HK1050692B - Process for the formation of polyhedral oilgomeric silsesquioxanes - Google Patents
Process for the formation of polyhedral oilgomeric silsesquioxanes Download PDFInfo
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Description
Background
Methods are described that enable selective control of the silicon-oxygen backbone structure in polyhedral oligomeric silsesquioxane (POSS) cage molecules. Selective control of the framework structure of POSS is desirable because they serve as chemical species that can be further converted or incorporated into a wide variety of chemical feedstocks for the preparation of catalyst supports, monomers, polymers, and as silicas in solubilized form to replace fumed and precipitated silicas or for biological applications and surface modification. POSS when incorporated into polymeric materials can provide new and improved thermal, mechanical, and physical properties to conventional polymeric materials.
A wide variety of POSS framework structures can be prepared in useful amounts by hydrolytic condensation of alkyl-or aryl-trichlorosilane. However, in most cases, hydrolytic condensation reactions of trifunctional silicone monomers provide complex polymeric resins and POSS molecules that are not suitable for polymerization or grafting reactions because they do not have the desired type or reactive functionality. In view of the fact that many silsesquioxane resins with well-defined structures [ RSiO ]1.5]And a homo fragment (homoleptic) of the formula [ (RSiO)1.5)n]#(where R ═ includes, but is not limited to, aliphatic, aromatic, olefinic, or alkoxy groups and n ═ 4-14) POSS molecules can be prepared in good or excellent yields from readily available silicone monomers, and so there is a tremendous incentive to develop a technology that can convert these POSS species into systems bearing functionalities that are highly desirable for polymerization, grafting, catalysis, or compatibilization with general purpose organic resins. Examples of such desired functionalities include, but are not limited to: silanes, silyl halides, silanols, silylamines, organohalides, alcohols, alkoxides, amines, cyanates, nitriles, alkenes, epoxides, organic acids, esters, and strained alkenes.
The prior art in the field of silsesquioxanes has taught methods for the chemical control of the organic functionality (substituents represented by R) contained on the silicon oxygen backbone in polyhedral oligomeric silsesquioxanes. While these methods are very useful for modifying the organic functionality (substituents) contained on POSS molecules, they are not all low cost to manufacture nor do they provide the ability to selectively cleave and or control the siloxane backbone structure of these compounds. Thus, these methods have no utility for converting most readily available and low cost silane, silicate, polysilsesquioxane (aka T-resin or T-type siloxane) or POSS systems.
The prior art also reports that bases (e.g., NaOH, KOH, etc.) can be used to catalyze the polymerization of POSS into lightly networked resins or to convert selected polysilsesquioxane resins into homosegmented polyhedral oligomeric silsesquioxane structures. More recently, Marsmann et al have revealed that a number of bases can be used to redistribute smaller homosegmented POSS cages into larger size homosegmented cages. While the literature is premised on the use of base-controlled silsesquioxane and POSS systems, the prior art does not provide selective control of the siloxane backbone structure and the subsequent controlled production of POSS fragments, homo-fragment POSS nanostructures, hetero-fragment (heteroleptic) POSS nanostructures, and functionalized hetero-fragment POSS nanostructures. Moreover, the prior art does not provide a method for preparing POSS systems suitable for functionalization reactions and subsequent polymerization or grafting reactions. This lack of oversight in the prior art reflects the fact that POSS-based reagents, monomers, and polymers technology has only advanced in recent years and is therefore later than the date of this prior art. Thus POSS compositions and methods relating to the type of system desired for POSS monomer/polymer technology are not envisioned by the prior art. In addition, the prior art does not demonstrate the effect of alkali on silane, silicate or silsesquioxane feedstocks suitable for the preparation of low cost and high purity POSS systems.
In contrast to the prior art (Brown et al and Marsmann et al), the methods taught herein are particularly capable of developing low cost, high purity functionality-loaded POSS systems for use as derivatizable (derivitizable) chemical reagents and feedstocks.
Summary of The Invention
The present invention teaches three methods that enable the control and development of POSS compounds from readily available and low cost silicon-containing feedstocks. Examples of such low cost feedstocks include, but are not limited to: polysilsesquioxane [ RSiO ]1.5]∞Homo-segmented polyhedral oligomeric silsesquioxanes (POSS) [ (RSiO)1.5)n]∑#Functionalized homofragment POSS [ (RSiO)1.5)m(RXSiO1.0)n]∑#Hetero fragment POSS [ (RSiO)1.5)m(R’SiO1.5)n]∑#Functionalized heterofragment POSS [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#And polyhedral oligomeric silicates [ (XSiO)1.5)n]∑#And POSS fragment [ (RXSiO)1.5)n]。
Definition of POSS nanostructure expression
For purposes of explaining the methods and chemical compositions of the present invention, the expression of the nanostructure-cage formula is defined as follows:
the polysilsesquioxane is represented by the general formula [ RSiO1.5]∞The materials of (a) are represented, wherein ∞ is the degree of polymerization of the material and R ═ organic substituents (H, cyclic or linear aliphatic or aromatic groups, which groups may additionally contain reactive functionalities such as alcohols, esters, amines, ketones, olefins, ethers or halides). Polysilsesquioxanes may be either homo-or hetero-segmented. The homo-fragment system contains only one type of R group and the hetero-fragment system contains more than one type of R group.
The POSS nanostructure composition is represented by the formula:
[(RSiO1.5)n]∑#compositions representing the homogeneous fragments
[(RSiO1.5)m(R’SiO1.5)n]∑#Represents a heterofragment composition
[(RSiO1.5)m(RXSiO1.0)n]Σ＃Denotes a functionalized homofragment composition
[(RSiO1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#Denotes a functionalized heterosegment composition
[(XSiO1.5)n]∑#Indicating a homo-segmented silicate composition
All R above are as defined above, and X includes, but is not limited to, OH, Cl, Br, I, alkoxide (OR), acetate (OOCR), peroxide (OOR), amine (NR)2) Isocyanate (NCO), and R. The symbols m and n refer to the stoichiometric composition. The symbol Σ indicates that the composition forms a nanostructure and the symbol # means the number of silicon atoms contained by the nanostructure. The value of # is usually the sum of m + n. It should be noted that sum # is not to be confused as a multiplier for determining stoichiometry, as it merely describes the overall nanostructure characteristics of the POSS system (aka cage size).
POSS fragments are defined as structural subunits that can be assembled into POSS nanostructures and are composed of the general formula [ (RSiO)1.5)m(RXSiO1.0)n]And (4) representing. The lack of the notation Σ # is due to the fact that these fragments are not polyhedral nanostructures.
Polysilsesquioxane resins [ RSiO1.5]∞Examples of (2)
[(RSiO1.5)6]∑6 [(RSiO1.5)8]∑8
[(RSiO1.5)10]∑10 [(RSiO1.5)12]∑12
Homofragment POSS system [ (RSiO)1.5)]∑#Examples of (2)
[(RSiO1.5)7(R’SiO1.5)1]∑8
Heterofragment POSS system [ (RSiO)1.5)m(R’SiO1.5)n]∑#Examples of (2)
[(RSiO1.5)6(RXSiO1.0)2]∑8
Functionalized homosegmented POSS systems [ (RSiO)1.5)m(RXSiO1.0)n]∑#Examples of (2)
[(RSiO1.5)3(R’SiO1.5)1(RXSiO1.0)3]∑7
Functionalized heterosegment POSS systems [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#Examples of (2)
[(XSiO1.5)8]∑8
Polyhedral oligomeric silicate systems [ (XSiO)1.5)n]∑#Examples of (2)
Examples of fragments: RSiX3(1)、[(RXSiO0.5)n](2)、[(RXSiO1.0)n](3)、[(RSiO1.5)m(RXSiO1.0)n](4)
FIG. 1 examples of generic silsesquioxane, silicate, POSS nanostructures and fragments
General process variables applied to all methods
As is typical in chemical processing, there are many variables that can be used to control the purity, selectivity, rate and mechanism of either process. For polysilsesquioxane conversion to POSS structure [ (RSiO)1.5)n]∑#、[(RSiO1.5)m(R’SiO1.5)n]∑#、[(RSiO1.5)m(RXSiO1.0)n]∑#、[(RSiO1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#Variables that affect this process include, but are not limited to, the following: chemical grade of base, size of silicon-oxygen ring, composition type [ RSiO ]1.5]∞(silsesquioxane), [ (RSiO)1.5)n(R2SiO)n]∑#(silsesquioxane-siloxane), [ (RSiO)1.5)m(XSiO1.5)n]∑#(silsesquioxane-silicate), the effect of organic substituents, processing temperature, processing solvent, processing temperature, stoichiometry of base, and presence of catalyst. Each of these variables is discussed briefly below.
Auxiliary agent accelerator
Specific chemical agents may be used to promote or enhance the effectiveness of the base used in the process. In particular, nucleophilic base mixtures that act in a binding manner first accelerate silsesquioxane dissolution and second accelerate POSS nanostructure formation. Examples of such systems may include, but are not limited to, KOR (where OR is an alkoxide), RMgX including all common Grignard reagents, OR alkali metal halides such as LiI, OR any of a variety of molten OR melted salt media. In a similar manner, auxiliary bases such as [ Me ]3Sn][OH]And [ Me ]4Sb][OH]Have been shown to promote chemical transformations in POSS systems, but have not been used as co-reagents in the formation of POSS cages. Electrophilic promoters such as zinc compounds (i.e., ZnI)2，ZnBr2，ZnCl2，ZnF2Etc.), aluminum compounds (i.e., Al)2H6，LiAlH4，AlI3，AlBr3，AICl3，AlF3Etc.), boron compounds including (i.e., RB (OH)2，BI3，BBr3，BCl3，BF3Etc.) known to play an important role in the solubilization and opening polymerization of cyclic siloxanes and in the opening of polyhedral oligomeric silsesquioxanes.
Chemical base
The purpose of the base is to cleave the silicon-oxygen-silicon (Si-O-Si) bond in different silsesquioxane structures. The exact type of base, its hydrated sphere, concentration and solvent interaction play an important role in the utility of the base for cleaving siloxane bonds. Proper knowledge and control of conditions can selectively cleave and/or combine silsesquioxane, silicate, POSS, and POSS fragment systems in a desired manner. Bases may also participate in the combination of POSS fragments.
There are a number of bases that can be used in the process, these include, but are not limited to: hydroxide [ OH]-Organic alkoxide [ RO ]]-Carboxylic acid salts [ RCOO]-Amide [ RNH ]]-Carbonamides [ RC (O) NR)]-Carbon anion [ R ]]-Carbonate [ CO3]-2Sulfate salt [ SO ]4]-2Phosphate [ PO ]4]-3Hydrogen phosphate [ HPO ]4]-2Phosphonium ylides [ R ]4P]-Nitrate [ NO ]3]-Borate [ B (OH)4]-Cyanate ester [ OCN]-Fluoride [ F ]]-Hypochlorite [ OCl ]]-Silicate [ SiO ]4]-4Stannate [ SnO ]4]-4Alkali metal oxide (e.g., Al)2O3CaO, ZnO, etc.), amine R3N and amine oxide R3NO and organometallic compounds (e.g. RLi, R)2Zn、R2Mg, RMgX, etc.). Moreover, the methods taught herein are not limited to the bases described above; any agent capable of producing a pH in the range of 7.1 to 14 may be used.
Alternatively, the process can also be carried out using a mixture of bases. One advantage of this approach is that each base of a given mixture can function differently. For example, in a mixed base system, one base is used to cleave a silicon-oxygen bond or a silicon-X bond and a second base is used to assemble the POSS structure. There is thus a synergy among several types of bases and these can be exploited to optimize and refine these processes.
Size of silicon-hydrogen ring, type of ring and size of cage
The methods discussed herein are not limited to a particular size POSS cage (i.e., [ (RSiO))1.5)n]∑#Σ # in (c). Similarly the method should not be limited to a particular type of silsesquioxane (i.e., resin, cage or fragment). These methods can be implemented to produce POSS cages containing four to eighteen or more silicon atoms in the silicon-oxygen backbone. It should be noted, however, that the size of the silicon-oxygen ring contained in these POSS systems does affect the rate at which the opening of the caged siloxane ring occurs. For example, as shown in equation 1, a ring containing three silicon atoms and three oxygen atoms appears to open faster than a larger ring containing 4 silicon atoms and 4 oxygen atoms. The relative rate of POSS silicon-oxygen ring opening appears to be six-membered rings with three silicon atoms > eight-membered rings with four silicon atomsRing > ten-membered ring with five silicon atoms > twelve-membered ring with six silicon atoms. Thus, the selective opening process can be controlled by the use of an appropriate base, and this knowledge of the information allows the user of these processes to control the selective formation of POSS molecules.
Effect of organic substituent, processing solvent and processing temperature
The method of the present invention is not limited to POSS systems in which the silicon atom of the silicon oxygen ring system carries a specific organic group (defined as R). They belong to the silsesquioxane starting materials carrying a wide variety of organic groups (R ═ as defined above) and functionalities (X ═ as defined above). The organic substituent R does have a large effect on the solubility of the final product and starting POSS materials. Thus, it is envisioned that the different solubilities of the starting silsesquioxane and POSS products can be used to accelerate the isolation and purification of the final reaction product. We have now found that there is no limitation on the type of solvent used in the process, which can be carried out in common solvents including, but not limited to, ketones, ethers, dimethyl sulfoxide, CCl4、CHCl3、CH2Cl2Fluorinated solvents, aromatic compounds (halogenated and non-halogenated), aliphatic compounds (halogenated and non-halogenated). Other methods may also be performed in supercritical fluids, including but not limited to CO2、H2O and propane. The variables of solvent type, POSS concentration, and processing temperature should be adapted according to standard methods to match the particular cage opening method to the available equipment. Preferred solvents for this process are THF, MIK and toluene. In many cases, the solvent is an integral part of the processing method, which enables the base to act on the particular silsesquioxane system, and thus the effect of the solvent greatly affects the degree of ionization of the base used in these methods.
The method I comprises the following steps: POSS systems formed from polymerized silsesquioxanes
Acid catalyzed alkyltrichlorosilane (RSiCl)3) Is reducedThe current method of synthesizing POSS molecules is inefficient because it produces a mixture of POSS cage species, i.e., [ (RSiO) homo1.5)n]∑#Functionalized homofragment POSS [ (RSiO)1.5)m(RXSiO1.0)n]∑#Hetero fragment POSS [ (RSiO)1.5)m(RSiO1.5)n]∑#Functionalized heterofragment POSS [ (RSiO)1.5)m(RXSiO1.0)n]∑#And polymeric silsesquioxanes [ RSiO ]1.5]∞. In some cases, the undesired polymeric silsesquioxanes are prepared in yields of up to 75%. It is therefore desirable to develop a new system that enables [ RSiO1.5]∞Efficiently converted to the desired POSS nanostructures or POSS fragments [ (RXSiO)1.5)n]The method of (1). Such a process would not only reduce the amount of hazardous waste produced in these reactions, but would also reduce the cost of producing POSS systems.
The process was developed by polymerizing silsesquioxane [ RSiO ] with a base (as defined above), especially a base of the hydroxide type (e.g., sodium hydroxide, potassium hydroxide, lithium hydroxide, benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, etc.)1.5]∞Conversion to homo fragment (POSS) [ (RSiO)1.5)n]∑#Functionalized homofragment POSS [ (RSiO)1.5)m(RXSiO1.0)n]∑#Hetero fragment POSS [ (RSiO)1.5)m(R’SiO1.5)n]∑#And functionalized heterofragment POSS [ (RSiO)1.5)m(R’XSiO1.0)n]∑#。
In the present process, polymeric silsesquioxanes [ RSiO ]1.5]∞Dissolved or suspended in a process grade solvent such as acetone or methyl isobutyl ketone, followed by addition of an aqueous or alcoholic solution of the base with stirring. Sufficient base should be added to the reaction mixture to facilitate the preparation of a basic solution (pH 7.1-14). The reaction mixture was stirred at room temperature for 3 hours, followed by heating to reflux3-12 hours. During this time, the desired POSS cages typically precipitate out of the reaction medium due to their insolubility in the reaction medium. This precipitation aids in the isolation of the desired product and ensures that the product (e.g., functionalized POSS species) is not subjected to further reaction. In some cases, it is desirable to be able to reduce the volume of solvent by distillation or by reduced pressure in order to increase the yield of product or to isolate the dissolved POSS product. The desired POSS product is collected by filtration or decantation and purified by thorough washing with water.
