WO2007022367A2

WO2007022367A2 - Preparation of polyhedral oligomeric silsesquioxane silanols and siloxides functionalized with olefinic groups

Info

Publication number: WO2007022367A2
Application number: PCT/US2006/032166
Authority: WO
Inventors: Joseph J. Schwab; Yi-Zhong An; Sr. W.A. Reinerth; Sukhendu B. Hait; H.C.L. Abbenhuis
Original assignee: Hybrid Plastics, Inc.
Priority date: 2005-08-16
Filing date: 2006-08-16
Publication date: 2007-02-22
Also published as: WO2007022367A3; TW200722430A; JP2009504890A; KR20080036148A; EP1931687A4; RU2008110068A; CN101568546A; EP1931687A2

Abstract

A synthetic process for polyhedral oligomeric silsesquioxanes (POSS) and polyhedral oligomeric silicates (POS) produces silanol and siloxide molecules containing both olefinic groups and alkyl or aromatic groups. Olefin-bearing POSS silanol/siloxides are derivatized into a variety of chemical species while retaining the ability to further derivatize the silanol/siloxide.

Description

PREPARATION OF POLYHEDRAL OLIGOMERIC SILSESQUIOXANE SILANOLS AND SILOXIDES FU NOTION ALIZED WITH OLEFINIC GROUPS

RELATED APPLICATIONS

This application claims priority from U.S. Provisional Patent Application Serial No. 60/708,966 filed August 16, 2005.

FIELD OF THE INVENTION

This invention relates to a process for functionalization of polyhedral oligomeric silsesquioxane silanols and siloxides with olefinic groups, enhancing their physical, chemical, and electronic properties, and their suitability for incorporation into catalytic, metallic, polymeric, electronic, medical, cosmetic, and biological products.

BACKGROUND OF THE INVENTION

Nanostructured chemicals are best exemplified by those based on low-cost Polyhedral Oligomeric Silsesquioxanes (POSS) and Polyhedral Oligomeric Silicates (POS). POSS and POS systems contain hybrid (i.e. organic-inorganic) compositions in which the internal cage framework is primarily comprised of rigid inorganic silicon- oxygen bonds. The exterior of the nanostructure is covered by both reactive and nonreactive organic functionalities (R), which ensure compatibility and tailorability of the nanostructure with organic and inorganic materials. These and other properties and features of nanostructured chemicals are discussed in detail in U.S. Patent Nos. 5,412,053 and 5,484,867, which are incorporated herein by reference.

Current engineering methods produce POSS silanols bearing one through four silanol groups per cage. Control over the stereochemistry and silation of the silanols has been discussed extensively in the U.S. Patent No. 6,660,823, and a significant number of POSS silanols and POSS siloxide anions have become items of commerce.

Certain microelectronic, medical, catalytic, and biological applications could benefit from POSS silanols containing mixtures of R groups on the cage where one or more types of R group are greatly different in reactivity or properties (e.g. hydrophilic vs hydrophobic) from other R groups on the cage. Under such a scenario it would be desirable to maintain the silanol groups for bonding to metallic, biological, or polymeric surfaces, via covalent silation, hydrogen bonding, ion paring, or Van der Waals contact. Thus a need exists to provide POSS silanols bearing one or more different R groups on the same POSS silanol cage molecule. It is especially desirable to produce POSS cages with reactive olefinic groups R² which can participate in other chemistry than that available to the R¹ groups and the silanols or siloxides (Figure 1).

A key to the utility of POSS molecules and their compatibility with man-made and organic materials and surfaces is that their dispersion is thermodynamically

governed by the Gibbs free energy of mixing equation (ΔG = ΔH-TΔS). The nature

of the R group and ability of the reactive groups on the POSS cage to react or

interact with polymers and surfaces greatly contributes to a favorable enthalpic (ΔH)

term while the entropic term (ΔS) is highly favorable when the cage size is

monoscopic.

Consequently a need exists for improvement upon the prior art of POSS cage compositions. An improved process yielding high purity and molecularly precise POSS silanols or POSS siloxides bearing combinations of hydrophobic and hydrophilic and saturated and unsaturated R groups on the same molecule is described.

SUMMARY OF THE INVENTION

The present invention describes synthetic methods of preparing POSS or POS cage compositions bearing combinations of hydrophobic, hydrophilic, saturated, unsaturated, and biologically active R groups on the same molecule.

