HK1105100A

HK1105100A - Compound for optical materials and methods of fabrication

Info

Publication number: HK1105100A
Application number: HK07110416.8A
Authority: HK
Inventors: Christoph Georg Erben; Eric Michael Breitung; Ryo Tamaki
Original assignee: General Electric Company
Priority date: 2004-03-29
Filing date: 2005-03-23
Publication date: 2008-02-01

Description

Compound for optical material and method for producing the same

Background

The invention relates to an optical material, an apparatus and a method for manufacturing the same.

Optical materials used in optical devices (e.g., optical fibers and optical waveguides) are widely used in electronics and communications to convey data and signals across large geographic distances and variations in terrain. Optical materials may also be used in signaling devices and computer communications for shorter range data transmission. The selective design and selection of optical fibers and optical cladding materials ensures high fidelity signals, low optical loss (or low signal loss), and desirably long lifetime. Optical waveguide devices take advantage of the ability to control the path of the light beam and then the refractive index of the materials used. Optical waveguide materials are increasingly in demand in many optical focusing, propagating, bending and delivery applications.

Typically, optical waveguide materials are prepared from a variety of materials (e.g., quartz, glass, acrylates, epoxies, and transparent plastics and composite polymers). Silica-based materials have been found to be potentially useful for applications requiring low optical losses, but these materials are generally expensive to produce.

There is a need for a cost effective method of forming optical devices using optical materials with low optical losses. There is also a need to improve the reliability and thermal stability of optical materials.

Summary of The Invention

One aspect of the present invention is a polycyclic or monocyclic perfluorovinyl compound comprising at least one structural unit selected from the group consisting of formula I and formula II:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and R is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical. The polycyclic or monocyclic compound includes at least two perfluorovinyl groups.

A second aspect of the invention is a method of forming an optical film of the disclosed polycyclic or monocyclic perfluorovinyl compound. The method includes providing a blend of monomer a and monomer B. Monomer a includes polycyclic or monocyclic perfluorovinyl compounds comprising at least one structural unit selected from formula I and formula II:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and R is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical; the polycyclic or monocyclic compound includes at least two perfluorovinyl groups. Monomer B is a monomer comprising at least two CF₂Organic compounds of CF-units. The method includes providing the blend, mixing the blend with a photoinitiator and a photocurable monomer C to obtain a mixed blend, wherein the photocurable monomer C includes at least one of an acrylate, an epoxide, a polyimide, a silicone, a vinyl compound, a carbonate, and a diene; partially polymerizing at least one of the blend or the mixed blend; depositing the mixed blend on a substrate to form a film; selectively exposing the membrane to radiation to at least partially polymerize monomer C; and curing the film.

A third aspect of the present invention is an optoelectronic device comprising a polymer prepared from a polycyclic or monocyclic perfluorovinyl compound, wherein the polycyclic or monocyclic perfluorovinyl compound comprises at least one structural unit selected from the group consisting of formula I and formula II:

A fourth aspect of the invention is a polymer made by reacting components (a), (B) and (c), wherein component (a) is a blend of monomer a and monomer B, said monomer a comprising a polycyclic or monocyclic perfluorovinyl compound comprising at least one structural unit selected from formula I and formula II:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and R is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical. The polycyclic or monocyclic compound comprises at least two perfluorovinyl groups, monomer B is a compound comprising at least two CF₂Component (b) is at least one photocurable monomer C, wherein the photocurable monomer comprises at least one of an acrylate, an epoxide, a polyimide, a silicone, a vinyl compound, a carbonate, a diene, and combinations thereof, and component (C) is at least one photoinitiator.

The polycyclic or monocyclic perfluorovinyl compounds, methods of forming optical films, electroactive devices, polymers, and embodiments disclosed herein are particularly useful in optical waveguide systems, holograms, holographic devices, combinations thereof, and similar applications known to those skilled in the art. These and other aspects, advantages and salient features of the present invention will become more fully apparent from the following detailed description and appended claims.

Detailed Description

In referring to the general chemical structures, it is to be understood that these statements are intended to describe particular embodiments of the present invention and are not intended to limit the present invention thereto.

Optical waveguide materials and systems typically focus, diverge, guide, or propagate a light beam or signal in a desired direction. Their efficiency often depends on the control of the refractive index in the system, their thermal stability and the adhesion to the components in which the waveguide material is disposed. The high thermal stability and substrate adhesion ensures continuous material functionality over time. Compared to conventional molten glasses, polymers, especially polymers with silicon-oxygen networks (or Si-O linkages), are well suited for optical waveguide applications because these polymers are processed at low temperatures, are disposed on a number of substrates, and can be tailored for optical and mechanical properties.

For waveguide applications where low optical loss is critical, optical materials from inorganic silica or from fluorinated polymers have been found to be particularly suitable. One problem associated with conventional synthetic fluoropolymers is the relatively low adhesion to the optical component or substrate, resulting in device failure and limited operating conditions. In addition, the thermal stability of conventional fluoropolymer systems is low, resulting in degradation of the material under fluctuating operating conditions. Conventional methods of making optical materials using fluoropolymers do not impart improved adhesion, greater thermal stability, or optimally utilize the low optical loss properties of the waveguide materials.

In one embodiment, the present invention provides compounds for use as optical grading materials. In another embodiment, a method for forming an optical film is disclosed. A third embodiment provides an optoelectronic device comprising an optical waveguide material. A fourth embodiment provides a polymer prepared from the claimed compound.

In one embodiment of the disclosed polycyclic or monocyclic perfluorovinyl compounds, the aliphatic group is alkyl, alkoxy, perhaloalkyl, partially halogenated alkyl. In another embodiment, the aromatic group is an aryl, aryloxy, perhaloaromatic group, or partially halogenated aromatic group. In a third embodiment, the perfluorovinyl compound has the formula III:

[RSiO_3/2]_n

III

wherein R is independently at each occurrence hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical; n is a number from 2 to about 1000.

