WO2003043805A2 - Procede de fabrication d'une fibre optique plastique, et fibre optique plastique obtenue par ce procede - Google Patents
Procede de fabrication d'une fibre optique plastique, et fibre optique plastique obtenue par ce procede Download PDFInfo
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- WO2003043805A2 WO2003043805A2 PCT/FR2002/003932 FR0203932W WO03043805A2 WO 2003043805 A2 WO2003043805 A2 WO 2003043805A2 FR 0203932 W FR0203932 W FR 0203932W WO 03043805 A2 WO03043805 A2 WO 03043805A2
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- optical fiber
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- 0 CC(C)C(*)(C(C(C)C)(F)F)F Chemical compound CC(C)C(*)(C(C(C)C)(F)F)F 0.000 description 2
Classifications
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- 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
-
- 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
Definitions
- the present invention relates to a process for manufacturing a plastic optical fiber, as well as a plastic optical fiber obtained by this process. It relates in particular to plastic optical fibers with index jump and those with index gradient.
- Plastic index-jump optical fibers which can be used in a spectral range covering the visible to the near infrared, are advantageous because their installation is simpler than that of silica fibers because of their larger diameter.
- Gradient index plastic optical fibers which can be used in the same spectral range, are interesting because they can be applied to broadband access networks.
- a graded index plastic optical fiber comprises at least one basic polymer and another compound, called dopant, comprising one or more monomers or polymers. The proportion of the base polymer is substantially the same over the entire fiber and the proportion of the dopant varies from the core to the periphery of the fiber so as to form the desired gradient or index jump.
- the manufacture of such plastic optical fibers is delicate, since it is necessary to distribute the dopant varying from the core to the periphery of a plastic optical fiber.
- the fiber must have a refractive index profile of the gradient index type as regular as possible, the variation of refractive index between the center and the periphery of the fiber is generally between 0.01 and 0.03.
- document EP-1 067 222 discloses a method for manufacturing a plastic optical fiber with index gradient, the index of which varies continuously between the center and the periphery of the fiber.
- the fiber is made from at least one polymer P and at least one reactive diluent D1 serving as a dopant making it possible to vary its refractive index.
- This process comprises the following stages: • preparation of two compositions of different refractive index, the difference in refractive index between the two compositions being at least 5.10 ⁇ 3 , each comprising at least the polymer P, one of the compositions, known as the first composition, further comprising at least the reactive diluent D1, a radical polymerization initiator being present in at least one of the compositions,
- the polymer P and the reactive diluent D1 are also chosen such that:
- the polymer P has a molar mass of between 1,000 and 20,000 g. moles "1 and the reactive diluent D1 has a molar mass of between 100 and 1000 g. moles " 1 ,
- the reactive diluent D1 comprises at least one unsaturated group reactive with respect to UV, such as vinyl groups and acrylic groups.
- the molar masses mentioned above are number average molar masses. This is also the case for the molar masses mentioned in all that follows.
- a preferred base polymer is of the poly (fluoro) methacrylate type, and more generally of the PMMA (polymethylmethacrylate) type.
- PMMA polymethylmethacrylate
- the aim of the present invention is therefore to develop a process for manufacturing an index gradient optical fiber making it possible to obtain plastic optical fibers capable of operating at wavelengths greater than 500 nm without causing prohibitive attenuation of the transmitted optical signal.
- the present invention provides for this purpose a method of manufacturing a plastic optical fiber from at least one polymer P, said method being characterized in that said polymer P is a copolymer comprising at least two repeating units P1 and P2 of following general formulas, i and j corresponding to a repetitive number of units:
- the methods according to the invention apply as well to the production of index gradient optical fibers as to that of index jump fibers.
- the copolymer P can be obtained from chlorotrifluoroethylene or tetrafluoroethylene, industrial fluorinated monomers, and from vinylene carbonate, a readily accessible non-halogenated monomer.
