SILOXANE BASED POLYMERIC LIQUID MATERIAL AND METHOD FOR PREPARING THE SAME

Abstract

A new class of liquid polysiloxane materials obtainable from cost-effective commodity precursors allow tailoring a plurality of (multi)—functional properties. The materials are classified in terms of their chemical identity, which comprises Q-type nonorganofunctional, T-type monoorganofunctional and optional D-type diorganofunctional moieties. The T-type organofunctional species within a polymeric MBB can be present in various preferred combinations defined by spatial, stereochemical and compositional factors. The corresponding method of production for the liquid polymeric polysiloxanes involves a scalable, non-hydrolytic acetic anhydride method either in a simple one-step format to create statistically distributed “core-only” hyperbranched poly-alkoxysiloxanes or as a two— or multistep process to create “core-shell” materials.

Claims

1. A polymeric liquid hyperbranched polysiloxane material composed of: non-organofunctional Q-type alkoxysilicate moieties ##STR00010## R′ substituted mono-organofunctional T-type alkoxy terminated siloxane moieties ##STR00011## wherein: each R is independently methyl or ethyl, and each R′ is either (i) selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, tbutyl, hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H, 2H, 2H-perfluoro)octyl, (1H,1H, 2H, 2H-perfluoro)dodecyl, and (1H,1H, 2H, 2H-perfluoro)hexadecyl, or L—Z, wherein L is an aliphatic linker selected from the group consisting of —CH.sub.2—, —CH.sub.2CH.sub.2—,—CH.sub.2CH.sub.2CH.sub.2—, —C.sub.6H.sub.4—, —C.sub.6H.sub.4—CH.sub.2—, and —CH.sub.2—CH.sub.2-C.sub.6H.sub.4—CH.sub.2—, and Z is a functional terminus selected from the group ##STR00012## wherein R* is selected from the group consisting of —CH.sub.3 (Me), —CH.sub.2CH.sub.3 (Et), and —CH.sub.2CH.sub.2CH.sub.2CH.sub.3 (Bu), or (iii) R.sub.s wherein: ##STR00013## wherein: n is 1, 2, 3, 4, or 5, R* is selected from the group consisting of —CH.sub.3 (Me), —CH.sub.2CH.sub.3 (Et), and—CH.sub.2CH.sub.2CH.sub.2CH.sub.3 (Bu) and R** is selected from the group consisting of —(CH.sub.2).sub.5CH.sub.3 (Hexyl), —(CH.sub.2).sub.6CH.sub.3 (Heptyl), —(CH.sub.2).sub.7CH.sub.3 (Octyl), —(CH.sub.2).sub.8CH.sub.3 (Nonyl), —(CH.sub.2).sub.9CH.sub.3 (Decyl), —(CH.sub.2).sub.11CH.sub.3 (Dodecyl), and —(CH.sub.2).sub.13CH.sub.3 (Tetradecyl), the material having a degree of polymerization of the non-organofunctional Q-type moieties (DP.sub.Q-type) in the range of 1.3 to 2.7, and the mono-organofunctional T-type moieties having a degree of polymerization of the mono-organofunctional T-type moieties (DP.sub.T-type) in the range of 1.1 to 2.7, the material optionally further containing R1—,R2—substituted di-organofunctional D-type siloxane moieties ##STR00014## wherein: R.sub.1 and R.sub.2 are independently selected from the group consisting of —CH.sub.3, —C.sub.2Hs, —C.sub.6H.sub.5, —C.sub.6H.sub.11, —CH═CH.sub.2, —CH.sub.2—CH.sub.2—Cl, and —C.sub.5H.sub.5, and the di-organofunctional D-type moieties having a degree of polymerization of the di-organofunctional D-type moieties DP.sub.D-type in the range of 1.0 to 1.9, and the total content of di-organofunctional D-type siloxane moieties in the material does not exceed 10 molar percent, the material having a viscosity in the range of 10-100′000 cP, the material containing less than 5 molar percent hydroxy moieties {Si—OH) and the total silicon to free hydrolysable alkoxy molar ratio in the material being in the range of 1:1.25 to 1:2.75, wherein the total molar content of ethoxy terminating units (—OCH.sub.2—CH.sub.3) is at least twice the total content of methoxy terminating units (—OCH.sub.3), and wherein the relative atomic ratio of T to Q species in the material is in the range 0.01:1 to 1:1, with the following conditions: the material comprises at least two non-identically R′-substituted mono-organofunctional (T-type) alkoxy terminated siloxane moiety populations, each population making up at least 3 molar percent of all mono-organofunctional T-type alkoxy terminated moieties in the material, and/or the material comprises chiral mono-organofunctional T.sup.1-type alkoxy terminated moieties in an amount of at least 3 molar percent relative to all mono-organofunctional T-type alkoxy terminated moieties in the material.

