KR20000036108A - Graded index polymer optical fibers and process for manufacture thereof - Google Patents

Abstract

PURPOSE: An improved method involving microwaves for making polymer optical fiber cable and graded index optical fibers is provided. CONSTITUTION: The polymer can be any shape including, but not limited to, sheets, films or cable. Also provided are improved polymer optical fibers that incorporate quinine and quinone based compositions that shift the wavelength of radiation from ultra violet radiation to visible radiation. A graded index preform rod is prepared by combining one or more prepolymer compositions with different refractive indices to make a mixture; adding bromobenzene to the mixture; adding initiator and trifluoroethylacrylate to the mixture; exposing the mixture to microwave radiation; cooling the mixture until a gel forms; adding butanethiol in methylmethacrylate to the gel; and curing the gel.

Description

GRADED INDEX POLYMER OPTICAL FIBERS AND PROCESS FOR MANUFACTURE THEREOF}

Plastic or polymer optical fibers have been produced in the art over the past decades. However, in the conventional optical fiber manufacturing method, a fiber which is relatively inefficient in terms of transmission efficiency is produced, in particular, compared to glass optical fiber.

For example, for long distance optical communication, single mode glass fiber is widely used due to its high transparency and high bandwidth. In contrast, in the case of short-range communication, a great deal of attention has recently been focused on the development of polymer optical fibers. For short range communications (e.g., local area network systems, interconnects, terminating areas of fiber homes, and domestic passive optical network concepts), numerous splices and connections of the two optical fibers are required. In the case of single mode fibers, the core diameter is approximately 5 to 10 micrometers (μm), so that when the two fibers are joined, even a slight amount of displacement, such as a few micrometers, causes significant coupling losses. Polymer optical fibers are one of the promising possible solutions to this problem, because commercially available polymeric optical fibers generally have large diameters on the order of 1 mm. Thus, low transmission loss and high bandwidth are required to be used as a short range communication medium.

Most commercial polymer optical fibers, however, are step-indexed. Thus, even in the case of short-range optical communications, step-index polymeric optical fibers will not cover the full bandwidth of hundreds of megahertz (MHz) which may be needed for high-speed datalink or local area network systems in the near future, because This is because the bandwidth of the step-index polymer optical fiber is only about 5 MHz / km.

In contrast, graded-index polymeric optical fibers are expected to have significantly higher bandwidths than step-index polymeric optical fibers while maintaining large diameters. Several reports have been made on graded-index polymer optical fibers by Koike and colleagues (eg, Ishigure, T., et al., "Graded-index polymer optical fiber for high-speed data communication" Applied Optics Vol 33, No. 19, pg, 4261-4266 (1994). However, the method described in the above document by Ishigure et al. Is cumbersome and expensive as a gel diffusion method for producing grading index fibers.

Existing fiber optic polymer preparations include the production of fibers by extrusion or by producing an extrudable preform for drawing in a high temperature oven. In both processes, the polymerization process lasts for approximately 48 to 72 hours, after which the polymer is degassed for about 48 to 72 hours to ensure that there are no monomer residues or other solvents. The whole process can take 4 to 6 days or more, thus increasing the possibility of introducing impurities which hinder large-scale production and reduce light transmission.

Thus, there is a need for an inexpensive and simple method of high speed production of grading index polymer optical fibers. There is a need for a high speed production method of low impurity preform rods that does not require a degassing step. The method should produce a low loss and high bandwidth grading index polymeric optical fiber and include controlling the grading refractive index and solubility of the fiber. The fibers produced in this way must be flexible. In addition, the method should be readily applied to current manufacturing techniques for extruding polymeric optical fibers.

The present invention relates to an improved polymer optical fiber and a method and apparatus for manufacturing the same. The present invention includes grading index polymeric optical fibers and methods for their preparation. The present invention also includes optical fibers or polymers that can shift the absorbed electromagnetic radiation wavelength to other wavelengths. The present invention includes a method for chemically cleaning radicals for the production of highly transparent polymers and a method capable of radiation curing the polymer fibers. The present invention includes methods for achieving high speed polymerization of known monomers. The invention also includes a method that can use microwaves to achieve high speed casting of the polymer and to draw the resulting preform rod without the need for degassing.

1 is a rupture view of a rotating polymerization vessel.

2 is an end view of the polymerization vessel.

3 is a cross sectional view along line 3-3 of one end of a rotary polymerization vessel showing injection of reactants into the vessel.

4 is a schematic diagram illustrating an injection and discharge system.

5 is a schematic representation of a distillation system.

6 is an end view of a polymerization vessel attached to a transmission motor.

The term “prepolymer composition” includes monomers and oligomers that can be used to prepare polymers having the desired physical properties. As used herein, the term “preform rod” means a polymer rod produced in a polymerization vessel according to the present invention. As used herein, the term "wavelength shifting additive" means any additive that can add to the polymer the ability to change the wavelength of the electromagnetic radiation transmitted through the polymer. Wavelength shifting additives are preferably added to the prepolymer mixture prior to polymerization. As used herein, the term “patient” refers to a person or animal. As used herein, the term "health care professional" means an individual engaged in providing health care to a patient, including but not limited to: a radiographer, a gastroenterologist, a nuclear medicine doctor, and an oncologist. doctor; Nurses, including nuclear medicine nurses; Specialists, including radiation specialists, digestive specialists, and neurologists; Veterinarians and their assistants; Dentist, dental assistant; And language pathologists. As used herein, the term "research specialist" refers to a scientist; Laboratory experts; student; And individuals engaged in research that may be exposed to radiation, including, but not limited to, post doctors.

The term "relative percentage" refers to the amount of one component divided by another component x 100. Thus, if substance X is present at twice the concentration of substance Y, then the relative% of X: Y will be 200%, expressed as relative% of X: Y = (X / Y) × 100.

The present invention provides a low loss and high bandwidth grading index fiber optic cable that is inexpensive and simple to produce. The present invention also provides a method for producing a fast grading index fiber optic cable. The method of the present invention produces a super flexible fiber. The present invention provides a method for producing an optical fiber having the desired flexibility.

The present invention can be used in the production of grading index fiber optic cables from various monomers, including but not limited to the monomers listed in Table 1. The refractive index is represented by n _D.

Monomer N _{D of} polymer Methyl methacrylate 1.49 Ethyl methacrylate 1.483 n-propyl methacrylate 1.484 n-butyl methacrylate 1.483 n-hexyl methacrylate 1.481 Isopropyl methacrylate 1.473 Isobutyl methacrylate 1.477 Tert-butyl methacrylate 1.463 Cyclohexyl methacrylate 1.507 Benzyl methacrylate 1.568 Phenyl methacrylate 1.57 1-phenylethyl methacrylate 1.549 2-phenylethyl methacrylate 1.559 Perfuryl methacrylate 1.538 Methyl acrylate 1.4725 Ethyl acrylate 1.4685 n-butyl acrylate 1.4634 Benzyl acrylate 1.5584 2-chloroethyl acrylate 1.52 Vinyl acetate 1.47

Monomer N _{D of} polymer Vinyl benzoate 1.578 Vinyl phenyl acetate 1.567 Vinyl chloroacetate 1.512 Acrylonitrile 1.52 a-methylacrylonitrile 1.52 Methyl-a-chloroacrylate 1.5172 Atrophic acid, methyl ester 1.560 o-chlorostyrene 1.6098 p-fluorostyrene 1.566 o, p-difluorostyrene 1.475 Pentabromophenylacrylate 1.7 Pentachlorophenyl methacrylate 1.63 Pentabromophenyl methacrylate 1.71 Chlorophenyl acrylate 1.5 Benzyl methacrylate 1.56 2,4,6 tribromophenyl acrylate 1.6 α, ω, dichloropropyl-dimethylsiloxane 1.42 p-isopropyl styrene 1.554 2,2,2-trifluoroethylacrylate 1.37 2,2,2-trifluoroethyl methacrylate 1.39 Tribromoneopentyl methacrylate 1.6

Useful monomers for the cladding for the polymer fiber optical cable of the present invention include the following monomers.