A synthetic process that renders polyhedral oligomeric silsesquioxane and polyhedral oligomeric silsesquioxane silanols and siloxides rapidly, in high yield, and containing wholly olefinic groups, or mixtures of olefinic and aromatic or alkyl, or biologically compatible groups is provided. The process involves the use of hydroxide bases with silane coupling agents of the formula R¹SiX₃ and R²SiX₃ to form POSS cages functionalized with silanols of the formula types [(R¹SiOi.s)_7-

X(R²SiOL₅)X(HOSiOL₅)I]₁₈, [(R¹SiOLs)₆-X(R²SiOL₅)X(R¹HOSiOi)_2-X(R²HOSiO₁)X]₁₈, [(R¹SiO₁.₅)₂-χ(R²SiθL₅)χ(R¹HOSiO₁)_4-x(R²HOSiOi)_x]_∑6i [(R¹SiOLs)₄(R²SiOLs)₄- _x(R¹HOSiOi)_3-x(R²HOSiOi)_x]_∑7 where R¹ is an alkyl or aryl group and R² is an olefin. The olefin groups can be subsequently derivatized though oxidative addition reactions, reductive addition reactions, metathesis, or polymerization as a means to afford additional properties such as polarity, hydrophobicity, lubrication, and biological compatibility or to immobilize to the POSS cage while rendering the silanols or siioxides for surface modification, reactive silation, or association with metals or other materials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a representative formula of a POSS cage bearing silanol/siloxide groups and two types of organic groups where the R¹ and R² groups are randomly incorporated into the cage.

FIG. 2 shows a mass spectrum of products from Example 1. DEFINITION OF FORMULA REPRESENTATIONS FOR NANOSTRUCTURES

For the purposes of understanding this invention's chemical compositions, the following definition for formula representations of Polyhedral Oligomeric Silsesquioxane (POSS) and Polyhedral Oligomeric Silicate (POS) nanostructures is made.

Polysilsesquioxanes are materials represented by the formula [RSiO_{1 5}]~

where °° represents molar degree of polymerization and R = represents an organic substituent (H, siloxy, cyclic or linear aliphatic or aromatic groups that may additionally contain reactive functionalities such as alcohols, esters, amines, ketones, olefins, ethers or halides or which may contain fluorinated groups, silicones, or aliphatic and aromatic groups). Polysilsesquioxanes may be either homoleptic or heteroleptic. The designation R includes R¹ and R² functionalities. Homoleptic systems contain only one type of R group while heteroleptic systems contain more than one type of R group.

POSS and POS nanostructure compositions are represented by the formula:

[(RSiOi _₅)_n]_∑# for homoleptic compositions

[(RSiO-) ^)_n(R¹SiO_{1 5})_m]_∑# for heteroleptic compositions (where R ≠ R')

[(RSiO₁ S)_n(RXSiO₁.₀)m]∑# for functionalized heteroleptic compositions (where R

groups can be equivalent or inequivalent)

In all of the above R is the same as defined above and X includes but is not limited to OH, ONa, OLi, OK, OCs, Cl, Br, I, alkoxide (OR), formate (OCH), acetate (OCOR), acid (OCOH), ester (OCOR), peroxide (OOR), amine (NR₂), isocyanate (NCO), and R. The symbols m and n refer to the stoichiometry of the composition.

The symbol ∑ indicates that the composition forms a nanostructure and the symbol

# refers to the number of silicon atoms contained within the nanostructure. The value for # is usually the sum of m+n, where n ranges typically from 1 to 24 and m

ranges typically from 1 to 12. It should be noted that ∑# is not to be confused as a

multiplier for determining stoichiometry, as it merely describes the overall nanostructural characteristics of the system (aka cage size).

DETAILED DESCRIPTION OF THE INVENTION

The present invention teaches a method for polyhedral oligomeric silsesquioxane (POSS) or polyhedral oligomeric silicate (POS) synthesis that renders mixtures of dissimilar R groups on the cage.

A key feature of the invention is the use of synergistically tolerant stoichiometric ratios of R¹SiX₃ and R²SiX₃ silane coupling agents which allow for statistical incorporation of two types of organic groups (R¹ and R²) into the same cage while preserving the POSS silanol/siloxide groups. Additionally, the ability to prepare cages with R-groups bearing unsaturated functionality allows for the further functionalization of the POSS cage.