- the copolymer containing a lot of fluorine and therefore less hydrogen than the polymers of the prior art of PMMA type, which leads to increased transparency, and having a cyclic structure, which leads to an amorphous structure and therefore to properties optical transmission fibers, the fibers obtained by the method according to the invention are particularly suitable for applications at wavelengths greater than 500 nm, typically in the transmission windows located around 650, 850, 1300 and 1550 nm.
- the present invention provides a method of manufacturing a plastic optical fiber with index jump, the index of which varies discontinuously between the center and the periphery of the fiber, or with an index gradient, the index of which varies continuously between the center and the periphery of the fiber, from at least said polymer P and from at least one reactive diluent D1 making it possible to vary the refractive index of said fiber, said method comprising the following steps:
- compositions with different refractive index preparation of two compositions with different refractive index, the difference in refractive index between the two compositions being at least 5.10 "3 , each comprising at least polymer P, one of the compositions, known as the first composition, comprising in addition at least the reactive diluent D1, a radical polymerization initiator being present in at least one of the compositions, spinning • crosslinking of the reactive diluent leading to a plastic optical fiber.
- said method further comprises, after the step of preparing said compositions, a step of active mixing of the two compositions in order to obtain the continuous variation of the refractive index optical fiber, followed by spinning of said mixture.
- the crosslinking is a photo-crosslinking and the initiator is a photoinitiator.
- the molar mass of the polymer P is between 1000 and 20000 g. moles "1 and the reactive diluent D1 has a molar mass of between 100 and 1000 g. moles " 1 . These choices limit the viscosity of the composition and facilitate spinning.
- the reactive diluent D1 comprises at least one unsaturated group reactive with respect to UV rays chosen from the group formed by vinyl groups and acrylic groups.
- An active mixture according to the process of the invention is a mixture which is helped to form, that is to say which is not produced only by diffusion; this active mixture can be obtained statically by forcing by a static diffusion means the mixture of the two compositions, most often by forced flow, or by dynamic means which actively produces such a mixture.
- Such a method has the advantage of being rapid, in particular much faster than if only the diffusion between the compositions is used, and of making it possible to obtain a concentration gradient and therefore a continuous refractive index and practically regular.
- the crosslinking kinetics are generally such that, under maximum exposure and complete transformation of the photoinitiator, the gel time is less than 10 s, preferably less than 2 s.
- the spinning of the index gradient mixture is followed by a photochemical or thermal crosslinking of the diluent reagent leading to the production of a cross-linked three-dimensional network. This process advantageously makes it possible to at least partially freeze the components of the plastic optical fiber.
- the plastic optical fiber thus obtained and its index gradient therefore have stability over time and stability in temperature.
- At least one of the two compositions comprises a monomer; in addition, at least one of the two compositions comprises at least one radical polymerization initiator, and preferably each of the two compositions comprises at least one radical polymerization initiator.
- the radical polymerization initiator is a compound which makes it possible to generate initiator radicals by thermal or photochemical decomposition of the crosslinking reaction.
- the second composition comprises at least one reactive diluent D2 also making it possible to vary the refractive index, the reactive diluent D2 being of refractive index substantially different from the refractive index of D1, having a molar mass of between 100 and 1000 g. moles "1 , and comprising at least one UV-reactive unsaturated group chosen from the group formed by vinyl groups and acrylic groups.
- the reactive diluents D1 and D2 have respective viscosities which are practically identical and the proportion by mass of the polymer P relative to the constituents of the composition is practically constant for each of the compositions, thus the process is easier to implement since the variation in the proportion of diluent (s) reactive (s) D1 and / or D2, mainly used to modulate the refractive index, does not significantly influence the viscosity of the compositions.
- the mixing of the two compositions is carried out at a temperature such that the viscosity at 20 ° C. of each of the two compositions is included between 1 and 25 Pa.s, preferably between 1 and 15 Pa.s.