In a fourth embodiment, the perfluorovinyl compound has formula IV

[R₂SiO]_n

IV

In a fifth embodiment, the monocyclic or polycyclic perfluorovinyl compound further comprises a structural unit selected from the group consisting of formula V and formula VI:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and R is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical. In one embodiment, M comprises at least one of silicon and germanium. In another embodiment, the monocyclic or polycyclic perfluorovinyl compound comprises a silicon-oxygen network. In another embodiment, the silicon-oxygen network comprises an oligomeric silsesquioxane. In another embodiment, the oligomeric silsesquioxane comprises polyhedral oligomeric silsesquioxane. In another embodiment, the polyhedral oligomeric silsesquioxane includes an octahedral structure.

Most often, silsesquioxanes are built up from trifunctional organosilicon monomers (e.g., RSiCl)₃Or RSi (OMe)₃) The hydrolysis condensation reaction. Many hydrolytic condensation reactions produce the synthesis of useful quantities of fully condensed polyhedral oligomeric silsesquioxane backbones containing 6, 8, 10, 12 Si atoms and combinations thereof. The silsesquioxane backbone is built up on Si-O linkages and clusters.

Analogous Si-O clusters catalyze tetrafunctional silicon monomers by base (e.g., tetraethoxysilane Si (OEt)₄) And (4) preparation. The tetraethoxysilane cluster is of [ (SiO)₂)_n(SiO₄)_m]^4M-Type structures other than those present in silsesquioxanes [ RSiO_3/2]There are also many similarities between functionalized silicates of type structure and condensed silsesquioxane backbones. For example, tetramethoxysilane, tetraethoxysilaneAlkane, silicic acid, SiO₂And combinations thereof, can be such that the predominant Si-containing species in solution is [ Si₈O₂₀]^8-Is well balanced.

Hydrolysis of incompletely condensed polyhedral oligomeric silsesquioxane backbones to fully condensed backbones (e.g., R)₈Si₈O₁₂) Many intermediates need to be formed. Usually, the intermediates are present in small amounts, which are unstable under the reaction conditions and are very difficult to separate from the typical crude product mixture. However, RSiX₃The condensation of (a) sometimes yields very high yields of compounds that are logical intermediates for fully condensed silsesquioxane backbones. The most widely used silsesquioxane backbone is (C-C)₆H₁₁)₆Si₆O₉Trisilanol (molecule 6a) and trisilanol obtained together by (C-C)₆H₁₁)SiCl₃Hydrolysis of the condensed molecule 7. The synthesis of trisilanol (molecule 6a) is known to those skilled in the art and typically requires an incubation time of about 3 weeks to about 6 weeks to provide useful amounts. Cyclopentyl-substituted trisilanols (molecule 6b) were also prepared in a similar manner, while the reaction time was greatly reduced by carrying out the reaction at elevated temperature. (C-C)₇H₁₃)SiCl₃And (norbornyl) SiCl₃Hydrolytic condensation of (a) produces tetrasilanol (molecules 8a and 8 b). These structures are known to those skilled in the art.

Polyhedral oligomeric silsesquioxane frameworks are also synthetically synthesized. Mention may be made, as examples, of Si₈O₁₂R₈(12) Structures, but the preparation method can be applied to other networks by suitable variations known to those skilled in the artIn the structure.

The R groups on each molecule may all be the same but may also be different. The R groups are selected from all known organic functional groups including hydrides, aliphatic compounds, aromatic compounds, alkyl compounds, aryl compounds, alkoxy compounds, phenoxy compounds, partially or fully halogenated compounds, groups containing polymerizable functionality such as acrylates, epoxides, vinyls, hydroxyls, cyanos, and combinations thereof.

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and R is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical; the polycyclic or monocyclic compound includes at least two perfluorovinyl groups. Monomer B is a monomer comprising at least two CF₂Organic compounds of CF-units. The method includes providing the blend, mixing the blend with a photoinitiator and a photocurable monomer C to obtain a mixed blend, wherein the photocurable monomer C includes at least one of an acrylate, an epoxide, a polyimide, a silicone, a vinyl compound, a carbonate, and a diene; partially polymerizing at least one of the blend or the mixed blend; depositing the mixed blend on a substrate to form a film; selectively exposing the membrane to radiation to at least partially polymerize monomer C; and areCuring the film, thereby producing the final strength and adhesion properties in the disclosed optical film. Typically, curing involves heating to a temperature of about 150 ℃ to about 300 ℃.

In a more specific embodiment, M comprises at least one of silicon and germanium. In one embodiment, the polycyclic or monocyclic perfluorovinyl compound comprises a silicon-oxygen network. In one embodiment, the silicon-oxygen network comprises an oligomeric silsesquioxane. In another embodiment, the oligomeric silsesquioxane comprises polyhedral oligomeric silsesquioxane. In another embodiment, the polyhedral oligomeric silsesquioxane includes an octahedral structure. Various structural representatives of polycyclic or monocyclic perfluorovinyl compounds are shown below:

