JP2009504890A - Preparation of polyhedral oligomeric silsesquioxane silanols and siloxanes functionalized with olefinic groups - Google Patents

Abstract

  Synthetic processes for polyhedral oligomeric silsesquioxane (POSS) or polyhedral oligomeric silicate (POS) produce silanol and siloxide molecules that contain both olefinic and alkyl or aromatic groups. Olefin-supported POSS silanol / siloxanes are derivatized to various chemicals while retaining the ability to derive additional silanol / siloxanes.

Description

  This application claims the benefit of US Provisional Patent Application No. 60 / 708,966, filed Aug. 16, 2005.

FIELD OF THE INVENTION The present invention is functionalized with olefinic groups, improving its physical, chemical and electronic properties and compatibility for incorporation into catalysts, metals, polymers, electronic, medical, cosmetic and biological products. Relates to a process for functionalization of functionalized polyhedral oligomeric silsesquioxane silanols and siloxanes.

BACKGROUND OF THE INVENTION Nanostructured chemicals are best represented by those based on low cost polyhedral oligomeric silsesquioxanes (POSS) and polyhedral oligomeric silicates (POS). The POSS and POS systems include hybrid (ie, organic-inorganic) compositions in which the internal soot framework is composed primarily of strict inorganic silicon-oxygen bonds. The exterior of the nanostructure is covered by both reactive and non-reactive organic functional groups (R), ensuring compatibility and adaptability of the nanostructure with organic and inorganic materials. These and other properties and characteristics of nanostructured chemicals are discussed in detail in US Pat. Nos. 5412053 and 5484867, which are hereby incorporated by reference.

  Current engineering methods produce POSS silanols carrying 1 to 4 silanol groups per cage. Control over silanol stereochemistry and silylation has been intensively discussed in US Pat. No. 6,668,823, with numerous POSS silanols and POSS siloxide anions being commercial products.

In certain microelectronics, medical, catalytic and biological applications, one or more types of R groups differ significantly from other R groups on the cage in reactivity or properties (eg, hydrophilic versus hydrophobic) Could be benefited from POSS silanol containing a mixture of R groups on the cage. In this scenario, it may be desirable to maintain silanol groups for bonding to metal, biological or polymer surfaces by covalent silylation, hydrogen bonding, ion pairing or van der Waltz contact. Thus, there is a need to provide POSS silanols that carry one or more different R groups on the same POSS silanol molecule. It is particularly preferred to produce a POSS soot having a reactive olefinic R ² group that can participate in a chemistry different from those available for R ¹ groups and silanols or siloxanes. (Figure 1)
The key to the usefulness of POSS molecules and their compatibility with artificial and organic materials and surfaces is that their dispersibility is thermodynamically expressed in the Gibbs mixing free energy equation (ΔG = ΔH−TΔS). It is being ruled. The nature of the R group on the POSS cage and the ability of the reactive group to react or interact with the polymer and the surface greatly contribute to the beneficial enthalpy term (ΔH), while the entropy term (ΔS) is It is very beneficial when it is a pick.

  Thus, there is a need for improvements over the prior art with respect to POSS soot composition. An improved process is described that produces high purity, molecularly accurate POSS silanols or POSS siloxides that carry a combination of hydrophilic and hydrophobic and saturated and unsaturated R groups on the same molecule.

SUMMARY OF THE INVENTION The present invention describes a synthetic method for preparing POSS or POS sputum compositions that carry a combination of hydrophilic, hydrophobic, saturated, unsaturated, and biologically active R groups on the same molecule. To do.

Rapid polyhedral oligomeric silsesquioxanes and polyhedral oligomeric silsesquioxane silanols and siloxanes containing olefinic groups or mixtures of olefinic and aromatic or alkyl or biologically compatible groups as a whole Is provided in a high yield yield. The process consists of [(R ¹ SiO _1.5 ) _7-x (R ² SiO _1.5 ) _x (HOSiO _1.5 ) ₁ ] _Σ8 , [(R ¹ SiO _1.5 ) _6-x (R ² SiO _{^{1.5) x (R 1 HOSiO 1}} ) 2-x (R 2 HOSiO 1) x] Σ8, [(R 1 SiO 1.5) 2-x (R 2 SiO 1.5) x (R 1 HOSiO 1 ) _4-x (R ² HOSiO ₁ ) _x ] _{Σ 6} , [(R ¹ SiO _1.5 ) ₄ (R ² SiO _1.5 ) _4-x (R ¹ HOSiO ₁ ) _3-x (R ² HOSiO ₁ ) _x ] _Σ7 (wherein R ¹ is an alkyl or aryl group and R ² is an olefin) of formula R ¹ SiX ₃ to form a silanol-functionalized POSS cage of the formula Includes the use of hydroxide bases with R ² SiX ₃ silane coupling agents.

  Olefin groups are a means for imparting additional properties such as polarity, hydrophobicity, lubricity and biocompatibility, or for surface modification, reactive silylation or association with metals or other materials. As a means for immobilizing silanol or siloxane on the POSS cage during that time, it can be subsequently derivatized by oxidative addition reaction, reductive addition reaction, metathesis or polymerization.