1H, 1H pentadecafluorooctylacrylate 1.33 1H, 1H pentadecafluorooctyl methacrylate 1.35 1H, 1H, 4H hexafluorobutyl methacrylate 1.39 1H, 1H, 4H hexafluorobutylacrylate 1.39 1H, 1H, 2H, 2H heptadecafluorodecylacrylate 1.35 1H, 1H, 2H, 2H heptadecafluorodecyl methacrylate 1.35 Hexafluoro-iso-propylacrylate 1.40 Hexafluoro-iso-propylmethacrylate 1.40 1H, 1H heptafluorobutyl methacrylate 1.37 1H, 1H octafluoropentamethacrylate 1.39 1H, 1H Heptafluorobutylacrylate 1.39

Prepolymer compositions useful in the practice of the present invention include polycarbonates (e.g., those sold under the trademark LEXAN ^{™ by} General Electric Company, Schenectady, NY), polyesters, polyolefins, acrylic acid polymers (e.g., Polymers such as those sold under the trademark ACRYLITE ^{™ by} Cyro Industries, Inc., and other thermoplastic polymers. Another example of a suitable acrylic acid polymer is polymethyl methacrylate. Other polymers that can be used in the present invention include halide-terminated organosiloxanes (eg, chlorine-, bromine-, and fluorine-terminated organosiloxanes), alkoxy functional siloxanes with alcohol splits (ie, OH side chain groups). , Hydroxy terminated polymer borate, dihydric phenols with easy removal of ammonia groups, and diphenol propane bischloroformates.

The present invention is particularly useful for the production of grading index polymer optical fibers with specialized non-linear grading index cross sections. Additives may be incorporated into the grading index polymeric optical fibers of the present invention to provide a useful effect. For example, a wavelength shifter can be added for shifting the wavelength of the electromagnetic beam transmitted through the fiber. By selecting the appropriate polymer, the flexibility of the grading index polymer optical fiber can be applied to a particular application. For example, in the present invention, the relative percentage of methyl methacrylate: styrene can vary from 10 to 400% to change the flexibility and refractive index of the polymer fibers. Methyl methacrylate: When the relative percentage of styrene is about 50%, the resulting fiber shows great flexibility.

The invention is also useful for single mode optical fibers that can be used for the visual transmission of images. Such fibers are particularly useful for endoscopy devices. By using the fibers according to the invention, the optical fibers can replace expensive glass fibers with little or no reduction in the intelligibility of the transmitted image.

For example, the addition process of the copolymer is adjusted such that the final polymer added is bis phenyl A polycarbonate or other phenols listed in Table 1 with a refractive index of 1.58. The resulting preform rod is a grading index rod with an index of 1.42 on the surface and this index gradually increases to 1.58 at the center of the preform rod. The rod may then be heat drawn using conventional extrusion techniques to provide a grading index polymeric optical fiber. According to the invention, the refractive index changes from the outer surface of the preform rod, so that the resulting optical fiber can be linear, non-linear, or even stepped, depending on how the polymer is added to the cylinder. It is important to note. To produce single mode optical fibers, a single concentration of polymer or polymer mixture is used for the synthesis of the preform. Two or more polymers are used to produce grading index optical fibers.

In one aspect, the present invention includes the high speed formation of the flexible optical fiber described in Examples 1-4. Various monomers are mixed together and then heated. By adjusting the ratio of methyl methacrylate: styrene, the flexibility of the fiber can be adjusted. In addition, by using N, N-dimethylaniline and tetrabutyl ammonium fluoride tetrahydrate (TAFT) in methanol, a high molecular weight polymer can be formed as in Example 2. The use of TAFT in methyl methacrylate and N, N-dimethylaniline as in Example 3 results in a fiber having increased flexibility, and a higher molecular weight polymer that is formed more quickly than the fiber formed by the process of Example 1 do. N, N-dimethylaniline and TAFT are believed to accelerate the polymerization process and increase the molecular weight of the resulting polymer in the fiber. Some of the chemicals mentioned in these examples may vary in the practice of the invention. For example, for Example 4, it is also possible to use mercurate chloride and mercuric oxide instead of mercuric-2-chloride in the practice of the process of the invention. The temperature conditions given in Examples 1-4 can also be varied in the practice of the present invention.

In short, one aspect of the present invention involves the formation of a grading index polymer on the inner surface of the tube of the cladding polymer. The refractive index of the cladding polymer is sufficiently lower than that of the core polymer. As the refractive index increases, the maximum possible light incident angle increases. Additional properties essential for cladding polymers are high transparency, mechanical strength, heat resistance and adhesion to the core. In the case of grading index fibers, the cladding may be the copolymer itself.

A refractive index gradient is formed by reacting these monomers or oligomers using two or more different monomers or oligomers, with varying concentration ratios of monomers or oligomers as the preformed rods are formed. In this way, a smoothing gradient is formed from the inner side of the cladding to the center of the preformed rod. The preformed rod can then be heat drawn to form the fibers. In the present invention, the relative percentage of methyl methacrylate: styrene can be changed according to the desired refractive index. In addition, as described in Example 5, the amount of 2,2,2-trifluoroethyl methacrylate or 2,2,2-trifluoroethyl acrylate added depends on the desired profile of the refractive index of the fiber. It can vary from about 1% to 20% by weight. In addition, the rate of temperature increase described in Example 5 can be varied to affect the grading index characteristics of the fiber.

Both the monomers and the required reactants should preferably be cleaned using, for example, an ultrafilter capable of removing particulates larger than 100 mm 3 in size. The monomer is cleaned in two successive processes: first, the monomer is washed with a suitable solvent (eg water) and then dried with anhydrous or non-aqueous solvent. The monomer can then be optionally vacuum distilled prior to introduction into the polymerization chamber.

In the drawings, the same reference numerals denote the same elements in each drawing, and in FIG. 1, there is shown a cross-sectional view of a polymerization vessel with a heating jacket 12 enclosing the polymerization vessel 10. The heating jacket 12 may be another commercial heating jacket, which is preferably electrically heated. The polymerization vessel 10 is preferably a stainless steel cylinder 15 with a right end cap 25 and a left end cap 26. Each cap 25, 26 is a hex knot (axial support) 20, 21 threaded respectively. The shafts 27 and 28 are inserted in the caps 25 and 26 respectively. The right end cap 25 and the left end cap 26 each have bearings and slip rings 30, 31. The right end cap 25 and the left end cap 26 are attached to the stainless steel cylinder 15 by seal screws for the end caps 25, 26. In operation, the outer polymer cladding and polymer growth substrate 18 are inserted into the polymerization vessel 10 prior to the polymerization of the polymer.

2 is an end view of the polymerization vessel 10 showing the slip ring 30 and the shaft support 20. Also shown is a seal screw for the end cap 35. As shown in FIG. 6, the polymerization vessel 10 on the support 155 attaches the belt 145 to the shaft 28 and the transmission motor 150 between the threaded hex nut 20 and the slip ring 30. By attaching it can be rotated during the polymerization process.

3 is a cutaway view of the right end cap 25 of the polymerization vessel 10 along line 3-3. 3 also shows a right injection system 55 inserted into the shaft 27 and shows a bearing and slip ring 30, a shaft 27, and a right end cap 25. It is also shown that the recess 60 has a sealing disc for the injection system 40, 45 on one side of the cylindrical spacer 50. The injection and discharge system 55 is inserted into the shaft 27 with the cylindrical spacer 50 into which the needle 57 and the prepolymer are introduced into the polymerization vessel 10 through the ceiling discs 40 and 45.