the monomers B disclosed in the present invention include the compounds consisting of CF₂＝CF-X_m-R-X_m-CF＝CF₂A molecule represented by a type structure, wherein X is independently at each occurrence a bond, an oxygen linkage, an amine linkage, a sulfur linkage, a silicon-containing linkage, an aliphatic group, an alicyclic group, or an aromatic group, m is independently at each occurrence an integer from 0 to about 100, and R is a bond, an aliphatic group, an alicyclic group, or an aromatic group. In one embodiment, monomer B comprises at least one of 1, 6-bis (trifluorovinyl) dodecafluorohexane (hereinafter 16), 4' -bis (4-trifluorovinyl) oxy) biphenyl (hereinafter 17), 1, 1, 1-tris (4-trifluorovinyloxyphenyl) ethane (hereinafter 18), bis (4-trifluorovinyl) oxy) perfluorobiphenyl (hereinafter 19), and combinations thereof. Some of the molecules listed are commercially available, for example 4, 4' -bis (4-trifluorovinyl) oxy) biphenyl (hereinafter 17) and 1, 1, 1-tris (4-trifluorovinyloxyphenyl) ethane (hereinafter 17)18) available from Oakwood Products inc, West Columbia, SC 29172. Non-limiting structural representatives of monomer B are shown below:

when structure 20 represents a partially cured polymeric structure, Z is a molecule that includes all known organic functional groups, including R, hydride, aliphatic-, aromatic-, alkyl-, aryl-, alkoxy-, phenoxy-, partially or fully halogenated compounds, groups containing polymerizable functionality, such as acrylates, epoxides, vinyls, hydroxyls, cyanos, and combinations thereof. When copolymerized or blended with monomer a, monomer B is typically used to obtain the desired material properties. In one embodiment, X comprises O, N, S, Si, -CH₂-、-CF₂-、-CR₂-, alkyl, alkoxy, partially halogenated aliphatic group or fully halogenated aliphatic group and combinations thereof, wherein R is as defined for formula I.

In one embodiment of the invention, the step of partially polymerizing at least one of the blend and the mixed blend comprises partially polymerizing the blend of monomers a and B such that the partial polymerization occurs prior to forming the mixed blend. In another embodiment, the curing step is carried out by at least one of heat irradiation, exposure to light, or a combination thereof. In a third embodiment, the step of partially polymerizing at least one of the blend and the mixed blend comprises heating the blend at a temperature of about 100 ℃ to about 200 ℃ for about 2 minutes to about 60 minutes. In a fourth embodiment, the step of selectively exposing the membrane to radiation to at least partially polymerize monomer C further comprises diffusing monomer C from unexposed regions of the membrane to exposed regions after selectively exposing the membrane to radiation; and in some embodiments, this step is performed using a photomask. Typically, the steps of selective exposure and diffusion are performed to produce a desired contrast (or gradient) of optical refractive index between exposed and unexposed regions of the film. In a fifth embodiment, the mixed blend has a viscosity of about 10 centistokes (cSt) to about 10000 centistokes (cSt). In a sixth embodiment, the mixed blend is deposited on a substrate comprising at least one of a metal, a ceramic, a glass, a plastic, an organic material, an inorganic material, a semiconductor, an electronic device, a microelectromechanical system (MEMS) device, a sensor, a refractive index adjustment device, a beam splitter, and combinations thereof. In a seventh embodiment, the mixed blend is deposited onto a substrate using at least one technique including spin coating, doctor blading, dip coating, casting, extrusion, and combinations thereof.

The disclosed methods of forming optical films are equally applicable to forming optical materials, particularly graded optical materials. As used herein, an optical material refers to a material having desirable light transmission properties. As used herein, a graded optical material refers to a material that has structural non-uniformity in its properties across one of its dimensions. The optical path between two poles in a material may follow along the length, width or height dimension within the material. Graded optical materials typically have a controlled refractive index within their bulk so that the optical signal can be flipped along a desired profile. It is therefore desirable to have an optical waveguide that contains graded optical material. In another embodiment, the optically graded material has a refractive index of about 1.0 to about 2.42. In a third embodiment, the optical grade material provided by the disclosed method has an optical loss of less than about 1dB/cm at wavelengths from about 600nm to about 1600nm, more specifically less than about 0.1dB/cm at wavelengths of about 850nm, 1310nm, and 1550nm, and even more specifically less than about 0.05dB/cm at wavelengths of about 850nm, 1310nm, and 1550 nm.

The polymers prepared by the disclosed methods have high adhesion to substrates. As used herein, high adhesion means that laminates made from different materials that are bonded together to form a structural unit remain integral without physically separating into layers under normal environmental changes or anticipated stress loads. Adhesion is typically measured by various methods including scratch, peel, pull, blister and score tests, where the interface is subjected to very high stress levels and thus causes uneven deformation. For example, the Standard Test Method for measuring adhesion by tape testing is described in the U.S. Standard Test Method (ASTM) D3359, which classifies the adhesion Test results into 5 categories, with 5 Test results indicating the highest measurable adhesion. The disclosed substrate generally comprises at least one of a metal, a ceramic, a glass, a plastic, an organic material, an inorganic material, a semiconductor material, an electronic device, a microelectromechanical system (MEMS) device, a sensor, a refractive index adjustment device, or a combination thereof. The disclosed polymers have high adhesion to plastic, glass, silicon substrates, according to ASTM standards, above 3B, more preferably above 4B.

In one embodiment, the disclosed compounds are flame retardants. Flame retardants are generally known as materials that retard ignition and reduce the spread of a flame along their surfaces. In another embodiment, the compounds have high thermal stability. High thermal stability means that the desired properties change with minimal or no change when the material is exposed to temperatures of about 100 ℃ for extended periods of time. Thermally stable materials are defined as materials that retain their pyrolytic weight and chemical integrity in a high temperature range, with temperature stability up to about 250 ℃ being preferred.

Polymers prepared from the disclosed compounds are attractive candidates for optical lenses, focusing devices, and systems or materials designed to confine or guide light waves to a direction defined by the physical boundaries of the system or material (i.e., in an optical waveguide).