Nanostructure Expression Definitions To understand the chemical compositions of the present invention, the following for the expression of polyhedral oligomeric silsesquioxane (POSS) and polyhedral oligomeric silicate (POS) nanostructures: Definitions are made.

In polysilsesquioxane, ∞ represents the degree of molar polymerization, R is an organic substituent (H, siloxy, cyclic or linear aliphatic or aromatic group, and additionally, alcohol, ester, amine, ketone Or a reactive functional group such as a halide which may contain an olefin, an ether or a fluorinated group), and a material represented by the formula [RSiO _1.5 ] _∞ . The polysilsesquioxane may be either homoleptic or heteroleptic. The symbol R includes R ¹ and R ² functional groups. A homoleptic system contains only one type of R group, while a heteroleptic system contains more than one type of R group.

  POSS and POS nanostructure compositions are represented by the following formula:

[(RSiO _1.5 ) _n ] _{Σ #} for homoleptic compositions
For heteroleptic compositions, [(RSiO _1.5 ) _n (R′SiO _1.5 ) _m ] _{Σ #} (where R and R ′ are different).
For functionalized heteroleptic compositions, [(RSiO _1.5 ) _n (RXSiO _1.0 ) _m ] _{Σ #} (wherein the R groups may be the same or not the same).
All of the above R are the same as defined above, and X is not limited, but includes OH, ONa, OLi, OK, OCs, Cl, Br, I, alkoxide (OR), formate (OCH), acetate ( OCOR), acid (OCOH), ester (OCOR), peroxide (OOR), amine (NR ₂ ), isocyanate (NCO) and R. The symbols m and n mean the stoichiometry of the composition. The symbol Σ indicates that the composition forms a nanostructure, and the symbol # indicates the number of silicon atoms contained in the nanostructure. The value of # is usually the sum of m and n, the range of n is typically 1-24, and the range of m is typically 1-12. It should be noted that Σ # should not be confused with a multiplier that determines stoichiometry, since it merely describes the overall nanostructure characteristics of the system (known as the cocoon size). is there.

DETAILED DESCRIPTION OF THE INVENTION The present invention teaches a method for polyhedral oligomeric silsesquioxane (POSS) and polyhedral oligomeric silicate (POS) synthesis that provides a mixture of different R groups on the cage. .

A key feature of the present invention is that R ¹ SiX ₃ that allows statistical incorporation of two types of organic groups (R ¹ and R ² ) in the same cage while retaining the POSS silanol / siloxane group. The use of a synergistically tolerated stoichiometric ratio of the R ² SiX ₃ silane coupling agent. In addition, the ability to prepare soots with R groups bearing unsaturated functional groups allows further functionalization of the POSS soot.

Methods for the preparation of POSS silanols have been described in US Pat. No. 6972312 and US patent application Ser. No. 11/371195, which are incorporated by reference. As previously described, the process of synthesizing the soot total involves reacting with a silane coupling agent of the formulas R ¹ SiX ₃ and R ² SiX ₃ to form POSS cages functionalized with silanol or siloxane groups. Including the use of hydroxide bases.

POSS silanol is a preferred composition because it provides maximum versatility in application and derivatization chemistry. Suitable POSS silanol formula types are [(R ¹ SiO _1.5 ) _7-x (R ² SiO _1.5 ) _x (HOSiO _1.5 ) ₁ ] _Σ8 , [(R ¹ SiO _1.5 ) _6-x (R ² SiO _1.5 ) _x (R ¹ HOSiO ₁ ) _2-x (R ² HOSiO ₁ ) _x ] _Σ8 , [(R ¹ SiO _1.5 ) _2-x (R ² SiO _{1.5 ^{) x (R 1 HOSiO 1)}} 4-x (R 2 HOSiO 1) x] Σ6 and _{^{[(R 1 SiO 1.5) 4}} (R 2 SiO 1.5) 4-x (R 1 HOSiO 1) 3- _x (R ² HOSiO ₁ ) _x ] _Σ7 , where R ¹ is an alkyl or aryl group and R ² is an olefin. A valuable tool useful in this process for the production of POSS silanol / siloxide carrying a mixture of olefinic R ² and aliphatic R ¹ groups is two R ¹ SiX ₃ and R ² SiX ₃ silanes. The molar ratio of coupling agent is maintained at about 15:85 to 25:75, preferably 20:80. 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 olefins can be prepared in a similar manner by changing the ratio to the limit of 100: 0. The process is effective for all expected composition ranges of R ¹ SiX ₃ and R ² SiX ₃ .

  The olefinic group on the POSS cage can be subsequently derivatized by any number of oxidation or addition reactions. These are metathesis (US Pat. No. 5,842,638) or oxidation reactions (US Pat. No. 6,100417 and US Pat. No. 6,767,930), addition reactions (US Pat. No. 5,939,576 and US Pat. No. 5,047,492) or polymerization. This advance in POSS technology provides the ability to perform chemical derivatization of R groups while maintaining non-reactive R groups and reactive silanol / siloxide groups on the cage.