We have found that for aliphatic or aromatic polysilsesquioxanes [ RSiO ]1.5]∞Conversion to homo fragment (POSS) [ (RSiO)1.5)n]∑#Functionalized homofragment POSS [ (RSiO)1.5)m(RXSiO1.0)n]∑#And heterosegment POSS [ (RSi)O1.5)m(R’SiO1.5)n]∑#And functionalized heterofragment POSS [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#Hydroxide [ OH ]]-Type bases are very effective at concentrations of 1-10 equivalents per mole of silicon (the preferred range is 2-5 equivalents per mole of silicon atoms). Hydroxy-base for the preparation of [ (RSiO)1.5)m(RXSiO1.0)n]∑#POSS species are particularly effective. We have found that mild bases such as acetates and carbonates convert vinyl-or allyl-loaded [ RSiO1.5]∞The system is more effective. It is also acknowledged that the use of other co-agents may facilitate the formation by this method
FIG. 2. description of method I wherein polymerized silsesquioxane resins are converted into POSS fragments and nanostructures
For the above reaction scheme, the silsesquioxane is polymerized according to the type of base and the conditions usedThe resin is converted to either POSS fragments or nanostructured POSS cage species. By manipulating the processing variables discussed above, polysilsesquioxane [ RSiO ] can be selectively controlled1.5]∞To POSS-species (homo fragment [ (RSiO)1.5)n]∑#Functionalized homofragment POSS [ (RSiO)1.5)m(RXSiO1.0)n]∑#A heterofragment [ (RSiO)1.5)m(R’SiO1.5)n]∑#And a functionalized heterofragment [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#) Or POSS fragment [ (RXSiO)1.5)n]Is performed. The process is carried out using polysilsesquioxane resins containing only one type of R group to prepare the homo-segment [ (RSiO)1.5)n]∑#And (3) obtaining the product. It is also possible to carry out the process using polysilsesquioxane resins containing more than one type of R group or a mixture of polysilsesquioxanes each containing a different R group to provide the heterosegment [ (RSiO)1.5)m(R’SiO1.5)n]∑#And (3) obtaining the product. For the above reaction formulas, where mixtures of homoleptic POSS cages (i.e., R of one POSS cage ≠ R of a second POSS cage) are substituted for polysilsesquioxane resins, the method efficiently converts mixtures of homoleptic (homoleptic) substituted POSS cages into heteroleptic POSS cages (functionalized and unfunctionalized) that each contain a statistical distribution of different R groups. In most cases, POSS fragments and various different homo-or heterosegmented nanostructured POSS species can be separated from each other by crystallization or by extraction using differences in solubility between the reaction product and the starting silsesquioxane.
The purpose of the base in this process is to cleave the silicon-oxygen bond in the starting silsesquioxane, thus allowing rearrangement and formation of a variety of POSS fragment, homo-fragment, and hetero-fragment species, while also aiding rearrangement and formation of a variety of POSS fragment, homo-fragment, and hetero-fragment species. Both the strength of the base and the base-solvent-silsesquioxane interaction are critical factors that can control the type of product formed in these reactions. For example, increasing the basicity of the medium can afford production of POSS fragments, while lower basic conditions plus the absence of water can promote the formation of non-functionalized POSS species. It would be desirable to form a functionalized POSS system by conducting this process at moderate pH with very little water in a relatively short period of time.
Method II: reaction between POSS systems and silsesquioxane/siloxane segments
The method was developed using a base (as previously defined) to couple the fragment and functionalized POSS nanostructures [ (RSiO)1.5)m(RXSiO1.0)n]∑#Conversion to alternating functionalized POSS nanostructures [ (RSiO)1.5)m(RXSiO1.0)n]∑#. In this method, POSS fragments are dissolved or suspended in acetone, benzene or alcohol solvents, after which a solution of base is added with stirring. In general, the reaction conditions used in the process are milder than those used in process I, and both hydroxide-type bases and non-hydroxide-type bases can be used, with a molar ratio of base to silicon of 1: 10 (preferably a ratio of 1: 1 or 1: 2).
Segmented POSS cages and functionalized POSS
POSS fragments POSS cages and functionalized POSS
POSS fragments POSS cages and functionalized POSS
FIG. 3 conversion of POSS fragments into POSS cages
The purpose of the base in this process is to cleave the silicon-oxygen bond of the starting POSS fragment. Bases can also help assemble POSS structures from the fragments. Many different bases (as previously defined) can be used to convert POSS fragments into POSS compounds. The net reaction results in the assembly of POSS fragments into POSS nanostructures with either homo-or heterofragment compositions. In addition, the resulting POSS cage may contain functional groups (i.e., [ (RSiO)1.5)m(RXSiO1.0)n]∑#And [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#)。
When mixtures of POSS fragments are employed, they are statistically incorporated into POSS structures and their final composition is based on the stoichiometry of the starting POSS fragments. In some cases, the statistical degree of substitution between these groups is controlled by the isomorphism, which arises from the nearly identical topological shape of the R groups (e.g., vinyl and ethyl). Isomorphic dominance is often observed for closely related R groups (such as allyl and propyl groups, etc.), however sometimes this trend is not followed due to other factors such as reaction rates, addition of reagents, or solubility between various POSS fragments and the product. For example 1 equivalent of ethyl undecanoate Si (OMe)3Or vinyl Si (OMe)3With 7 equivalents of MeSi (OMe)3The reaction of (a) produces one molecule of the composition of formula 2[ (Visio1.5)1(MeSiO1.5)7]∑8Or [ (ethyl undecanoate SiO)1.5)1(MeSiO1.5)7]∑8Despite the topological differences between the R groups.
In many cases, desired homo-or heterosegmented nanostructured POSS species can be separated from each other via crystallization, extraction, or utilization of the difference in solubility of the product from the starting POSS segment.
The continuation of the method is base pair functionalized POSS nanostructures (i.e., [ (RSiO) s1.5)m(RXSiO1.0)n]∑#And [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#) The function of (1). It should be noted that these systems are chemically similar to POSS fragments in terms of their chemical composition. They differ in their topological and physical properties, such as melting point, solubility and volatility.
FIG. 4 illustrates the actual reaction using the conditions described in method II, demonstrating that the base and the conditions described in method II are effective for the conversion of functionalized POSS cages (i.e., [ (RSiO) into the desired POSS structures1.5)m(RXSiO1.0)n]∑#And [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#) Is effective. It should also be noted that in most cases, these methods result in an increase in the number of functionalities (X) in the POSS nanostructure while maintaining the initial number of silicon atoms contained within the original nanostructure backbone. This is desirable for the control and derivatization of the products of various sequential syntheses.
(RSiO1.5)6(R(X)SiO1.0)1]∑7 [(RSiO1.5)4(RXSiO1.0)4]∑7
X＝OH X＝OH
Functionalized POSS alternating functionalized POSS nanostructures
[(RSiO1.5)4(RXSiO1.0)2]∑6 [(RSiO1.5)2(RXSiO1.0)4]
Functionalized POSS POSS fragments
FIG. 4. Interchangeable POSS cages
The first example in FIG. 4 illustrates the selectivity of base cleavage of a 6-membered silicon oxygen ring in the presence of an 8-membered silicon oxygen ring to provide a trifunctional POSS species. This reaction is initiated by releasing the strain energy of the larger ring from the cleavage of a 6-membered silicon oxygen ring versus an 8-membered silicon oxygen ring, and is thermodynamically favored. In a second example, the cleavage can simultaneously release energy from the twisted conformation to form a more open structure.
The last variation and one point of great utility of method II is that it also allows the introduction of POSS fragments into the POSS and POSS silicate nanostructures present. This is very important and useful for this method as it allows for the expansion of POSS and POSS silicate cage species. This is analogous to the formation of carbon-carbon bonds in organic systems. The method can thus be used to prepare larger POSS nanostructures as well as POSS nanostructures having the aforementioned difficult-to-reach dimensions. Of particular importance is the use of this method for the preparation of nanostructures with odd and even silicon atoms.
POSS nanostructure segment extended POSS nanostructures
POSS-silicate nanostructures extended by silicate nanostructure fragments
POSS nanostructure segment extended POSS nanostructures
POSS-silicate nanostructures extended by POSS nanostructure fragments
POSS nanostructure segment extended POSS nanostructures
POSS-silicate nanostructures extended by silicate nanostructure fragments
POSS nanostructure segment extended POSS nanostructures
POSS nanostructure segment extended POSS nanostructures
FIG. 5 fragments of silsesquioxane/siloxanes inserted into POSS cages
The net reaction of the example shown in FIG. 5 is the cleavage of the Si-O-Si bond and the insertion of POSS fragments in the POSS or POSS silicate nanostructure. This reaction results in the expansion of the silicon-oxygen ring in the POSS nanostructure product. It should be noted that the expansion of the ring in these reactions by the release of the ring strain in the silsesquioxane starting material is thermodynamically favored in some cases. For example, 1 equivalent of vinyl (OMe)3And [ ((C-C)6H11)SiO1.5)6]∑6Is reacted to form a compound having [ ((C-C)6H11)SiO1.5)4(c-C6H11)(HO)SiO1.0)2(ViSiO1.0)1]∑7A POSS molecule.
Mixtures of bases may also be used to carry out the process. One advantage of this approach is that the combined use of different types of bases can serve different functions. For example, one base may be particularly useful for cleavage of Si-X groups, while a second base may play a role in the assembly of POSS fragments into POSS nanostructures. Synergy between different types of bases is also envisioned.
Of particular importance is the use of mixtures of POSS fragments (i.e., where R ≠ R of one fragment is R of another fragment) or POSS fragments with more than one type of R group. The use of mixed fragments or fragments with mixed R groups can provide heterosegmented POSS species [ (RSiO)1.5)m(RSiO1.5)n]∑#The heterofragment POSS species comprise more than one type of R group. Typically, the products of POSS nanostructures formed comprise a statistical mixture of R, as determined by the stoichiometry of the starting segments. As a result, numerous isomers may be formed.
Method III: selective opening, functionalization and rearrangement of POSS nanostructures
The process uses a base (as defined above) and a compound having a homomeric segment [ (RSiO)1.5)n]∑#And heterofragments [ (RSiO)1.5)m(R’SiO1.5)n]∑#A POSS nanostructure of the composition. The method can convert low cost and easily prepared unfunctionalized POSS nanostructures into more desirable [ (RSiO)1.5)m(RXSiO1.0)n]∑#Functionalized POSS systems of the type. [ (RSiO)1.5)m(RXSiO1.0)n]∑#The types of POSS nanostructures can be used as stand alone chemical reagents or further derivatized to provide other POSS nanostructures in different arrangements. The method provides a novel synthetic route for the preparation of very important and useful incompletely condensed trimethylsilanol reagents [ (RSiO)1.5)4(RXSiO1.0)3]∑7Especially wherein X ═ OH.
By using the bases shown in FIG. 6, homosegmented POSS nanostructures [ (RSiO) are easily fabricated1.5)n]∑#Converted to have the general formula [ (RSiO)1.5)m(RXSiO1.0)n]∑#And POSS nanostructures of the formulaRSiX3、[(RXSiO0.5)n]、[(RXSiO1.0)n]Or [ (RSiO)1.5)m(RXSiO1.0)n]The POSS fragment of (1). It should be noted that not all possible geometric and stereochemical isomers of each product are shown.
[(RSiO1.5)4(RXSiO1.0)3]∑7 [(RSiO1.5)6(RXSiO1.0)2]∑8 [(RSiO1.5)6(RXSiO1.0)2]∑8 [(RSiO1.5)6(RXSiO1.0)2]∑8
Functionalized heterosegment POSS systems [ (RSiO)1.5)m(RXSiO1.0)n]∑#
FIG. 6 description of method III
Moreover, as a transformation of this approach, interconversion of different sized POSS nanostructures can be made. For example, as shown in FIG. 6, the appropriate base, [ (RSiO) is added1.5)6]∑6Or cleaved into smaller POSS fragments (e.g., [ RSiX ]3]、[(RXSiO0.5)n]、[(RXSiO1.0)n]Or [ (RSiO)1.5)m(RXSiO1.0)n]) Or functionalized to be the same size (e.g., [ (RSiO)1.5)4(RXSiO1.0)2]∑6) Or larger (e.g., [ (RSiO) size1.5)4(RXSiO1.0)3]∑7) The heterosegment POSS nanostructures of (a).
POSS fragment [ (RXSiO)0.5)1]，[(RXSiO1.0)4]，[(RSiO1.5)2(RXSiO1.0)4]
[(RSiO1.5)4(RXSiO1.0)2]∑6 [(RSiO1.5)4(RXSiO1.0)3]∑7 [(RSiO1.5)6(RXSiO1.0)2]∑8 [(RSiO1.5)8]∑8
Functionalized heterosegmental and homosegmental POSS systems
FIG. 7 description of method III
As a variation of the above, it was determined that the method uses mixtures and distributions of POSS cages and polyhedral oligomeric silicate species (e.g., [ ((CH))3)3SiO)SiO1.5)6]∑6、[((CH3)4NO)SiO1.5)6]∑6、[((CH3)3SiO)SiO1.5)8]∑8、[((CH3)4NO)SiO1.5)8]∑8). In these cases, the base can efficiently convert several sizes of cages into functionalized and unfunctionalized heterofragment POSS nanostructures as shown in figure 8. This represents a novel synthetic route for the preparation of very useful incompletely condensed trimethylsilanol reagents [ (RSiO)1.5)4(RXSiO1.0)3]∑7Especially wherein X ═ OH.
FIG. 8. illustration of the conversion of POSS and silicate nanostructures-method III
The final variation of this approach is the selective effect of the base on the heterosegmental POSS nanostructures. POSS nanostructures bearing more than one type of R group per cage due to the action of a base [ (RSiO)1.5)m(RSiO1.5)n]∑#Can be easily converted into functionalized POSS nano-structure [ (RSiO)1.5)m(RXSiO1.0)n]∑#. It should be noted that not all possible geometric and stereochemical isomers are shown.
FIG. 9 illustration of the transformation of POSS nanostructures-method III
The action of the base described in the preceding paragraph can also be selectively controlled so as to enable the complete removal of silicon atoms from the siloxane backbone of the polyhedral oligomeric silsesquioxane. This represents a novel synthetic route for the preparation of very useful incompletely condensed trimethylsilanol reagents such as [ (RSiO)1.5)4(RXSiO1.0)3]∑#In particular wherein X ═ OH. It should be noted that not all stereochemical and geometric isomers have been listed.
Additional material-part B: isomers of POSS systems
Method for controlling stereochemistry
It is important to recognize that many isomeric forms of any given formula can be prepared by the methods taught by this work, given the three-dimensional nanoscopic state of the POSS system. The stereochemistry of these isomers is controlled by the direct method taught by this patent, however geometric isomers will still exist in some cases. We provide a number of examples to show our knowledge of the existence of these isomers, but we in no way limit the claims to any one particular stereochemical or geometric isomer.
As shown in FIG. 10, difunctional, incompletely condensed POSS nanostructures [ (RSiO)1.5)4(RXSiO1.0)2]∑6There may be six isomers.
Exo-exo isomer endo-endo isomer endo-exo isomer
Exo-endo isomer
FIG. 10 bifunctional incompletely condensed POSS nanostructures [ (RSiO)1.5)4(RXSiO1.0)2]∑6Isomer of (1)
Examples
In Omega-500(1H，500MHz；13C，125MHz；29Si, 99 MHz). Tetrahydrofuran and methyl isobutyl ketone are distilled before being used. All other solvents were used as purchased without purification.