4 completely shows the right inlet and outlet system 55. The inlet and outlet system 55 consists of a mixing vessel 85 with a sealing cap 87. In the embodiment shown in FIG. 4, there is an inlet for vacuum 65 with an inlet for vacuum valve 67. There is a first injection port 70 with a first injection valve 73. There is also a second injection port 75 with a second injection valve 77. In the present invention, one or more injection ports may be inserted into the mixing vessel 85 depending on how many prepolymer compositions are introduced into the polymer vessel 10. Mixing vessel 85 also has an injection port from distillation apparatus 80 and an injection port valve from distillation apparatus 83. In use, distillation apparatus 80 may or may not be used. In addition, one or more distillation apparatus 80 may be attached to the mixing vessel 85. The mixing vessel 85 has a mixing vessel port 102 that opens to the injection vessel 95 through the mixing vessel port valve 105. The injection vessel opens to the first injection port 100 inserted into the shaft 27 or the left shaft 28 during the loading of the rotary polymerization 10. The injection vessel has two discharge ports 90 and two discharge port valves 93. This discharge port is used to remove gas from the polymerization vessel 10 as the polymerization vessel is loaded.

The distillation apparatus 107 is shown in FIG. 5 and includes a distillation flask 120 set in the heater 115. The distillation flask 120 has a thermometer 110 inserted at the top of the distillation flask 120. Distillation flask 120 is attached to condenser 125 which can be cooled with water or other coolant. Condenser 125 is connected to receiving flask 135 via a connector having an outlet for vacuum 130. The receiving flask 135 has a port 140 for the mixing vessel 85. The port 140 for the mixing flask has a receiving flask valve 137 for controlling the transport of material to the mixing vessel 85.

In preparing the preform rods, the outer polymer cladding and polymer growth substrate 18 are placed in the polymerization vessel 10 and the end caps 25, 26 are attached to the polymerization vessel and then sealed. The polymerization vessel 10 is heated to a desired temperature with a heater 12. As shown in FIG. 6, the polymerization vessel 10 is rotated by turning on the motor 150 at a desired speed.

Subsequently, the prepolymer compound is mixed in the mixing container 85 by introducing various prepolymer compounds into the mixing container 85 through the injection ports 70, 75, and 80. Once the prepolymer compound is transported into the mixing vessel 85, they can be injected directly into the polymerization vessel 10 via the injection system 55. The polymerization vessel 10 is then heated to the desired temperature and the prepolymer mixture is injected into the polymerization vessel 10 at the desired rate via the injection and discharge system 55. At the other end of the polymerization vessel 10, an initiator such as phosgene is added by injection. This process continues until the polymer is formed to fill the polymerization vessel 10. It should be noted that a mixture of prepolymer compounds can be added at various rates, thus changing the proportion of prepolymer components in the final polymer as the polymer is formed in the polymerization vessel 10. In this way, the grading index preform polymer can be easily produced and the proportion of the prepolymer compound can be varied in any way to form a preformed polymer with the desired index change from cladding to the center of the preformed polymer. Can be.

After the preformed rod is formed, the rod can be removed from the polymerization vessel 10 and extruded by means well known in the art to form the polymer fibers.

In one aspect of the invention, the prepolymer compound is mixed in the mixing vessel by introducing various prepolymer compounds into the mixing vessel through the injection port. Once the prepolymer compounds are transported to the mixing vessel, they can be injected directly into the polymerization vessel via an injection system. The polymerization vessel is then heated to the desired temperature and the prepolymer mixture is introduced into the polymerization vessel at the desired rate via an injection and discharge system. At the other inlet, preferably at the other end of the polymerization vessel, an initiator such as phosgene is added by injection. This process continues until the polymer is formed to fill the polymerization vessel. It should be noted that a mixture of prepolymer compounds can be added at various rates, thus changing the proportion of prepolymer components in the final polymer as the polymer is formed in the polymerization vessel. In this way, the grading index preform polymer can be easily produced and the proportion of the prepolymer compound can be varied in any way to form a preformed polymer with the desired index change from cladding to the center of the preformed polymer. Can be.

After the preformed rods have been formed, the rods can be removed from the polymerization vessel and extruded by means well known in the art to form polymer fibers.

As another aspect of the invention, the preform grading index polymer can be produced at high speed in a single step. Various monomers are mixed together and then heated. During the polymerization process, by adjusting the rate of temperature increase or decrease, the refractive index profile of the preform rod can be adjusted to any desired profile. As an embodiment described in detail in Example 5, styrene and methyl methacrylate are mixed. Methyl methacrylate: the relative percentage of styrene can be about 10 to 500%, the desired relative percentage is about 40 to 400%, the most preferred ratio is about 80 to 400%.

A polymerization promoter such as dibenzoyl peroxide is then added. It is noted that the refractive index profile can be determined by the proportion of monomers in the initial mixture. Then 2,2,2-trifluoroethyl methacrylate (1-20 wt%) or 2,2,2-trifluoroethyl acrylate (1-20 wt%) is added and mixed with other reagents . The mixture is then left under nitrogen at about 50 ° C. for several hours. The temperature is then gradually increased depending on the% of desired polymer and the desired refractive index profile. Preferably, the rate of temperature increase is 10 ° C. per 30 minutes until approximately 100 ° C. is achieved. The temperature is then increased to about 130 ° C. for about 1 hour and the procedure is finished. Rapid temperature increase results in maximum refractive index change near the surface of the preform rod. Increasing the temperature slowly will result in more linear refractive index changes. Other temperature profiles may be used in the practice of the present invention depending on the desired refractive index profile. This embodiment has the advantage of producing grading index polymer fibers in a single reaction in a relatively short period of time. No mechanical manipulation of the reaction mixture is required.

In another aspect of the invention, exposure of the mixture of prepolymer composition and initiator to microwaves for approximately 1 to 60 minutes can lower the amount of initiator or polymerization promoter required, significantly increase the transparency of the resulting polymer and further increase the grading index profile. It has been found that it can be precisely adjusted. In practice, after exposing the monomer mixture to microwaves, the resulting partial polymer gel can be completely cured using microwaves, or more preferably heat. A preferred method of exposing the non-polymerized solution to microwaves is to expose the solution to microwaves for a short time, for example 30 seconds, and then to cool the solution in an ice bath. The exposure / cooling procedure can be repeated until the gel is formed. The power of the electronic oven is preferably approximately 700 watts. The power of the microwave and the length of exposure time for exposing the monomer mixture to the microwave is dictated by the desired final profile of the preform rod.

In one aspect of the present invention, high molecular weight prepolymer compositions such as methyl methacrylate and polymethyl methacrylate in high molecular weight form may be used to prepare preform rods including grading index preform rods. In some cases, the molecular weight of such prepolymer compositions can be 20,000, 50,000, 75,000, 1,000,000 or more. Methods of using microwaves to form preform rods are illustrated in Examples 17, 18, 19, 20, and 21. The proportion of the prepolymer composition can vary to achieve the desired characteristics. For example, the ratio of methyl methacrylate: polymethylmethacrylate may be 90 to 10% by weight. Initiators such as 2,2'-azobisisobutyronitrile, peroxides, benzyl peroxides, tertiary butyl peroxides and dibenzoyl peroxides can be used in the process of the invention.