2. The polymeric liquid material according to claim 1, wherein the material contains less than 0.5 molar percent hydroxy moieties {Si—OH).

3. The polymeric liquid material according to claim 1, wherein the degree of polymerization of the non-organofunctional Q-type moieties DP.sub.Q-type is in the range of 1.5 to 2.5, and/or the degree of polymerization of the mono-organofunctional T-type moieties DP.sub.T-type is in the range of 1.3 to 2.2.

4. The polymeric liquid material according to claim 17, wherein the total content of terminally bonded di-organofunctional D-type siloxane moieties in the material is zero.

5. The polymeric liquid material according to claim 1 4, wherein the mono-organofunctional T-type moieties comprise a first population of mono-organofunctional T-type alkoxy terminated siloxane moieties, wherein R′ is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H, 2H, 2H-perfluoro)octyl, (1H,1H, 2H, 2H-perfluoro)dodecyl, and (1H,1H, 2H, 2H-perfluoro)hexadecyl, and either a second population of mono-organofunctional T-type alkoxy terminated siloxane moieties that is non-identical to the first type, wherein R′ is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H, 2H, 2H-perfluoro)octyl, (1H,1H, 2H, 2H-perfluoro)dodecyl, and (1H,1H, 2H, 2H-perfluoro)hexadecyl, or a third population of mono-organofunctional T-type alkoxy terminated siloxane moieties, wherein R′ is L—Z or Rs.

6. The polymeric liquid material according to claim 1, wherein the relative atomic ratio of T to Q species is in the range 0.02:1 to 0.75:1 and preferably 0.03:1 to 0.5:1.

7. A hydrolysis product obtainable by reacting a polymeric liquid material according to claim 1 with a predetermined amount of water or with a predetermined amount of a water-solvent mixture.

8. An emulsion obtainable by emulsifying a polymeric liquid material according to claim 1 with a predetermined amount of water, optionally in the presence of at least one surfactant.

9. A method for preparing a polymeric liquid material according to claim 1, comprising the following steps: a) charging an amount of tetraethoxysilane as Q-type precursor, and a1) optionally, adding at least one mono-organofunctional trialkoxysilane R′—Si(OR).sub.3 and a2) optionally, adding at least one di-organofunctional dialkoxysilane R.sub.1—Si(OR).sub.2—R.sub.2, in monomeric or in oligomeric form, into a reaction vessel together with a first stoichiometric amount of acetic anhydride in the presence of a catalyst; b) heating up the reaction mixture provided in step a) in a water-free, inert atmosphere under stirring to reach a desired reaction temperature and distilling off any resulting acetic acid ester reaction side product until the reaction and the flow of distillate cease, thereby forming a polysiloxane core material, c) optionally carrying out the steps of c1) adding at least one further mono-organofunctional trialkoxysilane R′—Si(OR).sub.3 and c2) optionally, adding at least one further di-organofunctional dialkoxysilane R.sub.1—Si(OR).sub.2—R.sub.2, in monomeric or in oligomeric form, together with a second stoichiometric amount of acetic anhydride, optionally with additional catalyst, to the hot reaction mixture formed in step b) with continuing stirring, distilling over any further acetic acid ester formed, and continuing the reaction until any distillate flow ceases again, thereby forming a functional shell layer grafted onto the core species previously prepared in step a); d) optionally building at least one further functional shell layer by repeating the addition and reaction protocol described in step c) at least once; e) optionally removing low-molecular reaction products and/or residual starting materials in the reaction mixture by vacuum distillation through gradually lowering the pressure inside the reaction vessel and holding a final pressure in the range of 5 to 250 mbar for a period of time between 2 and 60 minutes, f) cooling down and isolating the polymeric liquid material thus obtained, with the provision that at least one of the optional steps al) and c1) is carried out and that stirring is carried out for at least 30 minutes after the last one of said adding steps.