Films prepared according to the disclosed method include polymers prepared from monomer a at a concentration of about 1 wt% to about 100 wt% and monomer B at a concentration of about 99 wt% to about 0 wt%. In the disclosed method, monomer a and monomer B provide desirable material properties (e.g., refractive index, adhesion, and fracture resistance) when blended. In one embodiment, precursor blending is performed by mixing monomer a and monomer B in a round bottom flask and stirring the mixture with a magnetic stirrer. In some embodiments, monomer a and monomer B are chemically reacted to provide a modified precursor. In other embodiments, monomer a and monomer B physically interact to provide a physically blended mixture. In one embodiment of the invention, the chemically modified precursor obtained by blending monomer a and monomer B produces another monomer a for further processing. Blending monomer a and monomer B provides a method by which the advertised molecular weight is provided by a polymer of relatively low molecular weight through a polymer chain extension or crosslinking mechanism, or both. Providing a modified precursor is known in the art as prepolymerization. In some embodiments, monomer a and monomer B are blended and prepolymerized in the presence of common organic solvents known in the art. In some embodiments, the prepolymerization is carried out to obtain a solution of processable viscosity, and various solvents including benzene, toluene, alcohols, ethers, esters, and combinations thereof are used for this purpose.

In some embodiments, the pre-polymerized blend is heated at a temperature of from about 100 ℃ to about 200 ℃ for from about 2 minutes to about 60 minutes. Heating results in at least one of a deposit or a pre-polymerized blend having a controlled viscosity to aid in application to a selected substrate. The sediment may be separated by at least one of filtration, centrifugation, chromatography, and combinations thereof and used for application to a substrate. The pre-polymerized blend has a viscosity of from about 10cSt to about 10000 cSt.

To provide regions of different refractive index in the material, photocurable monomer C is mixed with the pre-polymerized blend. Curing is understood in the art to mean the process of polymerizing a monomer or oligomer or cross-linking an existing polymer to obtain its final physical, chemical, mechanical and optical properties. As described above, the photocurable monomer C includes at least one of an acrylate, an epoxy, a polyimide, a silicone, a vinyl compound, a carbonate, a diene, and combinations thereof to produce a mixed blend.

In some embodiments, a photoinitiator is added to the pre-polymerization blend. Photoinitiators are compounds that absorb energy directly or indirectly from light to form reactive species, radicals or ions that initiate polymerization. The photoinitiator generally includes at least one of dibromoethane, benzophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylphenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, N-hydroxyphthalimide trifluoromethanesulfonate, (4-phenoxybenzyl) trimethylammonium chloride, benzoin methyl ether, dimethyl iodonium hexafluorophosphate, and combinations thereof. In some embodiments, a sensitizer is added to the pre-polymerized blend. The sensitizer is a compound that increases the wavelength response range of the photoinitiator system, and preferred sensitizers include at least one of 2, 4- (bis (4-diethylaminobenzylidene) cyclopentanone (commonly referred to as DEAW), 2, 4 (bis-julolidinyl) cyclopentanone (commonly referred to as JAW), camphorquinone (commonly referred to as CQ), methylbenzoyl formate (commonly referred to as MBF), and combinations thereof.

The partial polymerization is carried out in at least one of the blend and the mixed blend. In one embodiment, the partial polymerization is carried out by partially polymerizing the blend prior to mixing. In a second embodiment, the partial polymerization is carried out after mixing some or all of the components.

The pre-polymerized and mixed blend is deposited as a film on a selected substrate using techniques including at least one of spin coating, doctor blading, dip coating, casting, extrusion, and combinations thereof. The substrate comprises at least one of a metal, a ceramic, a glass, a plastic, an organic material, an inorganic material, a semiconductor, an electronic device, a microelectromechanical system (MEMS) device, a sensor, a refractive index adjuster, a beam splitter, and combinations thereof.

The deposited film is then exposed to radiation to at least partially polymerize monomer C. Selectively exposing the deposited film provides diffusion of monomer C from unexposed areas of the deposited film to exposed areas of the deposited film, thereby obtaining a material with graded properties. In one embodiment, the film is exposed to light of a suitable wavelength using a photomask. In another embodiment, the entire film is exposed to radiation and no photomask is used. In a third embodiment, selective exposure and diffusion is performed to produce a desired refractive index contrast between exposed and unexposed regions of the film, thereby providing a graded optical material.

The deposited blend is fully polymerized by the application of at least one of thermal energy and light energy. The step of applying thermal energy comprises, for example, heating the substrate to a temperature of about 150 ℃ to about 300 ℃. The final physical, chemical, mechanical and optical properties of the film are obtained by curing. In another embodiment, the film is exposed to a temperature of about 100 ℃ to about 200 ℃ for about 2 minutes to about 60 minutes.

Stoichiometrically, each of monomer a and monomer B undergoes a chemical addition reaction by a 2+2 cycloaddition mechanism to produce a product having a ring structure. In one embodiment of the invention, a cyclobutane ring structure is obtained. With more complex and advanced monomers a and B, polycyclic and network ring structures are obtained. In one embodiment, several cyclobutane ring structures are obtained in three dimensions.

The silicon-oxygen cage network reduces the chemical bonds that lead to absorption of vibrational harmonics at the desired wavelength. Such bonds are primarily X-H linkages, where X includes C, O, N and at least one of the other elements. The disclosed fluorinated silsesquioxanes (when used as monomer a) do not contain such a bond. By using a cyclic structure, good control of the end groups and improved material properties are achieved. Crosslinking groups are further uniquely suited for waveguide materials because the reaction is catalyst free and does not produce X-H containing subgroups. Properties (e.g. refractive index, toughness, T) are achieved by selecting a spacer group between the Si atom and the crosslinking group_gAnd other optical, mechanical, and holographic properties). In one embodiment, phenyl is used due to its low C-H content and high stability. Other property adjustments are made by incorporating different highly fluorinated monomers having at least two trifluorovinyl groups into the sesqui-or sesqui-substituted vinyl monomersAnd then copolymerized in the siloxane monomer. In one embodiment of the invention, if photo-patterning is desired, highly fluorinated photosensitive monomers are added to a partially polymerized silsesquioxane matrix and exposed cross-linking followed by complete polymerization by application of thermal energy.