Gels can be cured using a variety of temperature conditions and durations. In one aspect, the curing step of the gel includes curing for about 24 hours at a temperature of approximately 70-90 ° C. in an oven and then for at least 12 hours at a temperature of about 100 ° C. in an oven. In another embodiment, the curing step of the gel includes curing for about 24 hours at a temperature of approximately 55 ° C. in an oven and then for about 36 hours at a temperature of about 80 ° C. in an oven. In another embodiment, the curing step of the gel includes curing for about 12 to 24 hours at a temperature of about 70 to 80 ° C. in an oven and then for about 12 hours at a temperature of about 90 to 110 ° C. in an oven. In another embodiment, the curing step of the gel includes curing for about 12 to 24 hours at about 70 to 80 ° C. in an oven, or curing for about 12 hours at a temperature of about 90 to 110 ° C. in a chamber.

The grading index polymer optical fibers of the present invention are particularly suitable for short-range communications such as local area networks (LAN), datalinks, and multinoded bus networks because of their easy processing and large diameter and high efficiency. This is because it enables fiber coupling and beam insertion. The grading index polymer optical fiber of the present invention has a much higher bandwidth (> 500 MHz / km) than the bandwidth (2-5 MHz / km) of multimode step index polymer optical fiber.

The present invention also includes a method of increasing the transparency of a polymer optical fiber by adding a free radical scavenger such as dibutyl-1-phthalate at a concentration of approximately 0.5 volume percent. Other free radical scavengers that may be added to the polymer in the production of preform rods include, but are not limited to, propanol, cyclohexane, and butylnitrile. Other formulations that may be used to increase the transparency of the final fiber include, but are not limited to, various low temperature glass transition small molecules such as siloxane oligomers and different Lewis acids. It should be appreciated that the formulations that can be used to increase the transparency of the final fiber can be used alone or in combination. Preferably, the concentration of the transparency agent should be about 0.01 to 2% by weight, more preferably about 0.1 to 1%, and most preferably about 0.5% by weight.

The present invention also includes additives capable of shifting the wavelength of the electromagnetic radiation as it passes through the polymer containing the additive. The additive can be used for any polymer or polymer fiber. Additives are unique in that they can cause very large shifts in the electromagnetic wave wavelength. For example, certain additives may shift the wavelength of the intake electromagnetic radiation from the ultraviolet range to the visible range. Another additive may shift the infrared electromagnetic beam into visible light. Another additive can shift X-ray electromagnetic radiation into visible light. The additives of the present invention can shift electromagnetic radiation over a wavelength range of about 200 nm. For example, the additive described in Example 6 can shift the wavelength of ultraviolet electromagnetic radiation at a wavelength of 250 nm to visible light observed as green light at a wavelength of approximately 420 nm.

The present invention includes compositions and methods for the preparation of such compositions which are additives capable of shifting the wavelength of electromagnetic radiation from ultraviolet to cyan and blue visible light. Such compositions are described in Examples 15 and 16 and include quinoline, quinine, and quinine monohydrochloride dihydrate base compositions. These may be added to preform rods, including the grading index preform rods of the present invention, and polymer films, sheets, fibers, and other objects made in accordance with the methods of the present invention.

Although not wishing to be bound by the theory below, it is assumed that the wavelength shift is due to intramolecular proton shifts. Additives are generally "ladder" shaped polymers with crosslinkers comprising aromatic moieties capable of donating or accepting protons when exposed to electromagnetic radiation. The proton shift is supposed to cause a shift in the wavelength of the electromagnetic beam.

The present invention can be applied to films for various uses involving various imaging processes, all of which are considered to be within the scope of the present invention. Conventional radiographic procedures involve passing X-rays through an object to produce an image of various shades of white, black and gray, depending on the radiation density of the object. Such images are generally captured on a film and then developed and fixed to a film processing machine using various chemicals. The present invention is very sensitive to electromagnetic radiation and can be used with substantially significantly less incident radiation (approximately 25%) of the electromagnetic radiation which is usually required for the generation of radiographs. Films coated and exposed to X-rays according to the present invention produce a color image without the need to capture the image and convert it to color via intermediate means such as a computer. Using the present invention, for example, a healthcare professional can easily obtain color images of damaged limbs after exposing the limbs to X-rays. Such color images can be obtained using only about 25% of the line of incidence typically required for radiographic generation, thereby significantly reducing direct and reflected radiation exposure to patients and healthcare professionals. Reduced radiation levels also reduce the amount of lead shielding required, thereby reducing the weight of shielding screens and clothing, and associated occupational injuries such as low back strain due to the need to wear heavy lead aprons. Decrease. Moreover, these color images can be viewed immediately after X-ray exposure, reducing time lag in film processing, reducing the costs associated with the purchase of radiographic printing developing devices and power supplies, and inducing toxic chemicals with advanced radiographic phenomena. Processing cost is reduced.

The coating film of the present invention is also useful for the preparation of fluorescence procedures. Various fluorescence procedures, such as mannofluorography, involve continuous exposure of the patient to X-rays and produce black and white images of differential radiation density of the patient. Such images are often stored on tape and viewed as continuous images. In this procedure, radiocontrast materials such as barium are observed as they move within the subject. For example, after swallowing a round barium mass, a healthcare professional may watch the barium migration path in the oral pharynx, esophagus and stomach in the oral cavity. Since the use of the present invention requires significantly less incident radiation, an online color image of the patient is provided while significantly reducing the radiation exposure of both the patient and the caregiver. The present invention includes, but is not limited to, upper and lower gastrointestinal series, arterial imaging, inflation X-rays, intravenous pyelograms, lymphangiography X-rays, gallbladder angiography, spinal cord X-rays, and other procedures. It is useful for various similar radiological procedures. The invention is also useful in the field of nuclear medicine and radiation oncology, where the manufacture and use of medicinal forms of radiation, or the intensive application of radiation for therapeutic reasons, is common.

The use of the present invention in other imaging procedures is also contemplated as being within the scope of the present invention. These imaging procedures include, but are not limited to, certain types of electromagnetic radiation, including but not limited to magnetic resonance imaging (MRI), computed tomography (CRT or CAT), positron emission tomography (PET), and their improvements. Include other procedures that apply to the patient.

In addition to patients and other living animals and plants, other objects subject to radiation exposure may be non-living. In this case, safety inspections at the airport include radiographic analysis of cargo, coats, bags, and the like. The use of the film of the present invention incorporating a wavelength shifter reduces the required incident radiation level to approximately 25% of the current level, while providing an online color image that can facilitate identification of suspicious articles. Provides radiotoxicity and reduces shielding costs.

The present invention can be applied to the improvement of radiation monitoring equipment. For example, radiation badges are worn by a large number of individuals, particularly those in research, healthcare professionals, and nuclear facilities, or in industries involving radiation use. These badges should be developed to provide an ex post evaluation of the degree of radiation exposure of the individual. The use of the wavelength shifting additive of the present invention incorporated into film badges provides an immediate visible color representation of the radiation exposure range without the need for badge development using conventional means such as chemical developers or fixatives. This capability is particularly useful during procedures involving relatively high level radiation, such as radioiodination, or in the manufacture of radiotherapy formulations. Film badges incorporating the films of the present invention may be worn in other locations as desired for radiation monitoring, such as in fingers, belts and lapels.

The films of the present invention can be incorporated into garments for aviation, aerospace, and nuclear industry workers exposed to astronauts and high level radiation. The films of the present invention can be incorporated into cockpits and windshields of airplanes that are exposed to higher levels of high level radiation in the atmosphere. Such films of the present invention may be incorporated into the garments of aviation workers, such as pilots, airplane engineers, stewards and stewardess, who are exposed to elevated levels of radiation in badges or in flight. Other industry workers, including but not limited to those exposed to high-level solar radiation in industries such as construction, transportation, agriculture, shipbuilding, petroleum, and recreation, also benefit from the present invention.