10. The method according to claim 9, wherein step a) comprises carrying out steps a1), and optionally a2), followed optionally by step e), and followed by step f).

11. The method according to claim 9, wherein step a) does not comprise carrying out steps a1) and a2) and wherein step c) is carried out.

12. The method according to claim 9, wherein the reaction temperature for steps b) through e) is in the range from 70° C. to 170° C., the pressure during steps b) through d) is in the range of 0.1 bar to 2 bar.

13. The method according to claim 9, wherein acetic acid ester reaction products are removed from the system through a distillation column comprising several theoretical plates in such a way that the lower boiling reaction product is separated from higher boiling residual reactants in solution whereby the latter are continuously fed back into the reaction mixture.

14. The method according to claim 9, wherein: the catalyst is selected from the group of Ti(OR″).sub.4 and Zn(II) alkanolates Zn(OR″).sub.2, wherein R″—CH.sub.2CH.sub.3, —CH(CH.sub.3).sub.2, —CH.sub.2CH.sub.2CH.sub.3, —C(CH.sub.3).sub.3, or —CH.sub.2CH.sub.2CH.sub.2CH.sub.3 the catalyst is a dibutyl-tin(IV) compound, or the catalyst is Ti(O—Si(CH.sub.3).sub.3).sub.4, wherein the catalyst amount added in each of steps a) or c) is between 0.01 and 1.5% on a mol basis of total alkoxysilane precursor used in said step.

15. The polymeric liquid material according to claim 6, comprising at least one T-type species alkoxy terminated siloxane moity having an R′ that is Rs or that is selected from vinyl, methacrylate, butacrylate, and acrylate, with a content of the polymeric liquid material in the range of 0.2% to 25% by weight with respect to the formulation.

16. The polymeric liquid material according to claim 1, wherein at least one T-type alkoxy terminated siloxane moity having an R′ selected from methyl, ethyl, vinyl, methacrylate, n-propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, (3,3,3-trifluoro)propyl, (1H,1H, 2H, 2H-perfluoro)octyl, (1H,1H, 2H, 2H-perfluoro)dodecyl, and (1H,1H, 2H, 2H-perfluoro)hexadecyl, in a hydrophobic formulation, wherein the loading of the polymeric liquid, hydrolysis product or emulsion in the formulation is 0.5% to 25% by weight.

17. The polymeric liquid material according to claim 1, wherein the material contains R1—,R2-substituted di-organofunctional D-type siloxane moieties ##STR00015##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0168] The above mentioned and other features and objects of this invention and the manner of achieving them will become more apparent and this invention itself will be better understood by reference to the preceding description of various embodiments of this invention taken in conjunction with the accompanying drawings, wherein are shown:

[0169] FIG. 1 a rough classification of molecular and nano science in terms of number of constituent atoms and effective size;

[0170] FIG. 2 limitation of classical hydrolytic sol-gel methods to prepare functional nanoscale building blocks (NBBs); the product distribution of NBBs is determined by stochastic events in solution and relative reaction rates of the different alkoxide and silane precursors and hence poorly controllable;