- the spinning is carried out at a temperature such that the viscosity of each of the two compositions is greater than 500 mPa.s, preferably greater than 1000 mPa.s.
- the reactive groups carried by the constituents D1 and D2 are chosen from the group formed by vinyl groups and acrylic groups, that is to say chosen in particular from acrylates, methacrylates, vinyl ethers or propenyl ethers, these groups can be at least partially halogenated, most often fluorinated and / or chlorinated.
- any component of one of the compositions is an at least partially halogenated material, most often fluorinated and / or chlorinated.
- one of the two reactive diluents D1 or D2 is at least partially fluorinated and the other of the two reactive diluents D2 or D1 is at least partially chlorinated or chloro-fluorinated, and therefore has a refractive index substantially higher than that of the at least partially fluorinated monomer.
- the present invention provides a method for manufacturing a plastic optical fiber with an index gradient, the index of which varies continuously between the center and the periphery of the fiber, from at least said polymer.
- P and at least one dopant D making it possible to vary the refractive index of said fiber, the refractive index of said dopant being greater than that of said polymer P, said method comprising the following steps: • melting of polymer P in a tube • rotation of said tube around its axis • cooling of said tube so as to form inside said tube a tubular body of polymer P
- the present invention provides a method of manufacturing a plastic index-hopping optical fiber, the index of which varies discontinuously between the center and the periphery of the fiber, from at least said polymer P, said polymer P being spun in the molten state and simultaneously coated with a photocrosslinkable resin with a refractive index lower than that of polymer P, which is then photopolymerized.
- the present invention provides a method of manufacturing a plastic optical fiber with index jump, the index of which varies discontinuously between the center and the periphery of the fiber, starting from at least said polymer P, by coextrusion of said polymer P with another polymer of refractive index lower than that of said polymer P.
- the method according to the invention can of course also be implemented for the manufacture of optical waveguides.
- the present invention also relates to a plastic optical fiber with an index gradient obtained by the method according to the invention, as well as an optical waveguide obtained by this method.
- FIG. 1 schematically shows a device for implementing the method according to the invention.
- FIG. 2 shows a schematic view of the index profile of an optical fiber obtained by means of the device of Figure 1
- FIG. 3 shows the attenuation spectra of a plastic optical fiber with an index gradient obtained from methods of the prior art and from a method according to one of the embodiments of the invention.
- the common elements have the same reference numbers.
- two compositions are prepared, each comprising a copolymer P.
- One of these compositions further comprises at least one reactive diluent D1, which is preferably a monomer.
- the other composition comprises at least one reactive diluent D2, which is also preferably a monomer.
- the concentration of D1 is different in each of the two compositions, which gives a different refractive index to each composition.
- the two values of refraction index thus obtained constitute the maximum and the minimum of the parabolic index gradient gradient curve that one seeks to obtain for the plastic optical fiber resulting from the process (see FIG. 2).
- the copolymer P used in the process of the invention comprises the repeating units P1 and P2 shown below.
- the unit P1 is derived from the polymerization of i monomers M1 and the unit P2 is derived from the polymerization of j monomers M2.
- the repeating entities P1 can come from a mixture of monomers of formula M1.
- the comonomer M2 giving rise to the repeating entities P2 is the vinylene carbonate of the following formula:
- any polymerization process known to a person skilled in the art using a solvent medium, in suspension in water or in emulsion for example, can be used. It is generally preferable to work in a solvent medium in order to control the exothermicity of the polymerization and to favor an intimate mixture of the different monomers.
- solvents commonly used there may be mentioned ethyl, methyl or butyl acetate, chlorofluorinated solvents such as F141b® (CFCl 2 -CH 3 ) or F113® (CF 2 Cl-CFCl 2 ).
- radical polymerization initiator it is possible to use free radical generators such as peroxide, hydroperoxide, percarbonate derivatives or even diazo compounds such as azobisisobutyronitrile (AlBN). It is also possible, in the case of processes carried out in an aqueous medium, to use inorganic free radical generators such as persulfates or so-called redox combinations.