The film of the present invention is incorporated into recreational clothing and equipment including, but not limited to, visors, caps, sunglasses, swimwear, sportswear, umbrellas, blankets, towels, and chairs so that individuals can accurately monitor exposure to solar radiation. And thus reduce the incidence of burns and various forms of skin cancer, especially melanoma, which are expected to increase significantly in recent years and to increase further in the future.

Another item of radiation detection equipment to which the present invention can be applied is a small piece of film attached to a swab, filter paper, towellet, or wipe for use in radiation monitoring wipe tests performed to determine whether a radiation leak has occurred. Include. The present invention obviates the need to measure the radioactivity of conventional pieces of filter paper in a gamma counter since the paper with the film becoming radioactive or transmitting radiation is immediately discolored. The present invention saves time and cost in unnecessary counting of wipe tests in a gamma counter, increasing the usability of the analytical gamma counter and providing immediate results. The films of the present invention can also be incorporated into sheets of laboratory bench-top paper so that radioactive leaks can be immediately visualized during the procedure, warning the individual of the risk so that the correct procedure can be initiated. The present invention is particularly useful for research professionals and healthcare professionals.

Films of the invention can also be used in separation science. The film can provide color printing of the radiolabeled band on the gel used for the separation of molecules including, but not limited to, proteins, nucleoproteins, and nucleic acids, indicating the location of various radiolabeled molecules and displaying conventional photographic films. The juxtaposition of and the need for its development are eliminated. The film can be used to monitor the passage of radiolabelled material through the chromatography column. Such films also contain ethidium bromide or other markers that are activated by electromagnetic radiation, such as ultraviolet light, and emit electromagnetic radiation in the form of ultraviolet light, and can provide color prints of bands on a gel. The susceptible film of the present invention allows the use of significantly lower amounts of toxic dyes, such as ethidium bromide, required to visualize the band upon ultraviolet exposure.

The invention can also be incorporated into detection systems that measure radiation emissions, such as gamma counters, scintillation counters, and spectrophotometers.

The films of the present invention may also be used in applications involving the preparation of radiological phenomena such as radiation emitted from stars, nuclear facilities, nuclear storage facilities, nuclear test sites, from shipping bins and radionuclide containers. For example, the incorporation of the film of the present invention into a bin used for the shipment of radionuclides may warn isotope users before the bin is contaminated and open to the risk of exposure to enriched dose of radiation. This application eliminates the need for time consuming radiation monitoring "wipe test".

Summary of the Invention

The present invention provides a low loss and high bandwidth fiber optic cable that is flexible, fast and inexpensive and easy to produce. The present invention also includes a method of producing a grading index preform rod that can be used in the manufacture of highly flexible grading index fiber optic cables. The present invention also provides a method for producing such fibers faster and more economically than current methods.

In the case of grading index fiber optic cables, the method of the present invention involves starting with a cylinder of homogeneous cladding polymer. The cylinder of the cladding is inserted into the reaction chamber which can be heated and rotate along its longitudinal axis. For example, the cladding may be a preformed silicone oligomer, ie, α, ω, dichloropropyldimethylsiloxane having a refractive index of 1.42. Alternatively, microwaves can be used with certain prepolymer compositions to prepare preform rods.

Then, for example, the monomer mixture of the cladding and excess bisphenyl A polycarbonate is added to the interior of the cladding continuously or stepwise with the bisphenyl A pyridine methylene chloride solution and the chamber is heated and rotated. As the preform rod is formed, phosgene gas is also continuously added to the chamber. As the copolymer is polymerized on the inner surface of the cladding, the ratio of bisphenyl A: dimethylsiloxane can be changed to provide a copolymer in which the refractive index is gradually changed. As the copolymer builds up inside the cladding, the amount of polydimethylsiloxane decreases and the amount of bisphenyl A polycarbonate increases until filled with the preform rod. The preform rod can then be removed from the reaction chamber and used in a conventional extrusion apparatus to produce the optical fiber.

Other monomer mixtures that may be used in the practice of the present invention are styrene, methylmethacrylate, and monomers that polymerize with low surface energy polymers such as fluorinated monomers or siloxanes. While the following theory is not desired, it is assumed that during polymerization, the low surface energy polymer moves outward and the refractive index profile of the preform rod is controlled by temperature conditions.

The invention also includes a method of increasing the transparency of a polymer optical fiber by adding a radical scavenger, such as dibutyl-1-phthalate, at approximately 0.5 volume percent. Other free radical scavengers that may be added to the polymer in the production of preform rods include, but are not limited to, propanol, cyclohexane, and butylnitrile. Other agents that can be used to increase the transparency of polymeric optical fibers include, but are not limited to, various low temperature glass transition small molecules such as siloxane oligomers and different Lewis acids.

The resulting fibers can easily be bundled together into bundles which can be placed in a container and fused by applying a vacuum to the bundles. The temperature is raised to the glass transition point of the cladding. The bundle is then cooled. The process is preferably repeated several times, preferably four to five times, resulting in a uniform fiber bundle.

Finally, the present invention includes existing optical fibers capable of very large wavelength shifting between intake and emission electromagnetic radiation and additives that can be added to the optical fibers of the present invention. Some of these additives cause wavelength shifts, including shifts from ultraviolet to cyan and blue visible light. Such additives may be added to preform rods, films or other shaped optical fibers made according to the method of the present invention.

It is therefore an object of the present invention to provide a grading index polymer fiber optical cable.

Another object of the present invention is to provide a low loss and high bandwidth grading index polymer fiber optical cable.

It is another object of the present invention to provide a high speed manufacturing method of flexible grading index polymer fiber optical cable.

It is a further object of the present invention to provide a method for producing fused bundles of grading index polymer fiber optical cables.

Another object of the present invention is to provide a preform rod that can be produced at high speed compared to conventional methods which require even more time.

Another object of the present invention can be produced without the vacuum application or degassing step required in conventional methods, thus preforming rods and grading index preform rods which facilitate the production of preform rods which are immediately drawn into fibers. To provide.

Another object of the present invention is to provide a preform rod and a grading index preform rod using microwaves.

Another object of the present invention is to provide a photopolymer that can cause a large shift in wavelength between intake and emission electromagnetic radiation, suitable for use as a film, gel or fiber optical cable.

Another object of the present invention is to provide a polymer which can be produced in different forms and shapes, and which contains a wavelength shifter that can be incorporated into radiation monitoring equipment, radiation detectors, and workwear and recreational clothing.

Another object of the present invention is to provide a polymer composition containing a wavelength shifter that can be used to view X-rays, ultraviolet rays, or infrared rays as visible light. The present invention also encompasses shifting from visible light to X-rays, ultraviolet light, or infrared light.

Another object of the present invention is to pre-visible invisible light in real time at reduced levels of incident light currently required to visualize objects and polymer compositions containing wavelength shifters used to view X-rays, ultraviolet rays, and infrared rays as visible light. Thereby providing the ability to reduce radiation exposure of patients and healthcare professionals.

Another feature of the photopolymer fibers of the present invention is that they provide the ability to magnify images with high resolution.

Another object of the present invention is to provide a polymer fiber optical cable suitable for use in endoscopy devices.

Another object of the present invention is to provide a very flexible optical fiber.

The above and other objects, features and advantages of the present invention will become apparent only after a review of the following detailed description of the described embodiments.

The invention is illustrated in more detail by the following examples, although the scope of the invention is not limited thereto in any way. In contrast, it will be apparent to those skilled in the art that various other aspects, modifications, and equivalents thereof are possible after reading the detailed description herein without departing from the spirit of the present invention and / or the appended claims. Unless otherwise noted, all chemicals are obtained from Aldrich Chemical Company, Milwaukee, WY.