Preparative methods for POSS silanols have been described in U.S. Patent No. 6,972,312 and in U.S. Patent Application Serial No. 11/371 ,195, which are incorporated by reference. As described previously, the cage assembly synthesis process involves the use of hydroxide bases in reaction with silane coupling agents of the formula R¹SiX₃ and R²SiX₃ to form POSS cages functionalized with silanols or siloxide groups. POSS silanols are preferred compositions as these offer the most versatility in application and derivatization chemistry. Preferred POSS silanol formula types include [(R¹SiO_Ls)₇-_X(R²SiO_L5)X(HOSiOL₅)I]₁₈, [(R¹ SiOLs)₆-X(R²SiO₁.₅)_X(R¹ HOSiOi)_2- x(R²HOSiOi)_x]_∑8) [(R¹Siθ_L5)₂-x(R²SiOi.₅)_x(R¹HOSiO₁)₄-_x(R²HOSiO₁)χ]_∑6, and [(R¹SiO_Ls)₄(R²SiO_Ls)^x(R¹HOSiO₁)_S-_X(R²HOSiOi)_X]₁₇ where R¹ is an alkyl or aryl group and R² is an olefin. For the generation of POSS silanol/siloxides bearing a mixture of olefinic R² and aliphatic R¹ groups, a valuable tool in the utility of this process is to maintain an approximately 15:85 to 25:75, and preferably a 20:80 molar ratio of the two R¹SiX₃ and R²SiX₃ silane coupling agents. This is particularly effective when incorporating vinyl and isobutyl groups into the same POSS cage. POSS silanol/siloxide cages in which all R groups are olefinic can also be prepared in a similar manner through variation of the ratio to the extreme of 100:0. The process is valid for all conceivable compositional ranges of R¹SiX₃ and R²SiX₃.

Olefinic groups on POSS cages can be subsequently derivatized though any number of oxidation or addition reactions. These include metathesis (U.S. Patent No. 5,942,638) or oxidation reactions (U.S. Patent Nos. 6,100,417 and 6,767,930), addition reactions (U.S. Patent Nos. 5,939,576 and 5,047,492), or polymerizations. This advancement in the art of POSS provides the ability to carry out chemical derivatization of the R groups while maintaining nonreactive R groups on the cage and reactive silanol/siloxide groups.

General Process Variables Applicable To All Processes

As is typical with chemical processes there are a number of variables that can be used to control the purity, selectivity, rate and mechanism of any process. Variables influencing the process include the size, polydispersity, and composition of the nanostructured chemicals, separation and isolation methods, and use of catalyst or cocatalysts, solvents and cosolvents. Additionally, kinetic and thermodynamic means of controlling the synthesis mechanism, rate, and product distribution are also known tools of the trade that can impact product quality and economics.

The following examples are provided to demonstrate practice of the invention and in no way indicate limitation of the scope or range of the invention.

POSS Olefinic Silanol/Siloxide Synthesis

Example 1. Preparation of mixed R¹ and R² POSS trisilanols.

In order to demonstrate the stoichiometic range for incorporation of R¹ and R² into a POSS cage the following series of formulations were preformed. A mixture of (R¹SiX₃) ¹BuSi(OMe)₃ and (R²SiX₃) allylSi(OMe)₃ was added slowly to a slurry containing LiOH-H₂O (3.3 g, 0.079 mol) in ethanol (75 ml_) and water (1.0 ml_, 0.055 mol). The reaction was refluxed for 2 days and then quenched by addition of solution of HCI (15 ml_ 37 wt.-% HCI) in ice slurry water (100 ml_) and mixed thoroughly for 15 min. The desired mixed R group POSS cages were then extracted into an organic layer through the addition of pentane (100 ml_), and aqueous NaCI. The organic layer was then washed with a 4 wt.-% HCI solution (3 x 100 ml_), and the volatiles were removed under reduced pressure. The desired products were collected as white solids and verified by MALDI-TOF and ¹H NMR spectroscopy. MALDI-TOF spectra include M/Z for the parent POSS formula and an associated sodium atom from the ablation matrix. See Figure 2.

For R² =allyl (C₃H₅) = 0 groups [(C₄H₉SiO₁._S)₄(C₄H₉HOSiOi)₃J₁₇ M/Z calculated 813 and found 813. For R² =allyl = 1 group = [(C₄H₉SiOi.₅)₄(C₃H₅HOSiOi)i (C₄H₉HOSiOi )₂]_∑7 M/Z calculated 797 and found 797. ¹H NMR (300 MHz, CDCI₃, 25 ⁰C) δ 6.69 (br s, 3 H, OH), 5.79 (m, 2 H, -CH=), 4.93 (m, 4 H, =CH₂), 1.85 (m, 5 H, -CH-), 1.61 (m, 4 H, - CH^rCH=CH₂), 0.95 (m, 30 H, -CH₃), 0.59 (m, 10 H, CH₂).

For R² =allyl = 2 groups = [(C₄H₉SiOi.₅)₄(C₃H₅HOSiOi)₂(C₄H₉HOSiOi)i]_∑7 M/Z calculated 781 and found 781.

For R² =allyl = 3 groups = [(C₄H₉SiOLs)₄(C₃H₅HOSiOi)₃]X₇ M/Z calculated 766 and found 766.