- the polymerization temperature is dictated, in general, by the rate of decomposition of the selected initiator and is, in general, between 0 and 200 ° C, preferably between 40 and 120 ° C.
- the pressure is, in general, between atmospheric pressure and a pressure of 50 bars, more particularly between 2 bars and 20 bars.
- a pressure of 50 bars more particularly between 2 bars and 20 bars.
- the copolymer P used in the process according to the invention has a glass transition temperature (Tg) situated between 60 and 160 ° C, preferably between 80 and 140 ° C. This glass transition temperature is mainly linked to the content of units P2 present in the copolymer.
- the transparency of the polymer obtained also depends on the content of units P2.
- the content of motif P2, repeating unit resulting from the polymerization of monomers M2 can vary in the copolymer depending on the nature of X in P1.
- X F or Cl in P1
- the content of motif P2 in the copolymer is between substantially 30 and 70 mol%.
- the polymer P of the process according to the invention has a number-average molar mass (Mn) of between 500 and 10 6 g. moles "1 and preferably between 10 3 and 10 4 g. moles " 1 .
- Mn number-average molar mass
- VCA vinylene carbonate
- TBPP tertiobutyl perpivalate, at 75% by mass in isododecane
- F141b® 1, 1 , 1 -dichlorofluoroethane
- the Mn (number-average molar masses) are determined by CES analysis (steric exclusion chromatography). An apparatus from the company Spectra Physic "Winner Station” is used. Detection is carried out by refractive index.
- the column is a mixed C column
- PL gel of 5 microns from the company Polymer Laboratory and the solvent used is THF at a flow rate of 0.8 ml / min.
- Mn molar masses in number
- the Tg glass transition temperatures
- DSC differential scanning calorimetry
- a first temperature rise is carried out at 20 ° C./min followed by cooling and then a second rise in temperature during which the Tg or Tf (melting temperatures) are recorded
- the temperature range is from 50 ° C to 200 ° C if the Tg is greater than 60 ° C.
- the chlorine levels are determined in a conventional manner by mineralization in a PARR bomb with Na 2 O 2 followed by determination of the chlorides by argentimetry.
- the operation is carried out in a 160 ml stainless steel reactor, purged two to three times with 5 bars of nitrogen. 50 ml of an F141b® solution containing 0.6 ml (or 2.25 mmol) of TBPP initiator and 8.53 g are introduced by suction into the vacuum reactor (approximately 100 mbar of pressure).
- Example 2 The procedure is the same as in Example 1 with the same reagents and the same proportions using the ethyl acetate solvent in place of F141 b®. At the end of the reaction, a solution of polymer in ethyl acetate is obtained. The solvent is evaporated until a volume of about 20 ml is obtained and then the reaction product is precipitated with n-heptane. The precipitated polymer is filtered and then dried under vacuum at 60 ° C. 10 g of a colorless, transparent copolymer, soluble in THF or acetone, are obtained. The P1 / P2 molar ratio is 49/51 and the Tg is 106 ° C.
- Comparative examples 3, 5, 6 and 7 are carried out, as well as example 4, operating in the same manner as in example 2 with the amounts of CTFE and VCA reagents indicated in TABLE 1 below.
- examples and comparatives of TABLE 1 are brought into play at the start of the reaction x mmoles of CTFE and y mmoles of VCA, x and y having the following values according to the examples:
- Example 2 The procedure is the same as in Example 2 but with 7 g (or 81.3 mmol) of VCA and 11 g (or 110 mmol) of TFE in place of the CTFE. 14.6 g of copolymer are obtained. The copolymer is very soluble in acetone or THF. By evaporation of the acetone, a colorless, transparent film is obtained. 19 F NMR analysis indicates a P1 / P2 molar ratio of 70/30. The Tg of the copolymer is 82 ° C (DSC analysis).
