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WO1996019742A1 - Polyolefines comme support de transmission optique - Google Patents

Polyolefines comme support de transmission optique Download PDF

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Publication number
WO1996019742A1
WO1996019742A1 PCT/US1995/016537 US9516537W WO9619742A1 WO 1996019742 A1 WO1996019742 A1 WO 1996019742A1 US 9516537 W US9516537 W US 9516537W WO 9619742 A1 WO9619742 A1 WO 9619742A1
Authority
WO
WIPO (PCT)
Prior art keywords
waveguide
copolymer
light
transmission medium
set forth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1995/016537
Other languages
English (en)
Inventor
Michael E. Carter
Aspy K. Mehta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
Exxon Chemical Patents Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Priority to AU45239/96A priority Critical patent/AU4523996A/en
Publication of WO1996019742A1 publication Critical patent/WO1996019742A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating
    • G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/045—Light guides
    • G02B1/046—Light guides characterised by the core material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands

Definitions

  • This invention relates to the use of polyolefins, particularly those produced by metallocene catalysis, as the transmission medium for visible light and other forms of electromagnetic radiation.
  • Particular applications include “fiber optics” and other light-transmitting applications.
  • Polycarbonate and poly(methyl methacrylate) polymers are known to be useful in forming fiber optics of "plastics". Numerous patents and other publications are available relating to the use of these polymers in this manner. A few which may have distant relation to the materials useful for the practice of our invention are identified.
  • EP 362 814 A describes a random copolymer of ethylene and a polycyclic olefin which is copolymerized using a vanadium compound and a halogen containing aluminum compound.
  • the polymer has well balanced mechanical properties as well as high transparency, optical homogeneity, and small birefringence.
  • EP 446 051 A US 5,225,503, JP 92-002675/01, JP 92-101584/13, JP 92-101586/13, JP 93-160962/28, and JP 93-400420/58, describe groups of polycyclic polyolefins useful for optical disks and fibers.
  • the polymers are random copolymers of ethylene and specific polycyclic olefins having balanced optical, mechanical, and thermal properties which are apparently formed by catalysis with oxygen-containing vanadium compounds and specific groups of aluminum compounds.
  • the incorporation of polycyclic olefins into the chain backbone renders articles with increased rigidity, which is undesirable for applications requiring soft, flexible light guides.
  • optical fibers and other light waveguides can be produced from certain grades of single-site catalyzed, non-cyclic polymers, particularly ethylene-alpha-olefin copolymers.
  • the resulting optical fibers are readily processible, highly flexible, soft, smooth, highly transparent to visible light and certain other frequencies of the electromagnetic spectrum, and possess other advantageous properties.
  • the first embodiment affords transmission medium for electromagnetic energy, to which the medium is generally transparent, comprising polyolefin copolymer derived from non-cyclic olefin monomers.
  • Another embodiment provides transmission media for electromagnetic energy, to which the medium is generally transparent, comprising polyolefin copolymer produced by polymerization in the presence of single-site catalyst other than vanadium compound or a combination of other non-vanadium containing catalyst with vanadium containing catalyst.
  • a third embodiment provides transmission media for electromagnetic energy, to which the medium is generally transparent, comprising polyolefin copolymer produced by polymerization in presence of single-site catalyst comprising metallocene compound.
  • Preferred embodiments include those in which the transmission medium is formed into optical waveguides. These waveguides can be used with or without cladding. If cladding is used, the cladding should have a lower refractive index than the transmission medium. Preferably, the cladding will be substantially surrounded with insulation. Of course, in some applications it will not be necessary or desirable to use cladding.
  • Useful cladding materials include polycarbonate, acrylic or acrylate polymer, as well as furan or furfural polymer, epoxide polymer, or combinations thereof as well as others.
  • Useful characteristics of a good cladding material include lower index of refraction, ability to co-form with the transmission media, and minimal miscibility with the media of choice.
  • Insulation is useful for protecting the integrity of the waveguide and, if present, its cladding. Such protection will be from impact, heat, damaging radiation, and other hazards to which the waveguide may be exposed.
  • Useful insulation may include carbon, furan or furfural derivatives, epoxide polymer, vinyl or vinyl chloride derivatives, other polyolefins, latex, rubber, and urethane derivatives as well as other suitable materials, or combinations thereof. Of course, in many applications it will not be necessary or desirable to use an insulating material.
  • planar waveguides generally round fibers or filaments, films, and others.
  • the transmission media, particularly fibers will find use in communications transmissions, particularly for short distances. They are also useful in illumination devices, visual displays, medical diagnostic and/or treatment devices, toys, entertainment devices, and other novelty items.
  • polystyrene resins which are produced by single-site catalysts (SSC), particularly transition metal metallocenes or their analogues
  • SSC single-site catalysts
  • transition metal metallocenes or their analogues they are now possible to make polyolefins with exceptional clarity.
  • Their clarity is also enhanced by the narrow molecular weight distribution (MWD) and the narrow composition distribution (CD) of such products.
  • MWD molecular weight distribution
  • CD narrow composition distribution
  • the narrow MWD provides homogeneity in the length of the polymer molecules which assures minimal optical interference from high and low weight molecules.
  • the narrow composition distribution provides relatively homogeneous distribution of the comonomers throughout the polymer which helps minimize crystallization, and keep any existing crystallites small.
  • Useful polyolefins for the practice of this invention will include those produced by single site catalysis, particularly copo
  • any high clarity non-polycyclic derived polyolefin may be used in the practice of our invention, some may be more useful, particularly in some applications, than others.