Example of method I polysilsesquioxanes conversion to POSS fragments and nanostructures
From [ (C)6H1.5)SiO1.5]∞Resin Synthesis [ ((C)6H5)SiO1.5)8]∑8In toluene (100mL) at room temperature [ (C)6H5)SiO1.5]∞To the resin (13.0g, 100.6mmol) was added tetramethylammonium hydroxide (2.0mL, 5.57 mmol). The reaction mixture was heated to 80 ℃ for 12 hours, then cooled to room temperature, acidified with 1N HCl, and filtered to give 12.065g [ ((C)6H5)SiO1.5)8]∑8White solid of (2). The product was examined by EIMS and showed a molecular ion of 1032.5amu (atomic mass units) with daughter ions corresponding to the loss of one, two and three phenyl groups, respectively, 954.7, 877.4 and 800.6 amu. The above process can be improved for continuous and batch production. On the other hand, benzene, acetone and methyl ethyl ketone may also be used as a solvent for the reaction instead of toluene, and KOH may also be used instead of a base such as tetraalkylammonium. Further, phenyltrimethoxysilane can be used in place of the phenyl resin to prepare [ ((C)6H5)SiO1.5)8]∑8。
From [ (C)6H5)SiO1.5]∞Resin Synthesis [ ((C)6H5)SiO1.5)12]∑12Reaction of [ (C) in THF (7.8L) at room temperature6H5)SiO1.5]∞To the resin (1000g, 7740mmol) was added potassium hydroxide (46.5g, 829 mmol). The reaction mixture was heated under reflux for 2 days, then cooled to room temperature, and filtered to give 443g [ ((C)6H5)SiO1.5)12]∑12A microcrystalline white solid. Adding additional [ (C) to the reaction mixture6H5)SiO1.5]∞Resin (912g, 7059mmol), heating the refluxed solution for 2 days, then cooling to room temperature, and filtering to giveTo 851g [ ((C)6H5)SiO1.5)12]∑12A microcrystalline white solid. Characterization was achieved by EIMS, which showed a molecular ion of 1548.2 amu. The above process can be improved for continuous and batch production. Alternatively, methylene chloride may be used as a solvent for the reaction in place of THF, and bases such as tetraalkylammonium may be used in place of KOH. Furthermore, phenyltrimethoxysilane may be used in place of [ (C)6H5)SiO1.5]∞Preparation of resin [ ((C)6H5)SiO1.5)12]∑12。
From [ (C-C)5H9)SiO1.5]∞Resin Synthesis of [ (C-C)5H9)SiO1.5]∑8A1.80 gram sample of the resin was dissolved in 90ml of acetone and 90mg of NaOH was added to the reaction mixture. The mixture was stirred at room temperature for 3 hours, then heated to reflux overnight. The solution was then cooled and filtered to yield 1.40g (77% yield) of pure product. The white microcrystalline powder was confirmed by X-ray diffraction and by HPLC against authentic samples.
From [ (CH)2＝CH)SiO1.5]∞Resin with [ Si ]8O20][NMe4]∑8Synthesis of [ ((CH)2＝CH)SiO1.5)8]∑8
0.63g of the resin sample and 2.22g of tetramethylammonium silicate were dissolved in 20ml of ethanol, and NMe was added to the reaction mixture4OH until it becomes highly basic (pH about 12). The mixture was stirred at room temperature for 6 days, and then filtered to obtain 1.9g [ ((CH)2＝CH)SiO1.5)8]∑8. On the other hand, from CH in cyclohexane2＝CHSi(OCH3)3And NMe4The reaction of OH followed by azeotropic distillation of water and methanol produces [ ((CH)2＝CH)SiO1.5)n]∑nDistribution of cages, wherein n is 8, 10, 12, 14. The resulting white solid product [ (CH) was obtained in a yield of 40%2＝CH)SiO1.5]∑8-14This solid product is very desirable because it is very soluble in common solvents/reagents and melts at about 150 ℃.
[((c-C6H9)SiO1.5)4((c-C6H11)SiO1.5)4]∑8The synthesis of (2): in a typical reaction, a mixture of (cyclohex-3-enyl) trichlorosilane and cyclohexyltrichlorosilane is added to a solution of methanol (200mL) and water (5mL) with vigorous stirring. The mixture was then refluxed for 2 days. While cooling, volatiles were removed in vacuo to provide a resin containing both cyclohexyl-Si groups and cyclohex-3-enyl-Si groups. With sufficient C in methyl isobutyl ketone (25ml)6H5CH2N(CH3)3The OH refluxed for 48 hours to complete the base catalyzed redistribution of the resin prepared a strongly basic solution (approximately 2mL of 40% MeOH in solution). Evaporation of the solvent (25 ℃ C., 0.01 torr) gave a white resinous solid, which was stirred with acetone (15mL) and filtered to provide a [ ((R) SiO ] having both cyclohexyl and cyclohex-3-enyl groups1.5)n((R’)SiO1.5)n]∑8Mixtures of skeletal structures. The isolated yields are generally from 70 to 80%.
It should be noted that: not including the enantiomer, 22 of them carrying (cyclohexyl)n(cyclohex-3-enyl)8-nSi8O12(0. ltoreq. n. ltoreq.8) formula [ ((R) SiO)1.5)n((R’)SiO1.5)n]∑8And (3) a framework. All of these are assumed to be present in the product mixture. The relative percentage of each compound depends largely on the relative amounts of (cyclohex-3-enyl) trichlorosilane and cyclohexyltrichlorosilane used in the reaction, but it may also depend on other factors. Of high resolution per product mixture29Si NMR Spectrum (C)6D6) A series of well-resolved resonances are shown for backbone Si atoms with cyclohexyl and cyclohexenyl groups. The chemical shifts of these resonances are constant, but the relative strengths of these resonances depend on what is being reactedWith (cyclohex-3-enyl) SiCl3And cyclohexyl SiCl3The amount of (c). It is clear that the product is [ ((C-C)6H11)SiO1.5)n((c-C6H9)SiO1.5)n]∑8Mixtures of skeletal structures. To be compared with pure, reliable [ ((C-C)6H11)SiO1.5)8]∑8、[((c-C6H9)SiO1.5)8]∑8And [ ((C-C)6H11)SiO1.5)n((c-C6H9)SiO1.5)n]∑8Based on the comparison of the samples, the following values of chemical shifts (C) were determined6D6The following are added:
values for the Si-cyclohexenyl group with the three nearest Si-cyclohexyl groups: delta-67.40
Values for the Si-cyclohexenyl group with the two nearest Si-cyclohexyl groups: delta-67.46
Value of Si-cyclohexenyl group with one nearest Si-cyclohexyl group: delta-67.51
The value of Si-cyclohexenyl group with zero nearest neighbor Si-cyclohexyl group: delta-67.57
Si-cyclohexyl with three Si-cyclohexenyl groups: delta-67.91
Si-cyclohexyl with two Si-cyclohexenyl groups: delta-67.97
Si-cyclohexyl with one Si-cyclohexenyl group: delta-68.02
Si-cyclohexyl with zero Si-cyclohexenyl groups: delta-68.08
As described above, the sample prepared by reacting equimolar amounts (0.0125mol) of (cyclohex-3-enyl) trichlorosilane with cyclohexyltrichlorosilane exhibited a total of 8 resonances with a relative overall strength of approximately 4: 17: 5: 4: 21: 22: 10. Since many have slightly different chemical shifts: delta 127.45(br m), 127.07, 27.47, 26.85, 26.6325.51, 25.08, 23.15, 22.64, 18.68 overlap so that close to Si8O12Of frameworks13The resonance peak of the C nucleus is much wider, in addition to this, the same sample (CDCl)3In (1) are13The C NMR spectrum is similar to that of pure [ ((C-C)6H11)SiO1.5)8]∑8Spectrum sum [ ((C-C)6H9)SiO1.5)8]∑8And (4) spectrum superposition. When the following ratio of (cyclohex-3-enyl) trichlorosilane and cyclohexyltrichlorosilane is used for the preparation of [ ((C-C)6H11)SiO1.5)n((c-C6H9)SiO1.5)n]∑8Similar results were observed with mixtures.
| Item(s) | (cyclohex-3-enyl) SiCl3 | Cyclohexyl SiCl3 |
| 1 | 2.7g(12.5mmol) | 2.72g(12.5mmol) |
| 2 | 2.7g(12.5mmol) | 8.18g(37.5mmol) |
| 3 | 2.7g(12.5mmol) | 10.88g(50mmol) |
| 4 | 6.47g(30mmol) | 9.79g(45mmol) |
| 5 | 1.35g(6.25mmol) | 9.52g(44mmol) |
| 6 | 5.82g(27mmol) | 9.79g(45mmol) |
| 7 | 0.68g(3.13mmol) | 9.52g(44mmol) |
[(c-C6H9)SiO1.5]∑8The synthesis of (2): to a solution of methanol (200mL) and water (5mL) was added (cyclohex-3-enyl) trichlorosilane (10.78g, 0.05mol) with vigorous stirring. The mixture was then refluxed overnight. While cooling, volatiles were removed in vacuo to afford a yield [ ((C-C)6H9)SiO1.5)n]∞And (3) resin. Of resins29Si{1H } NMR spectra show resonance characteristics of broad featureless silsesquioxane resins and do not show resonance characteristics attributable to discrete polyhedral silsesquioxanes (e.g., ((R) SiO)1.5)n]∑nAnd n is 6, 8, 10, 12, 14). With sufficient C in methyl isobutyl ketone (25ml)6H5CH2N(CH3)3OH was refluxed for 48 hours to complete the reaction [ ((C-C)6H9)SiO1.5)n]∞Base-catalyzed redistribution of the resin produced a strongly basic solution (approximately 2mL of 40% MeOH in). The solvent was evaporated (25 ℃ C., 0.01 torr) to give a white resinous solid which was stirred with acetone (15mL) and filtered to provide a white microcrystalline solid [ ((C-C) in 80% yield (5.33g)6H9)SiO1.5)8]∑8. Characterization data:1H NMR(500.2MHz，CDCl3，300K)δ5.76(br s，2H)，2.09(br m，4H)，1.92(br m，4H)，1.52(br m，1H)，1.08(br m，1H)。13C NMR(125.8MHz，CDCl3，300K)δ127.33，127.08，25.46，25.03，22.60，18.60。29Si NMR(99.4MHz，C6D6300K) delta-67.4. The product can also be characterized by single crystal X-ray diffraction studies.
[(((CH3)2CH)SiO1.5)8]∑8The synthesis of (2): under vigorous stirring (CH)3)2CHSiCl3Water (1mL) was carefully added (6.15g, 34.8mmol) in methanol (100 mL). The solution was then refluxed for 24 hours. On cooling, the solvent was evaporated to give a yield of a pale yellow liquidForm [ i-PrSiO3/2]nAnd (3) resin. Of resins29Si{1H } NMR spectra show the resonance characteristics of broad and closed silsesquioxane resins and indicate the presence of very small amounts of discrete polyhedral silsesquioxane, if any (e.g., ((CH)3)2CH)SiO1.5]nAnd n is 6, 8, 10, 12, 14). In methyl isobutyl ketone (25mL) with water (1.4mL) and sufficient C6H5CH2N(CH3)3OH was refluxed for 6 hours to complete the reaction [ ((CH)3)2CH)SiO1.5]nBase-catalyzed redistribution of the resin produced a strongly basic solution (approximately 1mL of 40% MeOH in). With Et2The crude equilibrium mixture was diluted O (200mL), washed several times with water, over anhydrous MgSO4Dried and concentrated to provide [ ((CH)3)2CH)SiO1.5)8]∑8White microcrystalline powder of (4). The yield after one equilibration is generally between 15 and 30%, but by comparison of [ ((CH) s) present in the mother liquor3)2CH)SiO1.5]Base catalyzed redistribution of the [ ((CH) resin) to obtain additional [ ((CH)3)2CH)SiO1.5)8]∑8. The compound prepared in this way is equivalent to [ ((CH) prepared by the method described by Unno (chemical letters 1990, 489)3)2CH)SiO1.5)8]∑8. Characterization data:1H NMR(500.2MHz，CDCl3，300K)δ1.036(d，J＝6.9Hz，48H，CH3)；0.909(sept，J＝7.2Hz，8H，CH)。13C NMR(125.8MHz，CDCl3，300K)δ16.78(s，CH3)；11.54(s，SiCH)。29Si NMR(99.4MHz，CDCl3，300K)δ-66.3。
[((CH3)2CHCH2)SiO1.5]∑8the synthesis of (2): to CH under vigorous stirring2Cl2(200mL) and Water (5mL) to a mixture was added (CH)3)2CHCH2SiCl3(8.3mL, 0.05 mol). The mixture was then refluxed overnight. On cooling, the CH is decanted2Cl2Layer of CaCl2(5g) Dried and evaporated to give a yield of [ ((CH)3)2CHCH2)SiO1.5]∞And (3) resin. Of resins29Si{1H } NMR spectra show resonance characteristics of broad featureless silsesquioxane resins and do not show resonance characteristics attributable to discrete polyhedral silsesquioxanes (e.g., ((CH)3)2CHCH2)SiO1.5)n]∑nAnd n is 6, 8, 10, 12, 14). With sufficient C in methyl isobutyl ketone (25ml)6H5CH2N(CH3)3OH was refluxed for 48 hours to complete the pair [ ((CH)3)2CHCH2)SiO1.5]∞Base-catalyzed redistribution of the resin produced a strongly basic solution (approximately 2mL of 40% MeOH in). The solvent was evaporated (25 ℃ C., 0.01 torr) to give a white resinous solid which was stirred with acetone (15mL) and filtered to provide a white microcrystalline solid [ (((CH) (1.64 g)) in 30% yield (1.64g)3)2CHCH2)SiO1.5)∑8]. Evaporating the acetone solution to obtain more [ i-BuSiO ]3/2]∞Resins which undergo further base-catalyzed redistribution to produce more [ ((CH)3)2CHCH2)SiO1.5)8]∑8. After three resin redistribution reactions [ ((CH)3)2CHCH2)SiO1.5)8]∑8The mixing yield of (a) is generally greater than 60%. Characterization data:1H NMR(500.2MHz，C6D6，300K)δ2.09(m，8H，CH)；1.08(d，J＝6.6Hz，48H，CH3)；0.84(d，J＝7.0Hz，16H，CH2)。13C NMR(125.8MHz，C6D6，300K)δ25.6(s，CH3)；24.1(s，CH)；22.7(s，CH2)。29Si NMR(99.4MHz，C6D6，300K)δ-67.5。
from [ (C-C)6H11)SiO1.5]∞Resin preparation [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7：
From C6H5SiCl3Preparation of [ (C-C) by two-step Process6H11)SiO1.5]∞And (3) resin. In a first step, water is added to a toluene solution of phenyltrichlorosilane according to the procedure described by Brown (j.am.chem.soc., (1965), 87, 4317) to prepare [ C6H5SiO1.5]∞And (3) resin. Then the [ C ] is added6H5SiO1.5]∞The resin (1.0g) was dissolved in cyclohexane (50mL) and hydrogenated to [ (C-C) in a Parr microreactor (150 ℃, 220psi, 48 hours) using 10% Pd/C (1.3g) as a catalyst6H11)SiO1.5]∞And (3) resin. Filtration to remove the catalyst and evaporation of the solvent in vacuo afforded [ (C-C) as a white solid6H11)SiO1.5]∞And (3) resin. Of the resin1H NMR spectrum showed broad featureless C-C6H11Resonance characteristics of Si group, and not attributable to C6H5Resonance phenomenon of Si group. It is composed of29Si{1H } NMR spectra show resonance characteristics of broad featureless cyclohexyl silsesquioxane resins and do not appear to be attributable to discrete polyhedral silsesquioxanes (e.g., ((C-C)6H11)SiO1.5)]∑nAnd n is 6, 8, 10, 12, 14).