Structurally, the use of a silicon oxide matrix through the silsesquioxane core reduces the number of total C-H and C-F bonds. By reducing the number of C-H bonds, one embodiment of the present invention provides compounds with lower absorption light loss. The second embodiment of the present invention improves adhesion to a substrate by reducing the number of C-F linkages. The third embodiment of the present invention improves thermal stability by replacing the C-X linkage with a Si-O linkage.

A third aspect of the present invention is an optoelectronic device comprising a polymer prepared from a polycyclic or monocyclic perfluorovinyl compound, wherein the polycyclic or monocyclic perfluorovinyl compound comprises at least one selected from structural units of formula I and formula II:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and R is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical. The polycyclic or monocyclic compound contains at least two perfluorovinyl groups.

In one embodiment, the electroactive component of the disclosed optoelectronic devices comprises at least one of an organic light emitting diode, a photovoltaic cell, a light emitting diode, an electroluminescent material, a cathodoluminescent material, a phosphorescent material, a mirror, a laser, an optical fiber, a MEMS device, a device for concentrating or diverging light, a light guiding material, a beam splitter, and combinations thereof. In another embodiment, the optoelectronic device is designed to be driven by a power source.

A fourth aspect of the invention is a polymer prepared by reacting components (a), (B) and (c), wherein component (a) is a blend of monomer a and monomer B, said monomer a comprising a polycyclic or monocyclic perfluorovinyl compound comprising at least one structural unit selected from formula I and formula II:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and R is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical. The polycyclic or monocyclic compound contains at least two perfluorovinyl groups and monomer B is a compound containing at least two CF₂(ii) an organic compound of CF-units, component (b) is at least one photocurable monomer C, wherein the photocurable monomer comprises at least one of an acrylate, an epoxide, a polyimide, a silicone, a vinyl compound, a carbonate, a diene, and combinations thereof, and component (C) is at least one photoinitiator.

In one embodiment of the invention, the photoinitiator comprises at least one of dibromoethane, benzophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylphenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, N-hydroxyphthalimide trifluoromethanesulfonate, (4-phenoxybenzyl) trimethylammonium chloride, benzoin methyl ether, diphenyliodonium hexafluorophosphate, and combinations thereof.

The following examples are included to illustrate various features and advantages of the present invention, and are not intended to limit the invention.

Example 1: preparation of 4-bromophenyl trichlorosilane using tetrachlorosilane

Freshly activated magnesium (8.5g, 0.35mol) was slowly added over a period of 4 hours to a solution of 1, 4-dibromobenzene (80g, 0.34mol) in 200mL diethyl ether, maintaining the temperature below 30 ℃. The reaction mixture was stirred for 8 hours and then slowly added over 12 hours to a mixture of tetrachlorosilane (100mL, 0.87mol) in diethyl ether (50 mL). The mixture was stirred for 12 hours and unreacted tetrachlorosilane and diethyl ether were removed under vacuum. The remaining liquid was fractionally distilled through a Vigreux column under reduced pressure to give 4-bromophenyltrichlorosilane as an oil (350. mu. Hg/85 ℃ -37 g/37%).

¹HNMR(400

MHz，CDCl₃)：δ7.69(4H，dd).¹³CNMR(100MHz，CDCl₃)：δ134.6，131.9，130.4，128.2.GC-MS：290(M+).

Example 2: preparation of 4-bromophenyl triethoxysilane Using tetraethoxysilane

Freshly activated magnesium (8.5g, 0.35mol) was slowly added over a period of 4 hours to a solution of 1, 4-dibromobenzene (80g, 0.34mol) in 200mL diethyl ether, maintaining the temperature below 30 ℃. The reaction mixture was stirred for 8 hours and then slowly added to tetraethoxysilane (100mL, 0.44mol) in Et₂In a mixture in O (50 mL). The mixture was stirred for 12 hours and unreacted tetraethoxysilane and diethyl ether were removed under vacuum. The remaining liquid was fractionally distilled through a Vigreux column under reduced pressure to afford 4-bromophenyltriethoxysilane (37g, 37%, bp 80-90 ℃ C. at 250. mu. Hg) as a clear oil.

¹HNMR(400 MHz，CDCl₃)：δ7.56(4H，dd)，3.89(6H，q)，1.27(9H，t).¹³CNMR(100MHz，CDCl₃)：δ136.4，131.1，58.8，18.2.GC-MS：318(M+).

Example 3: preparation of octa (4-bromophenyl) silsesquioxane

4-bromophenyltrichlorosilane (29g, 0.1mol) was dissolved in 200mL of methanol and 20mL of water and refluxed for 36 hours. The liquid was decanted from the gel, and the gel was sonicated in methanol to yield a white powder. Filtration and column chromatography were used to purify the product, namely, octa (4-bromophenyl) silsesquioxane.

Example 4: preparation of 1- (trifluoroethyleneoxy) -4- [4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan ] benzene

1-bromo-4- (trifluoroethyloxy) benzene, commercially available from Oakwood Products, Inc., was used as a precursor. 12.65g (0.05mol) of 1-bromo-4- (trifluoroethyleneoxy) benzene in 100mL of THF (tetrahydrofuran) was added dropwise to 2.5g (0.1mol) of freshly activated magnesium in 100mL of THF in a 500mL 3-necked flask equipped with a dropping funnel, thermometer, stirrer and nitrogen inlet. The temperature was kept below 30 ℃ during the addition. After complete conversion to the Grignard intermediate, the solution was added dropwise to 10.2g (1.1 eq.) of 2-isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan in 50mL THF at room temperature. The solution was refluxed for 12 hours, diluted with water, extracted with dichloromethane, over MgSO₄Drying and concentrating. Fractional distillation at 300 μ Hg and 100 ℃ gave 37% of the desired product as a clear oil.