General process variables applicable to the whole process As is typical for chemical processes, there are a number of variables used to control purity, selectivity, speed and process mechanism. Variables affecting the process include nanostructured chemical size, polydispersity and composition, separation and isolation methods, catalyst or cocatalyst, solvent and cosolvent use. Additionally, kinetic and thermodynamic means of controlling the synthesis mechanism, speed and product distribution are also known to be trade tools that can affect product quality and economics.

  The following examples are provided to illustrate the practice of the present invention and are in no way indicative of the purpose and scope of the invention.

POSS Olefin Silanol / Silkoxide Synthesis Example 1 Preparation of Mixed R ¹ and R ² POSS Trisilanol The following series of recipes was carried out in order to show the stoichiometric range for incorporation of R ¹ and R ² into POSS cages. A mixture of (R ¹ SiX ₃ ) isobutyl Si (OMe) ₃ and (R ² SiX ₃ ) allyl Si (OMe) ₃ was dissolved in LiOH.H in ethanol (75 ml) and water (1.0 mL, 0.055 mol). Slowly added to a slurry containing ₂ O (3.3 g, 0.079 mol). The reaction was refluxed for 2 days, after which it was quenched by the addition of HCl solution (15 mL 37 wt% HCl) in ice slurry water (100 mL) and mixed thoroughly for 15 minutes. The desired mixed R group POSS 籠 was then extracted into the organic layer by the addition of pentane (100 mL) and aqueous NaCl. The organic layer was then washed with 4 wt% HCl solution (3 × 100 mL) and volatiles were removed under reduced pressure. The desired product was collected as a white solid and confirmed by MALDI-TOF and ¹ H NMR spectrometer. The MALDI-TOF spectrum contains M / Z for the nucleophilic POSS formula and related sodium atoms from the ablation matrix. (See Figure 2)
For R ² = Allyl _{(C 3 H} 5) = 0 groups _{[(C 4 H 9 SiO 1.5} ) 4 (C 4 H 9 HOSiO 1) 3] Σ7 MZ is calculated as 813, 813 Detected.

R ² = Allyl = 1 group = [(C ₄ H ₉ SiO _1.5 ) ₄ (C ₃ H ₅ HOSiO ₁ ) ₁ (C ₄ H ₉ HOSiO ₁ ) ₂ ] For _Σ7 , MZ is 797 Calculated and detected 797. ¹ H NMR (300MHz, CDCl ₃ , 25 ° C) δ6.69 (brs, 3H, OH), 5.79 (m, 2H, -CH =), 4.93 (m, 4H, = CH ₂ ), 1.85 (m, 5H , -CH -), 1.61 (m , 4H, -CH 2 -CH = CH 2), 0.95 (m, 30H, -CH 3), 0.59 (m, 10H, CH 2).

R ² = Allyl = 2 group = [(C ₄ H ₉ SiO _1.5 ) ₄ (C ₃ H ₅ HOSiO ₁ ) ₂ (C ₄ H ₉ HOSiO ₁ ) ₁ ] For _Σ7 , MZ is 781 Calculated and detected 781.

R ² = Allyl = 3 group = [(C ₄ H ₉ SiO _1.5 ) ₄ (C ₃ H ₅ HOSiO ₁ ) ₃ ] For _Σ7 , MZ was calculated to be 766 and 766 was detected.

Example 2. Preparation of [((CH ₃ ) ₂ CHCH ₂ ) SiO _1.5 ) ₄ ((CH ₂ CH) (OH) SiO _1.0 ) ₃ ] _{Σ7 According} to a procedure similar to that according to Example 1, 0.5 L The flask was filled with 75 ml ethanol and 1 ml (0.055 mol) water. To this mixture was added 3.3 g (0.079 mol) of solid lithium hydroxide monohydrate (LiOH—H ₂ O), and 15.3 ml of (R ¹ ) isobutyl Si (OMe) ₃ and 3. 1 ml of (R ² ) vinyl Si (OMe) ₃ was subsequently added. The reaction was refluxed for 8 hours and subsequently quenched by adding 100 ml ice slurry containing 15 ml concentrated (37%) HCl. The desired product was extracted into the organic layer by adding 100 mL of pentane and stirring for 30 minutes with the addition of NaCl. The pentane layer was removed and washed an additional 3 times with 100 ml of 4 wt% HCl solution. Organic volatiles were removed under reduced pressure and the desired product was isolated as a white solid in the compound (9.6 g, 55.8%) and analyzed using MALDI-TOF-MS, [(( CH ₃ ) ₂ CHCH ₂ ) SiO _1.5 ) ₄ ((CH ₂ CH) (OH) SiO _1.0 ) ₃ ] _Σ7 .