Example 2. Preparation of [((CH₃J₂CHCH₂)SiOi .5M(CH₂CH)(OH)SiOi .o)₃]∑₇

Following a similar procedure to that given in Example 1 , a 0.5L flask was charged with 75ml ethanol and 1 ml (0.055 mol) water. To this mixture was added 3.3g (0.079 mol) of solid lithium hydroxide-monohydrate (LiOH-H₂Q) was added followed by addition of 15.3 ml of (R¹) JBuSi(OMe)₃ and 3.1 ml of (R²) ViSi(OMe)₃. The reaction was refluxed for 8 hours and subsequently quenched by adding 100ml of an ice slurry containing 15ml of concentrated (37%) HCI. The desired product was extracted into an organic layer by addingiOOml of pentane and stirring for 30 minutes followed by addition of NaCI. The pentane layer was removed and washed three additional times with 100ml of a 4wt% HCL solution. The organic volatiles were removed under reduced pressure and the desired product was isolated (9.6g, 55.8%) as white solid in the compound was analyzed using MALDI-TOF-MS and identified as [((CH₃)₂CHCH₂)SiOi .5)₄((CH₂CH)(OH)SiOi ,o)3]∑₇.

Example 3. Preparation of [(0C₅H₉)SiOi .5)₄((CH₂CH)(0H)Si0i ),{{c-

C₅H₉)(OH)SiOi )₂]_∑7. Following a similar procedure to that given in Example 1 , R¹ Cyclopentyltrichlorosilane (36.2 g, 0.178 mol) and methanol (112 ml_) was added to a 2 L 3 neck flask fitted with mechanical stirrer and reflux condenser. LiOH-H₂O (23 g, 0.548 mol) was then added slowly over a period of 1 h. After stirring for another 30 min, acetone (700 ml_), R² vinyltrimethoxysilane (22.2 g, 0.15 mol), water (6.7 g) and LiOH.H₂O (7 g, 0.167 mol) was added and heated to reflux with stirring. After 24 h refluxing the mixture was acidified while hot by pouring dropwise a solution of ice/water (1 L) and HCI (24.5 mL, 37%) into the stirred reaction vessel. Hexane (250 mL) was then added and was separated and removed under vacuum. The resulting white powder was washed with methanol and dried under reduced pressure to yield 11.3 g (35%) of the desired product. The product was characterized by multinuclear NMR.

Example 4. Preparation of [((C-C₆H₉)SiOi .5M(C-C₆H₉)(OH)SiOi .o)₃]∑₇:

In a 500-mL flask containing a magnetic stir bar (R²) Cyclohexenyltrimethoxysilane (30.2 g, 150 mmol), LiOH-H₂O (3.15 g, 75 mmol, 3.5 eq), water (2.70 g, 150 mmol 7 eq), methanol (7.5mL) and MEK (150 mL) were combined. The flask was fitted with a reflux condenser and drying tube, and stirred while heating to reflux. After approximately 0.5 hr. the homogeneous reaction mixture began to deposit a white solid. After 24 hr the reaction mixture had deposited a large amount of white solid and appeared to be essentially heterogeneous. After 66 hrs the reaction mixture was then quenched into 1 N HCI (150 mL) and the heterogeneous quench mixture stirred for 1hr. The white solid collected by vacuum filtration and then slurried with methanol, stirred for 2 hrs filtered and dried under to provide 16.56g (80.7%) of the desired product. Example 5. Preparation of [((C-C₆Hg)CH₂CH₂SiOi .5M(C-

₆H₉)CH₂CH₂(OH)SiOi.o)₃]∑₇:

In a 100-mL roundbottom flask containing a magnetic stir bar (R²) [2-(3- cyclohexenyl)ethyl]triethoxysilane (10.0 g, 43.4 mmol), LiOH-H₂O (0.83 g, 19.8 mmol, 3.2 eq), water (0.89 g, 49.6 mmol 8 eq), methanol (1 mL) and MEK (44 mL) were combined. The flask was fitted with a reflux condenser and drying tube and placed into an oil bath kept at 80 ^°C and stirred. The reaction mixture remained homogeneous.

After 14hr the reaction mixture was quenched into a solution of water (150 mL) and phosphoric acid (2.02 mL, 1.5 eq relative to LiOH^»H₂O). An oily phase separated and was stirred for 1 hr. Hexane/THF were added to the quench to give a homogeneous organic phase and the organic phase washed with successive portions. of water and saturated brine. The organic phase was separated, dried over MgSO₄, filtered and then removed by rotary evaporation to provide a foamy solid which was dried by vacuum to provide 7.Og (98%) of a mixture of the desired

product [((C-C₆H₉)CH₂CH₂SiOi .5)₄((c-C₆H9)CH₂CH₂(OH)SiOi .o)3]∑₇ and desired

polymeric resin [((C-C₆H₉)CH₂CH₂SiOi .5)₄((c-C₆H₉)CH₂CH₂(OH)SiOi .ofel∑oo in a

70:30 ratio.