Example 1

Manufacturing method of polymer optical fiber

About 50 g of styrene (100% distillation) is added to about 50 g of methylmethacrylate (100% distillation). The following reagents are then added to the styrene: methyl methacrylate mixture in any order:

Dibenzoyl peroxide (1-2 wt%); Dodecyl mercaptan (1% by weight of 100% distilled stock solution); And butyl thiophene (0.5% by weight 100% distilled stock solution). The mixture is heated in the following order: first at 100 ° C. for about 3 hours, then at 120 ° C. for about 3 hours; About 2 hours at 150 ° C and finally about 12 hours at 85 ° C. In this and subsequent examples, the mixture is heated in a vacuum oven under a nitrogen atmosphere without applying vacuum.

Example 2

Manufacturing method of polymer optical fiber

About 50 g of styrene (100% distillation) is added to 50 g of methyl methacrylate (100% distillation). The following reagents are then added to the styrene: methylmethacrylate mixture in any order:

Dibenzoyl peroxide (1-2 wt%); Dodecyl mercaptan (1% by weight of 100% distilled stock solution); And butyl thiophene (0.5% by weight 100% distilled stock solution).

Then, N, N-dimethylaniline (1 wt% distilled stock) and 1.0 wt% tetrabutyl ammonium fluoride tetrahydrate (TAFT), 10 wt% in methanol, are added. N, N-dimethylaniline and TAFT catalyze the polymerization and increase the molecular weight of the polymer produced in the fiber.

The mixture is heated in the following manner: first at 100 ° C. for about 3 hours, then at 120 ° C. for about 3 hours; About 2 hours at 150 ° C and finally about 12 hours at 85 ° C. The polymerization takes place after about 10 hours and the resulting polymer has a higher molecular weight than in Example 1.

Example 3

High speed manufacturing method of flexible polymer optical fiber

The same procedure as in Example 2 is used except that 1.0 wt% TAFT added to 25 g styrene and 75 g methyl methacrylate is in 10 wt% methylmethacrylate. N, N-dimethylaniline (1 wt% distilled stock) was added. Heating conditions are the same as in Example 2.

The resulting fibers show increased flexibility and contain higher molecular weight polymers and are formed more quickly than the fibers formed by the method of Example 1.

Example 4

High speed manufacturing method of flexible polymer optical fiber

The same material is used except that N, N-dimethylaniline is not used. Mercury-2-chloride (0.5 to 1.0 wt%) in methanol solution (10 wt%) is added and the mixture is heated at 100 ° C. for 30 min. Then the mixture is cooled. After 20 minutes the procedure can be stopped at room temperature. At this time, the material is in the form of a viscous semi-polymer and can be polymerized by drawing it continuously. Although any extruder can be used to push the material out of the reaction vessel, the nitrogen gas pressure can be used to push the viscous material out of the vessel into the desired shape. The resulting fibers are free of discoloration, are flexible and very easily drawn into the fibers. The process described in this example provides fast polymerization rates and high molecular weight polymer manufacturability.

It is also possible to use mercurate chloride and mercuric oxide in place of mercuric-2-chloride in the process described in this example.

Example 5

Grading index fiber

About 50 g of styrene (100% distillation) is added to 50 g of methylmethacrylate (100% distillation). The following reagents are then added to the styrene: methylmethacrylate mixture in any order:

Dibenzoyl peroxide (10% by weight); Dodecyl mercaptan (1% by weight of 100% distilled stock solution); And butyl thiophene (0.5% by weight 100% distilled stock solution). The amount of styrene added varies depending on the desired refractive index. Then, 2,2,2-trifluoroethyl methacrylate (1-20 wt%) or 2,2,2-trifluoroethyl acrylate (1-20 wt%) is added and mixed with other reagents. The mixture is then placed in a vacuum oven at 50 ° C. for 2 hours under a nitrogen atmosphere. No vacuum is applied to the vacuum oven. The weight percent of 2,2,2-trifluoroethyl methacrylate or 2,2,2-trifluoroethyl acrylate added may vary depending on the desired refractive profile of the fiber (1-20 wt% ). In this example, 10% by weight 2,2,2-trifluoroethyl methacrylate is used. The temperature is then gradually increased depending on the% of desired polymer and the desired refractive index profile. The rate of temperature increase is approximately 10 ° C. per 30 minutes until it reaches 100 ° C. The rate of temperature increase can be varied to affect the grading index characteristics of the fiber. The temperature is then increased to 130 ° C. for 1 hour and the procedure ends.

Example 6

Wavelength shifting composition for wavelength shift from 250 nm to 420 nm

Wavelength shifting compositions are prepared with the following protocol. 5 g of piperonal and 5 g of cyanoacetate are mixed with 0.8 ml of piperidine. The mixture is then dissolved in 100 ml of toluene. 5 g of molecular sieve (Aldrich) is added to the solution. The mixture is heated at 70 ° C. for 6 hours. The mixture is then filtered through filter paper to remove molecular sieves. The mixture is then cooled and toluene is evaporated off to yield a powder. The powder can be dissolved in benzene at a concentration of 1 g / ml. The powder concentration in benzene can vary depending on the amount of wavelength shifter required for the final polymer matrix.

Various amounts of benzene solution are added to conventional methyl methacrylate prepolymers and the solution is polymerized according to conventional reaction protocols well known to those skilled in the art (eg, "Polymer Synthesis", Sandler et al., Vol. 1, pp. 5-12, second edition, Academic Press, 1992). The amount of benzene solution can vary depending on the fluorescence amplitude required. The resulting polymer is drawn into the fibers by conventional means. The resulting polymer fibers can shift the wavelength of the electromagnetic radiation from approximately 250 nm to 420 nm.

Example 7

Wavelength shifting composition for wavelength shift from 250 nm to 400 nm

A wavelength shifting composition having a narrower wavelength shift is prepared according to the protocol of Example 6 except that 7 g of piperonal is used in the initiation step. The resulting polymer fibers can shift the wavelength of the electromagnetic radiation from about 250 nm to 400 nm.

Example 8

Wavelength shifting compositions for wavelength shifting from ultraviolet electromagnetic radiation to visible light

A second wavelength shifting composition capable of shifting ultraviolet electromagnetic radiation into visible light is prepared using the following protocol. 0.5 g of 4,4'-methoxy biphenyl piperidine-N-oxide is dissolved in 40 ml of tetrahydrofuran (THF). 0.25 μL of 2.1 mM ethyl chloroformate is vigorously stirred into the solution at 20 ° C. for 20 minutes. After the polymerization step, the solution is cooled to -50 ° C. 19 ml of 2.28 mM (in THF) anisil magnesium bromide solution is added to the solution. The solution is kept at -50 ° C, stirred for 5 minutes and then cooled to -70 ° C for 30 minutes. The solution is then gradually warmed to 20 ° C. The solution is slowly titrated with 5 ml of methanol. The resulting mixture is filtered and the retained yellow powder is evaporated to dryness.

A solution is prepared by dissolving 10 g of methoxymethyl p-tolyl ether in 20 ml of THF. The solution is cooled to -60 ° C. About 2.8-3.0 ml of 2 mM n-butyllithium in hexane is added to the solution and mixed for 30 minutes. The solution is gradually warmed to room temperature and purged with nitrogen. 1.3 g of MgBr ₂ is added to the solution and stirred for 0.5 hour. 190 mg of yellow powder is then added to the methoxymethyl p-tolyl ether solution and heated to 25 ° C. for 2 hours. This solution is then added to a conventional fiber optical polymer to make a fiber optical cable. The resulting fiber optic cable can shift the wavelength from ultraviolet to visible light.