- the two compositions C1 and C2 are prepared, making it possible to produce an optical fiber according to the invention by a UV type process.
- Two different compositions comprising a commercial photoinitiator, the reactive copolymer P of Example 1, 2 or 3 above, and a reactive diluent composed of two monomers in different proportions according to the composition, the two monomers being ( D1) and (D2)
- the photoinitiator may for example be an ⁇ -hydroxyketone (IRGACURE 184, DAROCUR 1173), a mono acyl phosphine (DAROCUR TPO) or a bis acyl phosphine (IRGACURE 819).
- D1 and D2 can be monomers having at least one acrylic, methacrylic, ⁇ -fluoroacrylic, ⁇ , ⁇ -difluoroacrylic or vinyl function comprising halogen groups (fluorinated and chlorinated).
- compositions C1 and C2 prepared from the mixture of copolymer P of Example 1, the reactive diluent D1 being trifluoroethyl acrylate (including the homopolymer at 20 ° C has a refractive index equal to 1.407), and the reactive diluent D2 being trifluoroethyl methacrylate (the homopolymer of which at 20 ° C. has a refractive index equal to 1.437).
- the photoinitiator is from the class of bis acyl phosphines (BAPO - IRGACURE 819). The quantities are calculated for 700 grams of composition.
- the ratio, in% by weight, of the copolymer P to the sum of the constituents of each composition is constant, while within the reactive diluent the relative proportion, in% by mass of D1 relative to the sum of D1 and D2 , varies from composition to composition.
- the continuous index variation is created by producing an active mixture of the two starting compositions C1 and C2.
- a mixing means which can be a static or dynamic type mixer.
- FIG. 1 represents a very schematic sectional view, in a plane comprising a central axis X, of a device for manufacturing an optical fiber according to the method of the invention.
- the device 10 comprises a static mixer 1.
- the compositions C1 and C2 of the table above are mixed there.
- the mixer 1 comprises two concentric cylinders 3 and 4 serving as reservoirs for the compositions C1 and C2. It is the cylindrical enclosure 8 of the mixer 1 which serves as a reservoir 4 for the composition C2.
- the composition C1 with the highest refractive index is placed in the central reservoir 3.
- the enclosure 8 comprises a sealed upper closure 8d which has two respective inlets 8g and 8f making it possible to ensure a controlled pressure in each of the respective tanks 3 and 4, for example by means of two positive displacement pumps (not shown).
- a controlled pressure can be applied to the two compositions C1 and C2 in order to obtain an identical flow if the two compositions C1 and C2 have the same viscosity.
- the enclosure 8 also includes a zone 8e where the two tanks 3 and 4 are concentric, isolated from each other, as well as a zone 8a whose upper limit is the bottom of the central tank 3 and whose lower limit East the bottom of the peripheral tank 4.
- Zone 8a corresponds to a zone for mixing the two compositions C1 and C2 by the mixer 1, namely a set 2 of plates (2a, 2b) superimposed and perforated with holes 12.
- the enclosure 8 further includes a conical area 8b where a homothetic variation of the section occurs, and finally a calibrated area 8c comprising a die 15, which gives the desired order of magnitude to the diameter of a plastic optical fiber with an index gradient 6 obtained .
- the fiiere 15 is an attached part, which makes it possible to easily change the calibration without having to change the mixer 1.
- the mixer 1 comprises in its zone 8a at least two, and here seven, perforated plates (2a, 2b) superposed one on the other above the others.
- This set 2 of plates (2a, 2b) is placed at the lower end of the central reservoir 3 so as to ensure a radial mixing of the compositions C1 and C2.
- a mixture 5 is obtained having a concentration gradient of compositions C1 and C2, in zone 8a.
- the mixture 5 is formed by the superposition of the plates (2a, 2b).