Example 3 [(C-C ₅ H ₉ ) SiO _1.5 ) ₄ ((CH ₂ CH) (OH) SiO ₁ ) ₁ ((c-C ₅ H ₉ ) (OH) SiO ₁ ) ₂ ] Preparation Example 1 of _Σ7 R ¹ cyclopentyltrichlorosilane (36.2 g, 0.178 mol) and methanol (112 mL) were added to an a2L3 neck flask equipped with a mechanical stirrer and reflux concentrator, following a procedure similar to that by . Then after LiOH. H ₂ O (23 g, 0.548 mol) was added slowly over 1 hour. After stirring for another 30 minutes, R ² vinyltrimethoxysilane (22.2 g, 0.15 mol), water (6.7 g) and LiOH. H ₂ O (7 g, 0.167 mol) was added and heated to reflux with stirring. After refluxing for 24 hours, the mixture was hot acidified by dropwise addition of a solution of ice / water (1 L) and HCl (24.5 mL, 37%) to a stirred reaction vessel. Hexane (250 mL) was then added, separated and removed under vacuum. The resulting white powder was washed with methanol and dried under reduced pressure to give 11.3 g (35%) of the desired product. The product was characterized by multi-stage nuclear NMR.

Example 4 Preparation of [((c-C ₆ H ₉ ) SiO _1.5 ) ₄ ((c-C ₆ H ₉ ) (OH) SiO _1.0 ) ₃ ] _{Σ7 In} a 500 mL flask containing a magnetic stir bar (R ² ) Cyclohexynyltrimethoxysilane (30.2 g, 150 mmol), LiOH.H ₂ O (3.15 g, 75 mmol, 3.5 eq), water (2.70 g, 150 mmol, 7 eq), methanol (7 .5 mL) and MEK (150 mL) were combined. The flask was equipped with a reflux concentrator and a drying tube and stirred while being heated to reflux. After about 0.5 hours, the homogeneous reaction mixture began to precipitate a white solid. After 24 hours, the reaction mixture precipitated a large amount of white solid and appeared substantially heterogeneous. After 66 hours, the reaction mixture was quenched in 1N HCl (150 mL) and the heterogeneous quench mixture was stirred for 1 hour. The white solid collected by vacuum filtration was then slurried with methanol, stirred for 2 hours, filtered and dried to give 16.56 g (80.7%) of the desired product.

Example 5. Preparation of [((c-C ₆ H ₉ ) CH ₂ CH ₂ SiO _1.5 ) ₄ ((c-C ₆ H ₉ ) CH ₂ CH ₂ (OH) SiO _1.0 ) ₃ ] _Σ7 A 100 mL round bottom flask containing (R ² ) [2- (3-cyclohexylinyl) ethyl] triethoxysilane (10.0 g, 43.4 mmol), LiOH.H ₂ O (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 equipped with a reflux concentrator and a drying tube, kept at 80 ° C. in an oil bath and stirred. The reaction mixture remained homogeneous.

After 14 hours, the reaction mixture was quenched in a solution of water (150 mL) and phosphoric acid (2.02 mL, 1.5 equivalents to LiOH.H ₂ O). The oil phase was separated and stirred for 1 hour. Hexane / THF was added to the quench resulting in a homogeneous organic phase, which was washed with successive portions of water and saturated brine. The organic layer is separated, dried over MgSO ₄ , filtered, then removed on a rotary evaporator to provide a foamed solid, vacuum dried and 7.0 g (98%) of the desired product [((c- _{C 6 H 9) CH 2 CH} 2 SiO 1.5) 4 ((c-C 6 H 9) CH 2 CH 2 (OH) SiO 1.0) 3] Σ7 and desired polymeric resin [((c-C _{6 H 9) CH 2 CH 2} SiO 1.5) 4 ((c-C 6 H 9) CH 2 CH 2 (OH) SiO 1.0) 3] mixtures _Σ∞ is, 70: obtained in 30 ratio It was.

Example 6 Preparation of [((C ₇ H ₉ ) SiO _1.5 ) ₄ ((C ₇ H ₉ (OH) SiO _1.0 ) ₃ ] _Σ7 To a 100 mL round bottom flask containing a magnetic stir bar, _add (R ² ) norbornene. Iltrimethoxysilane [5- (bicycloheptenyl) triethoxysilane] (10.0 g, 39 mmol), LiOH.H ₂ O (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 and kept at 80 ° C. in an oil bath, After about 1 hour, the homogeneous reaction mixture began to precipitate a white solid, and after 14 hours the reaction mixture precipitated a large amount of white solid and appeared substantially heterogeneous. .

The reaction mixture was then quenched in a solution of water (150 mL) and phosphoric acid (1.82 mL, 1.5 equivalents to LiOH.H ₂ O) and the heterogeneous quench mixture was stirred for 1 hour. Hexane / THF was added to the quench resulting in a homogeneous organic phase, which was washed with successive portions of water and saturated brine. The organic layer is separated, dried over MgSO ₄ and filtered, after which the solvent is removed on a rotary evaporator to provide a white solid, stirred with acetone, collected by vacuum filtration and collected with 5.4 g (93 %) Of the desired product.