Example 6. Preparation of [((C₇H₉)SiOi .5M(C₇H₉)(OH)SiOi .o)₃]∑₇:

In a 100-mL roundbottom flask containing a magnetic stir bar (R²) Norbornenyltrimethoxysilane [5-(bicycloheptenyl)triethoxysilane] (10.0 g, 39 mmol), LiOH-H₂O (0.75 g, 17.8 mmol, 3.2 eq), water (0.80 g, 44.6 mmol 8 eq), methanol (1 mL) and MEK (39 mL) were combined. The flask was fitted with a reflux condenser and drying tube, placed into an oil bath kept at 80 ^°C and stirred. After approximately an hour the homogeneous reaction mixture began to deposit a white solid. After 14 hr the reaction mixture had deposited a large amount of white solid and appeared to be essentially heterogeneous.

The reaction mixture was then quenched into a solution of water (150 ml_) and phosphoric acid (1.82 imL, 1.5 eq relative to LiOH»H₂O) and the heterogeneous quench mixture stirred for 1 hr. Hexane/THF were added to the quench to give a homogeneous organic phase and the organic phase washed with successive portions of water and saturated brine. The organic phase was separated, dried over MgSO₄, filtered and then the solvent removed by rotary evaporation to provide a white solid which was stirred with acetone and collected by vacuum filtration to provide 5.4g (93%) of the desired product.

POSS Olefinic Silanol/Siloxide Derivatization Via Silation

The following examples are provided to demonstrate chemically derivatizing the silanol/siloxide functionality on the olefinic POSS systems.

Example 7. Preparation of [(c-

C₅H₉)SiOi .5MCH₂CH)SiOi .5)i(H₂N(CH₂)₃SiOi.5)i]_∑8 via chemical derivatization

of [(0C₅H₉)SiOi .5)4((CH₂CH)(OH)SiOi)₁((c-C₅H₉)(OH)SiOi)₂]_∑7.

[(C-C₅H₉)SiOi .5M(CH₂CH)(OH)SiOi)₁ ((C-C₅H₉)(OH)SiOi )₂]_∑7 (1 g) and

ethanol (15 ml_) were placed in a 100 ml_ round bottom flask and to it aminopropyltrimethoxysilane (0.521 g, 2.904x10^"3 mol) was added slowly with stirring. After reacting at room temperature for 24 h the white product was collected by filtration and washed with methanol to render 0.6 g (57%) of [(o

C₅H₉)SiOi .5)6((CH₂CH)SiOi .5)i(H2N(CH₂)₃SiOi .5)i]∑₈- The product was

characterized by multinuclear NMR.

Example 8. Preparation of

[((C₇H₉)SiO₁S)₇(CH₂=CCH₃C(O)OCH₂CH₂CH₂)SiO₁₀)I]₁₈ from

[((C₇H₉)SiO₁.₅)4((C₇H₉)(OH)SiO₁.o)₃]_∑7.

A solution of 3-methacryloxypropyltrichIorosilane (0.5 g, 0.4 ml_, 1.9 mmol, 1.01 eq) in THF (1.5 mL) was added dropwise to a solution of trisiianolnorbomene

POSS ([((C₇H₉)SiOi .5)₄((C₇H₉)(OH)SiOi .o)₃]∑₇) (2.0 g, 1.9 mmol) and dry triethylamine (0.63 g, 0.87 mL, 6.2 mmol, 3.25 eq) in anhydrous THF (10 mL). A precipitate of Et₃N^«HCI formed upon addition of the chlorosilane. After the addition was complete, the reaction mixture was stirred for 14 hr. The reaction was transferred to a separatory funnel and diethylether (10 mL) added. The organic layer was washed with 1 N acetic acid, water and saturated brine. The organic phase was dried over MgSO₄, filtered and the solvent removed by rotary evaporation. The resulting white solid was washed with MeOH collected by vacuum filtration and dried to provide 1.5 g (65%) of the product as a white solid.

Example 9. Preparation of [((c-

C₆H₉)SiOi .5)₇((CH₂=CCH₃C(O)O(CH₂)₃SiOi .₅)i]_∑8 from ([((*

C₆H₉)SiOL₅M(C₆H₉)(OH)SiOLo)₃]I₇:

Dry triethylamine (1.77 g, 2.44 mL, 17.5 mmol, 3.5 eq) was added dropwise to a cold (0 ⁰C solution of trisilanolcyclohexene ([((C-C₆H₉)SiOi.₅M(C- C₆H₉)(OH)SiOi. o)₃]∑₇) (4.79 g, 5.0 mmol) and S-methacryloxypropyltrichlorosilane (1.44 g, 1.15 mL, 5.5 mmol, 1.1 eq) in anhydrous THF (25 ml_). A precipitate of Et₃N-HCI formed upon addition of the Et₃N. After the addition was complete, the reaction mixture was warmed to room temperature and allowed to stir for 16 hr. The reaction was quenched with 1 N HCI (1OmL) and hexane (10 mL) added. The mixture was stirred well and the organic phase separated and washed once with saturated brine. The solvent was removed by rotary evaporation to give a solid paste, which upon stirring with acetone (50 mL) and methanol (50 mL) gave a white solid which was collected by vacuum filtration, washed with methanol and dried to provide 4.01 g (72%) of the product as a white solid.