- Each plate 2a (respectively 2b) has holes 12, generally arranged in opposition with respect to each other from a plate 2a to an adjacent plate 2b (respectively from a plate 2b to an adjacent plate 2a).
- the mixture 5 thus obtained is brought to the calibrated die 15 from the zone 8c of the enclosure 8 by the conical zone 8b, the upper limit of which is the lower end of the last plate 2a.
- This homothetic variation makes it possible to preserve the form of the variation in concentration of the compositions C1 and C2.
- the wire obtained which is a plastic optical fiber with an index gradient, 6, is drawn by a capstan 10.
- the plastic optical fiber 6 is cured by photo- crosslinking using a source 7 of ultraviolet (UV) rays in a polymerized plastic optical fiber 9.
- UV ultraviolet
- the plastic optical fiber 9 is wound on a reel 11.
- the diameter of the fiber 9 is given by the die 15, but it can be refined according to the strength of the spinning carried out by means of the capstan 10.
- FIG. 2 shows a schematic view of the index profile obtained for an optical fiber manufactured by the device of Figure 1.
- the profile of the refractive index n of the optical fiber 6 of Figure 1 practically smoothed so as to form a gradient of parabolic shape, as a function of the distance r from the center of the fiber 6, which is on the axis X.
- the fiber thus obtained is therefore a gradient index fiber, but the above method can also make it possible to obtain a index-jump fiber.
- the active mixture of compositions C1 and C2 is not carried out.
- C1 and C2 are then introduced into a distributor pot extended by a die, where the final fiber dimameter and the proportion of core and cladding are governed by the pressure and the temperature of the compositions C1 and C2 as well as by the diameter of the sector.
- the present invention also relates to other types of methods for obtaining plastic optical fibers.
- the preform method 100 g of polymer P of the CTFE / VCA copolymer type, the molar proportion of CTFE motif varies between 30 and 70% of average molar mass of approximately 5.10 5 are melted at a temperature between 200 and 250 ° C in a cylindrical glass tube, without completely filling it so that a vacant space is made in the tube containing the polymer P before sealing it under vacuum. The tube in glass is then placed in a horizontal position in an oven.
- the tubular body thus obtained has an outside diameter of 17 mm and an inside diameter of 5 mm, and its refractive index is 1.45.
- a dopant D is then introduced into the central part of this tubular body, still in the glass tube. Its proportion is 4% by weight relative to the polymer P.
- the dopant it is preferable that it meets the following two conditions:
- ⁇ p- ⁇ p I is less than or equal to 7 (cal / cm 3 ) 1/2 .
- the assembly is again rotated in an oven.
- the dopant D thermally diffuses through the molten polymer P for 6 hours.
- the oven is finally gradually cooled at a speed of 15 ° C / hour to room temperature.
- a tubular body 17 mm in outside diameter and 4.5 mm in inside diameter is obtained with a gradient index of refraction profile.
- This tubular body constituting the preform of the plastic optical fiber with an index gradient, is placed in a drawing oven at a temperature between 200 and 250 ° C. Its upper part is connected to a vacuum pump during the spinning step. In this way, the preform shrinks and an optical fiber with a refractive index gradient is recovered. Its dimensions depend on the spinning speed, preferably between 5 and 10 m / min and on the oven temperature.
- polymers P according to the invention having a glass transition temperature higher than those of PMMA or of CYTOP, materials conventionally used in the known “preform” process, leads to fibers having a transparency greater than those obtained. with classic materials.
- FIG. 3 where is represented as a function of the wavelength in nm, the attenuation (in dB / km) of a plastic optical fiber with an index gradient obtained according to the process which has just been describes, from CYTOP polymer of the prior art (curve 31), PMMA polymer of the prior art (curve 32) and polymer (CTFE) 0.50 (VCA) 0.50 according to the invention (curve 33).