[0171] FIG. 3 .sup.29Si NMR spectra of two samples prepared from D-40 (Q-type) and PTMS (Propyltrimethoxysilane), see upper (red) trace, or PTES (Propyltriethoxysilane), see lower (blue) trace;

[0172] FIG. 4 .sup.29Si NMR spectra of the two samples of FIG. 3 zoomed in on the T.sup.nspectral region; spectral confirmation of Ethoxy-Methoxy exchange of T-type species

[0173] FIG. 5 .sup.29Si NMR spectrum of a polymeric liquid material prepared from D-40 (Q-type), MTES (Methyltriethoxysilane) and OTES (Octyltriethoxysilane);

[0174] FIG. 6 a model sketch for a core-shell material obtained from TEOS (Q-type) and MTMS (T-type) precursors with an ethoxy-methoxy exchanged alkoxy chemistry;

[0175] FIG. 7 a model sketch for a core-only material obtained from TEOS (Q-type) and MTMS (T-type) precursors with an ethoxy-methoxy exchanged alkoxy chemistry;

[0176] FIG. 8 a model sketch for a core-shell material obtained from TEOS (Q-type) and mixed mono-organofunctional triethoxysilanes MTES (T-type #1) and VTES (T-type #2); and

[0177] FIG. 9 a model sketch for a core-only material obtained from TEOS (Q-type) and mixed mono-organofunctional triethoxysilanes MTES (T-type #1) and VTES (T-type #2).

DETAILED DESCRIPTION OF THE INVENTION

Example 1: Synthesis of TEOS/MTMS Material with n.SUB.Q-type.: n.SUB.T-type.=1:0.1

[0178] 52.0 g/0.25 mol Si of a Q-type precursor tetraethoxysilane (TEOS) and 0.87 ml of tetrakis(trimethylsiloxy) titanium (0.5 mol % with respect to moles of Q-type Si) were placed inside a 100 ml round bottom flask with distillation bridge together with 3.4 g 25 mmol of a T-type precursor methyltrimethoxysilane (MTMS). The reaction flask was then purged with nitrogen, sealed, left under nitrogen pressure (balloon) and immersed into a hot oil bath which was kept at 140° C. The reaction mixture was brought to temperature with stirring at 500 rpm. Once the temperature has been reached, a selected amount (0.275 mol/28.0 g) acetic anhydride was added slowly. The onset of the reaction was evidenced during the addition by an accelerating refluxing rate of the reaction byproduct ethyl acetate which started to make its way up to the distillation bridge. After approximately 15 minutes, a continuous stream of ethyl acetate was distilling over through the distillation bridge and collected in the capture vessel. The reaction continued for a total time of about 55 more minutes, at which point it stopped, commensurate with the ceasing of the ethyl acetate distilling over. The collection vessel was removed after a total reaction time of 1 h and 15 minutes and emptied, yielding a total mass of 42.1 g of collected condensate.

Example 2: Synthesis of Ethylsilicate-40/VTMS Core-Shell Material with n.SUB.Q-type.: n.SUB.T-type.=1:0.30

[0179] i) Fabrication of a hyPAS core from Ethylsilicate-40 Q-type precursor An oligomeric TEOS (ethylsilicate) derived hyPAS Q-type core only was prepared using an experimental setup analogous to Example 1 in a 11 round bottom flask and identical temperature and stirring rate. As a catalyst, 7.1 g/28 mmol of Ti(IV)-isopropoxide was used. Instead of TEOS, an oligomeric ethylsilicate 40 mixture (Dynasylan 40, Evonik Industries) was used as Q-type precursor. The amount of Ethylsilicate-40 and Ac.sub.2O used in the synthesis were 364 g/2.5 mol Si and 40.8 g 0.4 mol, respectively. The total reaction time was 1 h 05 minutes and produced 66.5 g of condensate byproduct. [0180] ii) Growth of a VTMS shell over a hyPAS core with g=1.33 The shell growth onto the core material prepared in step i) was done after its completion. To the reaction mixture from step i) still kept in the same vessel at 140° C. with stirring, an amount of T-type functional trialkoxysilane used for shell growth was added together with a stoichiometric amount of acetic anhydride for shell growth. Accordingly, 111 g/0.75 mol of vinyltrimethoxysilane (VTMS) and 102 g 1 mol of Ac.sub.2O were dosed to the reaction mixture over the course of 15 minutes with a syringe pump. At the end of the reaction after 40 minutes, excess byproducts and low-molecular components were removed by pulling a vacuum of 600 mbar for 5 minutes. The round bottom flask was then removed from the oil bath and allowed to cool to room temperature. The shell growth step yielded 162.6 g of collected condensate.