POSS olefin silanol / siloxide derivatization by silylation The following examples are provided to demonstrate the chemical derivatization of silanol / siloxide functionality on olefin POSS systems.

Example 7. [(C-C ₅ H ₉ ) SiO _1.5 ) ₄ ((CH ₂ CH) (OH) SiO ₁ ) ₁ ((c-C ₅ H ₉ ) (OH) SiO ₁ ) ₂ ] Chemical Derivative of _Σ7 Preparation of [(c-C ₅ H ₉ ) SiO _1.5 ) ₆ ((CH ₂ CH) SiO _1.5 ) ₁ (H ₂ N (CH ₂ ) ₃ SiO _1.5 ) ₁ ] _Σ8 [(8 c-C ₅ H ₉ ) SiO _1.5 ) ₄ ((CH ₂ CH) (OH) SiO ₁ ) ₁ ((c-C ₅ H ₉ ) (OH) SiO ₁ ) ₂ ] _Σ7 (1 g) and methanol ( 15 mL) was placed in a 100 mL round bottom flask to which aminopropyltrimethoxysilane (0.521 g, 2.904 × 10 ⁻³ mol) was added with slow stirring. After reaction at room temperature for 24 hours, the white product was collected by filtration, washed with methanol, and 0.6 g (57%) of [(c-C ₅ H ₉ ) SiO _1.5 ) ₆ ((CH ₂ CH) SiO _1.5 ) ₁ (H ₂ N (CH ₂ ) ₃ SiO _1.5 ) ₁ ] _Σ8 was obtained. The product was characterized by multi-stage nuclear NMR.

Example 8 _{[((C 7 H 9)} SiO 1.5) 4 ((C 7 H 9) (OH) SiO 1.0) 3] from _{Σ7 [((C 7 H 9} ) SiO 1.5) 7 (CH ₂ = CCH ₃ C (O) OCH ₂ CH ₂ CH ₂ ) SiO _1.0 ) ₁ ] Preparation of _Σ8 3-Methacryloxypropyltrichlorosilane (0.5 g, 0.4 mL, 1) in THF (1.5 mL) .9 mmol, 1.01 equiv.) Solution of trisilanol norbornene POSS [((C ₇ H ₉ ) SiO _1.5 ) ₄ ((C ₇ H ₉ ) (OH) SiO ₁ in anhydrous THF (10 mL) _{. 0} ) ₃ ] _Σ7 (2.0 g, 1.9 mmol) and anhydrous triethylamine (0.63 g, 0.87 mL, 6.2 mmol, 3.25 eq) was added dropwise. A precipitate of Et ₃ N · HCl was formed upon addition of chlorosilane. After the addition was complete, the reaction mixture was stirred for 14 hours. The reaction was transferred to a separatory funnel and diethyl ether (10 mL) was added. The organic layer was washed with 1N acetic acid, water and saturated brine. The organic phase was dried over MgSO ₄ , filtered and the solvent was removed on a rotary evaporator. The resulting white solid was washed with MeOH, collected by vacuum filtration and dried to give 1.5 g (65%) of product as a white solid.

Example 9. [((C-C ₆ H ₉ ) SiO _1.5 ) ₄ ((C ₆ H ₉ ) (OH) SiO _1.0 ) ₃ ] [((c-C ₆ H ₉ ) SiO _1.5 from _Σ7 ) ₇ ((CH _{2 ═CCH 3} C (O) O (CH ₂ ) ₃ SiO _1.5 ) ₁ ] Preparation of _Σ8 Anhydrous triethylamine (1.77 g, 2.44 mL, 17.5 mmol, 3.5 eq) Is trisilanol cyclohexene [((c-C ₆ H ₉ ) SiO _1.5 ) ₄ ((C ₆ H ₉ ) (OH) SiO _1.0 ) ₃ ] _Σ7 (4.79 g) in anhydrous THF (25 mL). , 5.0 mmol) and 3-methacryloxypropyltrichlorosilane (1.44 g, 1.15 mL, 5.5 mmol, 1.1 eq) were added dropwise to a cooled solution of 0 ° C. Et ₃ N · HCl. precipitate formed Et 3 _N upon addition. after the addition was complete, the reaction mixture is warmed to room temperature, 1 The reaction was quenched with 1N HCl (10 mL) and hexane (10 mL) was added The mixture was stirred well and the organic phase separated and washed once with saturated brine. The solvent is removed on a rotary evaporator to give a solid paste that is stirred with acetone (50 mL) and methanol (50 mL) to give a white solid, collected by vacuum filtration, washed with methanol, dried, and white 4.01 g (72%) of product was obtained as a solid.