  • olefinic polymers of lower densities will have comonomers incorporated into the polymer backbone; comonomers which disrupt the polymer crystalhnity will tend to make the structure less dense.
  • polymer density may be used as a crude measure of crystallinity. In the practice of our invention, lower density polymers are generally preferred over those having higher density.
  • polymers useful in the practice of our invention will include copolymers.
  • Such copolymers will be derived from other than polycyclic
  • - ⁇ olefins and will preferably be of densities in the range of about 0.85 g/cm to about
  • the copolymers will have densities in the range of about 0.86 g/cm to about 0.90 g/cm 3 , those in the range of about 0.865 g/cm 3 to about 0.89 g/cm 3 will be found to be particularly useful.
  • the copolymer used in producing the transmission media of the present invention has a substantially narrow composition distribution.
  • the composition distribution of a polymer may be measured in a number of manners.
  • composition distribution shall be measured by the "composition distribution breadth index” (CDBI) or the “solubility distribution breadth index” (SDBI) of the polymer. A description of these measurement parameters can be found in WO 93/03093.
  • the fewer impurities and fewer crystallites in the materials the better for high light transmission. This makes sense since the inclusion of such items will tend to scatter light or otherwise attenuate the intensity of the light by the end of the transmission. Impurities may be reduced by care in the manufacturing process and by enhancement of the reaction efficiency to reduce non-polymer residue.
  • the term "generally transparent" for the purpose of this description means that the chosen electromagnetic energy will pass through a substantial amount of the material with minimal interference, attenuation, or loss, of intensity. This will occur in a manner such that a relatively high fraction of the radiation will be received at the distal end of the transmission.
  • the desirable or useful intensities will be determined by the application in which the guides of this invention are used.
  • useful means of producing the materials, preferably copolymers, used in the practice of this invention involves polymerizing proper combinations of monomers with single site catalyst systems.
  • Particularly useful catalyst systems include metallocene, metallocene-type, amine or amido, or combinations, of transition metals with an activator, combinations of activators, scavengers, or combinations thereof.
  • suitable activators for these families of catalytic transition-metal compounds include various aluminum compounds including alumoxanes, particularly trimethyl alumoxane, and bulky labile anionic activators.
  • These catalyst systems may be used in numerous manufacturing processes including high pressure, liquid phase, and gas phase systems. Care must be used to recognize that some of these catalyst systems, particularly when used in supported form (e.g., in gas phase reactors) may appear to act as other than single-sited in light of variations in conditions during polymerizations. Such polymerization reaction systems are useful but may make catalyst systems which are inherently single-sited appear otherwise.
  • Single-site catalyst systems particularly the metallocene-type systems, produce polyolefins of notable clarity. This derives from the consistency of the length of the polymer molecules, as demonstrated in their narrow molecular weight distribution, and the efficiency of the catalyst systems to incorporate comonomer, thereby reducing crystallinity. Clarity of the polymer as well as optical transmittance characteristics are improved by the lack of non-polymer residue, or "ash". Generally, traditionally produced linear polyolefins are catalyzed by less efficient systems and thus include more ash which will tend to scatter and diffuse light transmission.
  • Numerous monomers and comonomers may be used in the practice of our invention; these will include ethylene, propylene, butene-1, pentene-1, 4- methylpentene-1, hexene-1, octene-1, cyclohexene, cyclopentene, cyclooctene, and many others, as well as combinations of these.
  • comonomers which interfere with the crystallization of the resulting polymer will be found to be useful. Any such comonomer including the cyclic olefins, with the exception of the polycyclic olefins, with specific exceptions, will find use in the practice of our invention.
  • the exceptions for the polycyclic olefin- derived polymers will be those produced by non-vanadium containing, particularly metallocene-type, single-site catalysts.
  • the usefulness of the media of this invention may be tailored and enhanced for specific applications, including tinting or dying the medium to provide transmittance selectivity for specific areas of the electromagnetic, particularly the visible range, spectrum. Such coloring may be accomplished by addition of any number of polymer-compatible dyes, tints or other such non-blocking, non- scattering, or interfering agents. This will find particular application in visual displays and novelty items.
  • the transmitting ability of these media may be enhanced by assuring higher, preferably complete, or approaching complete, internal reflectance.
  • Internal reflectance is enhanced by known techniques including use of a cladding layer around the transmission medium.
  • Useful methods include securing refractive index relationships between the transmission medium and the cladding such that the index of refraction of the transmission medium is greater than that of the cladding layer. This may be accomplished by increasing the index of the transmission medium or by decreasing the index of the cladding medium; use of different copolymers for the differing media, or use of an entirely different polymer or other materials, may be useful approaches here.
  • Metallocene catalyzed polymers will be particularly useful for such cladding and/or transmission medium, because such polymers have advantageous heat seal properties, including a relatively low seal initiation temperature.
  • Internal reflectance, or retention of the radiation, particularly visible light, within the waveguides or light guides of this invention may be improved by provision of a refractive index barrier, often a cladding layer, at the boundary of the transmission medium.
  • a diminishment of refractive index should occur when crossing out of the transmission media. While other cladding layers are preferred, such a diminishment can be arranged with a bare item of acceptable medium alone in air.
  • Far better waveguides may be created, though, by use of a cladding layer of an acrylic, acrylate, polycarbonate, or other suitable polymer with a melting range near that of the polyolefin and with, preferably, low miscibility with the polyolefin.