Example 2b: Synthesis of Ethylsilicate-40/VTMS Core-Shell Material with n.SUB.Q-type.: n.SUB.T-type.=1:0.30 with a Lower Stoichiometric Amount of Acetic Anhydride Added During Shell Growth (g=0.66)

[0181] The exact same synthesis procedure as in Example 2 above was used to prepare the material, with the sole difference that during the VTMS shell growth step ii), only 51 g (0.5 mol) of acetic anhydride Ac.sub.2O was added. This resulted in a lower degree of polymerization of the core and shell in the final material.

Example 2c: Synthesis of Ethylsilicate-40/VTMS Core-Shell Material with n.SUB.Q-type.: n.SUB.T-type.=1:0.30 with No Addition of Acetic Anhydride During the Shell Growth Step (g=0)

[0182] Again, the exact same synthesis procedure as in Example 2 above was used to prepare the material, with the sole difference that during the VTMS shell growth step ii), no acetic anhydride Ac.sub.2O was added. This resulted in an even lower degree of polymerization of the core and shell in the final material and a higher content of unreacted Q and T-type monomers (Q°, T.sup.0) compared to Example 2 and 2b, respectively.

Example 2d: Synthesis of Ethylsilicate-40/VTMS Core-Shell Material with n.SUB.Q-type.: n.SUB.T-type.=1:0.30 with No Addition of Acetic Anhydride During the Core Growth Step

[0183] The exact same synthesis procedure as in Example 2 above was used to prepare the material, with the sole difference that during the core formation step i), no acetic anhydride Ac.sub.2O was added, while the amount of acetic anhydride added in the shell growth step ii) was left unchanged. During core formation, the ethylsilicate/catalyst mixture was stirred at temperature for 45 minutes without any distillate boiling over. The shell growth step was then carried out as described in Example 2. This protocol resulted in a lower degree of polymerization of the core and shell in the final material and a higher content of unreacted Q and T-type monomers (Q°, T.sup.0) compared to Example 2.

Example 2e: Synthesis of Ethylsilicate-40/VTMS Core-Shell Material with n.SUB.Q-type.: n.SUB.T-type.=1:0.05 with Zero Addition of Acetic Anhydride During Both Core and Shell Preparation Steps

[0184] The synthesis was carried out analogous to the procedure described in Example 2, however, the amount of VTMS during shell growth was 18.5 g/0.125 mol, leading to n.sub.Q-typen.sub.T-type=1:0.05. During core preparation step i), the catalyst/ethylsilicate-40 mixture was stirred without addition of acetic anhydride for 45 minutes at temperature. During the shell grafting step ii), VTMS was dosed within 15 minutes but again without addition of acetic anhydride.

Example 3: Synthesis of a (Q.SUB.type.+D.SUB.type.) Core: T.SUB.type .Shell Material with n.SUB.Q-type.: n.SUB.T-type.=1 0.136 and n.SUB.D-type.: n.SUB.si,tot.=8.1%

[0185] The material was synthesized using the exact same procedure as described in example 2 but on a 10 times smaller scale, with the difference that during the core formation step i), in addition to the given amount of Ethylsilicate 40 (36.4 g/250 mmol), an amount of 25 mmol/3.6 g of dimethyldiethoxysilane (DMDES) was present in the original starting mixture and the amount of acetic acid used in the core growth step was 4.5 g/44 mmol. The entire reaction was carried out with a refluxing/distillation setup unit containing a 10 cm long Vigreux column in addition to the distillation bridge in order to prevent loss by boiling over of the more volatile DMDES (Bp=115° C.) component.