Example 10. Preparation of F(C₄HgSiOi S)₄(C₃H₅SiOi _s)₃( (H₃C)₂HCOTiOi s)i1va).

Ti(OCH(CH₃)₂)₄ (1.0 g, 3.5 mmol) was added under argon to a solution of [(C₄H₉SiOi.5MC₃H₅HOSiOi )₃]_∑7 (2.25 g, « 3.0 mmol) dissolved in hexane (20 mL) and the reaction was left stirring for 2 h at 50 ⁰C. Evaporation of solvents in vacuo gave the product as a slightly sticky white solid (2.58 g, 2.8 mmol). Characterization was carried out by multinuclear NMR spectroscopy. ¹H NMR (400 MHz, CDCI₃, 25 ⁰C) δ 5.79 (m, 2 H, -CH=), 4.93 (m, 4 H, =CH₂), 4.20 (br s, 1 H, OCH(CH₃)₂), 1.87 (m, 5 H, -CH-), 1.61 (m, 4 H, -CH^-CH=CH₂), 1.23 (m, 6 H, OCH(CHs)₂), 0.96 (m, 30 H₁CH₃), 0.60 (m, 10 H₁ CH₂).

Example 11. Preparation of MCM-

[(C₄H₉SiO₁.5MC₃H₅SiOi.₅)3((H₃C)2HCOTiOi.5)i]∑8) materials for catalysis application.

MCM zeolite type catalyst materials were prepared under the same conditions with variation of the [(C4H₉SiOi.5)4(C3H5SiOi.5)3((H3C)₂HCOTiOi.5)i]∑8)/tθtraθthylorthosilicate (TEOS) molar ratio. Water 6.0 g (0.33 mol) was mixed with 4.77 g NH₄OH (30 wt.-% NH₃; 0.07 mol NH₃) and stirred for 1 min. To this solution was added 0.33 g cetyltrimethylammonium bromide CTABr (0.91 mol) and the solution was stirred for 0.5 h at room temperature. A mixture of

[(C4H₉SiOi.5)4(C₃H5SiOi.5)₃((H3C)2HCOTiOi.5)i]_Σ8 and TEOS were added in various ratios from 10-80 mole% POMS in order to alter the amount of Ti incorporated into the catalyst from 0.3-2.7 wt%. For example,

[(C₄H₉SiOi .S)₄(C₃H₅SiOi ._B)3((H3C)₂HCOTiOi.5)i]∑8 was added at a high loading of 80/20 POSS:TEOS mol % ratio, and low loading of 13/87 POSSTEOS. The solution was stirred for 0.5 h at room temperature during which time a white precipitate slowly formed. The precipitate was aged in its supernatant at 80 ⁰C for 4 days. The product was filtered, washed with water and dried in air at 80 ⁰C. A final washing, for „6 h . at.5O⁰C was carried, out using a 5 g HCI (37 wt.-%)/150 g MeOH mixture followed by filtration, washing with MeOH and drying in air overnight at 80 ⁰C. The desired product was isolated in high yield as a white solid. Characterization was carried out by SEM, ICP, EDAX and BET analysis. The incorporation of Ti POMS into MCM was found to retain the original texture and structure of the initial MCM while favorably improving the mechanical and physical stability of the material.

MoI % TEOS: Wt% Ti by Surface Pore Average

[(C^gSiO^μCaHsSiOi.sMHaCkHCOTiOi.s)^"!]! ICP area m²/g volume pore diam.

8 analysis cm³/g

100:0 0 870.49 0.940 3.15 nm

87:13 0.39 335.45 0.329 3.15 nm

80:20 0.73 200.99 0.178 2.90 nm

50:50 2.68 19.51 0.018 3.32 nm POSS Olefinic Silanol/Siloxide Derivatization Via Oxidation of R²

The following examples are provided to demonstrate the ability to carryout chemical derivatization of the R² groups on the functionalized POSS cages.

Example 12. Epoxidation of [((C₆H₉)SiO₁. _JMC₆H₉)(OH)SiO_1-O)₃]I₇:

A 5Og sample of [((C₆H₉)SiOi .5)₄((C₆H₉)(OH)SiOi .ofel∑y was stirred into

peracetic acid (200ml) chloroform (500ml), sodium bicarbonate (62.1 g) and sodium acetate (1.1 g) mixture and refluxed. After 2 hours the reaction was stopped by cooling. At room temperature water (700ml) was added and the mixture stirred and filtered and was allowed to phase separate into an aqueous layer and organic layer. The organic layer was separated and treated with methanol (100ml) to yield a white solid of epoxidized product. Note that MCPBA (metachloroperbenzoic acid) is also an acceptable oxidizing agent in place of the peracetic acid.