Example 9

Wavelength shifting compositions for wavelength shifting from 250 nm to 400 nm incorporated in plastic sheets

An additive that can be added to the polymethylmethacrylate sheet, film or gel is prepared by mixing 20 ml of distilled 3-bromomethyl thiophene and 5 g of methoxy ethanol ethoxide. To this mixture is added 1 g CuO in 5 ml of 10% KI in ethanol. The solution is stirred at 110 ° C. for 3 hours. The resulting solution is filtered and dried under vacuum. The resulting powder is then added to conventional methyl methacrylate and initiator to produce a plastic sheet having a thickness of 100 μm to 2 mm. The plastic sheet can shift the wavelength from 250 nm to 400 nm.

Example 10

One mole of OH-terminal biphenol polycarbonate is added to 1.05 to 2 moles of Cl-terminal siloxane in THF along with the different tertiary amines. This is added to the OH-terminated polycarbonate with an alkoxy functional siloxane with alcohol splitting.

Other reagents can be used by substituting pyridine in the initial reaction of halide-terminated organosiloxanes (bromine and fluorine-terminated organosiloxanes can also be used) and dihydric phenols with ammonia which are readily fully removable.

To increase flexibility (for rubber fiber optics guides), diphenylolpropane bischlorobromate and Cl-terminal organosiloxane are polymerized as before.

Example 11

Method for producing a composition for wavelength shift from 200 nm to 700 nm

1.0 g (2.59 mmol) dialdehyde and 1.82 g (2.6 mmol) pentasulphide are added to 25 ml of 0.5 g LiCl in dimethyl formamide (DMF). Using a syringe, 15 ml of 1 M potassium tert-butoxide solution in THF is added dropwise. After 6 hours of stirring, 25 ml of 5% aqueous HCl was added; Dry under reduced pressure. The dry powder is dissolved in chloroform and washed twice in 2% HCl and then four times in purified water, then dried in a drier and precipitated in anhydrous ethanol.

While not wishing to be bound by the following references, such copolymers are believed to change the bond. The side chain position can be changed by changing the amount of dihalaldehyde and adding a small amount of terephthalaldehyde to the first solution.

Example 12

Production method and apparatus of grading index fiber

The method of producing a grading index fiber optic cable comprises starting with a cylinder of homogeneous cladding made of a suitable copolymer. The cladding is then inserted into a 200 ml volume tube chamber. The chamber can be heated and rotated along its longitudinal axis (see FIG. 1). For example, the cladding may be α, ω, dichloropropyl-dimethylsiloxane having a refractive index of approximately 1.42.

Example 13

As the chamber is heated and rotated, a monomer mixture of dimethylsiloxane and phenyl A polycarbonate with bisphenyl A pyridine methylene chloride and phosgene gas (carboxylic dichloride) is subsequently added inside the cladding. The polymer is added at a rate of approximately 5 ml / second. The phosgene gas is added continuously at a rate of approximately 1 ml / second. The chamber is heated to a temperature of approximately 100 ° C. during the addition of the reactants. The chamber is rotated at about 12 to 30 revolutions per minute.

The reactant may be added through the end of the tube via the side of the tube or preferably via a membrane such as a Teflon membrane (see FIG. 3). As the copolymer polymerizes on the inner surface of the cladding, it is possible to vary the ratio of bis phenyl A polycarbonate to dimethylsiloxane to provide a copolymer in which the refractive index changes gradually.

As the copolymer builds up on the inner surface of the cladding, the amount of polymethylsiloxane decreases and the amount of bisphenyl A polycarbonate increases until it is filled with the preform rod. The copolymer administration procedure is adjusted such that the final polymer administered is bis phenyl A polycarbonate having a refractive index of 1.58. The resulting preform rod is a grading index rod with a refractive index of 1.42 on the surface and this index is increased to 1.58 at the center of the preform rod. The rod may then be heat drawn using conventional extrusion techniques to provide a grading index polymeric optical fiber.

Example 14

Methods and compositions for increasing the transparency of grading index optical fibers

The transparency of the grading index optical fibers prepared according to Examples 12 and 13 is increased by adding the free radical scavenger dibutyl-1-phthalate to the premix at a concentration of approximately 0.5% by volume prior to injection into the reaction chamber.

The resulting fibers can easily be bundled together and fused by placing the bundle in a container and applying a vacuum to the bundle. The temperature is then raised to the glass transition point of the cladding. The bundle is then cooled. The process is preferably repeated 4 to 5 times to produce a uniform fiber bundle.

Example 15

Methods and Compositions for Wavelength Shift from Ultraviolet to Cyan

This example demonstrates the ability to shift the wavelength of ultraviolet light, for example, wavelengths from about 220 nm to wavelengths in the cyan visible light in the range of about 300 to 500 nm, including polymer optical fibers and polymer sheets made from the polymers of the present invention and others. It provides a composition in the form of a solution provided to the object. For example, the composition of this example can be added to the composition of example 9.

Solution 1 is prepared by mixing about 0.9-1.1 g of quinoline, about 9-11 ml of 1N sulfuric acid (H ₂ SO ₄ ) and about 5.5-6.5 ml of N-methylpyrrolidinone (NMP-100% distillation). . Solution 2 is prepared by mixing about 0.9-1.1 g pyridine-NO, about 9-11 ml methanol, and about 4.5-5.5 ml 1M potassium hydroxide. Solution 3 is prepared by mixing about 9-11 ml of Solution 2 and about 5.5-6.5 ml of 1N hydrochloric acid (HCl). Solution 4 is prepared by mixing the total amount of solution 3 and 0.4 ml of about 0.3 to 0.4 ml of polyaniline dissolved in NMP. Solution 5 is prepared by mixing about 0.9-1.1 ml of solution 4 and about 9-11 ml of solution 1. Solution 6 is prepared by mixing about 2.7-3.3 ml of anisil magnesium bromide with the entire solution 5. Solution 7 is prepared by mixing about 4.5-5.5 ml of Solution 1 and about 4.5-5.5 ml of Solution 6. Solution 8 is prepared by heating solution 7 at approximately 45-55 ° C. for about 13-17 minutes.

Solution 8 converts ultraviolet light into cyan visible light with an efficiency of at least 95%.

Anisil magnesium bromide is prepared in the following manner using 4-bromoanisole and magnesium. About 25 ml of tetrahydrofuran (THF) is combined with 12 ml of 4-bromoanisole and purged with nitrogen gas under stirring prior to adding 4.8 g of magnesium powder. The mixture is stirred for about 30 minutes. 100 ml THF is added and the mixture is stirred for about 1 hour. The THF is decanted, the precipitate is washed in acetone, vacuum filtered and then washed again with acetone.

Example 16

Methods and Compositions for Wavelength Shift to Blue Light

About 5-30 mg of quinine or quinine monohydrochloride dihydrate are dissolved in approximately 9-11 ml of methanol (dry and distilled). To this mixture is added about 0.1-1.0 ml of 1M H ₂ SO ₄ and stirred at high speed for about 55-65 minutes. Various amounts of the mixture are added to the methylmethacrylate / styrene solution and polymerized as in Examples 1 and 2. The resulting boule showed high efficiency fluorescence at a blue wavelength of about 340-460 nm.

Example 17

A grading index polymeric optical fiber is prepared by mixing methyl methacrylate and polymethyl methacrylate (approximately 75,000 Daltons, Aldrich) in a 90:10 wt% ratio. About 70 g of methylmethacrylate / polymethylmethacrylate is mixed with about 14 g of bromobenzene. This solution is thoroughly mixed and then approximately 0.03 g of 2,2'-azobisisobutyronitrile (AIBN) and about 5 ml of 2,2,2-trifluoroethylacrylate are added and mixed in a beaker. The solution is then exposed to microwaves (700 watts) for 30 seconds and then the solution is cooled in an ice bath. Microwave exposure and cooling in an ice bath are repeated until a thick gel is formed. After the gel was formed, about 250 μl of a butanol mixture in methylmethacrylate (250 μl to 5 ml) was added to the gel. Butanethiol is added at a concentration of approximately 0.01 to 0.5 weight percent. The resulting gel is then cured in an oven at about 80 ° C. for about 24 hours and then at about 100 ° C. for at least about 12 hours.