¹HNMR (400MHz, acetone-d)₆)：δ7.83(2H，dd)，7.22(2H，dd)，1.34(12H).¹³CNMR (100MHz, acetone-d)₆)：δ205.1，154.2，147(m)，136.9，133(m)，114.92，83.8，24.3.¹⁹FNMR (470MHz, acetone-d)₆)：δ-123.85(t)，-130.8(t)，-138.3(t).GC-MS：300(M+).

Example 5: preparation of octa [ 4-trifluoroethylene oxyphenyl) benzene ] silsesquioxane

Under a nitrogen blanket, the mixture contained 50mL of toluene and 10mL of Na₂CO₃And 2mL of ethanol in a 100mL three-necked round-bottomed flask, 1g of octa (4-bromophenyl) silsesquioxane and 8 equivalents of 1- (trifluoroethyloxy) -4- [4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan]Benzene and 0.5 equivalents of tetrakis (triphenylphosphine) palladium (0). The mixture was stirred for 24 hours, cooled to room temperature and washed twice with 100mL of water. Toluene phase over MgSO₄Dried, filtered, concentrated and the product was precipitated in methanol as a white powder. 19F-NMR (470MHz) delta-122.96 (dd.1F), -129.9(dd, 1F), -137.39(dd, 1F).

Example 6: preparation of trifluorovinyl triethoxysilane

To a dry three-neck round bottom flask with nitrogen and a stir bar were added about (9.5mL, 14.5g at-78 ℃, 0.12mol) iodotrifluoroethylene and 200mL of diethyl ether pre-cooled to-78 ℃. Sec-butyllithium (89mL, 1.4M solution, 0.12mol) was added dropwise over a period of 1 hour. The solution was stirred at-78 ℃ for 5 minutes. Chlorotriethoxysilane (24.35mL, 0.12mol) was added over 5 minutes at-78 ℃. The solution was allowed to warm slowly and stirred overnight. A clear yellow solution remained. Fractional distillation was used to purify the product.

Example 7: preparation of (4-trifluorovinylhydroxyphenyl) trichlorosilane

Activated magnesium (7g, 0.288mol) was added as a crumb to a three-necked round bottom flask with nitrogen and a stir bar. After cooling, the flask was equipped with a condenser, and 200mL of dry ether and 2 iodine crystals were added. 1/3 of 4-trifluorovinyl ether-1-bromobenzene (10 g in total, O.0.039mol) was added. Once started, the remaining 4-trifluorovinyl ether-1-bromobenzene was added. The solution slowly browned and the temperature was kept below 25 ℃. A slight excess of tetrachlorosilane (SiCl) in 100mL of tetrahydrofuran₄) Transfer to a 1000mL three-necked flask with a stir bar and nitrogen blanket. The solution was cooled to 20 ℃ and filtered grignard reagent was added dropwise. Fractional distillation was used to purify the product.

Example 8: preparation of octa (4-trifluoroethylene oxyphenyl) silsesquioxane

4-Trifluoroethyleneoxyphenyltrichlorosilane (31g, 0.1mol) was dissolved in 200mL of methanol and 20mL of water and refluxed for 36 hours. The liquid was decanted from the gel, and the gel was sonicated in methanol to yield a white powder. Filtration and column chromatography were used to purify the product octa (4-trifluoroethylenyloxy) silsesquioxane.

Example 9: preparation of 2- (triethoxysilane) tetrafluoroethyl trifluorovinyl ether

Activated magnesium (7g, 0.288mol) was added as a crumb to a three-necked round bottom flask with nitrogen and a stir bar. After cooling, the flask was equipped with a condenser, and 200mL of dry ether and 2 iodine crystals were added. 1/3 of 2-bromotetrafluoroethyltrifluoroethylvinylether (58 g in total, 0.209mol) was added. At least 1mL of dibromoethane is added to initiate the grignard reaction. Once started, the remaining 2-bromotetrafluoroethyl trifluorovinyl ether was added. The solution was heated under nitrogen for 3 days, cooled, filtered off from air and used immediately by adding one of the following three starting materials: a slight excess of tetraethoxysilane, tetrachlorosilane or chlorotriethoxysilane. Fractional distillation was used to purify the product.

Example 10: preparation of octa [ tetrafluoroethyl trifluorovinyl ether ] silsesquioxane

2- (triethoxysilane) tetrafluoroethyl trifluorovinyl ether was dissolved in 200mL methanol and 20mL water and refluxed for 36 hours. The liquid was decanted from the gel, and the gel was sonicated in methanol to yield a white powder. Filtration and column chromatography were used to purify the product octa [ tetrafluoroethyl trifluorovinyl ether ] silsesquioxane.

Example 11: polymerization of octa [ 4-trifluoroethylenyloxy) phenyl ] silsesquioxane

The monomer octa [ 4-trifluoroethylenyloxy) phenyl ] silsesquioxane was placed in a 1 liter three-neck flask containing 250mL perfluorodeca-tetrahydro phenanthrene, with mechanical stirring and heated to reflux under nitrogen. A polymer deposit formed after about 3 hours. The cooled polymer was removed from the flask and dried under high vacuum.

Example 12: copolymerization of octa [ 4-trifluoroethylenyloxy) phenyl ] silsesquioxane and 1, 6-divinyldodecafluorohexane

The monomers octa [ 4-trifluoroethylenyloxy) phenyl ] silsesquioxane and 1, 6-divinyldodecafluorohexane were sealed in a quartz ampoule with 25mL perfluorodecatetrahydrophenanthrene and heated to 250 ℃ in a high pressure apparatus. After about 5 hours the reaction mixture was cooled and the polymer formed precipitated. The cooled polymer was removed from the flask and dried under high vacuum.