Example 13. Epoxidation of [((c-C₆H₉)SiO₁.₅)7((CH₂=CCH₃C(O)O(CH₂)₃SiO₁.₅)₁]_∑8:

A solution of 35% peracetic acid (1.5 g, 7.0 mmol) in CHCI₃ (5 ml_) was added dropwise to a refluxing mixture of methacrylcyclohexene POSS ([((c-

C₆H₉)SiOi .557((CH₂=CCH₃C(O)OCH₂CH₂CH₂)SiOi .5)i]∑₈ (2.2 g, 2.0 mmol), sodium

bicarbonate (1.4 g), and sodium acetate (50 mg, 0.6 mmol) in chloroform (25 mL). After 40 min the progress of the reaction was checked by HPLC and found to be 75% complete. Additional peracetic acid (1.5 g, 7.0 mmol) and sodium bicarbonate (1.4 g) were added and the reaction progress checked 25 min after the second addition and found to be complete. The reaction mixture was cooled to room temperature and water (100ml) was added. After through stirring the organic phase was allowed to separate and the lower CHCI₃ layer isolated, filtered through a Celite^® pad and concentrated to give a syrup. Addition of methanol (80 ml_) and stirring provided a white solid which was collected by vacuum filtration and dried to provide 1.05 g (43%) of the epoxidized product. Note that MCPBA (metachloroperbenzoic acid) is also an acceptable oxidizing agent in place of the peracetic acid.

Example 14. Preparation of [((OC₆H9)SiO₁.₅)₇((CH2=CCH3C(O)O(CH₂)3SiO₁.₅)i]_∑8

from tUCeHgJSiO_LsJyαCHa^CHgC^OtCHaJaSiO_Ls)!]^.

A 5Og sample of [((C₆H₉)SiOi .5)₇((CH₂=CCH₃C(O)O(CH₂)₃SiOi .5)i]_∑8 was

stirred into peracetic acid (200ml) chloroform (500ml), sodium bicarbonate (62.1 g) and sodium acetate (1.1 g) mixture and refluxed. After 2 hours the reaction was stopped by cooling. At room temperature water (700ml) was added and the mixture stirred and filtered and was allowed to phase separate into an aqueous layer and organic layer. The organic layer was separated and treated with methanol (10OhIl) to yield a white solid of epoxidized product. Note that MCPBA (metachloroperbenzoic acid) is also an acceptable oxidizing agent in place of the peracetic acid.

Example 15. Preparation of

[(((OH)₂C6H₉)SiO₁.₅)₇(CH₂=CCH₃C(O)O(CH₂)₃SiO₁.₅)₁]_∑8 from

[((OCeHgJSiO_LsM^Hz^CHaC^OtCHg^SiO_Ls)!]^.

Concentrated HCIO4 (0.1 ml_, 1.2 mmol) was added dropwise to a solution of methacrylepoxycyclohexane POSS

([((OC₆H₉)SiOi ₁SM(CH₂=CCH₃C(O)OCH₂CH₂CH₂)SiOi .5)i]_∑8) (9.80 g, 8.01 mmol)

and water (5.00 g, 277 mmol) in THF (100 mL) at room temperature. After stirring 18 h, the solvent was removed under vacuum and the residue dissolved in 3:2 (vohvol) methanohethyl acetate (30 mL). This solution was precipitated into MTBE (330 mL) at room temperature. The white solid that precipitated was collected by vacuum filtration and dried under vacuum at 35° C overnight. The final product is insoluble in hydrocarbon solvents and has very limited solubility in ethyl acetate, THF, and acetonitrile yet is highly soluble in methanol and DMSO.

POSS Olefinic Derivatization of R²

The following examples are provided to demonstrate the ability to carry out chemical derivatization of the R² groups on functionalized POSS cages. The procedures are in no way limiting yet provide examples of how chemical derivatization of the R groups can be utilized to change solubility and physical properties of POSS as well as function.

Example 16. Hydrosilylation of [(C₄H₉SiOi_-5MC₃H₅SiO_{1 5}MH₃C)₂HCOTiO_1-5)Ik₈.