By reaction in methyl isobutyl ketone (40mL) with 35% aqueous NEt in MIK (40mL)4OH (2mL, 5mmol) at reflux for 10 h to complete [ (C-C)6H11)SiO1.5]∞Base-catalyzed redistribution of resin (0.5 g). After cooling, the solution was decanted and evaporated to dryness in vacuo to afford a brownish solid. By29Si{1H } NM Spectroscopy of the solid and HPLC showed that [ ((C-C) was formed in 10-15% yield6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7。
Example of method II: reaction between POSS systems and silsesquioxane/siloxane segments
[((CH3)SiO1.5)7((CH3CH2OOC(CH2)10)SiO1.5)1]∑8The preparation of (1): 1 eq Ethyl undecylenate triethoxysilane and 7 eq methyltrimethoxysilane (1.9g) were added dropwise to a refluxing solution of acetone (40mL) and 1mL water containing 0.15 eq (235.6mg) potassium acetate. The reaction was refluxed for 3 days, and after cooling, the white crystalline product was collected by filtration and washed with MeOH to remove the resin. The product was characterized by MS and X-ray diffraction. A similar procedure was also performed for each of the following compounds: [ ((CH)3)SiO1.5)6(CH3(CH2)7)SiO1.5)2]∑8，[((CH3)SiO1.5)7(CH2＝CH)SiO1.5)1]∑8，[((CH3)SiO1.5)4(CH2＝CH)SiO1.5)4]∑8，[((CH3)SiO1.5)6(CH2＝CH)SiO1.5)2]∑8，[((CH3)SiO1.5)7(H2N(CH2)3)SiO1.5)1]∑8，[((C6H5)SiO1.5)7((CH2＝CH)SiO1.5)1]∑8，[((CH3)SiO1.5)7(H2N(CH2)3)SiO1.5)1]∑8，[((c-C5H9)SiO1.5)7((CH3CH2OOC(CH2)10)SiO1.0)1]∑8，[((c-C5H9)SiO1.5)7((CH2＝CH)SiO1.0)1]∑8.
[((c-C6H11)SiO1.5)]∑6.8The preparation of (1): 1.23g of [ ((C-C)6H11)(OH)2SiOSi(OH)2(c-C5H11)]The batch was added to ethanol (50mL) followed by 5meq of KHCO3. The reaction mixture was then allowed to react at reflux for 3 hours by adding Bu4The mixture was made basic by NOH and refluxed for 2 days. The reaction was then allowed to cool, neutralized with acetic acid and the volatiles were removed under reduced pressure. The residue was washed repeatedly with MeOH and dried. The product yield was 93%. The product was characterized by MS and X-ray diffraction.
[((c-C6H11)SiO1.5)8]∑8The preparation of (1): will [ ((C-C)6H11)SiO1.5)6]∑6[((c-C6H11)SiO1.5)6((c-C6H11)(OH)SiO1.0)2]∑8And [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7Is dissolved in methyl isobutyl ketone and is reacted with 20% aqueous Et4NOH was reacted at reflux for 4 days to produce substantially [ ((C-C)6H11)SiO1.5)8]∑8. The authenticity of the product was confirmed compared to a reliable sample.
[((CH3)SiO1.5)]∑8The preparation of (1): 1.22kg (7.5 moles) of (CH)3Si(OCH3)3The batch was added to acetone (81) followed by 2.37 equivalents of Me4NOH and 405g of water. The reaction mixture was then allowed to react at reflux for 24 hours and the product was collected by filtration. The product was washed repeatedly with MeOH and dried. 466.2g of product are obtained in 93% yield. The product was characterized by MS and X-ray diffraction. Similar procedures can also be used to prepare [ (CH)2＝CH)SiO1.5)8]∑8、[(c-C6H11)SiO1.5]8]∑8. Improving the process will provide a continuous scaleAnd batch scale production.
[((CH3CH2)SiO1.5)8]∑8The preparation of (1): the reaction is carried out in acetone for [ ((CH)3)SiO1.5)8]∑8The above method is similar to the above method to prepare [ (CH)3CH2)SiO1.5]]∞Resin, which is then absorbed into THF using KOH, to produce [ (CH)3CH2)SiO1.5]8]∑8：1H NMR(500MHz，CDCl3)：δ(ppm)0.602(q，J＝7.9Hz，16H)，0.990(t，J＝7.9Hz，24H)；13C NMR(125MHz，CDCl3)：δ(ppm)4.06，6.50；29Si NMR(99.4MHz，CDCl3): delta (ppm) -65.42. Improving the process will provide both continuous-scale and batch-scale production.
[((CH3)2CH2CHCH3CH2)SiO1.5]n]∑nPreparation of n-8, 10. Performing the AND with KOH for [ ((CH)3)SiO1.5)8]]∑8By a process similar to the above-mentioned method, [ ((CH) is prepared in a certain yield3)2CH2CHCH3CH2)SiO1.5]n]∑nn＝8，10。1H NMR(500MHz，CDCl3)：δ(ppm)0.563(dd，J＝8.2，15.1Hz，1H)，0.750(dd，J＝5.6，15.1Hz，IH)，0.902(s，9H)，1.003(d，J＝6.6Hz，3H)，1.125(dd，J＝6.4，13.9Hz，1H)，1.325(br d，J＝13.9Hz，1H)，1.826(m，1H)；13C NMR(125MHz，CDCl3)：δ(ppm)23.72，24.57，25.06，25.31，25.71，25.75，25.78，26.98，29.52，30.22，30.28，31.22，53.99，54.02，54.33；29Si NMR(99.4MHz，CDCl3)：δ(ppm)-69.93，-67.75[((CH3)2CH2CHCH3CH2)SiO1.5]12]∑12，-67.95[((CH3)2CH2CHCH3CH2)SiO1.5]10]∑10，-66.95[((CH3)2CH2CHCH3CH2)SiO1.5]8]∑8。EIMS：m/e 1039(17％，M+[((CH3)2CH2CHCH3CH2)SiO1.5]10)∑10)，1207(100％，M+[((CH3)2CH2CHCH3CH2)SiO1.5]8)∑8. Improving the process will provide both continuous-scale and batch-scale production.
[(CF3CH2CH2SiO1.5)8]∑8And (4) preparing. Use of KOH and methanol as solvents for [ ((CH)3)SiO1.5)8]∑8The same procedure as described above was followed to prepare the following product [ (CF)3CH2CH2SiO1.5)8]∑12 97.5％、[(CF3CH2CH2SiO1.5)8]∑102.5 percent of the mixture, and the mixture,1HNMR(300MHz，THF-d8)：δ(ppm)0.978(m，CH2)，2.234(m，CF3CH2)；13C NMR(75.5MHz，THF-d8)：δ(ppm)4.99(s，CH2)，5.42(s，CH2)，28.14(q，J＝30.5Hz，CF3CH2)，28.32(q，J＝30.5Hz，CF3CH2)，128.43(q，J＝276Hz，CF3)，128.47(q，J＝276Hz，CF3)；29Si NMR(59.6MHz，THF-d8)：δ(ppm)-68.38(T12)，-65.84(T10)，-65.59(T12)；19F{1H}NMR(376.5MHz，THF-d8)δ(ppm)-71.67，-71.66。 EIMS：m/e 1715(100％，M+-H4CF3)。
[(CH3(CH2)16CH2SiO1.5)n]∑nwherein n is 8, 10, 12. Is subjected to and is used for [ ((CH)3)SiO1.5)8]∑8The above process was similar to the process described above to produce a mixture of the following products,1H NMR(500MHz，CDCl3)：δ(ppm)0.604(m，2H)，0.901(t，J＝7.0Hz，3H)，1.280-1.405(m，32H)；13C NMR(125MHz，CDCl3)：δ(ppm)12.02，14.15，22.79，22.89，29.49，29.75，29.79，29.85，29.90，32.05，32.76；29Si NMR(99.4MHz，CDCl3)：δ(ppm)-70.48，-68.04[(CH3(CH2)16CH2SiO1.5)12]∑12，-68.22[(CH3(CH2)16CH2SiO1.5)10]∑10，-66.31[(CH3(CH2)16CH2SiO1.5)8]]∑8。
from (CH)3)2CHCH2Si(OCH3)3Preparation of [ ((CH)3)2CHCH2)SiO1.5]4[(CH3)2CHCH2)(OH)SiO1.0)3]∑7: isobutyltrimethoxysilane (93.3g, 523.3mmol) was added dropwise to LiOH. H in 88/12 acetone/methanol (500ml) at reflux2O (10.0g, 238.3mmol) and water (8.0mL, 444 mmol). The reaction mixture was heated at reflux, acidified by quenching in 1N HCl (aqueous) (500ml) and stirred for 2 hours. Filtering the resulting solid and using CH3CN (2X 175mL) was washed and then air dried. Isolation of the product [ ((CH)3)2CHCH2)SiO1.5]4((CH3)2CHCH2)(OH)SiO1.0)3]∑7The yield was 94% and the purity 98.8%. It should be noted that the above process is also suitable for a continuous production method and a mass production method.
[(CH3CH2)SiO1.5]4(CH3CH2)(OH)SiO1.0]3]∑7The preparation of (1): the use of acetone and LiOH for [ ((C)H3)2CHCH2)SiO1.5]4((CH3)2CHCH2)(OH)SiO1.5]3]∑7By a procedure similar to the above method, [ (CH) is prepared in 40-80% yield3CH2)SiO1.5]4(CH3CH2)(OH)SiO1.0)3]∑7White crystalline solid of (2).1H NMR(500MHz，CDCl3)：δ(ppm)0.582(q，J＝7.9Hz，6H)，0.590(q，J＝7.9Hz，2H)，0.598(q，J＝7.9Hz，6H)，0.974(t，J＝7.9Hz，3H)，0.974(t，J＝7.9Hz，9H)，0.982(t，J＝7.9Hz，9H)，6.244(br，3H)；13C NMR(125MHz，CDCl3)：δ(ppm)3.98(1)，4.04(3)，4.50(3)，6.42(3)，6.46(4)；29Si NMR(99.4MHz，CDCl3): δ (ppm) -65.85(3), -64.83(1), -56.36 (3). MS (electro spray): m/e 617 (70%, [ M + Na ]]+)，595(100％，[M+H]+). Improving the process will provide continuous and batch scale production.
[((CH3)SiO1.5)7(CH3CH2OOC(CH2)10)SiO1.5]1]∑8The preparation of (1): one equivalent of triethoxy ethyl undecanoate and seven equivalents of methyltrimethoxysilane (1.9g) were added dropwise to a refluxing solution of acetone (40mL) with 1mL of water containing 0.15 equivalent (235.6mg) of potassium acetate. The reaction was refluxed for 3 days and cooled and the white crystalline product was collected by filtration and washed with MeOH to remove the resin. The product was characterized by MS and X-ray diffraction.
From [ ((C-C)6H11)SiO1.5)6((c-C6H11)(OH)SiO1.0)1]∑7Preparation of [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7: mixing 35% aqueous NEt4OH (20. mu.l, 0.05mmol) was added [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7(48mg, 0.05mmol) in THF (0.5mL) and mixed well by stirring. At 25 ℃ over 1.5 hours, a few drops of C were added6D6And record29Si{1H } NMR spectrum. The spectrum corresponds to [ ((C-C) reported previously6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7Data of alkaline solution (2).
From [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)2]∑6Preparation of [ ((C-C)6H11)SiO1.5)2((c-C6H11)(OH)SiO1.0)4]∑6：C2-symmetry- [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH) SiO1.0)2]∑6(38mg, 0.05mmol) with 35% aqueous NEt in THF (0.5mL)4OH (20. mu.l, 0.05mmol) reacted, after 30 minutes at 25 ℃ several drops of C were added6D6And record29Si{1H } NMR spectrum. The spectrum conforms to the formula [ ((C-C)6H11)SiO1.5)6]∑6With aqueous Net4Reliable [ ((C-C) prepared by reaction of OH6H11)SiO1.5)2((c-C6H11)(OH)SiO1.0)4]∑6Spectra.
From [ ((C-C)6H11)SiO1.5)6((c-C6H11)(OH)SiO1.0)1]∑7Preparation of [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7：[((c-C6H11)SiO1.5)6((c-C6H11)(OH)SiO1.0)1]∑7(0.46mmol) and 35% aqueous NEt4A solution of OH (0.2mL, 0.49mmol) was refluxed in THF (5mL) for 5 hours, thenIt was neutralized with dilute aqueous HCl. Evaporation of volatiles afforded a white solid which was dissolved in Et2O and over anhydrous MgSO4And drying. Filtration and evaporation of the solvent gave a white microcrystalline solid in high yield. By passing29Si NMR spectrum analysis of the product mixture showed that the main product was [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7(ii) a Also present in minor amounts [ ((C-C)6H11)SiO1.5)8]∑8。
From [ ((C-C)5H9)SiO1.5)8]∑8Preparation of [ ((C-C)5H9)SiO1.5)8((CH3)2SiO1.0)1]∑9：
[((c-C5H9)SiO1.5)8]∑8(2.21g, 2.28mmol) and octamethylcyclotetrasiloxane (1.35g, 4.56mmol) with Me in 2mL of toluene at 120 deg.C4NOH (9.4mg of 25% MeOH in 0.626mmol) was reacted and the reaction was allowed to proceed for 24 hours. The mixture was then quenched with 6N HCl (1mL) and Et2O (3mL) extraction, evaporation to dryness to obtain a white pasty solid containing 70% [ ((C-C)5H9)SiO1.5)8((CH3)2SiO1.0)1]∑9Polydimethylsiloxane and 29% [ ((C-C)5H9)SiO1.5)8]∑8A mixture of (a).29Si{1H}NMR(CDCl3) Spectral analysis showed [ ((C-C)5H9)SiO1.5)8((CH3)2SiO1.0)1]∑9At (. delta. -65.76, -68.30, -68.34, 2: 4).
From [ ((CH)3)2CHCH2)SiO1.5]6((CH3)2CHCH2(OH)SiO1.0)2]∑8Preparation of [ ((CH)3)2CHCH2) SiO1.5]8((5-norbornene-2-ethyl) (CH)3))SiO1.5]1]∑9. Dichloromethyl (5-norbornene-2-ethyl) silane (endo/exo-3/1, 282.3mg, 1.20mmol), Et at-35 deg.C3N (195. mu.l, 1.4mmol) and Et2O (5mL) was added as a mixture [ ((CH)3)2CHCH2)SiO1.5]6((CH3)2CHCH2)(OH)SiO1.0)2]∑8(890mg, 1.00mmol) of Et2O (5mL) solution. After addition, the resulting mixture was warmed to room temperature and stirred for 20 hours. The mixture was hydrolyzed and extracted with diethyl ether, washed with brine, over Na2SO4And drying. Evaporation of volatiles gave [ ((CH) in 68% yield3)2CHCH2)SiO1.5]8((5-norbornene-2-ethyl) (CH)3))SiO1.5]1]∑9(720mg, 0.68mmol) of white powder.1H NMR(CDCl3)δ0.10(s，9H)，0.12(s，3H)，0.48-0.68(m，72H)，0.84-1.05(m，194H)，1.06-1.36(m，18H)，1.40-1.50(m，4H)，1.80-1.94(m，32H)，1.95-2.03(m，3H)，2.55(br s，1H)，2.77(br s，3H)，2.78-2.83(m，4H)，5.93(q，3J＝5Hz，3J＝10Hz，3H)，6.04(q，3J＝5Hz，3J＝10Hz，1H)，6.09-6.14(m，4H)。13C NMR(CDCl3)δ-1.11，15.86，16.21，22.58，23.20，23.83，23.98，24.06，24.18，25.76，25.81，25.89，27.71，29.50，32.41，33.10，41.89，41.97，42.09，42.65，45.10，45.20，46.03，49.61，132.35，136.29，136.87，136.96。29Si NMR(CDCl3)δ-69.25，-69.23，-69.21，-69.15，-67.04，-21.73，-21.63。
[((CH3)SiO1.5)7(CH2＝CCH3(O)CO(CH2)3)SiO1.5]1]∑8The preparation of (1): at-35 deg.C, adding methyl acryloyl oxy propyl trichlorosilaneEt (0.69mL, 3.31mmol) and 1, 8-bis (dimethylamino) naphthalene (2.34g, 10.91mmol)2O (80mL) solution was added to a solution of [ ((CH)3)SiO1.5)4((CH3)(OH)SiO1.0)3]∑7(1.26g, 2.54mmol) of Et2O (20mL) solution. The mixture was further stirred at room temperature for 5 hours, and then concentrated under reduced pressure. The residue was extracted with ether. The insoluble material was filtered. The filtrate was concentrated to give an oil-like solid. With cyclohexane/Et2O (50: 1) was used as eluent to pass the solid through a silica gel column. Evaporation of volatiles gave [ ((CH) in 25% yield3)SiO1.5)7(CH2＝CCH3(O)CO(CH2)3)SiO1.5]1]∑8(415mg, 0.64mmol) of a white solid.1H NMR(CDCl3)δ0.136(s，3H)，0.142(s，12H)，0.146(s，6H)，0.64-0.72(m，2H)，1.72-1.82(m，2H)，1.94(s，3H)，4.11(t，J＝6.78Hz，3H)，5.54(t，J＝1.58Hz，1H)，6.10(br s，1H)。13C NMR(CDCl3)δ-4.56，-4.48，8.24，18.31，22.19，66.46，125.16，136.53，167.46。29Si NMR(CDCl3)δ-67.71，-66.00，-65.69。C14H32O14Si8The calculated value of (a): c, 25.91; h, 4.97. Measured value: c, 25.69; h, 4.99.