Example 10 [((C ₄ H ₉ ) SiO _1.5 ) ₄ (C ₃ H ₅ SiO _1.5 ) ₃ ((H ₃ C) ₂ HCOTiO _1.5 ) ₁ ] Preparation of _Σ8 Ti (OCH (CH ₃ ) ₂ ) ₄ (1.0 g, 3.5 mmol) was dissolved in hexane (20 mL) [(C ₄ H ₉ ) SiO _1.5 ) ₄ (C ₃ H ₅ HOSiO ₁ ) ₃ ] _Σ7 (2.25 g, 3.0 mmol) solution was added under argon and the reaction was left to stir at 50 ° C. for 2 hours. Solvent evaporation in vacuo gave the product as a slightly sticky white solid (2.58 g, 2.8 mmol). Characterization was performed with a multi-stage nuclear NMR spectrometer. ¹ H NMR (400MHz, CDCl ₃ , 25 ° C) δ5.79 (m, 2H, -CH =), 4.93 (m, 4H, = CH ₂ ), 4.20 (brs, 1H, OCH (CH ₃ ) ₂ ) , 1.87 (m, 5H, -CH-), 1.61 (m, 4H, -CH ₂ -CH = CH ₂ ), 1.23 (m, 6 H, OCH (CH ₃ ) ₂ ), 0.96 (m, 30 H, _{CH 3), 0.60 (m,} 10 H, CH 2).

Example 11 MCM-[(C ₄ H ₉ ) SiO _1.5 ) ₄ (C ₃ H ₅ SiO _1.5 ) ₃ ((H ₃ C) ₂ HCOTiO _1.5 ) ₁ ] _Σ8 Preparation for Catalytic Application MCM The zeolite type catalyst material is [(C ₄ H ₉ ) SiO _1.5 ) ₄ (C ₃ H ₅ SiO _1.5 ) ₃ ((H ₃ C) ₂ HCOTiO _1.5 ) ₁ ] _Σ8 / tetraethylorthosilicate ( The TEOS) molar ratio was varied and prepared under the same conditions. 6.0 g (0.33 mol) of water was mixed with 4.77 g NH ₄ OH (30 wt% NH ₃ ; 0.07 mol NH ₃ ) and stirred for 1 minute. To this solution was added 0.33 g cetyltrimethylammonium bromide CTABr (0.91 mol) and the solution was stirred at room temperature for 0.5 hours. [(C ₄ H ₉ ) SiO _1.5 ) ₄ (C ₃ H ₅ SiO _1.5 ) ₃ (in order to change the amount of Ti incorporated into the catalyst by 0.3 to 2.7% by weight. (H ₃ C) ₂ HCOTiO _1.5 ) ₁ ] A mixture of _Σ8 and TEOS was added to POMS at various ratios of 10-80 mol%. For example, [(C ₄ H ₉ ) SiO _1.5 ) ₄ (C ₃ H ₅ SiO _1.5 ) ₃ ((H ₃ C) ₂ HCOTiO _1.5 ) ₁ ] _Σ8 is 80 of the POSS: TEOS molar ratio. It was added at a high usage of / 20 and at a low usage of 13/87 of the POSS: TEOS molar ratio. The solution was stirred at room temperature for 0.5 hour, during which time a white precipitate slowly formed. The precipitate was aged in its supernatant at 80 ° C. for 4 days. The product was filtered, washed with water and air dried at 80 ° C. The final wash was made with a 5 g HCl (37 wt%) / 150 g MeOH mixture at 50 ° C. for 6 hours, the mixture was filtered, washed with MeOH and air dried at 80 ° C. overnight. The desired product was isolated as a white solid in high yield. Characterization was done by SEM, ICP, EDAX and BET analysis. Incorporation of TiPOMS into MCM has been found to preserve the original texture and structure of the original MCM while advantageously improving the mechanical and physical stability of the material.

POSS olefin silanol / siloxide derivatization by oxidation of R ² groups The following examples are provided to demonstrate the ability to perform chemical derivatization of R ² groups on functionalized POSS cages.

Example 12. [((C ₆ H ₉ ) SiO _1.5 ) ₄ ((C ₆ H ₉ ) (OH) SiO _1.0 ) ₃ ] _Epoxidation of _Σ7 [((C ₆ H ₉ ) SiO _1.5 ) ₄ ( (C ₆ H ₉ ) (OH) SiO _1.0 ) ₃ ] A 50 g sample of _Σ7 is a mixture of peracetic acid (200 ml), chloroform (500 ml), sodium bicarbonate (62.1 g) and sodium acetate (1.1 g). Stir in and reflux. After 2 hours, the reaction was stopped by cooling. Water (700 mL) was added at room temperature and the mixture was stirred, filtered, and allowed to phase separate into aqueous and organic layers. The organic layer was separated and treated with methanol (100 mL) to give a white solid epoxy product. It should be noted that MCPBA (metachloroperbenzoic acid) is also an acceptable oxidizing agent instead of peracetic acid.