[0186] The shell growth step was carried out in exactly the same way as in example 2, with the difference that a different stoichiometric loading of the T-type shell precursor VTMS was used (5.0 g/34 mmol) and the amount of acetic anhydride in the shell growth step was (5.1 g/50 mmol). An acetic anhydride stoichiometric factor g=1.5 was used in the shell growth step. The total amount of recovered condensate was 14.3 g.

Examples 5, 7, 8, 12,15: Synthesis of Core-Only Materials with a Range of Chemistries and Compositions

[0187] Additional experiments were performed with various other Q-type/T-type combinations and stoichiometries using the “core-only” protocol described in Example 1. The chemical synthesis parameters for these materials are summarized in Table 1.

Examples 4, 6, 9, 10, 11, 13, 14: Synthesis of Core-Shell Materials with a Range of Chemistries and Compositions

[0188] Additional experiments were performed with various other Q-type/T-type combinations and stoichiometries using the core-shell protocol described in Example 2. The chemical synthesis parameters for these materials are summarized in Table 1.

Example 15: Synthesis of a “Core-Only” Ethylsilicate Oligomer/MTMS MBB with n.SUB.Q-type.: n.SUB.T-type.=1:0.1 Using an Alternative Catalyst System

[0189] The material was synthesized in exactly the same way as the material in example 1, with the only difference, that the catalyst system consisted of a mixture of tetraisopropoxytitanium(IV) and dibutyltin(IV)-dilaurate.

Example 16: Hydrolysis of a Polymeric Liquid Material

[0190] 6.4 g (9.5 ml) of Ethanol and 5.1 g of a crude reaction product from Example 3 were mixed and heated to 40° C. in an Erlenmeyer flask with stirring. Once the temperature had equilibrated, 1.1 ml of a 0.02M HNO.sub.3 solution was added followed by 0.4 ml of distilled water. After a brief homogenization period, the beaker was sealed off with parafilm and kept for 12 hours in a convective oven at 40° C. The final hydrolysis product was then filtered and stored in the refrigerator.

Example 17: Preparation of a Water in Oil Emulsion

[0191] 12.5 g of a sample of a material sample of Example 7 was mixed with 5.0 ml of distilled water. The two-phase system was then vigorously shaken in a closed flask and further homogenized mechanically using an Ultra-Turrax homogenizer. The resulting emulsion was a creamy paste, which had a shelf life of several weeks when kept in a tightly sealed container.

