TWI433871B - Process for assembly of poss monomers - Google Patents

Description

Method for assembling a polyhedral siloxane oligomer (POSS) monomer Cross-references between related applications and patents

Priority is claimed on U.S. Provisional Patent Application Serial No. 60/659,722, which is incorporated herein by reference.

Field of invention

The present invention generally relates to a process for enhancing the properties of functionalized polyhedral siloxane oligomers (POSS) monomers which are combined to form polymerizable and biological products.

Background of the invention

The best examples of nanostructured chemicals are those based on Polyhedral Oligomeric Silsesquioxanes (POSS) and Polyhedral Oligomeric Silicates (POS). The POSS system contains a mixed (i.e., organic-inorganic) composition in which the inner cage-like skeleton is mainly composed of inorganic helium-oxygen bonds. The outer structure of the nanostructure is covered by both reactive and non-reactive organic functionalities (R), which ensure compatibility and susceptibility between the nanostructure and the organic monomer and polymer. (tailorability). The characteristics and characteristics of these and other nanostructured chemistries are discussed in detail in U.S. Patent No. 5,412,053, issued to U.S. Pat.

Current engineering practices produce high yielding functionalized POSS molecules, but some microelectronic, medical, and biological applications require higher purity or require chemical functional groups that cannot be readily or economically produced using conventional techniques. The prior art method comprises the use of a hydroxide base, an anion salt and a protonic acid catalyst for the assembly of a POSS cage and its functionalization (see U.S. Patent Application Serial Nos. 09/631,892 and 10/186,318, and U.S. Patent No. 6,770,724, 6,660,823, 6,596,821 and 3,390,163). While these means are generally known to be effective, the limitation is that both protonic acid and oxyhydrogen base can catalyze the self-condensation of POSS individual cages into resin-containing oligomeric POSS cages (Fig. 1). Such resins are undesirably in microelectronic, biological or medical applications due to their inaccurate molecular structure. Furthermore, the dispersion of the POSS molecules and their compatibility with the polymer are thermodynamically governed by the free energy of the mixing equation (ΔG = ΔH - T ΔS). The nature of the R group and the ability of the reactive groups on the POSS cage to react or interact with the polymer and surface greatly contribute to the favorable enthalpy (ΔH) term, while the size of the cage is monoscopic and When the corresponding distribution of oligomers is 1.0, the entropy (ΔS) term of POSS is highly advantageous.

Therefore, there is a need for improvement in the prior art methods of assembling and functionalizing monomers in POSS cages. An improved process for producing a higher purity and molecularly accurate POSS system is described.

Summary of invention

The present invention provides an improved synthesis process for polyhedral siloxane oligomers which rapidly produces high yield, low resin content and solvent free monomeric products which are suitable for use in polymerization, grafting And alloying applications. The synthesis process using phosphorus-nitrogen-based ultra base with the formula R Silane coupling agent ¹ SiX ₃ reacted to form POSS cages, such POSS cage train is of the formula types _{^{[(R 1 SiO 1. 5}} ) 7 (HOSiO 1. 5 ) ₁ ] _{Σ 8} , [(R ¹ SiO _{1 . 5} ) ₆ (R ¹ HOSiO ₁ ) ₂ ] _{Σ 8} , [(R ¹ SiO _{1 . 5} ) ₂ (R ¹ HOSiO ₁ ) ₄ ] _{Σ 6} , [( The sterol of R ¹ SiO _{1 . 5} ) ₄ (R ¹ HOSiO ₁ ) ₃ ] _{Σ 7} is functionalized. The synthesis process can also involve phosphazene base superalloy base and R ² SiX ₃ types of silane-coupling agent to form a reaction POSS cage polyfunctional groups, such POSS cage train is of the formula types [(R ² SiO _{1. 5 6} ] _{Σ 6} , [(R ² SiO _{1 . 5} ) ₈ ] _{Σ 8} , [(R ² SiO _{1 . 5} ) _{1 0} ] _{Σ 1 0} , [(R ² SiO _{1 5} ) _{1 2} ] _{Σ 1 2} The R ² group is functionalized and the cage is large in size.