While typical embodiments have been set forth for the purpose of illustration, the foregoing descriptions should not be deemed to be a limitation on the scope of the invention. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present invention.

Claims

1. A polycyclic or monocyclic perfluorovinyl compound comprising at least one structural unit selected from the group consisting of formula I and formula II:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and R is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

the polycyclic or monocyclic compound includes at least two perfluorovinyl groups.

2. The perfluorovinyl compound according to claim 1 wherein the aliphatic group is an alkyl, alkoxy, perhaloalkyl, partially halogenated alkyl.

3. The perfluorovinyl compound according to claim 1, wherein the aromatic group is an aryl group, an aryloxy group, a perhaloaromatic group, a partially halogenated aromatic group.

4. The perfluorovinyl compound of claim 1 comprising formula III

[RSiO_3/2]_n

III

Wherein R is independently at each occurrence hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical; and n is a number from 2 to about 1000.

5. The perfluorovinyl compound of claim 1 comprising formula IV

[R₂SiO]_n

IV

6. The monocyclic or polycyclic perfluorovinyl compound of claim 1, further comprising a structural unit selected from the group consisting of formula V and formula VI:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and R is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical.

7. The monocyclic or polycyclic perfluorovinyl compound of claim 1, wherein said M comprises at least one of silicon and germanium.

8. The monocyclic or polycyclic perfluorovinyl compound of claim 1, wherein the monocyclic or polycyclic perfluorovinyl compound comprises a silicone network.

9. The mono-or polycyclic perfluorovinyl compound of claim 8, wherein the silicon-oxygen network comprises an oligomeric silsesquioxane.

10. The mono-or polycyclic perfluorovinyl compound of claim 9, wherein the oligomeric silsesquioxane comprises polyhedral oligomeric silsesquioxane.

11. The mono-or polycyclic perfluorovinyl compound according to claim 10, wherein the polyhedral oligomeric silsesquioxane comprises an octahedral structure.

12. A method of forming an optical film, the method comprising:

(a) providing a blend of monomer a and monomer B, said monomer a comprising a polycyclic or monocyclic perfluorovinyl compound comprising at least one structural unit selected from formula I and formula II:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements,

r is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical; the polycyclic or monocyclic compound comprises at least two perfluorovinyl groups,

said monomer B is a monomer comprising at least two CF₂An organic compound of ═ CF-units;

(b) mixing the blend with a photoinitiator and a photocurable monomer C, wherein the photocurable monomer C comprises at least one of an acrylate, an epoxy, a polyimide, a silicone, a vinyl compound, a carbonate, and combinations thereof, to obtain a mixed blend;

(c) one of a partially polymerized blend and a mixed blend;

(d) depositing the mixed blend on a substrate to form a film;

(e) selectively exposing the membrane to radiation to at least partially polymerize monomer C; and

(f) curing the film.

13. The method of claim 12 wherein said M comprises at least one of silicon and germanium.

14. The method of claim 12, wherein the polycyclic or monocyclic perfluorovinyl compound comprises a silicon-oxygen network.

15. The method of claim 14, wherein the silicon-oxygen network comprises an oligomeric silsesquioxane.

16. The method of claim 15, wherein the oligomeric silsesquioxane comprises polyhedral oligomeric silsesquioxane.

17. The method of claim 16, wherein the polyhedral oligomeric silsesquioxane comprises an octahedral structure.

18. The method of claim 12 wherein said monomer B further comprises CF₂＝CF-X_m-R-X_m-CF＝CF₂Wherein X is independently at each occurrence a bond, an oxygen linkage, an amine linkage, a sulfur linkage, a silicon-containing linkage, an aliphatic group, an alicyclic group, an aromatic group,

m is independently at each occurrence an integer from 0 to about 100, and

r is a bond, an aliphatic group, a cycloaliphatic group, or an aromatic group.

19. The method of claim 18, wherein X comprises O, N, S, Si, -CH₂-、-CF₂-、-CR₂-, alkyl, alkoxy, partially halogenated aliphatic group, or fully halogenated aliphatic group, wherein R is a bond, an aliphatic group, a cycloaliphatic group, or an aromatic group.

20. The method of claim 12, wherein (c) comprises partially polymerizing the blend of monomers a and B, said partially polymerizing being carried out prior to forming the mixed blend.

21. The method of claim 12, wherein said curing in (f) is performed by at least one of thermal radiation, exposure to light, and combinations thereof.

22. The method of claim 12, wherein (c) comprises heating the blend to a temperature of about 100 ℃ to about 200 ℃ for about 2 minutes to about 60 minutes.

23. The method of claim 12, wherein (e) further comprises diffusing monomer C from unexposed regions to exposed regions of the membrane after selectively exposing the membrane to radiation.

24. The method of claim 23, wherein the selective exposing and diffusing are performed to produce a desired refractive index contrast between exposed and unexposed regions of the film.

25. The method of claim 12, wherein the mixed blend has a viscosity of about 10cSt to about 10000 cSt.

26. The method of claim 12, wherein the mixed blend is deposited on a substrate using a technique comprising at least one of spin coating, doctor blading, dip coating, casting, extrusion, and combinations thereof.