[((CH3C6H4SiO1.5)8((CH2＝CCH3)(O)CO(CH2)3)(H3C)SiO1.0)1]∑9The preparation of (1): will [ ((CH) at room temperature3C6H5)SiO1.5)6((CH3C6H5)(OH)SiO1.0)2]∑8/[((CH3C6H5)SiO1.5)8]∑8Et of (581.9mg, 4/1, 0.40mmol) mixture2O (20mL) solution was added dichloromethacryloxypropylmethylsilane (108.8. mu.l, 0.50mmol), Et3N (139.4. mu.l, 1.00mmol) and Et2In a mixture of O (3mL)And stirred for 20 hours, then hydrolyzed and extracted with diethyl ether. The extract was washed with brine over Na2SO4Dried over sodium chloride and evaporated to give [ ((CH) in 89% yield3C6H4SiO1.5)8((CH2＝CCH3)(O)CO(CH2)3)(H3C)SiO1.0)1]∑9(475.5mg, 0.36mmol) of a white solid.1H NMR(CDCl3)δ0.43(s，3H)，0.85-0.90(m，2H)，1.87-1.95(m，2H)，1.95(s，3H)，2.42(s，6H)，2.43(s，12H)，2.44(s，6H)，4.16(t，3J＝6.8Hz，2H)，5.56(br s，1H)，6.11(br s，1H)，7.19-7.29(m，18H)，7.59-7.68(m，10H)，7.71-7.79(m，4H)。13C NMR(CDCl3)δ-0.92，12.87，18.24，21.57，22.12，127.14，127.38，127.43，128.49，128.55，128.58，128.64，133.94，134.16，134.19，134.25，140.23，140.39，140.59，167.37。29Si NMR(CDCl3)δ-78.72，-78.51，-76.98，-18.75。
[((CH3C6H4SiO1.5)7((CH＝CH2)(CH3)2SiO1.0)3)∑7The preparation of (1): will [ ((CH) at room temperature3C6H5)SiO1.5)8]]∑8(572.9mg, 0.50mmol) in THF (15mL) was added Et4NOH (35%, 226.2. mu.l, 0.55mmol) in aqueous solution. After the addition, the resulting mixture was stirred at the same temperature for 6 hours. The mixture was neutralized with 1N HCI solution and extracted with diethyl ether. The organic layer was washed with brine over MgSO4Drying and evaporating off the volatiles to obtain [ ((CH)3C6H5)SiO1.5)4((CH3C6H5)(OH)SiO1.0)3]∑7. Will [ ((CH)3C6H5)SiO1.5)4((CH3C6H5)(OH)SiO1.0)3]∑7Dissolved in Et2In the presence of O (30mL),to this was added dimethylvinylsilane chloride (505. mu.l, 3.66mmol), Et at room temperature3N (595 μ l, 4.27mmol) and Et2O (3mL) and stirred for 7 hours. The mixture was hydrolyzed and extracted with diethyl ether, washed with brine, over MgSO4Dried and evaporated to obtain a solid. The solid was recrystallized from hexane to give colorless [ ((CH) in 36% yield3C6H4)SiO1.5)4((CH3C6H5)(OSi(CH3)2(CH＝CH2)SiO1.0)3]∑7(230mg, 0.18mmol) of crystals.1H NMR(CDCl3)δ0.38(s，18H)，2.33(s，9H)，2.34(s，9H)，2.39(s，3H)，5.90(dd，2J＝20.4Hz，3J＝3.8Hz，3H)，6.03(dd，3J＝14.9Hz，3J＝3.8Hz，3H)，6.28(dd，2J＝20.4Hz，3J＝3.8Hz，3H)，7.01(d，3J＝7.7Hz，12H)，7.19(d，3J＝7.7Hz，2H)，7.27(d，3J＝7.7Hz，6H)，7.41(d，3J＝7.7Hz，6H)，7.53(d，3J＝7.7Hz，2H)。13C NMR(CDCl3)δ0.42，21.51，21.54，21.60，127.51，127.97，128.14，128.26，128.55，129.51，132.26，134.06，134.11，134.17，138.78，139.65，139.77，140.37。29Si NMR(CDCl3)δ-77.81，-77.29，-77.15，-0.50。
From [ ((CH)3CH2)4NO)SiO1.5)6]∑6Preparation of [ ((CH)3)3SiO)SiO1.5)6]∑6: to a solution of trimethylchlorosilane (140.0mL, 1.10mol), heptane (500mL), and N, N-dimethylformamide (200mL) was added one [ ((CH, 1.10 mol.) at 0 deg.C over a period of about 30 minutes3CH2)4NO)SiO1.5)6]∑6(11.9g, 10.0mmol) of powder. Adding all [ (((CH)3CH2)4NO)SiO1.5)6]∑6Thereafter, the mixture was stirred for a further 30 minutes and then allowed to warm to room temperature overnightAnd (4) room temperature. Ice water (1L) was added and the mixture was stirred for 30 minutes. The organic layer was washed with water until neutral, over MgSO4Dried and concentrated. Methanol was added to the raffinate and the dissolved portion was removed by filtration leaving pure [ ((CH)3)3SiO)SiO1.5)6]∑6(4.1g, 4.84mmol) white solid, yield 48%:1H NMR(CDCl3)δ0.17(s，54H)。13C NMR(CDCl3)δ1.18。29Si NMR(CDCl3)δ14.27，-99.31。
[(((CH3)3SiO)SiO1.5)6((CH2＝CH)(CH3)2SiO1.0)4]∑6the preparation of (1): to vinyldimethylchlorosilane (121.5. mu.l, 0.88mmol) and NEt at room temperature3(139.4. mu.l, 1.00mmol) of Et2Adding one [ ((CH) to O (5mL) solution3)3SiO)SiO1.5)2(((CH3)3SiO)(OH)SiO1.0)4]∑6(174.7mg, 0.20mmol) of Et2And (4) O solution. The mixture was stirred at room temperature for 4 hours and then concentrated under reduced pressure. The residue was extracted with hexane. The insoluble material was filtered. The filtrate was concentrated to give spectrally pure [ ((CH)3)3SiO)SiO1.5)6((CH2＝CH)(CH3)2SiO1.0)4]∑6(225.6mg, 0.18mmol) of white foam in 92% yield:1H NMR(CDCl3)δ0.13(s，54H)，0.14(s，12H)，0.18(s，12H)，5.73(d，J＝4.0Hz，2H)，5.77(d，J＝4.0Hz，2H)，5.91(d，J＝4.0Hz，2H)，5.94(d，J＝4.0Hz，2H)，6.11(d，J＝15.0Hz，2H)，6.15(d，J＝15.0Hz，2H)。13C NMR(CDCl3)δ0.11，1.52，1.62，132.00，138.79。29Si NMR(CDCl3)δ11.24，10.17，-1.35，-108.31，-108.70。MS(ESI)：C34H90O17Si16calculated value of Na: 1243.2. measured value: 1243.6.
from [ ((CH)3)3SiO)SiO1.5)4((C6H5)(OH)SiO1.0)1(((CH3)3SiO)(OH)SiO1.0)2]∑7Preparation of [ ((CH)3)3SiO)SiO1.5)6((C6H5)SiO1.5)1((CH2＝CCH3)(O)CO(CH2)3SiO1.5)1]∑8: methacryloxypropyl trichlorosilane (340.3 microliters, 1.63mmol) and NEt were combined at-35 deg.c2Et (748.5. mu.l, 5.37mmol)2O (8mL) solution was added to [ (((CH)3)3SiO)SiO1.5)4((C6H5)(OH)SiO1.0)1(((CH3)3SiO)(OH)SiO1.0)2]∑7(817.0mg, 0.81mmol) of Et2To a solution of O (7mL), the mixture was stirred at room temperature for 6 hours, and then concentrated under reduced pressure. The residue was extracted with hexane, insoluble materials were filtered off, and the filtrate was concentrated to give an oil. Using silica gel column and hexane/Et2O (50: 1) as eluent to purify the oil. The volatiles were evaporated to obtain [ ((CH) as a white solid in 25% yield3)3SiO)SiO1.5)6((C6H5)SiO1.5)1((CH2＝CCH3)(O)CO(CH2)3SiO1.5)1]∑8(210.0mg，0.18mmol)。1H NMR(CDCl3)δ0.13(s，18H)，0.16(s，18H)，0.17(s，9H)，0.18(s，9H)，0.73-0.80(m，2H)，1.77-1.85(m，2H)，1.93(s，3H)，4.11(t，J＝6.62Hz，2H)，5.54(t，J＝1.58Hz，1H)，6.09(br s，1H)，7.35-7.41(m，2H)，7.43-7.48(m，1H)，7.66-7.72(m，2H)。13C NMR(CDCl3)δ1.24，7.95，18.30，22.11，66.39，125.22，127.70，130.22，130.69，134.08，136.41，167.37。29Si NMR(CDCl3) Delta-109.06, -108.88, -108.82, -78.86, -65.60, 12.55, 12.58, 12.59 for C31H70O20Si14The calculated value of (a): c, 32.21;h, 6.10. Measured value: c, 31.99; h, 6.35. MS (ESI) calculated value 1177.1[ M + Na]+，1193.1[M+K]+. Measured value: 1177.2[ M + Na ]]+，100％；1193.2[M+K]+，10％。
Example of method III: selective opening, functionalization and rearrangement of POSS nanostructures
From [ ((CH)2＝CH)SiO1.5)8]∑8Preparation of [ ((CH)2＝CH)SiO1.5)6((CH2＝CH)(HO)SiO1.0)2]∑8: will NEt4An aqueous solution of OH (33%, 2mL, 0.25mmol) in THF (10mL, -35 deg.C) was added to a stirred solution of [ ((CH)2＝CH)SiO1.5)8]∑8(2.95 g, 4.66mmol) of 1: 1THF/CH2Cl2In isopropanol (300mL) solution at-35 deg.C (1: 1 methanol/water and N2) Cooling in a cold bath. After 4.3 hours the reaction was quenched with 1M HCl (20mL, -35 ℃ C.), and the solution was washed with 1M HCl (2X 40mL), water (2X 40mL) and saturated aqueous NaCl (40 mL). In Na2SO4After drying, the solvent was removed in vacuo (25 ℃, 0.01 torr) and a white solid (3.01g, 99%) was isolated. Product prepared by this Process [ ((CH)2＝CH)SiO1.5)6((CH2＝CH)(HO)SiO1.0)2]∑8Is spectrally pure. Can be prepared by using CH2Cl2Recrystallization from/cyclohexane/acetic acid (25 ℃) completes the additional purification.1H NMR(CDCl3，500.2MHz，25℃)：δ6.12-5.74(m，SiCH＝CH2)，5.7(br，SiOH)。13C{1H}NMR (CDCl3，125.7MHz，25℃)：δ137.00，136.87，136.81(s，CH2，rel.int.1∶1∶2)，129.75，129.17，128.80(s，SiCH，rel.int.1∶2∶1)。29Si{1H}NMR(CDCl399.4MHz, 25 ℃): delta-71.39 (s, SiOH), -79.25, -80.56(s, SiCH, rel. int.1: 2). Mass Spectrometry (ESI) m/z vs. C16H26O13Si8The calculated value of (a): [ M + H ]]+650.96, found 651.2 (20%); [ M + Na ]]+672.94, found 673.1 (100%). Mass Spectrometry (EI) m/z for C16H26O13Si8The calculated value of (a): [ M ] A]+649.9528, found 649.9532 (4%); [ M-C ]2H3]+622.9, found 623.2 (100%).
From [ (tert-butyloxycarbonyl (Boc) -NHCH2CH2CH2)SiO1.5]8]∑8Preparation of [ ((tert-butyloxycarbonyl-NHCH)2CH2CH2)SiO1.5)6((tert-butyloxycarbonyl-NHCH)2CH2CH2)(HO)SiO1.0)2]∑8: reacting [ ((tert-butyloxycarbonyl-NHCH)2CH2CH2)SiO1.5)8]∑8(0.11mmol) in the range of 1: 1CH2Cl2THF/isopropanol (-35 ℃, 7.5mL) and aqueous NEt4A solution in OH (35 wt%, 50. mu.l, 0.13mmol) was stirred at-35 ℃ for 2 hours. Adding CH3CO2H (0.1mL, -35 ℃) was extracted with saturated aqueous NaCl (3X 10mL) over Na2SO4Dried and the solvent removed in vacuo (25 ℃, 0.001 torr) to provide a colorless paste [ ((tert-butyloxycarbonyl-NHCH) in 63% yield2CH2CH2)SiO1.5)6((tert-butyloxycarbonyl-NHCH)2CH2CH2)(HO)SiO1.0)2]∑8。29Si{1H}NMR(CDCl399.4MHz, 25 ℃): delta-57.798, -65.674, -67.419(s, rel. int.1: 1: 2). Mass Spectrometry (ESI) m/z vs. C64H130N8O29Si8The calculated value of (a): [ M + Na ]]+1721.7, found 1722.1.
From [ ((benzyloxycarbonyl (cbz) -Pro-NHCH)2CH2CH2)SiO1.5)8]∑8Preparation of [ ((benzyloxycarbonyl-Pro-NHCH)2CH2CH2)SiO1.5)6((benzyloxycarbonyl-Pro-NHCH)2CH2CH2)(HO)SiO1.0)2]∑8：
Will [ ((benzyloxycarbonyl-Pro-NHCH)2CH2CH2)SiO1.5)8]∑8(0.11mmol) in the range of 1: 1CH2Cl2THF/isopropanol (-35 ℃, 7.5mL) and aqueous NEt4A solution in OH (35 wt%, 50. mu.l, 0.13mmol) was stirred at-35 ℃ for 2 hours. Adding CH3CO2H (0.1mL, -35 ℃) was extracted with saturated aqueous NaCl (3X 10mL) over Na2SO4Dried and the solvent removed in vacuo (25 ℃, 0.001 torr) to provide a colorless paste [ ((benzyloxycarbonyl-Pro-NHCH) in 77% yield2CH2CH2)SiO1.5)6((benzyloxycarbonyl-Pro-NHCH)2CH2CH2)(HO)SiO1.0)2]∑8。29Si{1H}NMR(CDCl399.4MHz, 25 ℃): delta-58.4, -65.543, -67.470(s, rel. int.1: 1: 2). Mass Spectrometry (ESI) m/z vs. C128H170N16O37Si8The calculated value of (a): [ M + Na ]]+2772.54, found 2772.9.
From [ ((MeO)2CCH2CMe2CH2CH2CH2)SiO1.5)8]∑8Preparation of [ (MeO)2CCH2CMe2CH2CH2CH2)SiO1.5]6((MeO2CCH2CMe2CH2CH2CH2)(HO)SiO1.0)2]∑8：
Will [ ((MeO)2CCH2CMe2CH2CH2CH2)SiO1.5)8]∑8(0.11mmol) in the range of 1: 1CH2Cl2THF/isopropanol (-35 ℃, 7.5mL) and aqueous NEt4A solution in OH (35 wt%, 50. mu.l, 0.13mmol) was stirred at-35 ℃ for 2 hours. Adding CH3CO2After H (0.1mL, -35 ℃ C.), it was extracted with a saturated aqueous NaCl solution (3X 10mL)Taken in Na2SO4Dried and the solvent removed in vacuo (25 ℃, 0.001 torr) to provide a colorless paste [ (MeO) in 66% yield2CCH2CMe2CH2CH2CH2)SiO1.5]6((MeO2CCH2CMe2CH2CH2CH2)(HO)SiO1.0)2]∑8。29Si{1H}NMR(CDCl399.4MHz, 25 ℃): delta-57.551, -64.981, -66.841(s, rel. int.1: 1: 2). Calculated Mass Spectrometry (ESI) m/z C64H122O29Si8：[M+Na]+1601.61, found 1602.0.