Example 18

Methyl methacrylate is treated for approximately 1 hour in concentrated H ₂ SO ₄ and then distilled into a beaker containing about 14 g of bromobenzene under nitrogen. To this solution approximately 0.03 g of AIBN and about 5 ml of 2,2,2-trifluoroethyl acrylate are added and mixed in a beaker. The solution is then exposed to microwave (700 watts) for about 30 seconds and then the solution is cooled in an ice bath. Microwave exposure and cooling in an ice bath are repeated until a thick gel is formed. After the gel has been formed, about 250 μl of a butanethiol mixture in methylmethacrylate (250 μl to about 5 ml) is added to the gel. Butanethiol is added at a concentration of approximately 0.01 to 0.5 weight percent. The resulting gel is then cured in an oven at about 80 ° C. for about 24 hours and then at about 100 ° C. for at least about 12 hours.

Example 19

About 59.65 mole% methylmethacrylate is added to about 40 mole% ethylacrylate. To this mixture is added approximately 0.03 mole percent butyl thiophene, 0.005 mole percent dodecylmercaptan (100% distilled stock), and 0.05 mole percent initiator AIBN. Other initiators such as benzyl peroxide, tertiary butyl peroxide and dibenzoyl peroxide can be used. The solution is then exposed to microwave (700 watts) for about 2 minutes and then cooled in an ice bath. The solution is then exposed to microwaves for about 30 seconds and then cooled in an ice bath. This procedure is repeated several times until a thick gel is formed. The gel is then cured at approximately 55 ° C. for 24 hours. It is then heated to an additional 36 hours at approximately 80 ° C. The resulting preform has a notable transparency.

Example 20

About 5% by weight of 1,000,000 Mw polymethylmethacrylate (Aldrich) is dissolved in methylmethacrylate. The solution is then gelled by repeated exposure for about 30 seconds in a home oven (700 watts) and cooling in an ice bath between exposures. To the gel is added about 1-20 wt% bromobenzene and about 0.01-0.05 wt% butanethiol as chain transfer agent. Ethyl acrylate may then optionally be added at a concentration of approximately 0-10 wt%. The gel is cured in an oven at approximately 70-80 ° C. for 24 hours and then at 90-110 ° C. for an additional 12 hours to produce a high permeable bowl.

Example 21

The microwave treated gel from Example 20 is poured into a polymethylmethacrylate tube and then cured in an oven at approximately 70-80 ° C. for 12-24 hours. In contrast, the gel is added to the chamber as described in Example 13 and then cured at about 90-110 ° C. for approximately 12 hours. This creates a grading index preform load.

Of course, it is understood that the above embodiments are only related to preferred embodiments of the present invention, and that various modifications or changes can be made without departing from the spirit and scope of the present invention.

Claims (32)

Combining one or more prepolymer compositions with different refractive indices to form a mixture; Bromobenzene is added to the mixture; Initiator and trifluoroethylacrylate were added to the mixture; Exposing the mixture to microwaves; The mixture is cooled until a gel is formed; Butanethiol in methylmethacrylate is added to the gel; A method of making a grading index preform rod comprising curing a gel. The method of claim 1, wherein the prepolymer composition is methylmethacrylate and polymethylmethacrylate. The method of claim 2 wherein the prepolymer composition has a molecular weight of at least 75,000. 3. The method of claim 2 wherein methyl methacrylate is added to the polymethylmethacrylate in a ratio of about 90% by weight methylmethacrylate to 10% by weight polymethylmethacrylate. 2. The process of claim 1 wherein the prepolymer composition is methyl methacrylate and methyl methacrylate is pretreated and distilled with acid prior to addition to the bromobenzene. The method of claim 1 wherein the prepolymer composition is methyl methacrylate and ethyl acrylate. The method of claim 1 wherein the initiator is selected from the group consisting of peroxides, benzoyl peroxides, 2,2′-azobisisobutyronitrile and tertiary butyl peroxide. The method of claim 1, wherein the microwave exposure and cooling occur one or more times. Combining one or more prepolymer compositions with different refractive indices to form a mixture; Butanethiol, initiator and dodecyl mercaptan are added to the mixture; Exposing the mixture to microwaves; The mixture is cooled until a gel is formed; A method of making a grading index preform rod comprising curing a gel. 10. The method of claim 9, wherein the microwave exposure and cooling occur one or more times. 10. The method of claim 9, wherein the prepolymer composition is methyl methacrylate and ethyl methacrylate. Combining one or more prepolymer compositions with different refractive indices to form a mixture; Exposing the mixture to microwaves; The mixture is cooled until a gel is formed; Bromobenzene and butanethiol were added to the gel; A method of making a grading index preform rod comprising curing a gel. 13. The method of claim 12 wherein the prepolymer composition is methyl methacrylate and polymethyl methacrylate. The method of claim 13 wherein the polymethylmethacrylate is dissolved in methylmethacrylate and the polymethylmethacrylate has a molecular weight of about 1,000,000. The method of claim 12, wherein the microwave exposure and cooling occur one or more times. 13. The method of claim 12, further comprising adding ethylacrylate to the gel after addition of bromobenzene and butanethiol. A grading index preform load created according to the method of claim 1. A grading index preform load created according to the method of claim 9. A grading index preform load created according to the method of claim 12. The method of claim 1, wherein the curing step of the gel comprises curing for about 24 hours at a temperature of approximately 70-90 ° C., followed by curing for about 12 hours at a temperature of about 100 ° C. 3. The method of claim 9, wherein the curing step of the gel comprises curing about 24 hours at a temperature of about 55 ° C., followed by curing about 36 hours at a temperature of about 80 ° C. 11. The method of claim 12, wherein the curing step of the gel comprises curing for about 12 to 24 hours at a temperature of approximately 70 to 80 ° C., followed by curing for about 12 hours at a temperature of about 90 to 110 ° C. 13. The method of claim 12, wherein the curing step of the gel comprises curing for about 12 to 24 hours at a temperature of approximately 70 to 80 ° C. The method of claim 12, wherein the curing step of the gel comprises curing for about 12 hours at a temperature of about 90 to 110 ° C. Preparing a first solution of quinoline, sulfuric acid and N-methylpyrrolidinone; Preparing a second solution of pyridine, methanol and base; Preparing a third solution of acid and second solution; The third solution is combined with polyaniline dissolved in N-methylpyrrolidinone to prepare a fourth solution; Combining the fourth solution with the first solution in a ratio of about 1: 10 to form a fifth solution; The sixth solution is prepared by combining the anisil magnesium bromide with the fifth solution; Combining the first and sixth solutions to form a seventh solution; A composition useful for shifting electromagnetic radiation wavelengths from ultraviolet to visible light, prepared by a method comprising heating the seventh solution to produce an eighth solution. Quinine or quinine monohydrochloride dihydrate was dissolved in methanol to prepare a mixture; A composition useful for shifting electromagnetic wave wavelengths from ultraviolet to visible light, prepared by a method comprising mixing sulfuric acid into a mixture. The method of claim 1 further comprising the step of adding the composition of claim 25. The method of claim 1 further comprising the step of adding the composition of claim 26. The method of claim 9 further comprising the step of adding the composition of claim 25. The method of claim 9 further comprising adding the composition of claim 26. The method of claim 12 further comprising the step of adding the composition of claim 25. The method of claim 12 further comprising adding the composition of claim 26.