Mutually, the phosphorus-nitrogen superbase can be combined with the chemical formula [(R ¹ SiO _{1 5)} in the presence of a decane coupling agent of the formula R ² R ³ R ⁴ SiX, R ² R ³ SiX ₂ or R ² SiX ₃ . ₇ (HOSiO _{1 . 5} ) ₁ ] _{Σ 8} , [(R ¹ SiO _{1 . 5} ) ₆ (R ¹ HOSiO ₁ ) ₂ ] _{Σ 8} , [(R ¹ SiO _{1 . 5} ) ₄ (R ¹ HOSiO ₁ ) ₃ ] _{POS 7} POSS sterol reaction for a sufficient time, in the presence of solvent and superbase, the elimination of HX will occur, and the chemical formula is [(R ¹ SiO _{1 . 5} ) ₈ (R ² R ^{3 )} R ⁴ SiO ₁ )] _{Σ 9} , [((R ¹ SiO _{1 . 5} ) ₈ ) ₂ (R ² R ³ SiO ₂ )] _{Σ 1 7} , [((R ¹ SiO _{1 . 5} ) ₈ ) ₃ (R _{^{2 SiO 3)] Σ 2 5}} , [(R 1 SiO 1. 5) 6 (R 1 SiO 1) 2 (R 2 R 3 R 4 SiO) 2] Σ 1 0, [(R 1 SiO 1. 5) ₆ (R ¹ SiO ₁ ) ₂ (R ² R ³ SiO ₂ )] _{Σ 9} , [(R ¹ SiO _{1 . 5} ) ₆ (R ¹ HOSiO ₁ ) ₁ (R ² R ³ SiO)] _{Σ 8} , [( R ¹ SiO _{1 . 5} ) ₆ (R ¹ (R ² R ³ R ⁴ SiO)SiO ₁ )(R ² R ³ SiO)] _{Σ 9} , [(R ¹ SiO _{1 . 5} ) ₄ (R ¹ (R ^{2 _{R 3 R 4 SiO) SiO 1}} ) 3] Σ 1 0, [(R 1 SiO 1. 5) 7 (R 2 SiO 1. 5) 1] Σ 8 of monofunctional POSS monomer. The resulting monomer is substantially free of impurities and has controllable properties and topology by choice of composition, R groups, and nanostructure size. The highly purified nanostructure POSS single system is desirable because it exhibits improved filtration capacity, reduced contamination and viscosity, more reliable polymerization, lower cost, and reduced waste than impure systems.

A preferred process involves, in the presence of a solvent and Super base, the formula ^{_{[(R 1 SiO 1. 5}} ) 7 (HOSiO 1. 5) 1] Σ 8, [(R 1 SiO 1. 5) 6 ( R ¹ HOSiO ₁ ) ₂ ] _{Σ 8} , [(R ¹ SiO _{1 . 5} ) ₄ (R ¹ HOSiO ₁ ) ₃ ] _{POS 7} POSS sterol and the chemical formula is R ² R ³ R ⁴ SiX, R ² R ³ SiX ₂ , the reaction of R ² SiX ₃ decane coupling agent.

Simple illustration

Figure 1 shows a comparison of conventional techniques with an improved deuteration process.

Figure 2 shows various preferred phosphorus-nitrogen superbases; and Figure 3 shows the structure of the compounds synthesized in Example 5.

Definition of the chemical formula used for the nanostructure

For the purpose of understanding the chemical composition of the present invention, the definitions of the chemical formulas of polyhedral siloxane oligomers (POSS) and polyhedral silicate oligomer (POS) nanostructures are formulated as follows.

Silicon-based poly siloxane chemical formula [RSiO _{1. 5] ∞} represents the substance, where ∞ represents molar degree of polymerization (molar degree), R = represents organic substituent (H, Si-alkoxy, cyclic or linear aliphatic Or an aromatic group, which may additionally contain reactive functional groups such as alcohols, esters, amines, ketones, olefins, ethers or halides or such groups may contain fluorinated groups. The oxane may be either a homoleptic or a heteroleptic. The same substituent system contains only one type of R group, while the hetero substituent system contains more than one type of R group.

The POSS and POS nanostructures are represented by the chemical formula: [(RSiO _{1 . 5} ) _n ] _{Σ #} for the same substituent composition; [(RSiO _{1 . 5} ) _n (R'SiO _{1 . 5} ) _m ] _{Σ #} for hetero-substituent composition (where R ≠ R'); [(RSiO _{1 . 5} ) _n (RXSiO _{1 . 0} ) _m ] _{Σ #} hetero-substituent composition for functionalization (where R The groups can be equal or unequal).