[(((CH3)3SiO)SiO1.5)2(((CH3)3SiO)(OH)SiO1.0)4]∑6The preparation of (1): at-40 ℃ to [ (((CH)3)3SiO)SiO1.5)6]∑6(169.5 mg, 0.20mmol) in THF (4mL) was added NEt4OH (35%, 82.3. mu.l, 0.20mmol) in water. The resulting mixture was stirred at-40 ℃ to-25 ℃ for 40 minutes. The mixture was neutralized with aqueous HCl (1N, 3mL) and extracted with diethyl ether. The organic layer was washed with brine over MgSO4Dried and evaporated to give spectrally pure [ ((CH) in 99% yield3)3SiO)SiO1.5)2(((CH3)3SiO)(OH)SiO1.0)4]∑6(174.7mg, 0.20mmol) of a white waxy solid.1H NMR(CDCl3)δ0.14(s，54H)。13C NMR(CDCl3)δ1.24，1.28。29Si NMR(CDCl3)δ12.44，12.19，-100.12，-109.27。
[(((H3C)3SiO)SiO1.5)6(((H3C)3SiO)(OH)SiO1.0)2(((CH2＝CH)(OH)SiO1.0)1)∑7The preparation of (1): the method used was the same as Harrison et al in the Main Group Metals Chemistry (1997) volume 20, 137-The procedure disclosed on page 141 is similar to that for the preparation of the starting polyhedral oligomeric silicate [ (((H)3C)3SiO)SiO1.5)6]∑6. A solution of vinyltrimethoxysilane (0.04mL, 0.26mmol) and aqueous NEt was added4OH (0.1mL, 0.25mmol) was pre-reacted for 10 minutes and then added to [ ((H)3C)3SiO)SiO1.5)6]∑6(198 mg, 0.23mmol) and stirred at room temperature for 15 min. The reaction was then neutralized by addition of dilute HCl and the solvent was removed under reduced pressure. The residue was then taken up in diethyl ether, filtered and washed with anhydrous MgSO4And drying. A yellow oil (2.31 mg, 0.002mol) was obtained in 10.2% yield by solvent filtration and evaporation. Selected characterization data:29Si{1H}NMR(99.3MHz，CDCl3，25℃)δ-99.8，-100.1，-108.0，-108.9。MS(ESI，100％ MeOH)：m/e 977.1({M+Na]+。
from [ ((CH)3CH2)SiO1.5)8]∑8Preparation of [ ((CH)3CH2)SiO1.5)6((CH3CH2)(HO)SiO1.0)2]∑8: at-20 deg.C to one [ ((CH)3CH2)SiO1.5)8]∑8(259.7 mg, 0.40mmol) of CH2Cl2Et was added to a solution of/i-PrOH/THF (10/10/10mL)4NOH (35%, 493.5 μ l, 1.20mmol) in water. After the addition, the resulting mixture was stirred at the same temperature for 7 hours. The mixture was neutralized with 1N HCl solution and extracted with diethyl ether. The organic layer was washed with brine, over Na2SO4And drying. Evaporation of volatiles gave spectrally pure [ ((CH) in 99% yield3CH2)SiO1.5)6((CH3CH2)(HO)SiO1.0)2]∑8(263.5 mg, 0.39mmol) of a white solid.1H NMR(CDCl3)δ0.54-0.66(m，16H)，0.93-1.04(m，24H)，5.21(br s，2H)。13C NMR(CDCl3)δ3.94，4.36，4.41，6.42，6.46，6.50。29Si NMR(CDCl3) Delta-66.73, -64.95, -57.63. For C16H12O13Si8The calculated value of (a): c, 28.80; h, 6.35. Measured value: c, 28.78; h, 6.43.
From [ ((CH)3)2CH)SiO1.5)8]∑8Preparation of [ ((CH)3)2CH)SiO1.5)6(((CH3)2CH)(HO)SiO1.0)2]∑8: will [ ((CH)3)2CH)SiO1.5)8]∑8(302 mg, 0.397mmol) was dissolved in 15mL of a solvent mixture (isopropanol: CH)2Cl2THF 1: 1). At-12 ℃ to [ (((CH)3)2CH)SiO1.5)8]∑8Adding EtN to the solution4OH (0.8mL) in 35% aqueous solution. After 7 hours, the reaction mixture is decanted and Et2O (4X 3 mL). The extract is extracted with anhydrous Na2SO4Drying, then vacuum evaporating to obtain a yellow solid, purifying with a chromatographic column (SiO)260% CH in hexane2Cl2) The yellow solid was purified to provide a spectrally pure powder (189 mg, 61%).1H NMR(500MHz，CDCl3，25℃)：δ3.90(br s，SiOH，2H)，1.03(brm’s，48H)，0.91(br m’s，8H.13C{1H}NMR(125MHz，CDCl3，25℃)：δ16.91，16.79，16.64(8∶4∶4 for CH3)，11.91，11.77，11.38(4∶2∶2 forCH)，29Si{1H}NMR(99MHz，CDCl3，25℃)：δ-57.92，-65.29，-67.70(2∶2∶4)。IR(25℃，KBr，cm-1)：3352，2950，2869，1466，1260，1112.MS(ESI，100％ MeOH)：m/e 802.0{[M+Na]+，100％}，779.1(M+70%). For C24H57O13Si8Analytical calculation of (d) (found): c, 37.03(36.92), H, 7.38 (7.54).
[((c-C6H9)SiO1.5)4((c-C6H9)(OH)SiO1.0)2((CH2＝CH)(OH)SiO1.0)1]∑7The preparation of (1):
mixing a 35% NEt4An aqueous solution of OH (0.1mL, 0.25mmol) was added to THF (2.5mL) [ (C-C)6H9)SiO1.5]∑6(205 mg, 0.25mmol) and vinyl Si (OMe)3In the solution of (1). The solution was stirred for 1 hour and then neutralized with dilute aqueous HCl. Evaporation of volatiles afforded a white resin which was dissolved in Et2O and over anhydrous MgSO4And drying. Filtration and evaporation of the solvent provided a white solid in high mass yield. Analysis by multinuclear magnetic resonance spectroscopy and electrospray mass spectrometry showed that the product mixture contained one [ ((C-C)6H9)SiO1.5)2((c-C6H9)(OH)SiO1.0)4]And [ ((C-C)6H9)SiO1.5)4((c-C6H9)(OH)SiO1.0)2((CH2＝CH)(OH)SiO1.0)1]∑7A mixture of (1) and (6). Selected characterization data:29Si{1H}NMR(99.3MHz，CDCl3，25℃)δ-60.1(s，2 Si，Cy-Si-OH)，-68.2(s，1 Si)，-69.1(s，2 Si)，-69.7(s，1 Si)，-72.0(s，1 Si，V-Si-OH)。1H NMR(500MHz，CDCl3，25℃)δ5.90(m，3H，-CH＝CH2)；1.65，1.16(m，66H，C5H11)。13C{1H}NMR(125.8MHz，C6D6.25℃)δ135.4(s，＝CH2)；130.4(s，-CH＝)；27.53，27.47，26.82，26.67，26.59，26.56(s，CH2)；23.81，23.59，23.36，23.10(s，CH)。MS(ESI，100％ MeOH)：m/e 917([M+H]+，75％)；939({M+Na]+，100。
at room temperature [ ((C-C)6H11)SiO1.5)6]∑6And NEt4Reaction of OH: ((C-C) in THF6H11)SiO1.5)6]∑6(200 mg, 0.24mmol) of the solution and (2.5mL) of 35% aqueous NEt4OH (0.1mL, 0.25mmol) was stirred at 25 ℃ for 4 hours and then neutralized with dilute aqueous HCl. Evaporation of volatiles afforded a white solid which was dissolved in Et2In O and over anhydrous MgSO4And drying. Filtration and evaporation of the solvent provided a white solid in high mass yield. Product mixture29Analysis of Si NMR spectroscopy revealed that it mainly comprises [ ((C-C)6H11)SiO1.5)2(c-C6H11)(OH)SiO1.0]4]∑6(> 60%) and [ ((C-C)6H11)SiO1.5)4(c-C6H11)(OH)SiO1.0]3]∑7(＞30％)。
From [ ((C-C)6H11)SiO1.5)8]∑8Preparation of [ ((C-C)6H11)SiO1.5)6((c-C6H11)(OH)SiO1.0)2]Σ 8: THF (3mL) was placed in [ ((C-C) at room temperature6H11)SiO1.5)8]∑8(250 mg, 0.23mmol) in solution with 35% aqueous NEt4OH (0.1mL, 0.25mmol) was stirred for 1 hour and then neutralized with aqueous HCl. Evaporation of volatiles in vacuo afforded a white solid which was dissolved in Et2In O and over anhydrous MgSO4And drying. Filtration and evaporation of the solvent provided a white microcrystalline solid in high yield.29Analysis by Si NMR spectroscopy and electrospray MS showed that the product mixture contained-76% (by29Si NMR)[((c-C6H11)SiO1.5)6((c-C6H11)(OH)SiO1.0)2]∑8：29Si{1H}NMR(99.3MHz，C6D625 ℃ delta-60.4, -67.2, -69.8(s, 1: 2), and also small amounts of unreacted [ ((C-C)6H11)SiO1.5)8]∑8(δ-68.2，～20%). Also observed is a value attributable to tetramethylsilanol [ ((C-C)6H11)SiO1.5)6((c-C6H11)(OH)SiO1.0)2]∑8Is small29Si NMR resonance, and [ C-C ] in electrospray mass spectrometry6H11)SiO1.5)6((c-C6H11)(OH)SiO1.0)2]∑8(for H)+The ion of (2) is 1117.36 for Na+The ion of (3) is a distinct peak of 1139). [ ((C-C)6H11)SiO1.5)6((c-C6H11)(OH)SiO1.0)2]∑8The spectroscopic data of (a) correspond to the data reported for this compound.
From [ ((C-C)6H11)SiO1.5)8]∑8Preparation of [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7：[((c-C6H11)SiO1.5)8]∑8(500 mg, 0.46mmol) in water and 35% aqueous NEt4OH (0.2mL, 0.49mmol) was refluxed in THF (5mL) for 4 hours and then neutralized with dilute aqueous HCl. Evaporation of volatiles afforded a white solid which was dissolved in Et2In O and over anhydrous MgSO4And drying. Filtration and evaporation of the solvent gave [ ((C-C) in 23% yield6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7White microcrystalline solid (4). The product has a spectral data corresponding to the C-C6H11SiCl3Is hydrolyzed and condensed to obtain [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7Reported data for the sample.
From [ ((C-C)6H11)SiO1.5)]∑8Preparation of [ ((C-C)6H11)SiO1.5)2((c-C6H11)(OH)SiO1.0)4]∑6: THF (5mL) was placed in [ ((C-C) at 25 deg.C6H11)SiO1.5)]∑8(200 mg, 0.24mmol) solution and 35% aqueous NEt4OH (0.2mL, 0.49mmol) was stirred for 1 hour and then neutralized with dilute aqueous HCl. Evaporation of volatiles afforded a white solid which was dissolved in Et2In O and over anhydrous MgSO4And drying. Filtration and evaporation of the solvent gave [ ((C-C) in 63% yield (135mg)6H11)SiO1.5)2((c-C6H11)(OH)SiO1.0)4]∑6White solid of (2).29Si{1H}NMR(99.3MHz，CDCl3，25℃)δ-59.4，-68.8(s，2∶1).1H NMR(500MHz，CDCl3，25℃)δ1.78(v br m)；1.7(v br m).13C{1H}NMR(125.8MHz，CDCl3，25℃)δ＝27.55，27.47，26.86，26.62(CH2)；23.68，23.16(2∶1，SiCH).MS(ESI，100％ MeOH)：m/e 846(M+H+，48％)；M+Na+，95％)；885(M+-H+K，100％)。
From [ ((C)6H5CH＝CH)SiO1.5)8]∑8Preparation of [ ((C)6H5CH＝CH)SiO1.5)6((C6H5CH＝CH)(OH)SiO1.0)2]∑8: at-35 ℃ to [ ((C)6H5CH＝CH)SiO1.5)8]∑8(124.2 mg, 0.10mmol) of CH2Cl2Et was added to a solution of/i-PrOH/THF (4/4/4mL)4Aqueous solution of NOH (35%, 49.4mL, 0.12 mmol). After the addition, the mixture was stirred at the same temperature for 5 hours. The mixture was neutralized with 1N HCl solution and extracted with diethyl ether. The organic layer was washed with brine, over Na2SO4Dried and evaporated. Using hexane/Et2The residue was passed through a silica gel column using O (2: 1) as eluent. Evaporation of volatiles gave pure [ ((C) in 89% yield6H5CH＝CH)SiO1.5)6((C6H5CH＝CH)(OH)SiO1.0)2]∑8(112.4 mg, 0.09mmol) of a white solid.1H NMR(CDCl3)δ5.83(br s，2H)，6.31-6.45(m，16H)，7.21-7.59(m，40H)。13C NMR(CDCl3)δ117.41，117.76，117.96，126.90，128.43，128.50，128.53，128.75，128.83，128.90，137.17，137.23，137.29，149.11，149.15，149.21。29Si NMR(CDCl3)δ-78.05，-77.05，-68.66。
From [ ((C)6H5CH2CH2)SiO1.5)8]∑8Preparation of [ ((C)6H5CH2CH2)SiO1.5)6((C6H5CH2CH2)(OH)SiO1.0)2]∑8: at-35 ℃ to [ ((C)6H5CH2CH2)SiO1.5)8]∑8(251.6 mg, 0.20mmol) of CH2Cl2Et was added to a solution of/i-PrOH/THF (5/5/5mL)4Aqueous solution of NOH (35%, 247.0mg, 0.60 mmol). After the addition, the mixture was stirred at the same temperature for 4 hours. The mixture was neutralized with 1N HCl solution and extracted with diethyl ether. The organic layer was washed with brine, over Na2SO4Dried and evaporated. Using hexane/Et2The residue was passed through a silica gel column using O (2: 1) as eluent. Evaporation of volatiles gave pure [ ((C) in 88% yield6H5CH2CH2)SiO1.5)6((C6H5CH2CH2)(OH)SiO1.0)2]∑8(225.3 mg, 0.18mmol) of a colorless oil.1H NMR(CDCl3)δ1.11-1.25(m，16H)，2.86-2.98(m，16H)，5.24(br s，2H)，7.25-7.47(m，40H)。13C NMR(CDCl3)δ13.56，14.19，14.30，28.90，28.95，28.98，125.74，125.84，127.71，127.83，128.29，128.33，128.42，143.67，143.75，143.78。29Si NMR(CDCl3)δ-67.75，-65.99，-58.35。
From [ ((CH)3C6H5)SiO1.5)8]∑8Preparation of [ ((CH)3C6H4SiO1.5)6((CH3C6H5)(OH)SiO1.0)2)∑8: using and for [ ((C)6H5CH2CH2SiO1.5)6((C6H5CH2CH2)(OH)SiO1.0)2)∑8By a process similar to that of (A) [ ((CH))3C6H4SiO1.5)6((CH3C6H5)(OH)SiO1.0)2)∑8。1H NMR(CDCl3)δ2.36(s，6H)，2.41(s，12H)，2.42(s，6H)，6.03(br s，2H)，7.08(d，3J＝7.5Hz，4H)，7.16(d，3J＝7.5Hz，8H)，7.24(d，3J＝7.5Hz，4H)，7.56(d，3J＝7.5Hz，4H)，7.62(d，3J＝7.5Hz，8H)，7.72(d，3J＝7.5Hz，4H)。13C NMR(CDCl3)δ21.50，21.53，21.56，127.10，127.29，127.65，128.41，128.48，128.53，134.25，140.26，140.31，140.56。29Si NMR(CDCl3)δ-78.22，-76.86，-69.05。MS(ESI，100％ MeOH)：m/z C56H58O13Si8Calculated Na (100%): 1185.2. measured value: 1185.4. c56H58O13Si8H (20%): 1163.2. measured value: 1163.5. c56H58O13Si8K (20%): 1201.2. measured value: 1201.3.
from [ (C-C)6H11SiO1.5)8]∑8Preparation of [ (C-C)6H11SiO1.5)6((c-C6H11)(OH)SiO1.0)2]∑8：
At room temperature to [ (C-C)6H11SiO1.5)8]∑8Me was added to a solution of (5.41 g, 5.00mmol) in THF (100mL)4NOH (25%, 1.90mL, 4.50mmol) in methanol. After the addition, the resulting mixture was stirred at the same temperature for 1 hour. The mixture was neutralized with 1N HCl solution and extracted with diethyl ether. The organic layer was washed with brine over MgSO4Dried and evaporated. With hexane and CH2Cl2The residue was passed through a silica gel column as eluent. Evaporation of volatiles gave pure [ (C-C) in 84% yield6H11SiO1.5)6((c-C6H11)(OH)SiO1.0)2]∑8(4.60 g, 4.18mmol) of a white solid.1H NMR(500MHz，CDCl3，25℃)：δ4.30(br s，SiOH，2H)，1.76(br m’s，40H)，1.23(br m’s，40H)，0.74(br m’s，8H)。13C{1H}NMR(125MHz，CDCl3，25℃)：δ27.55，27.48，26.88，26.79，26.58，26.53(CH2)，23.79，23.69，23.07(4∶2∶2 for CH)，29Si{1H}NMR(99MHz，CDCl3，25℃)：δ-59.91，-67.60，-69.85(2∶2∶4)。IR(25℃，KBr，cm-1): 2916, 2838, 1447, 1197, 1109.MS (70eV, 200 ℃, relative intensity): m/e 1015([ M- (C)6H11)]+,100). For C48H90O13Si8Analytical calculation of (d) (found): c, 52.42(52.32), H, 8.25 (8.68).