27. The method of claim 12, wherein step (e) further comprises exposing the film to radiation using a photomask.

28. The method of claim 21, wherein said curing comprises heating to a temperature of from about 150 ℃ to about 300 ℃.

29. An optoelectronic device, comprising:

a polymer prepared from a polycyclic or monocyclic perfluorovinyl compound comprising at least one structural unit selected from formula I and formula II:

wherein M is independently at each occurrence a metal selected from group 14 of the periodic Table of the elements; and

r is independently at each occurrence a bond, hydrogen, an aliphatic radical, a cycloaliphatic radical, or an aromatic radical;

30. The optoelectronic device of claim 29, wherein the electroactive component comprises at least one of an organic light emitting diode, a photovoltaic cell, a light emitting diode, an electroluminescent material, a cathodoluminescent material, a phosphorescent material, a mirror, a laser, an optical fiber, a MEMS device, a device for concentrating or dispersing light, a beam splitter, and combinations thereof.

31. The optoelectronic device of claim 29, wherein the optoelectronic device is designed to be operated by a power source.

32. The optoelectronic device of claim 29, wherein the M comprises at least one of silicon and germanium.

33. The photovoltaic device of claim 29, wherein said polycyclic or monocyclic perfluorovinyl compound comprises a silicon-oxygen network.

34. The optoelectronic device of claim 33, wherein the silicon-oxygen network comprises an oligomeric silsesquioxane.

35. The optoelectronic device of claim 34, wherein the oligomeric silsesquioxane comprises polyhedral oligomeric silsesquioxane.

36. The optoelectronic device of claim 35, wherein the polyhedral oligomeric silsesquioxane comprises an octahedral structure.

37. The optoelectronic device of claim 29, wherein the polymer is an optical material.

38. The optoelectronic device of claim 37, wherein the optical material comprises an optically graded material.

39. The optoelectronic device of claim 38, wherein the optically graded material has a refractive index of about 1.0 to about 2.42.

40. The optoelectronic device of claim 38, wherein the optically graded material has an optical loss of less than about 0.05dB/cm over a wavelength range from about 600nm to about 1600 nm.

41. The optoelectronic device of claim 40, wherein the optical loss is less than about 0.05dB/cm at wavelengths of about 850nm, 1310nm, and 1550 nm.

42. The photovoltaic device of claim 29, further comprising a substrate bearing the photovoltaic component and the polymer, wherein the polymer has a high adhesion to the substrate of greater than 3B rating as determined by American Standard Test Method (ASTM) D3359.

43. The optoelectronic device of claim 42, wherein the substrate comprises at least one of a metal, a ceramic, a glass, a plastic, an organic material, an inorganic material, a semiconductor, an electronic device, a microelectromechanical system (MEMS) device, a sensor, a refractive index adjustment device, and combinations thereof.

44. The photovoltaic device of claim 29, wherein said polymer has high thermal stability up to a temperature of about 250 ℃.

45. A polymer prepared by reacting components (a), (b) and (c), wherein:

wherein component (a) is a blend of monomer A and monomer B, said monomer A comprising a polycyclic or monocyclic perfluorovinyl compound comprising at least one structural unit selected from formula I and formula II:

said monomer B is a monomer comprising at least two CF₂An organic compound of the CF-unit,

component (b) is at least one photocurable monomer C, wherein the photocurable monomer comprises at least one of an acrylate, an epoxide, a polyimide, a silicone, a vinyl compound, a carbonate, a diene;

and component (c) is at least one photoinitiator.

46. The polymer of claim 45, wherein the photoinitiator comprises at least one of dibromoethane, benzophenone, benzyl dimethyl ketal, 2-hydroxy-2-methylphenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, N-hydroxyphthalimide trifluoromethanesulfonate, (4-phenoxybenzyl) trimethylammonium chloride, benzoin methyl ether, and diphenyliodonium hexafluorophosphate.

47. The polymer of claim 45, wherein said M comprises at least one of silicon and germanium.

48. The polymer of claim 45, wherein said polycyclic or monocyclic perfluorovinyl compound comprises a silicon-oxygen network.

49. The polymer of claim 48, wherein the silicon-oxygen network comprises an oligomeric silsesquioxane.

50. The polymer of claim 49, wherein the oligomeric silsesquioxane comprises polyhedral oligomeric silsesquioxane.

51. The polymer of claim 50, wherein the polyhedral oligomeric silsesquioxane comprises an octahedral structure.

52. The polymer of claim 45 which is an optical material which is a photodefinable coating system.

53. The polymer of claim 52, wherein the optical material comprises an optically graded material.

54. The polymer of claim 53, wherein the optically graded material has a refractive index of about 1.0 to about 2.42.

55. The polymer of claim 53, wherein the optically graded material has an optical loss of less than about 0.05dB/cm at wavelengths from about 600nm to about 1600 nm.

56. The polymer of claim 55 wherein said optical loss is less than about 0.05dB/cm at wavelengths of about 850nm, 1310nm, and 1500 nm.

57. The polymer of claim 45, wherein the polymer has a high adhesion to a substrate of greater than 3B rating as determined by American Standard Test Method (ASTM) D3359.

58. The polymer of claim 57, wherein the substrate comprises at least one of a metal, a ceramic, a glass, a plastic, an organic material, an inorganic material, a semiconductor, an electronic device, a microelectromechanical system (MEMS) device, a sensor, a refractive index adjustment device, and combinations thereof.

59. The polymer of claim 45, wherein the polymer is a flame retardant.

60. The polymer of claim 45, wherein said polymer has high thermal stability up to a temperature of about 250 ℃.

61. The polymer of claim 45, wherein said monomer B comprises at least one of 1, 6-bis (trifluorovinyl) dodecafluorohexane, 4' -bis (4-trifluorovinyl) oxy) biphenyl, 1, 1, 1-tris (4-trifluorovinyloxyphenyl) ethane, bis (4-trifluorovinyl) oxy) perfluorobiphenyl, and combinations thereof.

62. The polymer of claim 45, wherein the polymer has a viscosity of from about 10cSt to about 10000 cSt.