- plastic optical fibers with index jump it is possible for example to spin a polymer P according to the invention, for example obtained according to one of the examples above, in the state molten, and simultaneous deposition of a photocrosslinkable resin with a refractive index lower than that of the polymer P, this resin then being photopolymerized.
- the thickness of the resin layer thus deposited is for example of the order of 100 ⁇ m.
- a polymer of refractive index lower than that of the polymer P such as for example PVDF, Teflon ® AF by du Pont de Nemours or the Hyflon AD ® by AUSIMONT.
- compositions and examples given are for information only, and they can be modified without departing from the scope of the invention as long as the copolymer P retains the general characteristics mentioned above.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2003545464A JP2005509912A (ja) | 2001-11-19 | 2002-11-18 | プラスチック光ファイバーの製造方法、及び前記方法により得られたプラスチック光ファイバー |
US10/496,100 US20050062180A1 (en) | 2001-11-19 | 2002-11-18 | Method for making a plastic optical fiber, and resulting plastic optical fiber |
KR10-2004-7007348A KR20040066812A (ko) | 2001-11-19 | 2002-11-18 | 플라스틱 광섬유의 제조 방법 및 이 방법에 의해 제조된플라스틱 광섬유 |
EP02803435A EP1451005A2 (fr) | 2001-11-19 | 2002-11-18 | Procede de fabrication d'une fibre optique plastique, et fibre optique plastique obtenue par ce procede |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0115038A FR2832514B1 (fr) | 2001-11-19 | 2001-11-19 | Procede de fabrication d'une fibre optique plastique a gradient d'indice et fibre optique a gradient d'indice obtenue par ce procede |
FR01/15038 | 2001-11-19 |
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WO2003043805A2 true WO2003043805A2 (fr) | 2003-05-30 |
WO2003043805A3 WO2003043805A3 (fr) | 2003-12-11 |
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PCT/FR2002/003932 WO2003043805A2 (fr) | 2001-11-19 | 2002-11-18 | Procede de fabrication d'une fibre optique plastique, et fibre optique plastique obtenue par ce procede |
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US (1) | US20050062180A1 (fr) |
EP (1) | EP1451005A2 (fr) |
JP (1) | JP2005509912A (fr) |
KR (1) | KR20040066812A (fr) |
CN (1) | CN1606494A (fr) |
FR (1) | FR2832514B1 (fr) |
WO (1) | WO2003043805A2 (fr) |
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FR2832515B1 (fr) * | 2001-11-19 | 2004-01-30 | Nexans | Procede de fabrication d'une fibre optique plastique a gradient d'indice et fibre optique a gradient d'indice obtenue par ce procede |
US20050157999A1 (en) * | 2002-12-27 | 2005-07-21 | Zhen Zhen | Graded index polymer optical fiber and a method of making the same |
CN109540847B (zh) * | 2018-12-13 | 2021-10-19 | 山东师范大学 | 一种石墨烯/金/d型塑料光纤spr传感器及制备方法 |
WO2024011245A2 (fr) * | 2022-07-08 | 2024-01-11 | Samtec, Inc. | Guide d'ondes obtenu par fabrication additive |
Citations (4)
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EP0710855A1 (fr) * | 1994-04-18 | 1996-05-08 | Yasuhiro Koike | Resine a usage optique du type a repartition d'indice de refraction et son procede de production de cette resine |
US5618896A (en) * | 1994-05-06 | 1997-04-08 | Minnesota Mining And Manufacturing Company | Energy polymerizable compositions, homopolymers and copolymers of oxazolines |
EP1067222A1 (fr) * | 1999-07-05 | 2001-01-10 | Alcatel | Procédé de fabrication d'une fibre optique plastique à gradient d'indice |