Example 13 [((C-C ₆ H ₉ ) SiO _1.5 ) ₇ ((CH _{2 ═CCH 3} C (O) O (CH ₂ ) ₃ SiO _1.5 ) ₁ ] _Epoxidation of _Σ8 in CHCl ₃ (5 ml) Of 35% peracetic acid (1.5 g, 7.0 mmol) in methacrylcyclohexene POSS [((c-C ₆ H ₉ ) SiO _1.5 ) ₇ ((CH ₂ ═CCH ₃ ) in chloroform (25 ml). C (O) OCH ₂ CH ₂ CH ₂ (SiO _1.5 ) ₁ ] _Σ8 (2.2 g, 2.0 mmol), sodium bicarbonate (1.4 g) and sodium acetate (50 mg, 0.6 mmol). After 40 minutes, the reaction progress was checked by HPLC and found to be 75% of the total, with additional peracetic acid (1.5 g, 7.0 mmol) and Sodium bicarbonate (1.4 g) was added and the reaction The progress was checked for 25 minutes after the second addition and found to be complete, the reaction mixture was cooled to room temperature and water (100 ml) was added, after thorough stirring, the organic phase separated The lower CHCl ₃ layer was isolated, filtered through a Celite® pad and concentrated to a syrup, adding methanol (80 ml) and stirring to give a white solid, vacuum Collected by filtration and dried to give 1.05 g (43%) of the epoxy product, it should be noted that MCPBA (metachloroperbenzoic acid) is also an acceptable oxidizing agent instead of peracetic acid. is there.

Example 14 [((C ₆ H ₉ ) SiO _1.5 ) ₇ ((CH _{2 ═CCH 3} C (O) O (CH ₂ ) ₃ SiO _1.5 ) ₁ ] [((OC ₆ H ₉ ) SiO from _{Σ8 1.5} ) ₇ ((CH _{2 ═CCH 3} C (O) O (CH ₂ ) ₃ SiO _1.5 ) ₁ ] Preparation of _Σ8 [(((C ₆ H ₉ ) SiO _1.5 ) ₇ ((CH ₂ = CCH ₃ C (O) O (CH ₂ ) ₃ SiO _1.5 ) ₁ ] A 50 g sample of _Σ8 was obtained from peracetic acid (200 ml), chloroform (500 ml), sodium bicarbonate (62.1 g) and sodium acetate (1 0.1 g) Stirred in the mixture and refluxed After 2 hours, the reaction was stopped by cooling, water (700 ml) was added at room temperature, the mixture was stirred, filtered, and the aqueous and organic layers were combined. The organic layer was separated and treated with methanol (100 mL), white A colored solid epoxy product was obtained and it should be noted that MCPBA (metachloroperbenzoic acid) is also an acceptable oxidizing agent instead of peracetic acid.

Example 15. _{[((OC 6 H 9)} SiO 1.5) 7 ((CH 2 = CCH 3 C (O) O (CH 2) 3 SiO 1.5) 1] from _{Σ8 [(((OH) 2} C 6 H ₉ ) SiO _1.5 ) ₇ (CH _{2 ═CCH 3} C (O) O (CH ₂ ) ₃ SiO _1.5 ) ₁ ] Preparation of _Σ8 Concentrated HClO ₄ (0,1 mL, 1.2 mmol) is Methacryl epoxy cyclohexane POSS [((OC ₆ H ₉ ) SiO _1.5 ) ₇ ((CH _{2 ═CCH 3} C (O) OCH ₂ CH ₂ CH ₂ ) SiO _1.5 ) ₁ ] _{Σ8 in} TNF (100 mL) (9.80 g, 8.01 mmol) was added dropwise to a solution of water (5.00 g, 277 mmol) After stirring for 18 hours, the solvent was removed under vacuum and the residue was 3: 2 (vol: vol). Of methanol: ethyl acetate (30 mL) was dissolved in MTBE (3 The precipitated white solid was collected by vacuum filtration and dried under vacuum overnight at 35 ° C. The final product was insoluble in hydrocarbon solvents, ethyl acetate, THF And very limited solubility in acetonitrile, but highly soluble in methanol and DMSO.

The POSS olefinic derivatization of R ² The following examples are provided to demonstrate the ability to perform chemical derivatization of R ² groups on functionalized POSS cages. The procedure is not limiting and provides an example of how chemical derivatization of the R group can be used to alter the solubility and physical properties of POSS as well as function.