TABLE-US-00001 TABLE 1 Synthesis conditions. T [Catalyst] [Q.sub.type] [T.sub.type1] [T.sub.type2] [D.sub.type] # n T/n Q (° C.) Catalyst (mol) Q.sub.type (mol Si) T.sub.type1 (mol Si) T.sub.type2 (mol Si) D.sub.type (mol Si) 1 0.10 140 Ti(OTMS).sub.4 0.002 TEOS 0.250 MTMS 0.025 2 0.30 140 Ti(OPr).sub.4 0.028 D-40 2.500 VTMS 0.749 3 0.14 140 Ti(OTMS).sub.4 0.002 D-40 0.250 VTMS 0.034 DMDES 0.025 4 0.14 125 Ti(OPr).sub.4 0.004 D-40 0.746 PTMS 0.104 OTES 0.104 5 0.13 140 Ti(OPr).sub.4 0.001 TEOS 0.303 MTES 0.040 OTES 0.040 6 0.14 140 Ti(OPr).sub.4 0.011 D-40 1.514 PTES 0.209 TESPT 0.417 7 0.03 140 Ti(OPr).sub.4 0.001 D-40 0.303 FPTMS 0.008 8 0.29 140 Ti(OPr).sub.4 0.006 TEOS 1.193 PTES 0.340 3-TESPM 0.068  9a 0.14 140 Ti(OPr).sub.4 0.002 D-40 0.303 PTMS 0.042  9b 0.14 140 Ti(OPr).sub.4 0.002 D-40 0.303 PTES 0.042 10  0.20 140 Ti(OPr).sub.4 0.001 TEOS 0.250 OTES 0.050 DEPETES 0.025 11  0.13 140 Ti(OPr).sub.4 0.001 D-40 0.303 MTES 0.040 NXT-100 0.020 12  0.20 140 Ti(OPr).sub.4 0.001 TEOS 0.250 MTES 0.050 GTMS 0.010 13  0.08 140 Ti(OPr).sub.4 0.001 mixed 0.400 CPTES 0.030 APTES 0.030 14  0.03 140 Ti(OPr).sub.4 0.001 D-40 0.303 4HPFOTES 0.010 15  0.03 140 Ti(OPr).sub.4 0.001 D-40 0.303 DDTES 0.010 PyTES 0.015 TEOS: tetraethoxysilane, VTMS: vinyltrimethoxysilane, MTMS: methyltrimethoxysilane, D-40: Dynasylane 40, PTMS: propyltrimethoxysilane, PTES: propyltriethoxysilane, OTES: octyltriethoxysilane, FPTMS: (3,3,3-trifluoropropyl)trimethoxysilane, TESPT: Deolink TESPT-100, 3-TESPM: 3-(trimethoxysilyl)propyl methacrylate, DEPETES: diethyl[2-(triethoxysilyl)ethyl]phosphonate, GTMS: (3-glycidyloxypropyl)trimethoxysilane, APTES: aminopropyltriethoxysilane, 4HPFOTES: 1H,1H,2H,2H-perfluorooctyltriethoxysilane, CPTES: 3-chloropropyltriethoxysilane, DDTES: dodecyltriethoxysilane, PyTES: 4-[2-(Triethoxysilyl)ethyl]pyridine

[0192] Table 2 below shows a selection of .sup.29Si-NMR results from samples made from Examples 1 through 9 including quantitative speciation of Q-type and T-type moieties.

TABLE-US-00002 TABLE 2 .sup.29Si NMR results. D0 D.sup.1 D.sup.2 T.sup.0 T.sup.1 T.sup.2 T.sup.3 Q.sup.0 Q.sup.1 Q.sup.2 Q.sup.3 Q.sup.4 n T/n # % % % % % % % % % % % % DP.sub.Dtype DP.sub.Ttype DP.sub.Qtype Si.sub.tot 1 0.17 1.8 4.2 2.04 1.5 12.2 38.1 32.5 7.35 1.99 2.35 0.08 2 1.55 8.63 10.1 3.92 2.44 15.6 28.6 24.4 4.82 1.68 2.18 0.24 3 1.7 2.99 3.34 0.79 3.06 4.56 2.02 1.85 16.5 36.1 22.3 4.79 1.20 1.75 2.14 0.10 4 6.17 1.71 5.98 4.93 0.42 10.1 33.5 30.8 6.4 1.51 2.40 0.19 5 1.8 4.72 9.06 5.23 1.27 10.7 33.1 27.8 6.31 1.85 2.34 0.21 6 13.2 5.96 8.1 2.29 0.56 13.4 31.1 21.5 3.84 1.62 2.21 0.30 7 0.26 1.13 1.52 0.21 3.66 23 41.7 22.4 6.17 1.54 2.05 0.03 8 1.88 7.62 10.6 3.96 2.57 15.5 29.7 23.6 4.58 1.69 2.16 0.24  9a 1.46 4.26 5.03 1.55 1.81 16.1 38.8 26.4 4.53 1.54 2.18 0.12  9b 1.98 1.87 4.47 1.47 1.29 15.8 39.5 29.7 3.91 1.55 2.21 0.10