  • Such strands were made using a temperature profile which would typically be about 88°C/110 o C/110 o C/99°C (190°F/230° F/230°F/210°F) with the screw speed being about 70 rpm and the melt temperature about 132°C (270°F).
  • the strands were cleanly cut into about 15 cm (6 in) lengths, placed in a bundle, and placed with their cut ends flush against the lens of a low voltage light source.
  • Opaque tape was wrapped around the bundle and the end of the light source to exclude a wash of light from the area around the bundle of strands. When the light was turned on in a darkened environment, the ends of the fibers distal from the light source became illuminated.
  • Different colors may be obtained. This could be accomplished by use of colored filters or gels between the light source and the fibers or strands.
  • Another method of obtaining different colors would be through incorporation of non-blocking or interfering dyes, stains, tints, or other coloring means within the waveguide itself prior to or during formation.
  • non-blocking or interfering dyes, stains, tints, or other coloring means within the waveguide itself prior to or during formation.
  • Olefinic optical waveguides would have application with toys. Since the materials useful in the practice of this invention are generally soft and pliable, there would not be the same danger of embedding minute glass shards or fragments within the skin as there might be with the more rigid and brittle glass waveguides. The generally lower densities of olefinic waveguides would be of benefit here also, as with other applications, in that shipping and handling costs, as well as overall product weight, would be lowered over the glass waveguides which would generally have specific gravities more than about 2.5 times that found in the optical material of our invention.
  • such waveguides particularly in the form of strands or fibers, would find use in medical applications. They would provide disposable visual probes useful for accomplishing less intrusive exploration and also be useful in providing a source of illumination in surgeries.
  • Such probes would also find use in delivery of specific electromagnetic energy to local spots. This would include ultraviolet, infra-red and other frequency lights, including lasers, capable of healing lesions or destroying tissue in a localized and minimally invasive fashion.
  • Fibers of these materials would also be useful in medical applications involving light therapy. Recognizing the softness and pleasant feel of these materials when formed into fibers or fabrics, as noted in US 5,322,728, fiber-type waveguides could be useful in forming light-delivering fabric. By providing numerous ends of fibers within the fabric, or abrading the fibers of a fabric on one side and having the other ends of such fibers communicate with a light source, light may be delivered to a large area. Such a fabric or blanket could be useful for wrapping, for example, jaundiced infants with high bilirubin counts. This would provide a more comfortable and less traumatizing means of delivering light, particularly, metered amounts of ultraviolet light, to the entire body of an infant or other individual, to aid the body's ability to process excess bilirubin.
  • Such illuminated, or illuminatable fabric would also find use in advertising, artistic, and other such displays.
  • Bundled fibers including those capable of transmitting different or varying colors, could be made into novelty lamps taking the form of a "light fountain".
  • Illuminated fabrics as described earlier would also be capable of providing pleasant, diffuse light for area lighting. Depending upon intensity of the source and the makeup of the fabric or bundle ends, such lighting could be generalized for wide area or limited for localized illumination.
  • a communication system comprising transmission media derived from single-site catalyzed polyolefins derived from olefins other than those which are polycyclic will be possible.
  • Such interfaces and amplifiers, or “repeaters”, are known from work with glass waveguides. Such communications systems would be useful for
  • Selected optical fibers within a visual display such as a billboard or artistic presentation may be made to move because of their inherent flexibility.
  • the display, or portions of it will provide a sense of movement, and likely, depth. It will therefore be possible to provide "moving" displays with, for example, walking or dancing people, speeding trains, charging animals, or other desirable "movement".
  • Such movement of the fibers may be caused by any suitable means including mechanical means, creation of a thermal differential across the fiber including through application of heat or cold, or combinations to specific fibers. Differential application of heat, cold, or combinations may cause a temporal change in refractive index within the fiber which may also provide a sense of movement, by altering the distal fiber end receipt of light energy.
  • Formation of fiber-type optical waveguides of our invention may be accomplished by coextrusion of the transmission medium, or core, the cladding layer, and optionally insulation. This may be accomplished by use of relatively unsophisticated multi-orifice coextrusion dies of the type known in the art. To obtain very thin fibers, the coextruded fibers may be drawn down under proper conditions of temperature, pressure, use of draw-down dies, or combinations thereof.
  • Such fiber optics would include draw-down of a preformed "billet".
  • the round billet could be extruded such that the thicknesses of the desired layers are in proportion to their final desired thicknesses. Under proper conditions of temperature, pressure, use of draw-down dies, or combinations thereof the final desired fibers may be obtained.
  • Such a billet could also be made by pouring molten material to desired thicknesses in successive molds.
  • the billet of Example 15 may also be produced by successive deposition of the desired layers. This may be accomplished by vapor deposition, sputtering, or even in a polymerization reactor. Vapor deposition or sputtering under vacuum would provide a high purity method of deposition which may be used, beneficially, to remove undesirable residual low molecular weight polymer impurities.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Support de transmission destiné à la lumière visible ainsi qu'à d'autres formes d'énergie électromagnétique, auxquelles le support est généralement transparent, qui est constitué de copolymère de polyoléfine non dérivé de monomère d'oléfine polycyclique.
PCT/US1995/016537 1994-12-19 1995-12-18 Polyolefines comme support de transmission optique Ceased WO1996019742A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU45239/96A AU4523996A (en) 1994-12-19 1995-12-18 Polyolefins as a light transmission medium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35842294A 1994-12-19 1994-12-19
US08/358,422 1994-12-19