All R systems above are the same as defined above, and X includes, but is not limited to, OH, Cl, Br, I, alkoxy (OR), formate (OCH), acetate (OCOR), acid ( OCOH), ester root (OCOR), peroxygen (OOR), amine root (NR ₂ ), isocyanate (NCO) and R. The symbols m and n mean the stoichiometry of the composition. The symbol Σ indicates that the composition forms a nanostructure, and the symbol # means the number of germanium atoms contained in the nanostructure. The # value is typically the sum of m + n, where n is typically distributed from 1 to 24, while m is typically distributed from 1 to 12. It should be noted that Σ# is not to be confused as a multiple for determining stoichiometry, as it merely describes the total nanostructure characteristics of the system (also known as the size of the cage).

Detailed description of the preferred embodiment

The present invention teaches an improved synthesis process for POSS nanostructured chemistry that produces a higher purity, lower cost product than previously described.

The main feature of the invention is the use of a phosphorus-nitrogen superbase to catalyze the assembly of POSS cages. Applicable phosphorus-nitrogen groups include phosphorus-nitrogen groups which vary in molecular weight and composition. Phosphorus-nitrogen oligomers and molecules, especially in P1 type P(NtBu)(NH ₂ ) ₃ , P2 type (H ₂ N) ₃ P=N-P(NH ₂ ) ₄ , P3 type (H ₂ N) ₃ P =N-P(NH ₂ )-N=P(NH ₂ ) ₃ , P4 type (H ₂ N) ₃ P=N-P(NH ₂ ) ₃ =N-P(NH ₂ ) ₃ -N=P( NH ₂ ) ₃ is preferably used. The basicity of the phosphorus-nitrogen superbase increases with the number of phosphorus atoms, and this provides a valuable tool for the use of this reagent. The preferred concentration of the superbase relative to the triterpene alcohol is 2 mol%, but the effective range includes 0.1 mol% to 10 mol%.

General process variables that can be applied to all processes

As with typical chemical processes, there are variables that can be used to control the purity, selectivity, rate, and mechanism of any process. Variables affecting the process include the size, polydispersity and composition of the nanostructured chemical; separation and isolation; and the use of catalysts or cocatalysts, solvents and cosolvents. In addition, the dynamics and thermodynamics of controlling the synthesis mechanism, rate and product distribution are also known as trade tools that can impact the quality and economy of the product.

Example 1.

Synthesis [(isobutyl SiO _{1 . 5} ) ₇ (methacryl propyl SiO _{1 . 0} ) ₁ ] _{Σ 8} : [(isobutyl SiO _{1 . 5} ) ₄ (isobutyl (OH) SiO _{1 . 0) 3] Σ 7 (} 688g, 0.87 mole) was dissolved in tetrahydrofuran (THF), after addition of methacryl trimethoxy Silane (methacrylpropyltrimethoxysilane) (204g, 0.87 mole), and then the solution was cooled to 5 °C. Then, a phosphorus-nitrogen superbase (FW 234.32, 15.72 mmol) was added, and the mixture was stirred at room temperature for three days. The solution was then quenched with acetic acid (1.5 g). Next, 1 liter of methanol was added, and the mixture was stirred and filtered. The solid was dried to give a pure white product of 75% yield.

Example 2.

Synthesis of _{[(. EtSiO 1 5) 7} (. Glycidol _{SiO 1 0) 1] Σ 8} ([. (EtSiO 1 5) 7 (glycidalSiO 1 0) 1.] Σ 8): The _[(. EtSiO _{1 5) 4} (Et(OH)SiO _{1 . 0} ) ₃ ] _{Σ 7} (50 g, 84 mmol) dissolved in methanol, followed by 3-glycidoxypropyltrimethoxysilane (19.86 g, 84 millimoles), then the solution was cooled to 5 °C. Next, a phosphorus-nitrogen superbase (FW 234.32, 15.72 mmol) was added, and then the mixture was stirred at 5 ° C for three days. The solution was then quenched with acetic acid (87 mg). After filtration and removal of volatiles, the solution was dried to a solid. The solid was washed with methanol (1400 ml) and the solid was dried to afford 415 g,yiel.

Example 3.

Synthesis [(EtSiO _{1 . 5} ) ₇ (ethylnorbornene SiO _{1 . 0} ) ₁ ] _{Σ 8} : [(EtSiO _{1 . 5} ) ₄ (Et(OH)SiO _{1 . 0} ) ₃ ] _{Σ 7} (12 g, 20 mmoles was dissolved in methanol, then exo-norbornenylethyltrimethoxysilane (4.84 g, 20 mmol) was added and the solution was then cooled to 5 °C. Next, a phosphorus-nitrogen superbase was added, and then the mixture was stirred at 5 ° C for two days. The solution was then quenched with acetic acid (87 mg), filtered and evaporated to dryness eluting with EtOAc.

Example 4.