EP0990509B1 (fr) * | 1998-10-01 | 2002-05-02 | Nexans | Fibre optique plastique à gradient d'indice et procédé de fabrication en continu d'une fibre optique plastique à gradient d'indice |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4138194A (en) * | 1977-10-14 | 1979-02-06 | E. I. Du Pont De Nemours And Company | Low attenuation optical fiber of deuterated polymer |
JP2762416B2 (ja) * | 1988-04-15 | 1998-06-04 | 三菱レイヨン株式会社 | 光伝送体の製造方法 |
JP2762417B2 (ja) * | 1988-04-15 | 1998-06-04 | 三菱レイヨン株式会社 | 光伝送体の製造方法 |
US5760139A (en) * | 1994-04-18 | 1998-06-02 | Yasuhiro Koike | Graded-refractive-index optical plastic material and method for its production |
JP3951404B2 (ja) * | 1998-01-26 | 2007-08-01 | 旭硝子株式会社 | 電気二重層キャパシタ |
FR2832515B1 (fr) * | 2001-11-19 | 2004-01-30 | Nexans | Procede de fabrication d'une fibre optique plastique a gradient d'indice et fibre optique a gradient d'indice obtenue par ce procede |
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2001
- 2001-11-19 FR FR0115038A patent/FR2832514B1/fr not_active Expired - Fee Related
-
2002
- 2002-11-18 WO PCT/FR2002/003932 patent/WO2003043805A2/fr not_active Application Discontinuation
- 2002-11-18 CN CNA028257782A patent/CN1606494A/zh active Pending
- 2002-11-18 EP EP02803435A patent/EP1451005A2/fr not_active Withdrawn
- 2002-11-18 US US10/496,100 patent/US20050062180A1/en not_active Abandoned
- 2002-11-18 JP JP2003545464A patent/JP2005509912A/ja not_active Withdrawn
- 2002-11-18 KR KR10-2004-7007348A patent/KR20040066812A/ko not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0710855A1 (fr) * | 1994-04-18 | 1996-05-08 | Yasuhiro Koike | Resine a usage optique du type a repartition d'indice de refraction et son procede de production de cette resine |
US5618896A (en) * | 1994-05-06 | 1997-04-08 | Minnesota Mining And Manufacturing Company | Energy polymerizable compositions, homopolymers and copolymers of oxazolines |
EP0990509B1 (fr) * | 1998-10-01 | 2002-05-02 | Nexans | Fibre optique plastique à gradient d'indice et procédé de fabrication en continu d'une fibre optique plastique à gradient d'indice |
EP1067222A1 (fr) * | 1999-07-05 | 2001-01-10 | Alcatel | Procédé de fabrication d'une fibre optique plastique à gradient d'indice |
Non-Patent Citations (3)
Title |
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PATENT ABSTRACTS OF JAPAN vol. 014, no. 025 (P-991), 18 janvier 1990 (1990-01-18) & JP 01 265207 A (MITSUBISHI RAYON CO LTD), 23 octobre 1989 (1989-10-23) & DATABASE WPI Derwent Publications Ltd., London, GB; AN 1989-353291 * |
PATENT ABSTRACTS OF JAPAN vol. 014, no. 025 (P-991), 18 janvier 1990 (1990-01-18) & JP 01 265208 A (MITSUBISHI RAYON CO LTD), 23 octobre 1989 (1989-10-23) & DATABASE WPI Derwent Publications Ltd., London, GB; AN 1989-353292 * |
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 13, 30 novembre 1999 (1999-11-30) & JP 11 214263 A (ASAHI GLASS CO LTD), 6 août 1999 (1999-08-06) * |
Also Published As
Publication number | Publication date |
---|---|
FR2832514B1 (fr) | 2004-01-30 |
US20050062180A1 (en) | 2005-03-24 |
FR2832514A1 (fr) | 2003-05-23 |
KR20040066812A (ko) | 2004-07-27 |
CN1606494A (zh) | 2005-04-13 |
EP1451005A2 (fr) | 2004-09-01 |
WO2003043805A3 (fr) | 2003-12-11 |
JP2005509912A (ja) | 2005-04-14 |
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