Publications (1)

Publication Number Publication Date
WO1996019742A1 true WO1996019742A1 (fr) 1996-06-27

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/016537 Ceased WO1996019742A1 (fr) 1994-12-19 1995-12-18 Polyolefines comme support de transmission optique

Country Status (2)

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AU (1) AU4523996A (fr)
WO (1) WO1996019742A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1366221A4 (fr) * 2000-09-15 2006-01-18 First Quality Fibers Llc Appareil de fabrication d'une fibre optique faite d'un polymere semi-cristallin

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0191240A2 (fr) * 1984-12-18 1986-08-20 Mitsui Petrochemical Industries, Ltd. Composition de résine thermoplastique
EP0340558A2 (fr) * 1988-04-28 1989-11-08 Hoechst Aktiengesellschaft Guide de lumière
WO1994019719A1 (fr) * 1993-02-26 1994-09-01 Hoechst Aktiengesellschaft Procede pour la diminution de l'attenuation optique d'un corps moule transparent, partiellement cristallin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0191240A2 (fr) * 1984-12-18 1986-08-20 Mitsui Petrochemical Industries, Ltd. Composition de résine thermoplastique
EP0340558A2 (fr) * 1988-04-28 1989-11-08 Hoechst Aktiengesellschaft Guide de lumière
WO1994019719A1 (fr) * 1993-02-26 1994-09-01 Hoechst Aktiengesellschaft Procede pour la diminution de l'attenuation optique d'un corps moule transparent, partiellement cristallin

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; *
PATENT ABSTRACTS OF JAPAN *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1366221A4 (fr) * 2000-09-15 2006-01-18 First Quality Fibers Llc Appareil de fabrication d'une fibre optique faite d'un polymere semi-cristallin

Also Published As

Publication number Publication date
AU4523996A (en) 1996-07-10

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