4-diazabicyclo [2.2. 2]octane (DABCO) . The preparation was kept stirring for 16h at 45°C, after which residual solvent was removed by vacuum distillation at 45 ° C, yielding a sticky resinous preparation .

[0331] Example 6c

[0332] A preparation identical to Example 6a was prepared but with the difference that instead the preparation was prepared using hydroxyethylmethacrylate (HEMA) with the same 200% molar excess with respect to NCO .

[0333] Example 6d

[0334] A preparation identical to Example 6b was prepared but with the difference that instead of using a 1 : 1 blend on a mol basis of hydroxyethylacrylate (HEA) and hydroxyethylmethacrylate (HEMA) with a total of 20% molar excess with respect to NCO for the sum of both ( 0 . 6 mol equivalent each with respect to total NCO) . Furthermore , 2- (butylcarbamoyloxy) ethyl prop-2-enoate (Genorad 1122 , Rahn, Switzerland) was used as a reactive diluent instead of the butyl acetate solvent which also made the final distillation step obsolete . The resulting preparation was a homogeneous , viscous transparent liquid .

[0335] Example 6e

[0336] A preparation identical to Example 6c was prepared but with the difference that instead the 1 : 1 blend on a mol basis of constsited of hydroxyethylacrylate (HEA) and 2- mercaptoethylmethacrylate , of which a 10% molar excess with respect to NCO for the sum of both was used . 4-Acryloylmorpholin was used as a reactive diluent instead of 2- (butylcarbamoyloxy) ethyl prop-2-enoate .

Claims

Claims1. A composition comprising a polymeric liquid polysiloxane material comprising or consisting of:(i) non-organofunctional Q-type siloxane moieties selected from the group consisting of:and at least one of:(ii) mono-organofunctional T-type siloxane moieties selected from the group consisting of:and / or(iii) di-organofunctional D-type siloxane moieties selected from the group consisting of:D1D2whereinindicates a covalent siloxane bond to a silicon atom of another Q-, T- and / or D-type moiety as defined in (i) , (ii) and (iii) ;R1is selected from the group consisting of methyl, ethyl and propyl;R5is L-Z, whereinL is an aliphatic linker with the formula -(CH2)a_;Z is selected from the group consisting of -SR6, -NHR6, N(R6)2and -NR6R7, optionally -SR6, -NHR6, and -NR6R7,(III) comprises least one R6residue;wherein a is an integer selected from the group consisting of 1, 2, 3, 4, 5, 6, 7 and 8, b is an integer selected from the group consisting of 0, 1 and 2 ,R1' is selected from the group consisting of linear or branched methyl, ethyl, propyl, butyl, pentyl and hexyl;R4is a residue selected from the group consisting of -H, methyl, ethyl, -CH=CH2, -F, -Cl, -Br, -I, -CN, -SCN, -N3, - NO2, -SO2OH, -SO2OR1' and -C(=O)RV, andR6is selected from the group consisting of:ureas or thio-ureas, optionallyp-hydroxy aminesor p-hydroxy thioethers, optionally OH and p-hydroxy ethers, optionallyR7is selected from the group consisting of Me and linear or branched - (CH2)a-CH3;R8is- an aliphatic, aromatic or unsaturated, substituted or non-substituted C4-20 hydrocarbon, optionally a methylene diphenyl, optionally an isocyanate-terminated and / or a glycidoxy-terminated aliphatic, aromatic or unsaturated, substituted or non-substituted C4-20 hydrocarbon, and / or- an aliphatic, aromatic or unsaturated, substituted, optionally isocyanate-terminated and / or a glycidoxy- terminated, or non-substituted residue selected from the group consisting of p-hydroxy ethers, p-hydroxy thioethers, p-hydroxy amines, oxazolidones , ureas, cyanurates, thio-ureas, urethanes and combinations thereof in polymeric or oligomeric form having a massaverage molecular weight of 100 to 20'000 g / mol, 150 to 15'000 g / mol, or 170 to 10'000 g / mol, wherein R8comprises at least one moiety selected from the group consisting of an isocyanate and an epoxide,R9is selected from the group consisting of -OR7, -CgHs,R10is selected from the group consisting of -R7, -OR7and -OH,X is selected from the group consisting of 0, NH, and -NR7,R11is selected from the group consisting of -R7, -R9, -OR7and -OH, wherein the degree of polymerization of the T-type alkoxy-terminated siloxane moieties of the material DPT-type is in the range of 1.1 to 2.7; the degree of polymerization of the D-type alkoxy-terminated siloxane moieties in the material DPo-type is in the range of 1.0 to 1.9; the degree of polymerization of the Q-type alkoxy-terminated moieties of the material DPo-type is in the range of 1.4 to 2.8; if the composition comprises isocyanate groups, the molar ratio of all R5residues to all isocyanate groups in the composition is 1 to at least 5, optionally 1 to at least 6; if the composition comprises epoxide groups, the molar ratio of all R5residues to all epoxide groups in the composition is 1 to at least 10, optionally 1 to at least 17, optionally 1 to at least 25; the composition comprises less than 30 weight-%, less than 25 weight-% or less than 20 weight-% polyols that are not covalently bound to the polymeric liquid polysiloxane material relative to the total weight of the composition.