Example 16. [((C ₄ H ₉ ) SiO _1.5 ) ₄ (C ₃ H ₅ SiO _1.5 ) ₃ (H ₃ C) ₂ HCOTiO _1.5 ) ₁ ] _Σ8 Hydrosilylation [((C ₄ H ₉ ) SiO _1.5 ) ₄ (C ₃ H ₅ SiO _1.5 ) ₃ ((H ₃ C) ₂ HCOTiO _1.5 ) ₁ ] _Σ8 (2.3 g, 2.5 mmol) in argon purged toluene (6 mL) Once dissolved, (CH ₃ CH ₂ O) ₃ SiH (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 and then heated to 60 ° C. for 8 hours. Volatiles were removed under reduced pressure, dried under reduced pressure, [(C ₄ H ₉ ) SiO _1.5 ) ₄ ((CH ₃ CH ₂ O) ₃ SiC ₃ H ₆ SiO _1.5 ) ₃ (H ₃ C) ₂ HCOTiO _1.5 ) ₁ ] _Σ8 was obtained as a yellow solid (2.1 g). The product was characterized by a multi-stage nuclear NMR spectrometer. ¹ H NMR (400 MHz, CDCl ₃ , 25 ° C) δ 5.75 (m, 2 H, —CH =), 4.90 (m, 4H, = CH ₂ ), 4.40 (brs, 1 H, OCH (CH ₃ ) ₂ ), 3.82 (m, 6 H, -Si (OCH ₂ CH ₃ ) ₃ ), 1.84 (m, 5 H, -CH-), 1.58 (m, 4H, -CH ₂ -CH = CH ₂ ), 1.41- 1.21 (m, 15H, CH ₂ , -Si (OCH ₂ CH ₃ ) ₃ , OCH (CH ₃ ) ₂ ), 0.95 (m, 30 H, CH ₃ ), 0.59 (m, 10 H, CH ₂ )
Example 17. General procedure for hydroformylation of olefinic POSSs of PtCl ₂ (Sixantphos) (0.016 g, 0.019 mmol) and SnCl ₂ (0.0036 g, 0.019 mmol) in CH ₂ Cl ₂ (5 mL). The solution was stirred for 1 hour and transferred to a stainless steel autoclave (100 mL internal volume). Additional CH ₂ Cl ₂ (15 mL) was added followed by autoclaving to 60 ° C. followed by insertion of synthesis gas (CO / H ₂ ratio 1: 1) to 40 bar. The autoclave was allowed to equilibrate for 1 hour, after which time a silsesquioxane solution in CH ₂ Cl ₂ (total volume, 10 mL) was added and the reaction was continued for 17 hours at 60 ° C./40 bar. The autoclave was cooled with ice and depressurized, after which the reaction mixture was evaporated to dryness. Pentane (20 mL) was added and the catalyst was filtered. Evaporation of the filtrate gave a hydroformylated POSS product. The product was characterized by a multi-stage nuclear NMR spectrometer. Other hydroformylation catalysts such as [Rh (Acac) / (CO) ₂ ] / Xantphos can also be used.

  While certain representative embodiments and descriptions have been presented to illustrate the present invention, various modifications may be made to the methods and apparatus disclosed herein without departing from the scope of the invention as defined in the claims. It will be clear to those skilled in the art that this can be done.

A representative formula for a POSS cage carrying two types of organic groups in which silanol / siloxide groups and R ¹ and R ² groups are randomly incorporated into the cage is shown. 2 shows the mass spectrum of the resulting product of Example 1.

Claims (12)

Olefin functionalized polyhedral oligomeric silsesquioxane (POSS) or polyhedral oligomeric silicate comprising reacting a silane coupling agent of formula R ² SiX _{3 in} the presence of a hydroxide base ( POS) A method for preparing silanol or siloxane molecules, wherein the R ² group comprises an olefin group and X is OH, ONa, OLi, OK, OCs, Cl, Br, From the group consisting of I, alkoxide (OR), formate (OCH), acetate (OCOR), acid (OCOH), ester (OCOR), peroxide (OOR), amine (NR ₂ ), isocyanate (NCO) and R ³ are those selected, R ³ is, H, siloxy well as cyclic ring include additional reactive functional groups, straight And it represents an organic substituent selected from the group consisting of Jo aliphatic and aromatic groups, methods. Further comprising reacting a silane coupling agent of the formula R ¹ SiX _{3 in} the presence of a hydroxide base, wherein the R ¹ group comprises an alkyl or aromatic group, wherein said silanol or siloxane molecule The method of claim ¹ , wherein R comprises both R ¹ and R ² . The method further comprises the step of chemical derivatization of R ² , wherein the derivatization is selected from the group consisting of oxidation, addition and metathesis reactions while protecting R ¹ and silanol or siloxide functionality. The method described.   The method of claim 1, further comprising the step of modifying the silanol or siloxane group by a reaction selected from the group consisting of silation, reaction with a metal or reaction with a surface.   The method of claim 2, further comprising the step of modifying the silanol or siloxane group by a reaction selected from the group consisting of silylation, reaction with a metal or reaction with a surface.   4. The method of claim 3, further comprising the step of modifying the silanol or siloxane group by a reaction selected from the group consisting of silylation, reaction with a metal or reaction with a surface. R ² is converted amino acids, the biocompatible group selected from the group consisting of sugar and therapeutic agents The method of claim 3, wherein. The method of claim 1, wherein a plurality of R ² groups are reacted to prepare silanol or siloxide molecules functionalized with different olefins.   9. The method of claim 8, wherein the continuous process provides silanol or siloxane molecules.   5. A method according to claim 4, wherein the molecule metallized as a result of the reaction with the metal serves as a heterogeneous catalyst or core agent.   6. The method of claim 5, wherein the molecule metallized as a result of the reaction with the metal serves as a heterogeneous catalyst or co-reagent.   7. A method according to claim 6, wherein the molecule metallized as a result of the reaction with the metal serves as a heterogeneous catalyst or co-reagent.

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