[(C₄H₉SiO₁. S)₄(C₃H₅SiO₁.5^((H₃C)₂HCOTiOi.₅)i]_∑8 (2.3 g, 2.5 mmol) was dissolved in argon purged toluene (6 mL) and (CH₃CH₂O)₃SiH (600 μL, 3.2 mmol) was added followed by 20 mg of platinum-divinyltetramethyldisiloxane complex in xylene. The reaction was stirred for 30 minutes at room temperature followed by heating to 60 ⁰C for 8 hours. Volatiles were removed under reduced pressure to

render [(C₄H₉SiO₁.5)₄((CH₃CH₂O)₃SiC₃H6SiOi.5)₃((H₃C)₂HCOTiO₁.5)₁]_Σ8 as a yellow solid (2.1 g). The product was characterized by multinuclear NMR spectroscopy ¹H NMR (400 MHz, CDCI₃, 25 ⁰C) δ 5.75 (m, 2 H, -CH=), 4.90 (m, 4 H, =CH₂), 4.40 (br s, 1 H, OCH(CHs)₂), 3.82 (m, 6 H, -Si(OCH₂CHa)₃), 1.84 (m, 5 H, -CH-), 1.58 (m, 4 H, -CH₂-CH=CH₂), 1.41-1.21 (m, 15 H, CH₂, -Si(OCH₂CH₃)₃, OCH(CH₃)₂), 0.95 (m, 30 H, CH₃), 0.59 (m, 10 H, CH₂).

Example 17. General procedure for Hydroformylation of Olefinic POSS. A solution of PtCI₂(Sixantphos), (0.016 g, 0.019 mmol) and SnCI₂ (0.0036 g, 0.019 mmol) in CH₂CI₂ (5 mL) was stirred for 1 hour, than transferred into a stainless steel autoclave (100 mL internal volume). Additional CH₂CI₂ (15 mL) was added, followed by heating of the autoclave to 60 ⁰C and subsequent inlet of synthesis gas (CO / H₂ ratio 1 :1) to 40 bar. The autoclave was allowed to equilibrate for one hour, than a solution of silsesquioxane in CH₂CI₂ (total volume, 10 mL) was added, and the reaction was run at 60 °C/40 bar for 17 hours. The autoclave was cooled in ice and depressurized, after which the reaction mixture was evaporated to dryness. Pentane (20 mL) was added, and the catalyst was filtered off. Evaporation of the filtrate gave the hydroformylated POSS product. The products were characterized by multinuclear NMR spectroscopy. Other hydroformylation catalysts such as [Rh(Acac)/(CO)₂]/Xantphos can also be utilized.

While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the methods and apparatus disclosed herein may be made without departing from the scope of the invention which is defined in the appended claims.

What is claimed is:

Claims

1. A method for preparing olefinic functionalized polyhedral oligomeric silsesquioxane (POSS) or polyhedral oligomeric silicate (POS) silanol or siloxide molecules comprising reacting a silane coupling agent of the formula R²SiX₃ in the presence of a hydroxide base, wherein the R² group contains an olefin group and X is selected from the group consisting of OH, ONa, OLi, OK, OCs, Cl, Br, I, alkoxide (OR), formate (OCH), acetate (OCOR), acid (OCOH), ester (OCOR), peroxide (OOR), amine (NR₂), isocyanate (NCO), and R³, where R³ represents an organic substituent group selected from the group consisting of H, siloxy, and cyclic, linear aliphatic, and aromatic groups that may contain additional reactive functionalities.

2. The method of claim 1 , further comprising reacting a silane coupling agent of the formula R¹SiX₃ in the presence of a hydroxide base, where the R¹ group contains an alkyl or aromatic group, and wherein said silanol or siloxide molecules contain both R¹ and R².

3. The method of claim 2, further comprising the step of chemical derivatization of R², wherein the derivatization is selected from the group consisting of oxidation, addition, and metathesis reactions, while preserving the R¹ and silanol or siloxide functionality.

4. The method of claim 1 , further comprising the step of modification of the silanol or siloxide groups by a reaction selected from the group consisting of silation, reaction with a metal, or reaction with a surface.

5. The method of claim 2, further comprising the step of modification of the silanol or siloxide groups by a reaction selected from the group consisting of silation, reaction with a metal, or reaction with a surface.

6. The method of claim 3, further comprising the step of modification of the silanol or siloxide groups by a reaction selected from the group consisting of silation, reaction with a metal, or reaction with a surface.

7. The method of claim 3, wherein R² is converted to a biologically compatible group selected from the group consisting of amino acids, sugars, and therapeutics.

8. The method of claim 1 , wherein a plurality of R² groups are reacted to prepare silanol or siloxide molecules functionalized with different olefins.

9. The method of claim 8, wherein a continuous process renders the silanol or siloxide molecules.

10. The method of claim 4, wherein the metallized molecule from reaction with a metal serves as a heterogeneous catalyst or coreagent.

11. The method of claim 5, wherein the metallized molecule from reaction with a metal serves as a heterogeneous catalyst or coreagent.

12. The method of claim 6, wherein the metallized molecule from reaction with a metal serves as a heterogeneous catalyst or coreagent.