2. The composition according to claim 1, wherein the composition, optionally the polymeric liquid polysiloxanematerial, comprises at least 0.05 mmol / g, 0.1 mmol / g, 0.2 mmol / g, 0.5 mmol / g, or 1.0 mmol / g of isocyanate and / or epoxide groups on a total resins basis.

3. The composition according to claim 1 or 2, wherein Z is selected from the group consisting of -SR6, -NHR6, -NR6R7, moiety (I)moietywherein R4is H or CH=CH2 and wherein R4is H if b is 0, and moietywherein moiety (III) comprises least one R6residue, optionally wherein the composition or the polymeric liquid polysiloxane material comprises at least 0.1 mmol / g, optionally at least 0.2 mmol / g, optionally at least 0.35 mmol / g, optionally at least 0.5 mmol / g of isocyanate and / or epoxide groups on a total resins basis.

4. The composition according to any of claims 1 to 3, whereinR8is- an aliphatic or aromatic, substituted or non-substituted C4-20 hydrocarbon, and / or- an aliphatic or aromatic, substituted or non-substituted residue selected from the group consisting of p-hydroxy ethers, p-hydroxy thioethers, p-hydroxy amines, ureas, cyanurates, thio-ureas, urethanes and combinations thereof in polymeric or oligomeric form having a massaverage molecular weight of 170 g / mol to 10'000 g / mol .

5. The composition according to any of claims 1 to 4, wherein R4is H or CH=CH2.The composition according to any of claims 1 to 5, wherein for Z being -SR6or -NHR6, R8is not a residue selected from the group consisting of:y y ,7. The composition according to any of claims 1 to 6, wherein a is 1, 2, 3 or 4, and / or b is 0 or 1, and / orR1' is selected from the group consisting of methyl, ethyl, propyl and butyl;R4is selected from the group consisting of H or CH=CH2, and / orZ is selected from the group consisting of -SR6, -NHR6,-NR6R7,wherein moiety(III) comprises least one R6residue.

8. The composition according to any of claims 1 to 7, wherein R6comprises R8that is selected from the group consisting ofmonomeric, biuret, uretdione and triisocyanurate form;wherein 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.

9. The composition according to any of claims 1 to 8, wherein the atomic ratio of T- to Q-species in the polymeric liquid polysiloxane material is in the range of 0.01:1 to 0.5:1, optionally in the range of 0.03:1 to 0.35:1.