At room temperature [ ((CH)3)2CHCH2)SiO1.5]8]∑8And NEt4And (4) reaction of OH. To [ ((CH)3)2CHCH2)SiO1.5]8]∑8(0.20 g, 0.23mmol) in THF (5mL) was added 35% NEt4Solution of OH in water (0.11mL, 0.25 mmol). The solution was stirred at room temperature for 1 hour and then neutralized with aqueous HCl. THF was removed under vacuum to afford a white oil which was dissolved in Et2In O, over anhydrous MgSO4Dried and filtered. SolutionEvaporation of the agent gave a milky white oil with a mass yield of 85% (by weight)29Si NMR Spectroscopy and ESI MS) unreacted [ ((CH)3)2CHCH2)SiO1.5]8]∑8(9％)，[((CH3)2CHCH2)SiO1.5]4((CH3)2CHCH2)(OH)SiO1.0)3]∑7(29％)，[((CH3)2CHCH2)SiO1.5]6((CH3)2CHCH2)(OH)SiO1.0)2]∑8(13%) and [ ((CH)3)2CHCH2)SiO1.5)4((CH3)2CHCH2)(OH)SiO1.0)4]∑8(34%). For [ ((CH)3)2CHCH2)SiO1.5]8]∑82Selected characterization data:29Si{1H}NMR(99.3MHz，C6D6，25℃)δ-67.6；MS(ESI，100％
MeOH)：m/e 873(M+H+5%). For [ ((CH)3)2CHCH2)SiO1.5]4((CH3)2CHCH2)(OH)SiO1.0)3]∑7：29Si{1H}NMR(99.3MHz，C6D6，25℃)δ-58.9，-67.1，-68.5(3∶1∶3)；MS(ESI，100％ MeOH)：m/e：3791(M+H-2%) and 813(M + Na)+5%). For [ ((CH)3)2CHCH2)SiO1.5]6((CH3)2CHCH2)(OH)SiO1.0)2]∑8：29Si{1H}NMR(99.3MHz，C6D6，25℃)δ-59.6，-66.8，-68.7(1∶1∶2)；MS(ESI，100％ MeOH)：m/e 891(M+H+11%) and 913(M + Na)+5%). For [ ((CH)3)2CHCH2)SiO1.5)4((CH3)2CHCH2)(OH)SiO1.0)4]∑8：29Si{1H}NMR(99.3MHz，C6D6，25℃)δ(-58.4，-56.6，-66.5，-68.3，1∶1∶1∶1)；MS(ESI，100％ MeOH)：m/e 909(M+H+15%) and 931(M + Na)+，100％)。
From [ ((CH)3)2CHCH2)SiO1.5]∑8Preparation of [ ((CH)3)2CHCH2)SiO1.5)4((CH3)2CHCH2)(OH)SiO1.0]3]∑7：[((CH3)2CHCH2)SiO1.5)]∑8(400 mg, 0.46mmol) and 35% aqueous NEt4A solution of OH (0.2mL, 0.49mmol) was refluxed in THF (5mL) for 4 hours and then neutralized with dilute aqueous HCl. Evaporation of volatiles afforded a white resin which was dissolved in Et2In O and over anhydrous MgSO4And drying. Filtration and evaporation of the solvent afforded crude [ ((CH) in 44% yield3)2CHCH2)SiO1.5)4((CH3)2CHCH2)(OH)SiO1.5]3]∑7White resinous material of (2). Colorless crystals were obtained by recrystallization from acetonitrile/toluene. Selected characterization data: for [ ((CH)3)2CHCH2)SiO1.5)4((CH3)2CHCH2)(OH)SiO1.0)3]∑7：29Si{1H}NMR(99.3MHz，C6D6，25℃)δ-58.5，-66.9，-68.3(s，3∶1∶3)。1H NMR(500MHz，C6D6，25℃)δ2.21(m，7H，-CH-)；1.24(d，J＝6.6Hz，18H，CH3)；1.21(d，J＝6.6Hz，18H，CH3)；1.17(d，J＝6.6Hz，6H，CH3)；0.97(d，J＝7.1Hz，6H，CH2)；0.95(d，J＝7.1Hz，6H，CH2)；0.92(d，J＝7.0Hz，2H，CH2)。13C{1H}NMR(125.8MHz，C6D6，25℃)δ＝25.7(s，CH3)；25.6(s，CH3)；25.5(s，CH3)；24.1(s，CH2)；24.05(s，CH2)；24.0(s，CH2)；23.4(s，CH)；23.0(s，CH)；22.6(s，CH)。MS(ESI，100％ MeOH)：m/e 791.16(M+H+，80％)；813.08(M+Na+100%). Single crystal X-ray diffraction studies can also be performed.
From [ ((CH)3)2CHCH2)SiO1.5)8]∑8Preparation of [ ((CH)3)2CHCH2)SiO1.5]6((CH3)2CHCH2)(OH)SiO1.0)2]∑8: the reactor was charged with 2126g (2.438mol) [ ((CH)3)2CHCH2)SiO1.5)8]∑8And 20L of THF. Mixing Me with water4A basic solution of NOH (48mL, 25 wt% in MeOH) and THF (4L) was cooled to 0 ℃ and added slowly (3.5 hours) to the reaction, followed by stirring for 1 hour. The product formation was monitored by HPLC and the reaction was completed by adding 320mL concentrated HCl at 0 ℃ and 700mL H2O quenching it. The resulting solution was evaporated to give a waxy solid which was washed with water to pH7 and recrystallized from acetone and acetonitrile to give 1525g (70% yield) of 98% pure product.1H NMR(CDCl3)：3.99(2H，2 x OH，bs)；1.85(8H，8 x CH，m)；0.95(48H，16 x CH3，m)；0.60(16H，8 x CH2，m)。{1H}13C NMR(CDCl3): 25.80; 25.75; 25.65; 23.99; 23.93; 23.86 of the total weight of the steel; 23.07; 22.46. it should be noted that the above process is applicable to both continuous and batch production methods to produce the desired product in high yield and purity.
From [ ((CH)3)2CH2CHCH3CH2)SiO1.5]∑nn-8, 10 preparation of [ ((CH)3)2CH2CHCH3CH2)SiO1.5]6((CH3)2CHCH2)(OH)SiO1.0)2]∑8: the reactor was charged with 128.0 g (96.82mmol) [ ((CH)3)2CH2CHCH3CH2)SiO1.5]∑nAnd 2080mL of THF. 48mL (25 wt% in MeOH) Me4The basic solution of NOH was cooled to 0 ℃, added to the reaction mixture over 45 minutes and stirred for an additional 1.5 hours. The progress of the reaction was monitored by HPLC and was quenched by the addition of HCl (150mL, 1N) and hexane (500mL) over a 1 hour period with rapid stirring. The top layer was removed and evaporated to give 125.7 g (97%) of a colorless liquid product.1H NMR(CDCl3)：1.83(9.3，bm)；1.27(9.8，bm)；1.15(10，bm)；1.00(23，m)；0.89(64，s)；0.85(7.7，s)；0.73(8.1，bm)；0.58(8.0，bm)。{1H}13C NMR(CDCl3)：54.50；54.37；31.19；30.22；29.48；25.59；25.49；25.30；25.22；25.00；24.36；24.29。
From [ ((CH)3)2CH2CHCH3CH2)SiO1.5]∑nn-8, 10 preparation of [ ((CH)3)2CH2CHCH3CH2)SiO1.5]4((CH3)2CHCH2)(OH)SiO1.0]3]∑7: use of LiOH in acetone for [ ((CH) as described above3)2CH2CHCH3CH2)SiO1.5]6((CH3)2CHCH2)(OH)SiO1.0)2]∑8By a similar procedure, an oily trimethylsilanol product was obtained which contained 95% of two trimethylsilanols [ ((CH)3)2CH2CHCH3CH2)SiO1.5)4((CH3)2CHCH2)(OH)SiO1.0)3]∑7And [ ((CH)3)2CH2CHCH3CH2)SiO1.5)6((CH3)2CHCH2)(OH)SiO1.0)3]∑9。1H NMR(500MHz，CDCl3)：δ(ppm)0.562(m，1H)，0.755(m，1H)，0.908(s，9H)，1.002(m，3H)，1.137(m，1H)，1.303(m，1H)，1.831(m，1H)，6.240(br，3H)；13C NMR(125MHz，CDCl3)：δ(ppm)24.06，24.51，24.86，25.44，25.59，25.65，25.89，29.65，29.90，30.64，30.68，31.59，32.02，54.28，54.77；29Si NMR(99.4MHz，CDCl3)：δ(ppm)-68.66，-68.43，-67.54，-67.32，-58.75，-57.99。EIMS：m/e 1382(22％，M+(T9)-iOct-H2O)，1052(100％，M+(T7)-iOct-H2O)。
From [ ((CH)3CH2)SiO1.5)]∑8Preparation: [ ((CH)3CH2)SiO1.5)4(CH3CH2)(OH)SiO1.0)3]Σ7Mix 35% NEt4A solution of OH in water (0.2mL, 0.49mmol) was added to [ ((CH)3CH2)SiO1.5)]∑8(0.41 g, 0.46mmol) in THF (5 mL). The solution was refluxed for 7 hours and then neutralized with aqueous HCl. THF was removed in vacuo to afford a colorless oil, which was dissolved in Et2In O and over anhydrous MgSO4And drying. The solvent was evaporated in vacuo and crystallized from MeOH to give [ ((CH)3CH2)SiO1.5)4((CH3CH2)(OH)SiO1.0)3]∑7White solid of (2). Selected characterization data:29Si{1H}NMR(99.3MHz，C6D6，25℃)δ＝-56.4，-64.8，65.9(3∶1∶3MS(ESI，100％ MeOH)：m/e：595(M+H+，100％)；617(M+Na+60％)。
from [ ((CH)3)SiO1.5)8]∑8Preparation of [ ((CH)3)SiO1.5)4((CH3)(OH)SiO1.0)3]∑7: at room temperature to [ ((CH)3)SiO1.5)8]∑8(8.5 g, 15.83mmol) in THF (350mL) was addedEt4Aqueous solution of NOH (35%, 6.51mL, 15.83 mmol). After the addition, the resulting mixture was stirred at the same temperature for 20 hours. The mixture was neutralized with 1N HCl solution and extracted with diethyl ether. The organic layer was washed with brine over MgSO4And drying. The volatiles were evaporated to give a white oil-like solid. With mixed solvent (MeOH/H)2O2.5/1) the white solid was recrystallized providing [ ((CH) in 17% yield3)SiO1.5)4((CH3)(OH)SiO1.0)3]∑7(1.35g, 272mmol) of white powder.1H NMR(CDCl3)δ0.13(s，9H)，0.14(s，3H)，0.15(s，9H)，6.11(s，3H)。13C NMR(CDCl3)δ-4.50，-4.35。29Si NMR(CDCl3) Delta-65.70, -65.16, -55.84. For C7H24O12Si7The calculated value of (a): c, 16.92; h, 4.87. Measured value: c, 17.16; h, 4.89. MS (ESI, 100% MeOH): m/e: 496.96(M + H)+，100％)；518.86(M+Na+，75％)。
From [ ((C-C)6H11)SiO1.5)7((H)SiO1.0)1]∑8Preparation of [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7: is [ C-C ]6H11)SiO1.5)7((H)SiO1.0)1]∑8(460 mg, 0.46mmol) in water and 35% aqueous NEt4OH (0.2mL, 0.49mmol) was refluxed in THF (5mL) for 5 hours and then neutralized with dilute aqueous HCl. Evaporation of volatiles afforded a white solid which was dissolved in Et2In O and over anhydrous MgSO4And drying. Filtration and evaporation of the solvent provided a white microcrystalline solid in high yield. Of the product mixture29Si NMR spectroscopy analysis showed that the main product was [ ((C-C)6H11)SiO1.5)4((c-C6H11)(OH)SiO1.0)3]∑7(ii) a And alsoIn small amounts [ ((C-C)6H11)SiO1.5)]∑8。
From [ ((C-C)5H9)SiO1.5)]∑8Preparation of [ ((C-C)5H9)SiO1.5)4((c-C5H9)(OH)SiO1.0)2]∑8: into a 12-L reactor equipped with a mechanical stirrer, a feed pump and a drying tube were charged 443.4 g (457.2mmol) [ ((C-C)5H9)SiO1.5]∑8And 6.0L THF. Preparation of Me4A basic solution of NOH (25 wt% in MeOH, 212mL) and THF (1.4L) was added slowly to the reaction mixture, and the mixture was stirred for 3 hours. While the reaction was complete, the reaction mixture was quenched with 65mL of concentrated HCl cooled to 0 ℃ and 500mL of water in a mechanically stirred quench tank. Evaporating and filtering the resulting mixture to obtain [ ((C-C)5H9)SiO1.5)4((c-C5H9)(OH)SiO1.0)2]∑8364 g (81%) of a 98% pure white solid were thus prepared.1H NMR(CDCl3)：4.63(2H，2 x OH，bs)；1.72(16H，8 x CH2，m)；1.56(16H，8 xCH2，m)；1.46(32H，16 x CH2，m)；0.94(8H，8 x CH，m)。{1H}13C NMR(CDCl3): 27.41; 27.39; 27.36; 27.20; 27.06; 27.02; 27.00; 26.99; 22.88; 22.66; 22.16. variations of this manufacturing process can also be used to design continuous and batch processing methods.
Although the invention has been described above in terms of specific embodiments, it is anticipated that alterations and permutations thereof will no doubt become apparent to those skilled in the art. It is therefore contemplated that the following claims be interpreted to cover all such modifications and changes as fall within the true spirit and scope of the invention.
Claims (28)
1. A method of converting a polymerized silsesquioxane to polyhedral oligomeric silsesquioxane fragments comprising:
mixing a base with the polymeric silsesquioxane in a solvent to produce a basic reaction mixture, the base reacting with the polymeric silsesquioxane to produce polyhedral oligomeric silsesquioxane fragments,
wherein the polymeric silsesquioxane has the formula [ RSiO1.5]∞The polyhedral oligomeric silsesquioxane segment has the general formula [ (RSiO)1.5)m(RXSiO1.0)n]Wherein R representsDenotes an organic substituent, X denotes a substituent selected from the group consisting of inorganic substituents or alkoxides, acetates, peroxides, amines and isocyanates, ∞ denotes the degree of polymerization and is a number greater than or equal to 1, m and n represent the stoichiometry of the general formula,
wherein the base is selected from the group consisting of hydroxides, organic alkoxides, carboxylates, amides, carbonamides, carbanions, carbonates, sulfates, phosphates, hydrogenphosphates, phosphonium ylides, nitrates, borates, cyanates, fluorides, hypochlorites, silicates, stannates, basic metal oxides, amines R3N and amine oxide R3NO and an organometallic compound, the basic metal oxide being selected from Al2O3CaO and ZnO, the organometallic compound being selected from RLi, R2Zn、R2Mg, wherein R represents one or more organic substituents which are not necessarily the same, wherein the concentration of base is from 1 to 10 equivalents per mole of silicon present in the reaction mixture, and wherein the base cleaves at least one silicon-oxygen-silicon (Si-O-Si) bond in the polymerized silsesquioxane to facilitate conversion of the polymerized silsesquioxane into polyhedral oligomeric silsesquioxane fragments;
mixing together the base and the polymerized silsesquioxane by stirring the reaction mixture;
heating the reaction mixture to reflux;
cooling the reaction mixture to room temperature; and
isolating the polyhedral oligomeric silsesquioxane fragments wherein the polyhedral oligomeric silsesquioxane fragments are isolated by distillation, filtration, evaporation, decantation, crystallization, reduced pressure, or extraction or combinations thereof.