Synthesis of [(cyclohexyl SiO _{1 5.) 7} (aminoethyl aminopropyl _{SiO 1 0.) 1] Σ} 8: The _[(. Cyclohexyl SiO _{1 5) 4} (cyclohexyl (OH) SiO _{1. 0} ) ₃ ] _{Σ 7} (10 g, 10.3 mmol) dissolved in THF, followed by 3-(N-aminoethyl)aminopropyltrimethoxysilane (2.32) g, 10.27 mmol, followed by the addition of a phosphorus-nitrogen superbase (FW 234.32, 15.72 mmol) and the mixture was stirred at room temperature. The solution was quenched with acetic acid and methanol was added. After removal of the volatile material, the product was dried to afford a pure white solid with a yield of 62%.

Example 5.

Synthesis of [(phenyl SiO _{1 . 5} ) ₇ (aminopropyl SiO _{1 . 0} ) ₁ ] _{Σ 8} : [(phenyl SiO _{1 . 5} ) ₄ (phenyl(OH)SiO _{1 . 0} ) ₃ ] _{Σ 7} (5.9 g, 6.3 mol) was dissolved in toluene, then 3-aminopropyltrimethoxysilane (2.0 g, 11 mmol) was added, followed by stirring at room temperature for 12 hours. Acetonitrile was added and the solution was filtered and the product was dried to give a white solid, 40% yield.

Although certain representative specific embodiments and details have been shown to exemplify the invention, it will be apparent to those skilled in the art that the methods and apparatus disclosed herein can be variously modified without departing from the invention. The scope defined in the scope of the appended patent application.

Figure 1 shows a comparison of conventional techniques with an improved deuteration process.

Figure 2 shows various preferred phosphorus-nitrogen superbases; and Figure 3 shows the structure of the compounds synthesized in Example 5.

Claims (12)

A process for preparing a functionalized polyhedral oxyalkylene oligomer (POSS) monomer comprising the step of reacting a decane coupling agent of the formula RSiX ₃ in the presence of a solvent and a phosphazene superbase, Wherein R is selected from the group consisting of hydrogen, siloxy and aliphatic, aromatic and olefinic groups, wherein the groups may be selected from the group consisting of alcohols, esters, amines a reactive functional group of a group consisting of a ketone, an olefin, an ether, and a halide, and may contain a fluorinated substituent; the X system is selected from the group consisting of OH, Cl, Br, I. , alkoxide (OR), formate, acetate, acid (OCOH), ester, peroxygen (OOR), amine (NR ₂ ), isocyanate (NCO) and R; and each R and Each X can be the same or different. The method of claim 1, wherein the superbase is selected from the group consisting of P1, P2, P3 and P4 type phosphorus nitrogen groups. The method of claim 1, wherein a mixture having different decane coupling agents is reacted to utilize the functionalized POSS monomer. The method of claim 1, wherein a mixture having different superbases is used as a homogeneous catalyst or co-reagent. The method of claim 1, wherein a mixture having a different solvent or a reaction medium is utilized. For example, in the method of claim 1, a continuous process system for causing a functionalized POSS monomer is utilized, and the process uses the superalkaly It is a heterogeneous catalyst or a co-reagent. A method for preparing a functionalized POSS monomer comprising decane having a chemical formula selected from the group consisting of RSiX ₃ , R ₂ SiX ₂ and R ₃ SiX in the presence of a solvent and a phosphorus-nitrogen superbase a coupling agent for deuterating POSS sterol, wherein: R is selected from the group consisting of hydrogen, siloxy, and aliphatic, aromatic, and olefinic groups, wherein the groups are a reactive functional group selected from the group consisting of alcohols, esters, amines, ketones, olefins, ethers, and halides, and may contain a fluorinated substituent; X is selected from the group consisting of Group: OH, Cl, Br, I, alkoxide (OR), formate, acetate, acidate (OCOH), ester root, peroxygen (OOR), amine root (NR ₂ ), isocyanate ( NCO) and R; and each R and each X may be the same or different. The method of claim 7, wherein the superbase is selected from the group consisting of P1, P2, P3 and P4 type phosphorus nitrogen groups. The method of claim 7, wherein a mixture having different POSS sterols and decane coupling agents is deuterated. The method of claim 7, wherein a mixture having different superbases is used as a homogeneous catalyst or a co-reagent. The method of claim 7, wherein a mixture having a different solvent or a reaction medium is utilized. A method of claim 7, wherein a continuous deuteration process is utilized which uses the superbase as a heterogeneous catalyst or a co-reagent.