10. The composition according to any of claims 1 to 9, wherein - the degree of polymerization of the Q-type alkoxyterminated moieties of the material DPQ-typeis in the range of 1.6 to 2.4 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 / orthe degree of polymerization of the T-type alkoxyterminated siloxane moieties of the material DPT-type is in the range of 1 . 3 to 2 . 2 .11 . A hydrolysis or emulsion product , optionally a water-based composition, obtainable by reacting a composition according to any of claims 1 to 10 with a predetermined amount of water or with a predetermined amount of a water-solvent mixture, optionally in the presence of at least one surfactant for the hydrolysis product, or a predetermined amount of water, optionally in the presence of at least one surfactant for the emulsion product .12 . A method for preparing a composition comprising the polymeric liquid material according to one of claims 1 to 10 , comprising the following steps :(a) providing a Q-type polymethoxy, polyethoxy, polypropoxy or mixed poly (methoxy / ethoxy / propoxy) polysiloxane precursor, optionally comprising(al ) di-organofunctional D-type siloxane moieties ; and / or(a2 ) mono-organofunctional T-type siloxane moieties , optionally comprising less than 12 mol-% of (al ) and (a2 ) combined relative to the total amount of all Q- type species ; optionally further comprising a rearrangement catalyst and / or tri-organofunctional M-type siloxane moieties ; andwherein degree of polymerization of the Q-type polysiloxane of the material DPQ-typeis in the range of 1.5 to 2.5, optionally 1.6 to 2.4, optionally 1.65 to 2.35;(b) adding(bl) optionally tri-organofunctional M-type silane Si (OR1) (Me) 3; and at least one of:(b2) di-organofunctional D-type silane Si (OR1) 2 (R2) (R5) , and / or(b3) mono-organofunctional T-type silane Si (OR1) 3 (R5) ; in mono- or oligomeric form to the polysiloxane of (a) ;(c) optionally adding a rearrangement catalyst to the mixture of step (b) ;(d) heating the mixture of (c) , optionally in the absence of water;(e) optionally repeating steps (b) to (d) at least once;(f) retrieving, optionally isolating and optionally purifying the polymeric liquid material;(g) mixing the material of step (e) or (f) with a compound or mixture of compounds in oligomeric or polymeric form, each compound comprising at least one isocyanate or epoxide group, wherein if the compound comprises at least one isocyanate group, the compound is mixed in an amount such that the molar ratio of all R5residues to all isocyanate groups in the composition is 1 to at least 5, optionally 1 to at least 6; if the compound comprises at least one epoxide group, the compound is mixed in an amount such that the molar ratio of all R5residues to all epoxide groups in the composition is 1 to at least 10, optionally 1 to at least 17, optionally 1 to at least 25;optionally with the proviso that at least one of steps (a2 ) or (b3 ) is carried out, and with the proviso that a rearrangement catalyst is present in at least one of steps (a) or ( c) .13 . A product obtained or obtainable by the method of claim 12 .14 . A blocked isocyanate formulation comprising a composition according to any of claims 1 to 10 comprising free isocyanate groups , wherein the formulation further comprises a blocking agent for isocyanates , optionally selected from the group consisting of diethyl malonate , dibutyl malonate , sodium bisulfite , 3 , 5-dimethylpyrazole , methylethyl-ketone oxime (MEKO) , phenol and caprolactam, wherein a part or all of the isocyanate groups in the composition are reversibly blocked by chemical reaction with the blocking agent .15 . A urethane or thiourea acrylate or methacrylate preparation obtained or obtainable by reacting a composition according to any of claims 1 to 10 with a hydroxyl- or mercapto-functional acrylate or methacrylate in monomeric or oligomeric form, wherein the composition according to any of claims 1 to 10 comprises isocyanate groups and the molar ratio of all R5residues in the composition to all isocyanate groups in the composition is any molar ratio optionally is larger than 10 : 1 , optionally larger than 20 : 1 optionally larger than 100 : 1 .

16. The urethane or thiourea acrylate or methacrylate preparation according to claim 15, wherein the hydroxyl- or mercapto- functional acrylate or methacrylate is selected from the group consisting of 2-hydroxyethylacrylate (HEA) , 2- hydroxyethylmethacrylate (HEMA) , diethyleneglycol monomethacrylate, diethyleneglycol mono-acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, hydroxypentyl methacrylate, hydroxypentyl acrylate hydroxyhexyl methacrylate, hydroxyhexyl acrylate, 2-mercaptoethyl methacrylate, mercaptopropyl methacrylate, mercaptobutyl methacrylate, mercaptopentyl methacrylate, and mercaptohexyl methacrylate .

17. The urethane or thiourea acrylate or methacrylate preparation according to claim 15 or 16, wherein the mass ratio between the composition according to any of claims 1 to 10 and the sum of all the hydroxyl- and mercapto-functional acrylates or methacrylates is from 1:0,03 to 1:5, optionally from 1:0.05 to 1:2, optionally from 1:0.05 to 1:0.85.

18. A IK or 2K curable composition, optionally a water-based IK or 2K curable composition, comprising the composition according to any of claims 1 to 10 and / or the preparation according to any of claims 15 to 17.

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