2. The method of claim 1, further comprising the step of purifying the isolated polyhedral oligomeric silsesquioxane fragments by washing with water.
3. The process of claim 1, wherein a mixture of different bases is used.
4. The method of claim 1, further comprising mixing the base and the polymerized silsesquioxane with a co-agent in a solvent.
5. The process of claim 4, wherein the co-reagent is selected from the group consisting of general Grignard reagents RMgX, alkali metal halides, zinc compounds selected from the group consisting of ZnI2、ZnBr2、ZnCl2And ZnF2An aluminum compound selected from Al2H6、LiAlH4、AlI3、AlBr3、AlCl3And AlF3And a boron compound selected from RB (OH)2、BI3、BBr3、BCl3And BF3Wherein R represents an organic substituent and X represents an inorganic substituent.
6. A method of converting a polyhedral oligomeric silsesquioxane fragment to a polyhedral oligomeric silsesquioxane compound comprising:
mixing a base with the polyhedral oligomeric silsesquioxane fragments in a solvent to prepare a basic reaction mixture, reacting the base with the polyhedral oligomeric silsesquioxane fragments to prepare a polyhedral oligomeric silsesquioxane compound,
wherein the polyhedral oligomeric silsesquioxane moiety has the formula (RSiO)1.5)m(RXSiO1.0)nThe polyhedral oligomeric silsesquioxane compound is selected from the group consisting of formula [ (RSiO)1.5)n]∑#Shown as homofragment nanostructured chemical compound, formula [ (RSiO)1.5)m(R’SiO1.5)n]∑#Heterosegment nanostructured Compounds of formula [ (RSiO)1.5)m(RXSiO1.0)n]∑#Functionalized homosegmented nanostructured Compounds and the formula [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#Functionalized heterosegment nanostructured compounds and compounds of formula (RSiO)1.5)m(RXSiO1.0)nAn extended polyhedral oligomeric silsesquioxane fragment is shown wherein R and R' each represent an organic substitutionX represents a substituent selected from the group consisting of inorganic substituents or alkoxides, acetates, peroxides, amines and isocyanates, m, n and p represent the stoichiometry of the formula, Σ represents the nanostructure, and # represents the number of silicon atoms contained within the nanostructure,
wherein the base is selected from the group consisting of hydroxides, organic alkoxides, carboxylates, amides, carbonamides, carbanions, carbonates, sulfates, phosphates, hydrogenphosphates, phosphonium ylides, nitrates, borates, cyanates, fluorides, hypochlorites, silicates, stannates, basic metal oxides, amines R3N and amine oxide R3NO and an organometallic compound, the basic metal oxide being selected from Al2O3CaO and ZnO, the organometallic compound being selected from RLi, R2Zn、R2Mg, wherein R represents one or more organic substituents which are not necessarily the same, wherein the concentration of base is from 1 to 10 equivalents per mole of silicon present in the reaction mixture, and wherein the base cleaves at least one silicon-oxygen-silicon (Si-O-Si) bond in the polyhedral oligomeric silsesquioxane segment to facilitate conversion of the polyhedral oligomeric silsesquioxane segment to a polyhedral oligomeric silsesquioxane compound;
mixing together the base and the polyhedral oligomeric silsesquioxane fragments by stirring the reaction mixture;
heating the reaction mixture to reflux;
cooling the reaction mixture to room temperature; and
isolating the polyhedral oligomeric silsesquioxane compound, wherein the polyhedral oligomeric silsesquioxane compound is isolated by distillation, filtration, evaporation, decantation, crystallization, reduced pressure, or extraction, or a combination thereof.
7. The method of claim 6, further comprising the step of purifying the isolated polyhedral oligomeric silsesquioxane compound by washing with water.
8. The process of claim 6, wherein the concentration of hydroxide base is from 1 to 2 equivalents per mole of silicon present in the reaction mixture.
9. The process of claim 6, wherein a mixture of different bases is used.
10. The method of claim 6, further comprising mixing the base and the polyhedral oligomeric silsesquioxane fragment with a co-reagent in a solvent.
11. The process of claim 10 wherein the co-reagent is selected from the group consisting of general Grignard reagents RMgX, alkali metal halides, zinc compounds selected from the group consisting of ZnI2、ZnBr2、ZnCl2And ZnF2An aluminum compound selected from Al2H6、LiAlH4、AlI3、AIBr3、AlCl3And AlF3And a boron compound selected from RB (OH)2、BI3、BBr3、BCl3And BF3Wherein R represents an organic substituent and X represents an inorganic substituent.
11. The method of claim 6, wherein the polyhedral oligomeric silsesquioxane compound is [ (RSiO)1.5)4(RXSiO1.0)3]∑7。
12. A method of converting a first functionalized polyhedral oligomeric silsesquioxane nanostructure compound to a second functionalized polyhedral oligomeric silsesquioxane nanostructure compound different from said first functionalized polyhedral oligomeric silsesquioxane nanostructure compound comprising:
mixing a base with a first functionalized polyhedral oligomeric silsesquioxane nanostructured chemical in a solvent to produce a basic reaction mixture, the base reacting with the first functionalized polyhedral oligomeric silsesquioxane nanostructured chemical to produce a second polyhedral oligomeric silsesquioxane nanostructured chemical,
wherein each of the first and second polyhedral oligomeric silsesquioxane nanostructured chemicalsIs selected from the group consisting of formula [ (RSiO)1.5)n]∑#Shown as homofragment nanostructured chemical compound, formula [ (RSiO)1.5)m(R’SiO1.5)n]∑#Heterosegment nanostructured Compounds of formula [ (RSiO)1.5)m(RXSiO1.0)n]∑#Functionalized homosegmented nanostructured Compounds and the formula [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#A functionalized heterosegment nanostructured chemical shown, wherein R and R' each represent an organic substituent, X represents a substituent selected from the group consisting of an inorganic substituent or alkoxide, acetate, peroxide, amine, and isocyanate, m, n, and p represent stoichiometric compositions, Σ represents a nanostructure, and # represents the number of silicon atoms contained within the nanostructure;
wherein the base is selected from the group consisting of hydroxides, organic alkoxides, carboxylates, amides, carbonamides, carbanions, carbonates, sulfates, phosphates, hydrogenphosphates, phosphonium ylides, nitrates, borates, cyanates, fluorides, hypochlorites, silicates, stannates, basic metal oxides, amines R3N and amine oxide R3NO and an organometallic compound, the basic metal oxide being selected from Al2O3CaO and ZnO, the organometallic compound being selected from RLi, R2Zn、R2Mg, wherein R represents one or more organic substituents which are not necessarily the same, wherein the concentration of base is from 1 to 10 equivalents per mole of silicon present in the reaction mixture, and wherein the base cleaves at least one silicon-oxygen-silicon (Si-O-Si) bond in the first functionalized polyhedral oligomeric silsesquioxane nanostructured compound to facilitate conversion of the first functionalized polyhedral oligomeric silsesquioxane nanostructured compound into the second functionalized polyhedral oligomeric silsesquioxane nanostructured compound;
mixing together a base and a first functionalized polyhedral oligomeric silsesquioxane nanostructured chemical by agitating the reaction mixture;
heating the reaction mixture to reflux;
cooling the reaction mixture to room temperature; and
isolating a second functionalized polyhedral oligomeric silsesquioxane nanostructured chemical by distillation, filtration, evaporation, decantation, crystallization, depressurization or extraction or a combination thereof.
13. The method of claim 12, wherein the second functionalized polyhedral oligomeric silsesquioxane nanostructured chemical compound has more substituents X than the first functionalized polyhedral oligomeric silsesquioxane nanostructured chemical compound, but both functionalized polyhedral oligomeric silsesquioxane nanostructured chemical compounds have the same number of silicon atoms.
14. The method of claim 12, further comprising the step of purifying the isolated polyhedral oligomeric silsesquioxane nanostructured chemical by washing with water.
15. The method of claim 12, wherein a mixture of different bases is used.
16. The method of claim 12, further comprising mixing a base and the first functionalized polyhedral oligomeric silsesquioxane nanostructure compound with a co-reagent in a solvent.
17. The process of claim 16 wherein the co-reagent is selected from the group consisting of general Grignard reagents RMgX, alkali metal halides, zinc compounds selected from the group consisting of ZnI2、ZnBr2、ZnCl2And ZnF2An aluminum compound selected from Al2H6、LiAlH4、AlI3、AlBr3、AlCl3And AlF3And a boron compound selected from RB (OH)2、BI3、BBr3、BCl3And BF3Wherein R represents an organic substituent and X represents an inorganic substituent。
18. The method of claim 12, wherein the second functionalized polyhedral oligomeric silsesquioxane nanostructure compound is [ (RSiO)1.5)4(RXSiO1.0)3]∑7。
19. A method of converting a non-functionalized polyhedral oligomeric silsesquioxane nanostructured chemical into a functionalized polyhedral oligomeric silsesquioxane nanostructured chemical comprising:
mixing a base with a non-functionalized polyhedral oligomeric silsesquioxane nanostructured compound in a solvent to prepare a basic reaction mixture, the base reacting with the non-functionalized polyhedral oligomeric silsesquioxane nanostructured compound to prepare a functionalized polyhedral oligomeric silsesquioxane nanostructured compound,
wherein the non-functionalized polyhedral oligomeric silsesquioxane nanostructured compound is selected from the group consisting of formula [ (RSiO)1.5)n]∑#Shown are homosegmented nanostructured chemicals and the formula [ (RSiO)1.5)m(R’SiO1.5)n]∑#The heterosegmented nanostructured chemical compounds shown, and the functionalized polyhedral oligomeric silsesquioxane nanostructured chemical compound is selected from the group consisting of formula [ (RSiO)1.5)m(RXSiO1.0)n]∑#Functionalized homosegmented nanostructured Compounds and the formula [ (RSiO)1.5)m(R’SiO1.5)n(RXSiO1.0)p]∑#A functionalized heterosegment nanostructured chemical shown wherein R and R' each represent an organic substituent, X represents a substituent selected from the group consisting of inorganic substituents or alkoxides, acetates, peroxides, amines and isocyanates, m, n and p represent the stoichiometry of the general formula, Σ represents the nanostructure, and # represents the number of silicon atoms contained within the nanostructure,
wherein the base is selected from the group consisting of hydroxides, organic alkoxides, carboxylates, amides, carboxamides, carbanions, carbonates, sulfates, phosphates, hydrogenphosphates, phosphonium ylides, nitrates, borates, cyanate estersFluorides, hypochlorites, silicates, stannates, basic metal oxides, amines R3N and amine oxide R3NO and an organometallic compound, the basic metal oxide being selected from Al2O3CaO and ZnO, the organometallic compound being selected from RLi, R2Zn、R2Mg, wherein R represents one or more organic substituents which are not necessarily the same, wherein the concentration of base is from 1 to 10 equivalents per mole of silicon present in the reaction mixture, and wherein the base cleaves at least one silicon-oxygen-silicon (Si-O-Si) bond in the non-functionalized polyhedral oligomeric silsesquioxane nanostructured compound to facilitate conversion of the polymerized silsesquioxane into a functionalized polyhedral oligomeric silsesquioxane nanostructured compound;
mixing together the base and the non-functionalized polyhedral oligomeric silsesquioxane nanostructured chemical by stirring the reaction mixture;
heating the reaction mixture to reflux;
cooling the reaction mixture to room temperature; and
isolating the functionalized polyhedral oligomeric silsesquioxane nanostructured chemical by distillation, filtration, evaporation, decantation, crystallization, reduction in pressure, or extraction or combinations thereof.
20. The method of claim 19, further comprising the step of purifying the isolated functionalized polyhedral oligomeric silsesquioxane nanostructured chemical by washing with water.
21. The process of claim 19 wherein the base is a hydroxide and the concentration of the hydroxide base is from 1 to 10 equivalents per mole of silicon present in the reaction mixture.
22. The process of claim 21, wherein the concentration of hydroxide base is from 2 to 5 equivalents per mole of silicon present in the reaction mixture.
23. The method of claim 19, wherein a mixture of different bases is used.
24. The method of claim 19, further comprising mixing a base and the unfunctionalized polyhedral oligomeric silsesquioxane nanostructure compound with a co-reagent in a solvent.
25. The process of claim 24 wherein the co-reagent is selected from the group consisting of general Grignard reagents RMgX, alkali metal halides, zinc compounds selected from ZnI2、ZnBr2、ZnCl2And ZnF2An aluminum compound selected from Al2H6、LiAlH4、AlI3、AlBr3、AlCl3And AlF3And a boron compound selected from RB (OH)2、BI3、BBr3、BCl3And BF3Wherein R represents an organic substituent and X represents an inorganic substituent.
26. The method of claim 19, wherein the functionalized polyhedral oligomeric silsesquioxane nanostructured chemical is [ (RSiO)1.5)4(RXSiO1.0)3]∑7。
27. A method of converting a polymerized silsesquioxane to a polyhedral oligomeric silsesquioxane nanostructured chemical comprising:
mixing a base with the polymeric silsesquioxane in a solvent to produce a basic reaction mixture, the base reacting with the polymeric silsesquioxane to produce a polyhedral oligomeric silsesquioxane nanostructured compound,
wherein the polymeric silsesquioxane has the general formula [ RSiO1.5]∞And the polyhedral oligomeric silsesquioxane nanostructured chemical compound is [ (RSiO)1.5)4(RXSiO1.0)3]∑7Wherein R represents an organic substituent and X represents a substituent selected from the group consisting of an inorganic substituent or an alkoxide, acetate, peroxide, amine and isoalkoxideA substituent of cyanate, and ∞ represents the degree of polymerization and is a number greater than or equal to 1,
wherein the base is selected from the group consisting of hydroxides, organic alkoxides, carboxylates, amides, carbonamides, carbanions, carbonates, sulfates, phosphates, hydrogenphosphates, phosphonium ylides, nitrates, borates, cyanates, fluorides, hypochlorites, silicates, stannates, basic metal oxides, amines R3N and amine oxide R3NO and an organometallic compound, the basic metal oxide being selected from Al2O3CaO and ZnO, the organometallic compound being selected from RLi, R2Zn、R2Mg, wherein R represents one or more organic substituents which are not necessarily the same, wherein the concentration of base is from 1 to 10 equivalents per mole of silicon present in the reaction mixture, and wherein the base cleaves at least one silicon-oxygen-silicon (Si-O-Si) bond in the polymerized silsesquioxane to facilitate conversion of the polymerized silsesquioxane to polyhedral oligomeric silsesquioxane nanostructured chemical;
mixing together the base and the polymerized silsesquioxane by stirring the reaction mixture;
heating the reaction mixture to reflux;
cooling the reaction mixture to room temperature; and
isolating the polyhedral oligomeric silsesquioxane nanostructured chemical wherein the polyhedral oligomeric silsesquioxane nanostructured chemical is isolated by distillation, filtration, evaporation, decantation, crystallization, reduced pressure, or extraction or combinations thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14743599P | 1999-08-04 | 1999-08-04 | |
| US60/147,435 | 1999-08-04 | ||
| PCT/US2000/021455 WO2001010871A1 (en) | 1999-08-04 | 2000-08-03 | Process for the formation of polyhedral oligomeric silsesquioxanes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1050692A1 HK1050692A1 (en) | 2003-07-04 |
| HK1050692B true HK1050692B (en) | 2006-03-03 |
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